CA2016022A1 - Branched amido-amine dispersant additives - Google Patents
Branched amido-amine dispersant additivesInfo
- Publication number
- CA2016022A1 CA2016022A1 CA002016022A CA2016022A CA2016022A1 CA 2016022 A1 CA2016022 A1 CA 2016022A1 CA 002016022 A CA002016022 A CA 002016022A CA 2016022 A CA2016022 A CA 2016022A CA 2016022 A1 CA2016022 A1 CA 2016022A1
- Authority
- CA
- Canada
- Prior art keywords
- nitrogen
- adduct
- substituted
- groups
- containing compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 106
- 239000000654 additive Substances 0.000 title claims abstract description 85
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 192
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 63
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 54
- 239000002253 acid Substances 0.000 claims abstract description 48
- 229920000768 polyamine Polymers 0.000 claims abstract description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000098 polyolefin Polymers 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims description 107
- 238000006243 chemical reaction Methods 0.000 claims description 82
- 230000000996 additive effect Effects 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 57
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 239000003921 oil Substances 0.000 claims description 47
- 229910052757 nitrogen Inorganic materials 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 35
- 239000011541 reaction mixture Substances 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 239000010687 lubricating oil Substances 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
- 229920002367 Polyisobutene Polymers 0.000 claims description 22
- 125000000524 functional group Chemical group 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 150000002430 hydrocarbons Chemical group 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229940014800 succinic anhydride Drugs 0.000 claims description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 6
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229920000333 poly(propyleneimine) Polymers 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 claims description 3
- 150000005673 monoalkenes Chemical class 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims 4
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 claims 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 150000001412 amines Chemical class 0.000 abstract description 43
- 229920001281 polyalkylene Polymers 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 description 55
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 52
- 235000019198 oils Nutrition 0.000 description 42
- 239000000047 product Substances 0.000 description 31
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 30
- 150000002148 esters Chemical class 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 20
- 125000000217 alkyl group Chemical group 0.000 description 19
- 239000010802 sludge Substances 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 239000000446 fuel Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 14
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 239000012141 concentrate Substances 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 14
- 150000003141 primary amines Chemical class 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000002199 base oil Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 150000002596 lactones Chemical class 0.000 description 12
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 11
- 150000003335 secondary amines Chemical group 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000010688 mineral lubricating oil Substances 0.000 description 8
- 229910017464 nitrogen compound Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 125000003282 alkyl amino group Chemical group 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 150000003949 imides Chemical class 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 235000011044 succinic acid Nutrition 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 239000010689 synthetic lubricating oil Substances 0.000 description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical compound OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000002830 nitrogen compounds Chemical class 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 229960001124 trientine Drugs 0.000 description 4
- CXJAFLQWMOMYOW-UHFFFAOYSA-N 3-chlorofuran-2,5-dione Chemical compound ClC1=CC(=O)OC1=O CXJAFLQWMOMYOW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 230000000994 depressogenic effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004957 naphthylene group Chemical group 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003444 succinic acids Chemical class 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- CIRMGZKUSBCWRL-LHLOQNFPSA-N (e)-10-[2-(7-carboxyheptyl)-5,6-dihexylcyclohex-3-en-1-yl]dec-9-enoic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)C(\C=C\CCCCCCCC(O)=O)C1CCCCCC CIRMGZKUSBCWRL-LHLOQNFPSA-N 0.000 description 2
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 2
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
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- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 1
- 229960003986 tuaminoheptane Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2493—Organic compounds containing sulfur, selenium and/or tellurium compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds
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- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/42—Flashing oils or marking oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/50—Medical uses
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
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Abstract
ABSTRACT OF THE DISCLOSURE
The present invention is directed to branched amido-amine dispersant additives useful in oleaginous compositions formed by (a) reacting a first nitrogen-containing compound (e.g., ammonia or an organic amine) with an alpha, beta-unsaturated compound of the formula:
R1 - ? = ? - ? - Y
wherein W1 is sulfur or oxygen, Y is -OR4, -SR4, or -NR4 (R5), and R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl, to form a first adduct containing unreacted -C(W1)-Y groups; (b) reacting the first adduct with a polyamine (e.g., a polyalkylene polyamine) to form a second adduct containing unreacted -NH- groups (preferably primary amine groups) and comprising a branched amido-amine oligomer; and (c) reacting the second adduct with a long chain hydrocarbyl substituted mono- or dicarboxylic acid material comprising a polyolefin of 300 to 10,000 number average molecular weight substituted with at least 0.3 mono- or dicarboxylic acid producing moieties (preferably acid or anhydride moieties) per polyolefin molecule.
The present invention is directed to branched amido-amine dispersant additives useful in oleaginous compositions formed by (a) reacting a first nitrogen-containing compound (e.g., ammonia or an organic amine) with an alpha, beta-unsaturated compound of the formula:
R1 - ? = ? - ? - Y
wherein W1 is sulfur or oxygen, Y is -OR4, -SR4, or -NR4 (R5), and R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl, to form a first adduct containing unreacted -C(W1)-Y groups; (b) reacting the first adduct with a polyamine (e.g., a polyalkylene polyamine) to form a second adduct containing unreacted -NH- groups (preferably primary amine groups) and comprising a branched amido-amine oligomer; and (c) reacting the second adduct with a long chain hydrocarbyl substituted mono- or dicarboxylic acid material comprising a polyolefin of 300 to 10,000 number average molecular weight substituted with at least 0.3 mono- or dicarboxylic acid producing moieties (preferably acid or anhydride moieties) per polyolefin molecule.
Description
~016~22 FIELD OF THE INVENTION
This invention relates to improved oil soluble dispersant additives useful in fuel and lubricating compositions, and to concentrates containing said additives.
BACKGROUND OF TH~ INVENTION
U.S. Patent 2,921,085 relates to the preparation of beta-aminopropionamides by reaction of an alkyl amine with an acrylate to form an alkyl aminopropionate and reaction of the latter compound with an amine. The resulting compounds are disclosed to have utility as surface active agents, specifically as emulsifying, wetting, foaming and detergent agents.
U.S. Patent 3,337,60~ relates to adducts of hydroxyalkyl alkylene polyamines and acrylates. The resulting adducts are added to polyepoxides to provide compositions which are suitable for use as a barrier coating for polyethylene surfaces, and for additional end uses, such as in molding. In addition, the adducts are disclosed to be useful as catalysts in resin preparation and as corrosion inhibitors in water systems for ferrous metals.
U.S. Patent 3,417,140 relates to the preparation of amido-amine compositions, which are useful as epoxy resin curing agents, by reacting a polyalkylene polyamine and a fatty amine (comprising a mono- or diamine having as one of the substituents on a nitrogen atom a hydrocarbyl radical having 8 to 24 carbon atoms) with an alpha-beta unsaturated carbonylic compound. It is disclosed that this ~016~22 reaction occurs through the Michael addition of an amine group across the unsaturated group of the carbonylic compound and through the condensation of an amine group with the carbonylic group.
U.S. Patent 3,247,163 also relates to curing agents for polyepoxide compositions, which curing agents are prepared by reacting an organic amine and an acrylate.
U.S. Patent 3,445,441 relates to amino-amido polymers characterized by being a reaction product of at least a polyamine and an acrylate type compound, such as methyl or ethyl acrylate, and methyl or ethyl methacrylate. The patent states that the polymers are useful in a wide variety of applications, such as floculating agents, water clarifying additives, corrosion inhibitors in oil and gas wells, and as lube oil additives. The patent further discloses that the polymers may be derivitized, including acylation with monocarboxylic acids and polycarboxylic acids, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, for example, diglycolic, phthalic, succinic, etc., acids.
U.S. Patent 3,~03,003 relates to lubricating compositions containing an amido-amine reaction product of a terminally carboxylated isoprene polymer which is formed by reacting a terminally carboxylated substantially completely hydrogenated polyisoprene having an average molecular weight between about 20,000 and 250,000 and a nitrogen compound of the group consisting of polyalkylene amines and hydroxyl polyalkylene amines.
U.S. Patent 4,493,771 relates to scale inhibiting with compounds containing quaternary ammonium and methylene phosphonic acid groups. These compounds are derivatives of polyamines in which the amine hydrogens have been substituted with both methylene phosphonic acid groups or their salts and hydroxypropyl quaternary ammonium halide groups. The patent discloses that any amine that contains ~16022 reactive amino hydrogens can be utilized, for example, polyglycol amines, amido-amines, oxyacylated amines, and others.
U.S. Patent 4,459,241 contains a similar disclosure to U.S. Patent 4,493,771.
SUMMARY OF THE INVENTION
A process for forming a nitrogen-containing lubricating oil dispersant additive which comprises: (a) contacting in a first liquid reaction mixture a first nitrogen-containing compound having at least two reactive nitrogen moieties with a polyfunctional reactant having within its structure a first functional group reactive with a -NH- group, and at least one additional functional group reactive with a -NH- group, in an amount and under conditions sufficient to selectively react the first functional groups in the polyfunctional reactant with the reactive nitrogen moieties to form a first reaction mixture containing a first adduct; (b) contacting the first adduct with a second nitrogen-containing compound having at least two -NH- groups in an amount and under conditions sufficient to react the additional functional groups in the first adduct with said -NH- groups in the second nitrogen-containing compound to form a second adduct characterized by having within its structure on average (i) at least two nitrogen-containing moieties derived from the second nitrogen-containing compound per nitrogen-containing moiety derived from the first nitrogen-containing compound and (ii) at least two unreacted primary or secondary amine groups per molecule; and (c) contacting the second adduct in a second liquid reaction mixture with at least one long chain hydrocarbon-substituted reactant in an amount and under conditions sufficient to form the nitrogen-containng dispersant, said long chain hydrocarbon-substituted reactant comprising at least one member selected from the group consisting of;
tA) long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups;
(B~ halogenated long chain hydrocarbons;
(C) mixtures of formaldehyde and a long chain hydrocarbyl substituted phenol; and (D) mixtures of formaldehyde and a reaction product formed by reaction of long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups and an amino-substituted, optionally hydrocarbyl-sub-stituted phenol.
In one preferred embodiment, the present invention is directed to a branched amido-amine dispersant additive, and more preferably to a star branched amido-amine dispersant additive, useful in oleaglnous compositions formed by (a) reacting a first nitrogen- containing compound (e.g., ammonia or an organic amine) with an alpAa, beta-unsaturated compound of the formula:
~2 R3 wl R - C = C - C - Y
wherein W1 i5 sulfur or oxygen, Y is -oR4, -SR4, or ~R4 (R5) and Rl R2 R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstitut2d hydrocarbyl, to form a first adduct containing unreacted -C(Wl)-Y groups; (b) reacting the first adduct with a polyamine (e.g., a polyalkylene polyamine) to form a second adduct containing unreacted -NH- groups (preferably primary amine groups) and comprising a branched amido-amine oligomer, and (c) reacting said second adduct with a long chain hydrocarbyl substituted mono- or dicalboxylic acid material comprising a polyolefin of 300 to 10,000 number average molecular weight substituted with at least 0.3 (e.g., from about 1 to 4) mono- or dicarboxylic acid producing moieties ~0~22 (preferably acid or anhydrlde moieties) per polyolefin molecule.
The materials of the invention are different from the prior art because of their effectiveness and their ability to provide enhanced dispersancy. In fuels, the additives serve to minimize the degree of carburetor and fuel iniector fouling from deposits. In addition, the additives of this invention possess superior viscometric properties.
Therefore, the present invention is also directed to novel processes for preparing the dispersant fuel adducts of this invention.
DETAILED ~ESCRIPTION OF THE INVENTION
FIRST NITROGEN-CONTAINING COMPOUND
As described above, the first adduct employed in the present invention is prepared by contacting a polyfunctional reactant with a first nitrogen-containing compound containing at least two (e.g., from 2 to 20), preferably at least 3 te.g., from 3 to 15), and most preferably from 3 to 8, reactive nitrogen moieties (that is, the total of the nitrogen-bonded H atoms) per molecule of the first nitrogen-containing compound. The first nitrogen-containing compound will generally comprise at least on~ member selected from the group consisting of ammonia, organic primary monoamines and organic polyamines containing at least one primary amine group or at least two secondary amine groups per molecule. Generally, the organic amines will contain from about 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total carbon atoms and about 2 to 12, preferably 3 to 12, and most preferably from 3 to 8 (e.g., 5 to 9) total nitroyen atoms in the molecule. These amines may be hydrocarbyl amines or may be hydrocarbyl ~mines including other groups, e.g, hydroxy groups, alkoxy ~0~ ~022 groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularly useful. Preferred amines are aliphatic saturated amines, including those of the general formulas:
R-N-R', and R-N-(CH2)s ~ N-(CH2)s ~ N-R
R" R' L R''' R' t (I) (II~
wherein R, R', R'' and R''' are independently selected from the group consisting of hydrogen; Cl to C~5 straiqht or branched chain alkyl radicals; C1 to C12 alkoxy C2 to C6 alkylene radicals; C2 to C12 hydroxy amino alkylene radicals; and Cl to C12 alkylamino C2 to C6 alkylene radicals; and wherein R"' can additionally comprise a moiety of the formula:
~CH2)s' -N ~ H (III~
I t~
R' wherein R' is as defined above, and wherein s and s' can be the same or a different number of from 2 to 6, preferably 2 to 4; and t and t' can be the same or different and are numbers of from O to 10, preferably 2 to 7, and most preferably about 3 to 7, with the proviso that the sum of t and t' is not greater than 15. To assure a facile reaction, it is preferred that R, R', R'', R''', s, s', t and t' be selected in a manner sufficient to provide the compounds of Formulas I and II with typically at least one primary or secondary amine group, preferably at least two primary or secondary amine groups. This can be achieved by selecting at least one of said R, R', R" or R''' groups to be hydrogen or by letting t in Formula II he at least one when R"' is H or when the III moiety possesses a secondary amino group.
20~6~22 Non-limitinq examples of suitable organic amine compounds include~ 1,2-diaminoethane; 1,3-diaminopropane;
1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such as diethylene triamine; triethylene tetra;
tetraethylene pentamine; polypropylene amines such as 1,2-propylene diamine; di-(1,2-propylene)triamine;
d i - (1, 3 -p r op yl e n e) t ri am i ne ;
N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);
diisopropanol amine; diethanol amine; trie~hanol amine;
mono-, di-, and tri-tallow amines; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof.
Other useful amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl piperazines of the general formula (IV~:
H ~ -(C~)p ~ ~ 2 2~
wherein P1 and P2 are the same or different and are each integers of from 1 to 4, and nl, n2 and n3 are the same or different and are each integers of from 1 to 3. Non-limiting examples of such amines include 2~pentadecyl imidazoline: N-(2-aminoethyl) piperazine; etc.
Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines invol~es the reaction of an involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylen~ dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, ~16~22 triethylenetetra, tetraethylene pentamine and isomeric piperazines. Low cost poly~ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.
Useful amines also include polyoxyalkylene polyamines such as those of the formulae:
NH2 alkylene ~ O-alkylene ~ NH2 (V~
m where m has a value of about 3 to 70 and preferably 10 to 35; and R ~ alkylenef ~ -alkylen ~ NH2 n P (VI) where "n" has a value of about 1 to 40 with the provision that the sum of all the n's is from about 3 to about 70 and preferably from about 6 to about 35, and R is a polyvalent saturated hydrocarbon radical of up to ten carbon atoms wherein the number of substituents on the R group is represented by the value of "p", which is a number of from 3 to 6. The alkylene groups in either formula (V) or (VI~
may be straight or branched chains containing about 2 to 7, and preferably about 2 to 4 carbon atoms.
The polyoxyalkylene polyamines of formulas (V) or (VI) above, preferably polyoxyalkylene diamines and polyoxyalkylene triamines, may have average molecular weights ranging from about 200 to about 4000 and preferably from about 400 to about 2000. The preferred polyoxyal-kylene polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2000. The polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc.
~6~22 under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.
Additional amines useful in the present invention are described in U.S. Patent 3,445,441, the disclosure of which is hereby incorporated by reference in its entirety.
Most preferred as the first nitrogen-containing compound are members selected from the group consisting of ammonia and organic diprimary amines having fxom 2 to 12 carbon atoms and from 2 to 8 nitrogen atoms per molecule.
Examples of such preferred organic diprimary amines are ethylene diamine, propylene diamine, diethylene triamine, dipropylene triamine, triethylene tetraamine, tripropylene tetraamine, tetraethylene pentaamine, tetrapropylene pentaamine, polyhexamethylene diamine, phenyl diamine.
POLYFUNCTIONAL REACTANT
Polyfunctional reactants useful in this invention include compounds having the formula (VII):
~1 w2 x ~ c ~ (T)a ~ [ (C)b- Y]c wherein Wl and w2 are the same or different and are O
or S, X and Y are the same or different, and preferably are each groups reactive with a ~NH- group (i.e., with NH3 or with primary or secondary amine groups), T is a substituted or unsubstituted hydrocarbon moiety, "a" is 0 or 1, "b" is 0 or 1, and "c" is an integer of at least 1, with the provisos that c = 1 when a = 0 and b = 1 when a = 1 , and with the further proviso that at least two of X, Y and T
are reactive with a -NH- group.
The X and ~ functional groups are the same or different and include groups selected from the group consisting of: halide, -oR4, -SR4, -N(R4)(R5) _ z 1 C (O) oR4, - C (O) R4 , --(R3) C = C (R 1) (R2) -zl-nitrlle, -Zl-cyano, -Zl-thiocyano, -Z1-isothiocyano, and -Z1-isocyano, wherein Rl, R2, R3, R4 and R5 are the same or different and are H or substituted or unsubstituted hydrocarbyl and wherein zl is Cl to C20 (preferably Cl to C10) bivalent hydrocarbylene (preferably alkylene or arylene). If a = b = 1, and T contains at least one >C=C< group, X and Y can together further comprise -O- or -S-, to provide as reactants a class of ethylenically unsaturated and aromatic anhydrides and sulfo~anhydrides. Preferably the X and Y
groups in the selected polyfunctional reactant are different, and the reactivity of the X moiety with -N~-groups, under the selected reaction conditions, is greater than the reactivity of the Y moieties with such -NH- groups to permit a substantially selective reaction of the X
groups with the first nitrogen-containing compound as described below. The relative reactivity of these groups on a polyfunctional reactant can be readily determined by conventional methods.
Wh en R 1 R 2 R3, R4 or R 5 a r e hydrocarbyl, these groups can comprise alkyl, cycloalkyl, aryl, alkaryl r aralkyl or heterocyclic, which can be substituted with groups which are substantially inert to any component of the reaction mixture under conditions selected for preparation of the amido-amine. Such substituent groups include hydroxy, halide (e.g., Cl, Fl, I, Br), -SH and alkylthio. When one or more of R1 through R5 are alkyl, such alkyl groups can be straight or branched chain, and will generally contain from 1 to 20, more usually from 1 to 10, and preferably from 1 to 4, carbon atoms. Illustrative of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and the like. When one or more of Rl through R5 are aryl, the aryl group will generally contain from 6 to 10 carbon atoms (e.g., phenyl, naphthyl).
2~1 6~22 When one or more of Rl through R5 are alkaryl, the alkaryl group will generally contain from about 7 to 20 carbon atoms, and preferably from 7 to 12 carbon atoms.
Illustrative of such alkaryl groups are tolyl, m-ethyl-phenyl, o-ethyltolyl, and m-hexyltolyl. When one or more of R through R5 are aralkyl, the aryl component generally consists of phenyl or (Cl to C6) alkyl-sub-stituted phenol and the alkyl component generally contains from 1 to 12 carbon atoms, and preferably from 1 to 6 carbon atoms. Examples of such aralkyl groups are benzyl, o-ethylbenzyl, and 4-isobutylbenzyl. When one or more of Rl and R5 are cycloalkyl, the cycloalkyl group will generally contain from 3 to 12 carbon atoms, and preferably from 3 to 6 carbon atoms. Illustrative of such cycloalkyl groups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, and cyclododecyl. When one or more of Rl through R5 are heterocyclic, the heterocyclic group generally consists of a compound having at least one ring of 6 to 12 members in which on one more ring carbon atoms is replaced by oxygen or nitrogen. Examples of such heterocyclic groups are furyl, pyranyl, pyridyl, piperidyl, dioxanyl, tetra-hydrofuryl, pyrazinyl and 1,4-oxazinyl.
T is a polyvalent organic radical whose valence is equal to c + 1, wherein "c" is an integer of at least 1, preferably 1 to 3. Ordinarily T will not contain more than 20 carbon atoms and preferably not more than 10 carbon atoms. T can therefore include divalent groups such as as saturated and unsaturated hydrocarbylene (e.g., alkylene, alkenylene, arylene, and the like). When T ;s substituted, it can contain one or more substituents selected from the class consisting of halo, lower alkoxy, lower alkyl mercapto, nitro, lower alkyl, carboxy and oxo. It also may contain interrupting groups such as -O-, -S-, -S(O)-, -S(O)2-, -NH-, -C(O)- and the like.
Exemplary O f zl groups are Cl to C10 branched and straight chained alkylene such as -(CH2)f-wherein "f" is an integer of from 1 to 10 (e.g., -CH2-, C H ~ -C3 H7 -, - C4 H8 ~, - C 5H 1 o ~ a n like), and C6 to C20 arylene, and alkyl-substituted arylene such as -Ar-, -Ar-((CH2)f)-, -((CH2)f)-Ar-, -Ar-~(CH2)f)-~r- and the like, wherein Ar is phenylene, methylphenylene, naphthylene, methylnaphthylene and the like and wherein f is as defined above.
Examples of polyfunctional reactants of formula VII wherein X is (Rl)(R2)C=C(R3)-, a = b = O and c =
1 are difunctional reactants comprising alpha, beta-ethylenically unsaturated compounds selected from the group consisting of compounds of the formula:
R2 R3 wl R - C = C - C - Y (VIII) wherein Wl is sulfur or oxygen, Y is as defined above, and is preferably -oR4, -SR4, or -NR4(R5), wherein Rl, R2, R3, R4 and R5 are as defined above.
The alpha, beta-ethylenically unsaturated carboxylate compounds employed herein have the following formula:
R2 R3 o Rl- C = C - ~C - oR4 (IX) w h erein Rl, R2, R3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of such alpha, beta-ethylenically unsaturated carboxylate compounds of formula IX are acrylic acid, methacrylic acid, the methyl, ethyl, isopropyl, n-butyl, and isobutyl esters of acrylic and methacrylic acids, 2-butenoic acid, 2-hexenoic acid, 2-decenoic acid, 3-methyl-2-heptenoic acid, 3-methyl-2-butenoic acid, 3-phenyl-2-propenoic acid, 3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid, 2-propyl-2-propenoic acid, 2-isopropyl-2-hexenoic acid, 2,3-dimethyl ~Ot6022 -2-butenoic acid, 3-cyclohexyl-~-methyl-2-pentenoic acid, 2-propenoic acid, methyl 2-propenoate, methyl 2-methyl 2-propenoate, methyl 2-butenoate, ethyl 2-hexenoate, isopropyl 2-decenoate, phenyl 2-pentenoate, tertiary butyl 2-propenoate, octadecyl 2-propenoate, dodecyl 2-decenoate, cyclopropyl 2,3-dimethyl-2-butenoate, methyl 3-phenyl-2-propenoate, and the like.
The alpha, beta-ethylenically unsaturated reactants of formula IX wherein -oR4 is instead -R4 are aldehydes and ketones of the formula:
R2 R3 o Rl- C = C - C - R4 (IXa) wh erein R1, R2, R3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined abo~e. Examples of such alpha, beta-ethylenically unsaturated aldehydes and ketones of formula IXa are:
H2c=cH-c(o)-cH3 H2C=CH-C (O) -C2H5 H2C=CH-C~O)-C3H7 H2C=CH-C(O)-C~cH3)3 H2c=cH--c ()--C5~11 H2C=C(CH3)-C(O)-CH(cH3)2 H2C=C(CH3)-c(O)-c2H5 H(cH3)c=cH-c(o)-cH3 H(CH3)C=CH-C(O)-CH(CH3)2 H(CH3)C=CH-C()~C2H5 H(CH3)c=cH-c(o)-c3H7 H(C2H5)C=CH-C(O)-c(cH3)3 H(CH3)C=CH-c(O)-csHll (CH3)(c2Hs)c=c(cH3)-c(o)-cH3 H(CH3)C=C(cH3)-c(O)-c2H5 ~016~22 The alphal beta-ethylenically unsaturated carboxylate thioester compounds employed herein have the following formula:
Rl- C = C _ll _ SR4 (X) w h erein Rl, R2, ~3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of such alpha, beta-ethylenically unsaturated carboxylate thioesters of formula X are methylmercapto 2-butenoate, ethylmercapto 2-hexenoate, isopropylmercapto 2-decenoate, phenylmercapto 2-pentenoate, tertiary butylmercapto 2-propenoate, octa-decylmercapto 2-propenoate, dodecylmercapto 2-decenoate, cyclopropylmercapto 2,3-dimethyl-2-butenoate, methyl-mercapto 3-phenyl-2-propenoate, methylmercapto 2-pro-penoate, methylmercapto 2-methyl-2-propenoate, and the like.
The alpha, beta-ethylenically unsaturated carboxyamide compounds employed herein have the following formula:
R - C = C - C - NR4(R5) (XI~
wherein Rl, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated carboxyamides of formula XI
are 2-butenamide, 2-hexenamide, 2-decenamide, 3-methyl-2-heptenamide, 3-methyl-2-butenamide, 3-phenyl-2-propenamide, 3-cyclohexyl-2-butenamide, 2-methyl-2-butenamide, 2-propyl-2-propenamide, 2-isopropyl-2-hexenamide, 2,3-dimethyl-2-butenamide, 3-cyclohexyl-2-methyl-2-pentenamide, N-methyl 2-butenamide, N,N-diethyl 2-hexenamide, N-isopropyl 2-decenamide, N-phenyl 2-pentenamide, N-tertiary butyl 2-propenamide, ~01~22 N-octadecyl 2-propenamide, N,N-didodecyl 2-decenamide, N-cyclopropyl 2,3-dimethyl-2-butenamide, N-methyl 3-phenyl-2-propenamide, 2-propenamide, 2-methyl-2-pro-penamide, 2-ethyl-2-propenamide and the like.
The alpha, beta-ethylenically unsaturated thiocarboxylate compounds employed herein have the following formula:
R~ - oR4 (XII) wherein Rl, R2, R3 and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated thiocarboxylate compounds of formula XII are 2-butenthioic acid, 2-hexenthioic acid, 2-decenthioic acid, 3-methyl-2-heptenthioic acid, 3-methyl-2-butenthioic acid, 3-phenyl-2-propenthioic acid, 3-cyclohexyl-2-butenthioic acid, 2-methyl-2-butenthioic acid, 2-propyl-2-propenthioic acid, 2-isopropyl-2-hex-enthioic acid, 2,3-dimethyl-2-butenthioic acid, 3-cyclo-hexyl-2-methyl-2-pententhioic acid, 2-propenthioic acid, methyl 2-propenthioate, methyl 2-methyl 2-propenthioate, methyl 2-hutenthioate, ethyl 2-hexenthioate, isopropyl 2-decenthioate, phenyl 2-pententhioate, tertiary butyl 2-propenthioate, octadecyl 2-propenthioate, dodecyl 2-decenthioate, cyclopropyl 2,3-dimethyl-2-butenthioate, methyl 3-phenyl-2-propenthioate, and the like.
The alpha, beta-ethylenically unsaturated dithioic acid and acid ester compounds employed herein have the following formula:
R1- C = C - C - SR4 (XIII) wn erein R1, R2, R3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated dithioic acids and acid 20~ 6~22 esters of formula XIII are 2-butendithioic acid, 2-hexendithioic acid, 2-decendithioic acid, 3-methyl-2-hep-tendithioic acid, 3-methyl-2~butendithioic acid, 3-phenyl-2-propendithioic acid, 3-cyclohexyl-2-buten-dithioic acid, 2-methyl-2-butendithioic acid, 2-propyl-2-propendithioic acid, 2-isopropyl-2-hexendithioic acid, 2,3-dimethyl-2-butendithioic acid, 3-cyclohexyl-2-methyl-2-pentendithioic acid, 2-propendithioic acid, methyl 2-propendithioate, methyl 2-methyl 2-propendithioate, methyl 2-butendithioate, ethyl 2-hexendithioate, isopropyl 2-decendithioate, phenyl 2-pentendithioate, tertiary butyl 2-propendithioate, octadecyl 2-propendithioate, dodecyl 2-decendithioate, cyclopropyl 2,3-dimethyl-2-butendithioate, methyl 3-phenyl-2-propendithioate, and the like.
The alpha, beta-ethylenically unsaturated thiocarboxyamide compounds employed herein have the following formu:la:
R - C = C - C - NR4(R5) (XIV) wherein Rl, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated thiocarboxyamides of formula XIV are 2-butenthioamide, 2-hexenthioamide, 2-decen-thioamide, 3-methyl-2-heptenthioamide, 3-methyl-2-buten-thioamide, 3-phenyl-2-propenthioamide, 3-cyclohexyl-2-buten-thioamide, 2-methyl-2-butenthioamide, 2-propyl-2-propen-thioamide, 2-isopropyl-2-hexenthioamide, 2,3-di-methyl-2-butenthioamide, 3-cyclohexyl-2-methyl-2-penten-thioamide, N-methyl 2-butenthioamide, N,N-diethyl 2 hexenthioamide, N-isopropyl 2-decenthioamide, N-phenyl 2-pententhioamide, N-tertiary butyl 2-propenthioamide, N-octadecyl 2-propenthioamide, N,N-didodecyl 2-decen-thioamide, N-cyclopropyl ~,3-dimethyl-2-butenthioamide, ~016022 ~ 17 -N-methyl 3-phenyl-2-propenthioamide, 2-propenthioamide, 2-methyl-2-propenthioamide, 2-ethyl-2-propenthioamide and the liXe.
Exemplary of polyfunctional reactants of formula VII wherein a = b = c = 1 ar~ compounds of the formula (XV):
wl w2 X - C ~ T - C - Y
wherein Wl, W2, X, ~ and T are as defined above and wherein X and Y are different. Preferred members of this class of reactants are compounds of the formula (XVI):
O O
li \l X - C - T' - C - Y
wherein X and Y are as defined above, wherein X and Y are different and wherein T' is substituted or unsubstituted divalent Cl to C20 (preferably, Cl to C10) y or alkenylene e.g -C2H5-, -(CH2~3-' -(~H2)4-~
-CH=CH-, -C~CH2)-CH2-, and the like, or C6 to C20 ~preferably, C6 to C14) divalent substituted or unsubstituted arylene such as phenylene, naphthylene, bisphenylene, -phenyl-O-phenyl- and the like. Illustrative of bisfunctional reactants of formula XVI are:
H2C=CH-C(O)-CH-C(O)-OCH3 H2C=CH-C(O)-C2H4-C(O)-OCH3 2 CH C(O) C2H4-C(O)-OC2H5 H2C=CH-C (O) -C3H6-C (O) -Cl H2C=CH-c(o)-c2H4-c(o)-sH
2 CH C(O) C5H1o~C(O)~SCH3 H2c=c(CH3)-c(o)-c2H4-c(o)-OcH3 H2c=c~CH3)-c(o)-c2H4-c~o)-oc2H5 H2C=C~-C(O)-CH-C(O)-CH
H2C=CH-C(O)-C2H4-C(O)-CH3 20~6022 H2C=CH-C (O) -C2H4-C (O) -C2H5 H(CH3)C=CH-C(O)-CH2-C(O)-OCH3 H(cH3)c=cH-c(o)-c2H4-c(o)-ocH3 H(CH3)C=CH-C(O)-c2H4-c(O)-oc H
H(CH3)C=CH-C(O)-C3H6-C(O~-Cl H(C2H5)C=CH~C(O)-C2H4-C(O)-SH
H(cH3)c=cH-c(o)-c5Hlo-c(o)-sc~3 (CH3)(c2H5)c=c(cH3)-c(o)-c2H4-c(o~-OCH3 H(cH3)c=c(cH3)-c(o)-~2H4-c(o)-oc2H5 H(CH3)C=CH-C(O)-CH2-C(O)-CH3 H(CH3)C=CH-C(O)-C2H4-C(O)-CH3 H(cH3)c=cH-c(o)-c2H4-c(o)-c2H5 Cl-C(O)-C'H2-C(O)-OCH3 Cl-c(o)-c2H4-c(o)-OcH3 Cl C () C2H4 C (O) -OC2H5 Cl-C(o)-c3H6-c(o)-OH
Cl-C(O)-C2H4-C(O)-sH
Cl-C(o)-c5Hlo-c(o)-scH3 Cl-C(o)-c2H4-c(o)-OcH3 Cl-C(O)-C2H4-C(a)-oc2H5 Cl-C(O)-CH2-C(O)-CH3 Cl-c(o)-c2H4-c(o)-cH3 Cl-C (O) -C2H4-C (O) -C2H5 CH30-C(O)-CH2-C(O)-OH
CH3o-c(o)-c2H4-c(o)-oH
CH30 C(O) C2H4 C(O) SH
CH30 C(O) C3H6 C(O) Cl C2H5o-c(o)-c2H4-c(o)-sH
CH3o-c(o)-c5Hlo-c(o)-scH3 CH3s-c(o)-cH2-c(o)-ocH3 CH3-c(o)-cH2-c(o)-OH
CH3 C(O) C2H4 C(O) OH
~16~22 H3 C(O~ C2H4 C(O)-SH
Exemplary of reactants of fo~mula VII wherein a =
b = c - 1, Wl and w2 are O, T contains a >C=C< group and wherein X and Y togeth~r comprise O- or -S~ are:
Il~o ~ ~ b chloromaleic anhydride, and the like.
Exemplary of polyfunctional reactants of formula VII wherein a = b = 1 and c > 1 are compounds of the formula (XVII):
wl w2 ~1 11 X - C - T - [ (C)- Y]c wherein Wl, W2, X, Y, T and "c" are as defined above and wherein X and Y are different. Illustrative of compounds of formula XVII above are:
H~C=CH-C(O)-CH2--[C(O)-OCH3~2 H2c=cH-c(o)-c2H3-[c(o)-OCH3]2 H2C=CH-C(O)-ARYL-~C(O)-OCH3]2 H2C=CH-C(O)-ARYL-[C(O)-OCH3]2 2 H C(O) C2H3 [C(O)-OC2H5]2 C2C=CH-C(O)-NAPTHYL-[C(O)-OCH3]2 C2C=CH-C(O)-NA~HTHYL-~C(O)-OCH3]2 H2C=CH-C(O)-c2H3-[c(o)-oc2H5]2 H2C=CH-C(O)-C3H5-[C~O)-cl]2 H2C=CH-[C() -C2H3-[C(O) -SH]2 H2C=CH-C(O)-C5Hg-[~(O)-scH3]2 H2C=C(CH3) -C(O) -C2H3-[C(O) -OCH3]2 2~16~2 H2C=C(CH3) -C(O) -C2H3-[C(O) -OC2H5]2 H2c=cH-c(o)-cH2-[c(o)-cH3]2 H2C=CH-C(O)-C2H3-[C(O)-CH3]2 H2C=CH-C(O)-ARYL-[C(O)-CH3]2 H(CH3)C=CH-C(O)-CH-[C(O)-OCH3]2 H(CH3)C=CH-C(O) C2H3-[C(O)-OCH3]2 H(CH3)C=CH-C(O)-C2H3-[C(O)-OC2H5]2 H(CH3)C=CH-C(O)-c3H5-[c(Q)-cl]2 H(c2H5)c=cH-c(o)-c2H3-[c(o)-sH]2 H(CH3)C=CH-C(O)-C5H9-[C(O)-SCH3]2 (cH3)(c2H5)c=c(cH3)-c(o)-c2H3-[c(o)-OcH3]2 H(CH3)C=C(CH3)-C()-C2H3-[C()-C2H5]2 H(cH3)c=cH-c(o)-cH-[c(o3-cH3]2 H(cH3)c=cH-c(o)-c2H3-[c(o)-cH3]2 H(CH3)C=CH-C()-C2H3-[C()-C2H5]2 Cl-C(O)-CH-[C(O)-OCH3]2 Cl-C(O)-C2H3-[C(O)-OcH3]2 Cl-C(O)-C2H3-[c(o)-oc2H5]2 Cl-C(O)-C3H5-[c(O)-oH]2 Cl-C(O)-C2H3-[C(O)-sH]2 Cl-C(O)-C5Hg-[C(O)-scH3]2 Cl-C(O)-C2H3-[C(O)-OcH3]2 Cl-C(o)-c2H3-[c(o)-oc2H5]2 Cl-C(O)-CH-[C(O)-cH3]2 Cl-C(O)-C2H3-[C(O)-cH3]2 cl-C(o)-c2H3-[c(o)-c2H5]2 CH30-C(O)-CH-[c(O)-OH]2 CH30-C(O)-C2H3-[C(O)-OH]2 CH30-C(O)-C2H3-[C(O)-sH]2 CH30-C(O)-C3H5-[c(O)-cl]2 C2H5-C()-C2H3-[C()-SH]2 CH30-C(O)-C5Hg-[C(O)-SCH3]2 201~02~
CH3S-C(O)-CH-[C(O)-OcH3]2 CH3-C(O)-CH-[c(O)-oH]2 CH3-C(O)-C2H3-[c(o)-OH~2 CH3-CtO)-C2H3-[c(o)-sH]2 Exemplary of the polyfunctional reactants of formula VII wherein a = O and b = c = 1 are bisfunctional compounds of the formula (XIX):
~ W2 X -- C -- C -- Y
wherein Wl, W2, X and Y are as defined above and wherein X and Y are different. Illustrative of compounds of formula XIX above are:
C2c=cH-c(o)-c(o)-ocH3 C2C=CH-C(O)-C(O)-OCH3 H2C=C~-C (O)--C (O) -OC2H5 ~I2C=CH-C (O) -C (O) -Cl H2C=CH-C(O)-C(O)-SH
H2c=cH-c(o)-c(o)-scH3 H2C=C(CH3)~C()~C()~CH3 H2C=C(CH3)~C()~Ct)~C2H5 C2C=CH-C(O)-C(O)-CH3 C2c=cH-c(o)-c(o)-cH3 H2C=CH-C (O) -C (O) -C2H5 H(CH3)C=CH-C(O)-C(O)-OCH3 H(CH3)C=CH-C(O)-C(O)-OCH3 H(CH3)C=cH-c(o)-c(o)-oc2H5 H(CH3)C=CH-C(O)-c(O)-cl H(c2Hs)c=cH-c(o)-c(o)~sH
H(~H3)C=CH-C(O)-C(O)-SCH3 (CH3)(c2~s)c=c(cH3)-c(o)-c(o)-ocH3 H(CH3~C=C(CH3)_c(o)-c(o)-oc2H5 ~016~22 ~ 22 -H(CH3)C=CH-C~O)-C(O)-C~3 H(CH3)C=CH-C(O)-C(O)-CH3 H(CH3)C=CH-C(O)-C(O)-c2H5 Cl-C(O)-C(O)-OCH3 Cl-C(O)-C(O)-OCH3 Cl C (O~ -C (O) -OC2H5 Cl-C(O)-C(O)-OH
Cl-C(O)-C(O)-SH
Cl-C(O)-C(O)-SCH3 Cl-C(O)-C(O)-OCH3 Cl-C (O) -C (O) -OC2H5 Cl-C(O)-C(O)-CH3 Cl-C(O)-C(O)-CH3 Cl--C (O) -C (O) -C2H5 CH30-C(O)-C(O)-OH
C2H5-C(O)-C(O)-OH
CH30-C(O)-C(O)-SH
CH30-C(O)-C(O)-Cl C2Hso-c(o)~c(o)-sH
CH30-C(O)-C(O)-SCH
CH30-C(O)-C(O)-OCH3 CH3-C(O)-C(O)-OH
C2H5-C(O)-C(O)-OH
CH30-C(O)-C(O)-SH
Also useful as polyfunctional reactants in the present invention are compounds of the formula (XX):
wl O
1~ 11 RlOC -(CH2)dlS((cH2)d2 CH C \
~
o ~6022 wherein Rl and Wl are as defined above, and wherein "dl" and "d2" are each integers of from 1 to 10;
compounds of the formula (XXI):
~ 1 R l - C = C - S - Y "
wherein Rl, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above, and wherein Y" comprises a reactive functional group selected from the group consisting of:
halide, -oR4, -SR4, -N(R4)(R5), -ZlC(o)oR4 and -(R3)C=C(R1)(R2), wherein R4 is H or substituted or unsubstituted hydrocarbyl as defined above, and compound~ of the formula (XXIa):
Rl- C = C - CN
wherein Rl, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
Examples of such compounds of formula XX are:
CH30C(O)C2H4SCH2 ANHY
CH30C(O)CH2SCH2-ANHY
CH30C(O)C3H6SCH2-ANHy CH30C(0)C(CH3)2SCH2-ANHY
CH3oc(o)cH(cH3)scH2-ANHy C2H50C(O)C2H4SCH2 ANHY
C2H50C(O)CH2SCH2-ANHy C2H50C(O)C3H6SCH2 ANHY
C2H50C(0)C(CH3)2SCH2 ANHY
C2H50C(O)CH(CH3)SCH2 ANHY
wherein ANHY is thP moiety:
~016022 ~, O
-- C~ -- C
~o ~0 Examples of such compounds of formula XXI are:
H2C=CH-S () 2-0C113 H2C=CH--S(~)2-C~3 H2C=CH-S (O) 2-OC2H5 H2C=CH 'S (~)) 2-Cl H2c=c~-s~o)2-sH
H2C=C~-S () 2-SCH3 H2C=C(CH3)-s~o)2-ocH3 H2c=c(cH3)-s(o)2-oc2H5 H2C=CH-S(0)2-OCH(CH3)2 H(CH3)C=CH-S(o)2-OCH3 H(cH3)c=cH-s(o)-2-ocH3 H(CH3)c=cH-s(o)2-oc2H5 H(CH3)~=CH-S(o)2-cl H(c2H5)c=CH-S(o)2-sH
H(CH3)C=CH-S(o)2-scH3 (cH3)(c2Hs)c=c(cH3)-s(o)2 OCH3 H(CH3)C=C(CH3)-S(0)2-oc2H5 Examples of such compounds of formula XXIa are:
H2C=CH-CN
H2c=c(cH3)-cN
H(CH3)C=CH-CN
H(C2H5)C=CH-CN
H(cH3)c=c(cH3)-cN
(cH3)(c2H5)c=c(CH3)-CN
2Q~6~22 Preferred compounds for reaction with the first nitrogen-containing compound in accordance with this invention are lower alkyl esters of acrylic and lower alkyl alpha-substituted acrylic acid. Illustrative of suh preferred compounds are compounds of the formula:
CH2 = C ~ CoR4 (XXII) where R3 is hydrogen or a C1 to C4 alkyl group, such as methyl, and R4 is hydrogen or a C1 to C4 alkyl group, capable of being removed so as to form an amido group, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tart-butyl, aryl, hexyl, etc. e.g., propyl acrylate and propyl methacrylate. In the most preferred embodiments these compounds are acrylic and methacrylic esters such as methyl or ethyl acrylate, methyl or ethyl methacrylate.
The polyfunctional reactants useful in this invention are known materials and can be prepared by conventional methods known to those skilled in the art, which need not be decribed herein.
PREPARATION OF_THE FIRST ADDUCT
The selected first nitrogen-containing compound and polyfunctional reactant are contacted in a first reaction mixture in an amount and under conditions sufficient to react the X functional groups of the latter with at least a portion of, and preferably substantially all of, the reactive nitrogen moieties in the first nitrogen-containing compound.
In preparing the first adduct, it is preferred that the moles of the polyfunctional reactant employed be at least equal to the equivalents of the reactive nitrogen moieties in the first nitrogen-containing compound (that is, the sum of the nitrogen-bonded H atoms in the first nitrogen containing compound). Preferably, a molar excess 2016~22 of the polyfunctional reactant of about at least 10%, such as 10-300%, or greater, for example, 25-200%, is employed.
Larger excess can be employed if desired. For example, NH3 is herein considered to have three reactive nitrogen moieties per molecule, and preferably at least 3 (e.g., from 3.3-10) moles of the polyfunctional reactant are employed in the first reaction mixture per mole of N~3, to form a first adduct having, on average, three N-bonded moieties derived from the polyfunctional reactant, each such moiety containing the group (XXI~
wl w2 Il il - C - (T)a - [(C)b-(Y)Jc wherein W1, W2, Y, T, "a", "b" and "c" are as defined above. Preferably, the first adduct contains on average at least 3 groups, more preferably from 3 to 20, and most preferably from 3 to 8, groups of formula XXIII.
The polyfunctional reactant and first nitrogen compound are preferably admixed by introducing the first nitrogen compound into the liquid reaction mixture containing the polyfunctional reactant, with mixing, to provide an excess of the polyfunctional reactant during the charging of the first nitrogen compound.
The conditions of the temperature and pressure employed for employPd for contacting of the first nitrogen-containing compound and the polyfunctional reactant can vary widely but will be generally from about -lO to 40C (preferably from about 10 to 20C). The progress of the reaction can be followed by IR to observe the disappearance of -N-H- bondsO Lower temperatures can be used, although longer reaction times may be required.
Higher temperatures can also be employed but will tend to increase the amount of the less reactive Y functional groups which react with the reactive nitrogen moieties of the first nitrogen-containing compound, thereby decreasing ~0~ ~22 the desired selectivity for the reaction with the more reactive X functional groups.
The reaction time involved can vary widely depending on a wide variety of factors. For example, there is a relationship between time and temperature. In general, lower temperature demands longer times. Usually, reaction times of from about 2 to 30 hours, such as 5 to 25 hours, and preferably 3 to lO hours will be employed.
Although one can employ a solvent, the reaction can be run without the use of any solvent. It is preferred to avoid the use of an aqueous solvent such as water.
However, taking into consideration the effect of solvent on the reaction, where desired, any suitable solvent can be employed, whether organic or inorganic, polar or non-polar. Suitable solvents include alkanols (e.g., C1 to C6 alkanols such as methanol, isopropanol, ethanol and the like), ethers, xylene, benzene, toluene, tretrahydrofuran, methlyene chloride, chloroform, chlorobenzene, and the like.
The resulting first adduct product mixture is then preferably treated, as by stripping or sparging (with, e.g, nitrogen gas) (e.g., from about 20 to about 100C~
optionally under vacuum to remove any volatile reaction by-products and unreacted polyfunctional reactant to minimize the reaction of the second nitrogen-containing compound therewith in the second stage of the process of the present invention. Therefore, the second liquid reaction mixture, wherin the second adduct is formed, is preferably substantially free of unreacted polyfunctional reactant, e.g. contains less than about l wt%, and more preferably about 0.1 wt% unreacted polyfunctional reactant.
The reaction of the polyfunctional reactants of formula VII with a first nitrogen-containing compound can be illustrated as follows:
20~60~2 monoamines ( Eq . 1 ) O
NH3 + 3 H2C=CH-C-OCH3 --o N [C2H4C-Oc~3 ] 3 (Eq. 2) NH2Rl + 2 H2C=C(C~3)-C-Oc~3 -l Rl -N [ CH2 C ( CH3 ) C-OCH3 ] 2 polyamines l ~Eq- 3 ) H2NC2H4NH2 ~ 4 H2C=CH-C-OCH
o NC2H4N- [ C2H4C-CH3 ] 2 1l [ C2H4C--OCH3 ] 2 (Eq- 4 ) ~N (C2H4NH) 4C2~4NH2 + 8 H2c=cH-c-ocH
o k~
N[C2H4NH]4C2Ho,N~[C2H4(~~CH3]2 l ll [ C2H4C--OCH3 ]
[ C2H4C-OCH3 ] 2 Eq. 5) H2N(c2H4NH)c2~NH2 + 6 H2C=C~I-C-~3 - ~~
~16022 N [ C2H4NH] 2C~4N- [ C2H4C-ocH3 ~ 2 I O
[ C2H4C-CH3 ]
[C2H4C-OCH3 ] 2 (Eq- 6~ H2NC2H4NH2 + 4 H2C=CH-C-Cl NC2H4N- [ C2H4C~Cl ] 2 l ll [ C2H4 C-Cl ] 2 (Eq- 7 ) H2NC2H4NH2 + 4 H2C=CH-C-CH3 NC2H4N--[ C2H4C~CH3 ] 2 l O
[C2H4c-cH3 ] 2 O O
Il 11 (Eq- 8 ) H2NC2H4NH2 + 4 CH30-C-CH2CCH
O O
NC2H4N-[CcH2ccH3]2 t- 4 CH30H
[ ICl CH2~1CI CH3 ] 2 O O
The selective reaction of the first nitrogen-containing compound with an alpha- beta ethylenically unsaturated compound of formula VII results 2~16~22 in the addition of the reactive nitrogen equivalents across the double bond of these polyfunctional reactants.
The average degree of branching in the first adduct is increased as the number of reactive nitrogen moieties in the first nitrogen-containing compound increases.
The average degree of branching ("DBl") of the first adduct can be calculated from the expression:
DB1 = [3(na~ + 2(np) + (ns)] x c wherein "na" is 1 when ammonia is employed as the first nitrogen~containing compound and is zero when ammonia is not used, and wherein "np" and "nS" are the number of primary and secondary amine groups, respectively, in the organic amine, if employed as the first nitrogen-containing compound, and wherein "c" is an integer of at least 1 (and is equal to (r - 1), wherein "r" is the number of functional groups in each molecule of the polyfunctional reactant which are reactive with a -NH- group, as defined in formula VII above). DBl in the first adduct is at least 2 (e.g., from 2 to 30), preferably at least 3 (e.g., from 3 to 20), and more preferably from 3 to 15. When the first nitrogen-containing compound comprises a mixture of ammonia and an organic amine the average degree of branching can be determined by giving each of the factors in the above expression their weighted average of each such nitrogen-containing compound incorporated into the first adduct.
For example, ammonia provides a 3-branch first adduct (DBl = 3) ~ ~ ~y Y - N
~ ~ ~y ~16~22 whereas diethylene triamine provides a 5-branch first adduct (DB1 = 5) Y
~ N '¦~ N /~ N ~
wherein ...Y represents a difunctional reactant which has been bonded to the r~active nitrogen moieties. The degree of branching will be increased still further if a trifunctional reactant is employed. For example, ammonia preferably provides a first adduct of the structure (DB
- 6):
Y\ /\ Y
... N
/ \ Y
\ y and diethylene triamine provides a first adduct of the structure (DBl = 10~:
Y~ Y
N ~ N 3 N
Y/ ~ Y
. . .
2 ~
wherein .../ represent~ a trifunctional reactant which has been bonded to the reac~ive nitrogen moieties.
SECOND NITROGEN-CONTA~N~NG ~OMPOUND
The second nitrogen-containing compound will comprise at least one polyamine containing at least 2 (e.g.
from 2 to 20), preferably at least 3 (e.g. from 3 to 15), and most preferably from 3 to 10, reactive nitrogen moieties, that is the total of the nitrogen-bonded H atoms per molecule of the second nitrogen-containing compound.
The second nitrogen-containing compound will generally comprise at least one member selected from the group consisting of organic primary and secondary polyamines containing at least one primary amine group (and preferably containing at least two (e.g., 2 to 6, preferably 2 to 4) primary amine groups) or at least two secondary amine groups per molecule. Generally, the organic polyamines will contain from about 2 to 60, preferably 2 to 40 ~e.g. 3 to 20), total carbon atoms and about 2 to 12, preferably 3 to 12, and most preferably from 3 to 8 (e.g., 5 to 9) total nitrogen atoms in the molecule. These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularly useful. Preferred amines are aliphatic saturated amines, including those of the general formulas: .
R-N-(CH2)s- ~ p-(CH2)s ~ N R
R' l R''' J R' t (XXIV) 20~ 6~2 wherein R, R' and R' ' ' are independently selected from the group consisting of hydrogen; Cl to C25 straight or branched chain alkyl radicals; C1 to C12 alkoxy C2 to C6 alkylene radicals; C2 to C12 hydroxy amino alkylene radicals; and Cl to C~2 alkylamino C2 to C6 alkylene radicals: and wherein R" ' can additionally comprise a moiety of the formula:
_ ( C~2 ) s '--N~H ( XXV) IJt~
R' wherein R' is as defined abo~re, and wherein s and s' can be the same or a different number of from 2 to 6, preferably 2 to 4; and t and t' can be the same or different and are numbers of from O l:o 10, preferably 2 to 7, and most preferably about 3 to 7, with the proviso that the sum of t and t ' is not greater than 15 . To assure a facile reaction, it is preferred that R, R', R' ' ', s, s', t and t' be selected in a manner sufficient to provide the compounds of Formula XXIV with typically at least two primary or secondary amine group, preferably a total of from 2 to 8 primary and secondary amine groups. This can be achieved by selecting at least one of said R, R' or R' ' ' groups to be hydrogen or by letting t in Formula XXIV be at least one when R" ' is H or when the XXV moiety possesses a secondary amino group.
Non-limiting examples of suitable organic amine compounds include: 1, 2-diaminoethane; 1, 3-diaminopropane 1, 4-diaminobutane; 1, 6-diaminohexane; polyethylene amines such as diethylene triamine; triethylene tetra;
tetraethylene pentamine; polypropylene amines such as 1, 2-propylene diamine; di-(1,2-propylene)triamine;
di- ( 1, 3 -propylene) triamine;
N,N-di~nethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine; N-dodecyl-l, 3-propane ~01~022 diamine; tris hydroxymethylaminomethane (THAM);
diisopropanol amine; diethanol amine; triethanol amine;
mono-, di-, and tri-tallow amines; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof.
Other useful amine compounds include those d i s cu ss a d ab ov e w it h res p ect to the first nitrogen~containing adduct in formulae IV - VI.
Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines involves the reaction of an involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride~ with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylenetetra, tetraethylene pentamine and isomeric piperazines. Low cost poly(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.
The second nitrogen~containing compound can comprise an amido-amine formed by reacting a polyamine with an alpha, beta-ethylenically unsaturated compound ~e.g., of formula XXII), e.g. by reacting polyethylene amines (e.g., tetraethylene pentaamine, pentaethylene hexamine, and the like), polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof, with with an acrylate-type compound of formula (XXII) above, and most preferably with an acrylate-type reactant selected from the group consisting of lower alkyl alky-acrylates (e.g., methyl, ethyl, iso-propyl, propyl, iso-butyl, n-butyl, tert-butyl, etc., esters of methacrylic acid, acrylic acid, and the like).
~0~6~2~
Exemplary of such amido-amines are compounds of the formula:
NH2[ (CH2)zNH]xC(O)C2H4[NH(cH2)zJxNH2 wherein x is an integer of from 1 to 10, and z is an integer of from 2 to 6.
Most preferred as the second nitrogen-containing compound are members selected from the group consisting of organic diprimary amines having from ~ to 30 carbon atoms, from 2 to 12 total nitrogen atoms and from O to 10 secondary nitrogen atoms per molecule. Examples of such preferred organic diprimary amines are ethylene diamine, propylene diamine, diethylene triamine, dipropylene triamine, triethylene tetraamine, tripropylene tetraamine, tetraethylene pentaamine, tetrapropylene pentaamine, polyamino cyclohexylmethane and the like.
PREPARATION OF SECOND ADDUCT
The first adduct, containing an average of at least 2 (e.g., 2 to 10), and preferably at least 3 (e.g.
from 3 to 8), unreacted functional Y groups per molecule, is contacted with the second nitrogen-containing compound in an amount and under conditions sufficient to react the remaining functional groups with the reactive nitrogen moieties of the second nitrogen-containing compound to form a second adduct characterized by having within its structure on average (i) at least two, (e.g., 2 to 30), preferably at least 3 (e.g., 3 to 20), nitrogen-containing moieties derived from the second nitrogen-containing compound per nitrogen-containing moiety derived from the first compound and (ii) at least two (e.g., 2 to 6;
preferably 2 to 4) unreacted primary or secondary amine groups.
The reaction of a polyamine with the first adduct can be illustrated as followc:
2Q~6~2 ~ 36 -N--~C2H4C(O)OCH3]3 + 3 NH2C2H4NH2 (Eq. 9) N -~C2H4c(O)-NH-c2H4NH2]3 + 3 CH30H
o NC2H4N-[C2H4c--OcH3]2 i lC~ + 4 NH2C2H4NH2 [C2H4C-oCH3]2 ~
~ (Eq. lO) Nc2H4N-[c2H4c-NH-c2H4NH2]2 + 4 CH30 O
[C2H4C-NH-C2H~NH2]2 N--~2H4C(~C)CH3]3 + 3 NH2(C2H4NH)4C2 ~
(Eq. 11) N t C~H4c(o)-NH-(c2H4NH)4c2H4NH2]3 + 3 CH3OH
C
NC2H4N-[C2H4c-OcH3]2 + 4 NH2(C2H4N~)3C2H4NH2 [C 2H4C-OCH3]2 ~
(Eq. 12) NC2H4N-[C2H4C-NH-(C2H4NH)3C2H4NH2]2 + ~ CH30H
[C2H4c-NH-(c2H4NH)3c2H4NH2]2 ~016~22 C2H4N [C2H4C-CH3]2 + NH2(c2H4NH)3c2H4NH2 7 I I /
[C2H4c~cH3]2 ~
(Eq. 13) Nc2~4N-[c2H4~=N-(c2H4NH~3c2H4NH2~2 ¦ IH3 ~C2H4C=N-(C2H4N~)3c2H4NH2]2 The reaction between the selected polyamine and the first adduct is carried out at any suitable temperature. Temperatures up to the decomposition points of reactants and products can be employed. In practice, one generally carries out the reaction by heating the reactants below 100C, such as 80-90C, for a suitable p~riod of time, such as a few hours. Where the first adduct was formed using an acrylic-type ester is employed, the prograss of the reaction can be judged by the removal of the alcohol in forming the amide. During the early part of the reaction alcohol is removed quite readily below 100C in the case of low boiliny alcohols such as methanol or ethanol. As the reaction slows, the temperature is raised to push the reaction to completion and the temperature may be raised to 150C toward the end of the reaction. Removal of alcohol is a convenient method of judging the progress and completion of the reaction which is generally continued until no more alcohol is evolved.
Based on removal of alcohol, the yields are generally stoichiometric. In more difficult reactions, yields of at least 95% are generally obtained.
Similarly, it will be understood that the reaction of a polyamine with a first adduct prepared using an ethylenically unsaturated carboxylate thioester of formula ~16~22 IX liberates the corresponding HSX4 compound (e.g., H2S
when R4 is hydrogen) as a by-product, and the reaction of a polyamine with a first adduct prepared using an ethylenically unsaturated carboxyamide of formula X
liberates the corresponding HNR4(R5) compound (e.g., ammonia when R4 and R5 are each hydrogen) as by-product in forming the second adduct.
The reaction time involved can vary widely depending on a wide variety of factors. For example, there is a relationship between time and temperature. In general, lower temperature (e.g., at about 25~C) demands longer times. Usually, reaction times of from about 2 to 30 hours, such as 5 to 25 hours, and preferably 3 to 10 hours will be employed.
Although one can employ a solvent, the reaction can be run without the use of any solvent. I~ is preferred to avoid the use of an aqueous solvent such as water.
However, taking into consideration the effect of solvent on the reaction, where desired, any suitable solvent can be employed, whether organic or inorganic, polar or non-polar. Suitable solvents include alkanols (e.g., Cl to C6 alkanols such as methanol, isopropanol, ethanol and the like), ethers, xylene, benzene, toluene, tretrahydrofuran, methlyene chloride, chloroform, chlorobenzene, and the like.
When the selected polyfunctional reactant comprises an alpha, beta-unsaturated compound of formula VII wherein Wl is oxygen, the resulting first adduct reaction product contains at least one amido linkage (-C(O)N<) and such materials are herein termed "amido amines." Similarly, when the selected alpha, beta unsaturated compound of formula VII comprises a compound wherein W is sulfur, the resulting reaction product with the polyamine contains thioamide linkage (-C(S)N<) and these materials are herein termed "thioamido-amines." For convenience, the following discussion is directed to the preparation and use of amido-amines, although it will be understood that such discussion is also applicable to the thioamido-amines.
These amido-a~ine adducts so formed are characterized by both amido and amino groups. In their simplest embodiments they may be represented by units of the following idealized formula:
- N - A ~ ~ H2 ~H - C -wherein the R's, which may be the same or different, are hydrogen or a substituted group, such as a hydrocarbon group, for example, alkyl, alkenyl, alkynyl, aryl, etc., and A is a moiety of the polyamine which, for example, may be aryl, cycloalkyl, alkyl, etc., and n is an integer such as 1-10 or greater. The amido-amine adducts preferably contain an average of from 1 to 3 amido groups per molecule of the amido-amine adduct.
Preferably, however, the amido-amines of this invention are not cross-linked to any substantial degree, and more preferably are substantially branched.
Steps (a) and (b~ in the process of this invention can be repeated if desired to form more highly branched adducts. For example, a second adduct formed as described above can comprise the "first nitrogen-containing compound"
passed to the repeated step (a) and can be therein contacted with additional polyfunctional reactant (e.g., an alpha, beta-ethylenically unsaturated carboxylate~, preferably in a molar excess to the reactive nitrogen moieties in the second adduct (that is, the total number of -N-H- bonds remaining unreacted in the second adduct), to form a more highly branched "first" adduct which can then be treated to remove the excess unreacted polyfunctional 201 ~22 reactant and contacted in a separate step with an additional second nitrogen-containing compound, such as a polyalkylene polyamine, as described above. Such more highly branched nitrogen-containing adduct will be characterized as indicated above for the second adducts (that is, on average, will contain in its structure at least two unreacted primary or secondary amine groups, and at least two nitrogen-containing moieties derived from the additional second nitrogen-containing compound per nitrogen-containing moiety derived from the nitrogen-containing adduct so contacted in the repeat of step (a)) and can be employed in the subsequent reaction with the selected reactants A - D to for~ a dispersant of this invention.
~0~ 6~22 PR~PAR~aION OF LONG CHAIN HY~ROCAR~YL SUBSTITUTED REACTANT
(A) As indicated above, the dispersant materials of this invention can be prepared by reacting the second adduct with a hydrocarbyl-substituted acid, anhydride or ester material. The long chain hydrocarbyl polymer-substituted mono- or dicarboxylic acid material, i.e., acid, anhydride or acid ester used in this invention, includes the reaction product of a long chain hydrocarbon polymer, generally a polyolefin, with a monounsaturated carboxylic reactant comprising at least one member selected from the group consisting of (i) monounsaturated C4 to C10 dicarboxylic acid (preferably wherein (a) the carboxyl groups are vicinyl, ~i.e. located on adjacent carbon atoms) and (b)- at least one, preferably both, of said adjacent carbon atoms are part of said mono unsaturation); (ii) derivatives of (i) such as anhydrides or Cl to C5 alcohol derived mono- or di-esters of (i);
(iii) monounsaturated C3 to C10 monocarboxylic acid wherein the carbon-carbon double bond is conjugated to the carboxy group, i.e, of the structure 10~
--C=C--C-- ;
and (iv) derivatives of (iii) such as Cl to C5 alcohol derived monoesters of (iii). Upon reaction with the polymer, the monounsaturation of the monounsaturated carboxylic reactant becomes saturated. Thus, for example, maleic anhydride becomes a polymer substituted succinic anhydride, and acrylic acid becomes a polymer substituted propionic acid.
Typically, from about 0.7 to about 4.0 (e.g., 0.8 to 2.6), preferably from about 1.0 to about 2.0, and most preferably from about 1.1 to about 1.7 moles of said ~16~22 monounsaturated carboxylic reactant are charged to the reactor per mole of polymer charged.
Normally, not all of the polymer reacts with the monounsaturated carboxylic reactant and the reaction mixture will contain non-acid substituted polymer. The polymer-substituted mono- or dicarboxylic acid material (also referred to herein as "functionalized" polymer or polyolefin), non-acid substituted polyolefin, and any other polymeric by-products, e.g. chlorinated polyolefin, (also referred to herein as "unfunctionalized" polymer) are collectively referred to herein as "product residue" or "product mixture". The non-acid substituted polymer is typically not removed from the reaction mixture (because such removal is difficult and would be commercially infeasible) and the product mixture, stripped of any monounsaturated carboxylic reactant is employed for further reaction with the amine or alcohol as described hereinafter to make the dispersant.
Characterization of the average number of moles of monounsaturated carboxylic reactant which have reacted per mole of polymer charged to the reaction (whether it has undergone reaction or not) is defined herein as functionality. Said functionality is based upon (i~
determination of the saponification number of the resulting product mixture using potassium hydroxide; and (ii) the number average molecular weight of the polymer charged, using techniques well known in the art. Functionality is defined solely with reference to the resulting product mixture. Although the amount of said reacted polymer contained in the resulting product mixture can be subsequently modified, i.e. increased or d~creased by techniques known in the art, such modifications do not alter functionality as defined above. The terms "polymer substituted monocarboxylic acid material" and "polymer substituted dicarboxylic acid material" as used herein are 20~ 6~2 intended to refer to the product mixture whether it has undergone such modification or not.
Accordingly, the functionality of the polymer substituted mono- and dicarboxylic acid materiai will be typically at least a~out 0.5, preferably at least about 0.8, and most preferably at least about 0.9 and will vary typically from about 0.~ to about 2.8 (e.g., 0.6 to 2), preferably from about 0.8 to about 1.4, and most preferably from about 0.9 to about 1.3.
Exemplary of such monounsaturated carboxylic reactants are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyl (e.g., Cl to C4 alkyl) acid esters of the foregoing, e.g., methyl maleate, ethyl fumarate, methyl fumarate, etc.
Preferred olefin polymers for reaction with the monounsaturated carboxylic reactants to form reactant A are polymers comprising a major molar amount of C2 to C10, e.g. C2 to C5 monoolefin. Such olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-l, styrene, etc. The polymers can be homopolymers such as polyisobutylene, as well as copolymers of two sr more of such olefins such as copolymers of: ethylene and propylene; butylene and isobutylene; propylene and isobutylene; etc. Mixtures of polymers prepared by polymerization of mixtures of isobutylene, butene-1 and butene-2, e.g., polyisobutylene wherein up to about 40% of the monomer units are derived from butene-l and butene-2, is an exemplary, and preferred, olefin polymer. Other copolymers include those in which a minor molar amount of the copolymer monomers, e.g., 1 to 10 mole %, is a C4 to C18 non-conjugated diolefin, e.g., a copolymer of isobutylene and butadiene; or a copolymer of ethylene, propylene and 1,4-hexadiene: ~tc.
2~6~22 In some cases, the olefin polymer may be com-pletely saturated, for example an ethylene-propylene copolymer made by a Ziegler-Natta synthesis using hydrogen as a moderator to control molecular weight.
The olefin poly~ers used in the formation of reactant A will have number average molecular weights within the range of about 300 to 10,000, generally from about 700 and about S,000, preferably from about 1000 to 4,000, more preferably between about 1300 and about 3,000.
Particularly useful olefin polymers have number average molecular weights within the range of about 1500 and about 3000 with approximately one terminal double bond per polymer chain. An especially useful starting material for highly potent dispersant additives useful in ac~ordance with this invsntion is polyisobutylene, wherein up to about 40% of the monomer units are derived from butene-l and/or butene-2. The number average molecular weight for such polymers can be determined by several known techniques. A
convenient method for such determination is by gel permeation chromatography (GPC) which additionally provides molecular weight distribution information, see W. W. Yau, J.J. Kirkland and D.D. Bly, I'Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.
The olefin polymers will generally have a molecular weight distribution (the ratio of the weight average molecular weight to number average molecular w e i g ht~ i-e- ~w/~n) f from about 1. 0 t~
4.5, and more typically from about 1.5 to 3Ø
T h e p ol y m e r c a n b e reacted with the monounsaturated carboxylic reactant by a variety of methods. For example, the polymer can be first halogenated, chlorinat~d or brominated to about 1 to 8 wt.
%, preferably 3 to 7 wt. % chlorine, or bromine, based on the weight of polymer, by passing the chlorine or bromine through the polymer at a temperature of 60 to 250C, 2016~22 preferably 110 to 160 C, e.g. 120 to 140-C, for about 0.5 to 10, preferably 1 to 7 hours. The halogenated polymer may then be reacted with sufficient monounsaturated carboxylic reactant at 109 to 250~C, usually about 180 to 235-C, for about 0.5 to 10, e.g. 3 to 8 hours, so the product obtained will contain the desired number of moles of the monounsaturated carboxylic reactant per mole of the halogenated polymer. Processes of this general type are taught in U.S. Patents 3,087,436: 3,172,89~; 3,272,74~ and others. Alternatively, the polymer and the monounsaturated carboxylic reactant are mixed and heated while adding chlorine to the hot material. Processes of this type are disclosed in U.S. Patents 3,215,707; 3,231,587; 3,912,764;
4,110,349; 4,234,435; and in U.R. 1,440,219.
Alternately, the polymer and the monounsaturated carboxylic reactant can be contacted at elevated temperature to cause a thermal "ene" reaction to take place. Thermal "ene" reactions have been heretofore described in U.S. Patents 3,361,673 and 3,401,118, the disclosures of which are hereby incorporated by reference in their entirety.
Preferably, the polymers used in this invention contain less than 5 wt~, more preferably less than 2 wt%, and most preferably less than 1 wt% of a polymer fraction comprising polymer molecules having a molecular weight of less than about 300, as determined by high temperature gel premeation chromatography employing the corresponding pol~mer calibration curve. Such preferred polymers have been found to permit the preparation of reaction products, particularly when employing maleic anhydride as the unsaturated acid reactant, with decreased sediment. In the event the polymer produced as described above contains greater than about 5 wt% of such a low molecular weight polymer fraction, the polymer can be first treated by conventional means to remove the low molecular weight 2016~22 fraction to the desired level prior to initiating the ene reaction, and preferably prior to contacing the polymer with the selected unsaturated carboxylic reactant(s). For example, the polymer can be heated, preferably with inert gas (e.g., nitrogen) stripping, at elevated temperature under a reduced pressure to volatilize the low molecular weight polymer component3 which can then be removed from the heat treatment ves-~el. The precise temperature, pressure and time for such heat treatment can vary widely depending on such factors as as the polymer number average molecular weight, the amount of the low molecular weight fraction to be removed, the particular monomers employed and other factors. Generally, a temperature of from about 60 to 100C and a pressure of from about 0.1 to 0.9 atmospheres and a time of from about 0.5 to 20 hours (e.g., 2 to 8 hours) will be sufficient.
In this process, the selected polymer and monounsaturated carboxylic reactant and halogen (e.g., chlorine gas), where employed, are contacted for a time and under conditions effective to form the desired polymer substituted mono- or dicarboxylic acid material.
Generally, the polymer and monounsaturated carboxylic reactant will be contacted in a unsaturated carboxylic reactant to polymer mole ratio usually from about 0.7:1 to 4:1, and preferably from about l:l to 2:1, at an elevated temperature, generally from about 120 to 260C, preferably from about 160 to 240C. The mole ratio of halogen to monounsaturated carboxylic reactant charged will also vary and will generally range from about 0.5:1 to 4:1, and more typically from about 0.7:1 to 2:1 (e.g., from about 0.9 to 1.4:1). The reaction will be generally carried out, with stirring for a time of from about 1 to 20 hours, preferably from about 2 to 6 hours.
By the use of halogen, about 65 to 95 wt. % of the polyolefin, e.g. polyisobutylene will normally react with ~016022 the monounsaturated carboxylic acid reactant. Upon carrying out a thermal reaction without the use of halogen or a catalyst, then usually only about 50 to 75 wt. ~ of the polyisobutylene will react. Chlorination helps increase the reactivity. For ~onvenience, the aforesaid functionality ratios of mono- or dicarboxylic acid producing units to polyolefin, e.g., 1.1 to 1.~, etc. are based upon the total amount of polyolefin, that is, the total of both the reacted and unreacted polyolefin, used to make the product.
The reaction is preferably conducted in the substantial absence of 2 and water (to avoid competing side reactions), and to this end can be conducted in an atmosphere of dry N2 gas or other gas inert under the reaction conditions. The reactants can be charged separately or together as a mixture to the reaction zone, and the reaction can be carried out continuously, semi-continuously or batchwise. Although not generally necessary, the reaction can be carried out in the presence of a liquid diluent or solvent, e.g., a hydrocarbon diluent such as mineral lubricating oil, toluene, xylene, dichlorobenzene and the like. The polymer substituted mono- or dicarboxylic acid material thus formed can be recovered from the liquid reaction mixture, e.g., after stripping the reaction mixture, if desired, with an inert gas such as N2 to remove unreacted unsaturated carboxylic reactant.
If desired, a catalyst or promoter for reaction of the olefin polymer and monounsaturated carboxylic reactant (whether the olefin polymer and monounsaturated carboxylic reactant are contacted in the presence or absence of halogen (e.g., chlorine)) can be employed in the reaction zone. Such catalyst of promoters include alkoxides o f Ti, Zr, V and Al, and nickel salts (e.g., Ni acetoacetonate and Ni iodide) which catalysts or promoters will be generally 20~6022 employed in an amount of from about 1 to 5,000 ppm by weight, based on the mass of the reaction medium.
(B) Also useful as long chain hydrocarhyl reactants to form the improved dispersants of this invention are halogenated long chain aliphatic hydrocarbons (as shown in U.S. Patents 3,275,554 and 3,565,804, the disclosures of which are hereby incorporated by reference in their entirety~ where the halogen group on the halogenated hydrocarbon is displaced with the second adduct in the subsequent reaction therewith.
(C) Another class of long chain hydrocarbyl reactants to form the improved dispersants of this invention are any of the long chain hydrocarbyl-substituted hydroxy aromatic compounds which are known in the art as useful for forming Mannich condensation products. Such Mannich condensation products generally are prepared by condensing about 1 mole of a high molecular weight hydrocarbyl substituted hydroxy aromatic compound (e.g., having a number average molecular weight of 700 or greater) with about 1 to 2.5 moles of an aldehyde such as formaldehyde or paraformald4hyde and about 0.5 to 2 moles of the second adduct, using the condensation conditions as disclosed, e.g., in U~S. Patents 3,442,808; 3,649,229; and 3,798,165 (the clisclosures which are hereby incorporated by reference in their entirety). Such Mannich condensation products may include a long chain, high molecular weight hydrocarbon on the phenol group or may be reacted with a compound containing such a hydrocarbon, e.g., polyalkenyl succinic anhydride as shown in said aforementioned U.S.
Patent 3,442,808.
The optionally substituted hydroxy aromatic compounds used in the preparation of the Mannich base products include those compounds having the formula R21y - Ar - (OH)z 2~16~22 wherein Ar represents R2 x R2 x ~ or ~
wherein q is 1 or 2, R21 is a long chain hydrocarbon, R~ is a hydrocarbon or substituted hydrocarbon radical having from 1 to about 3 carbon atom2~ or a halogen radical such as the bromide or chloride radical, y is an integer from 1 to 2, x is an integer from O to 2, and z is an integer from 1 to 2.
Illustrative of such Ar groups are phenylene, biphenylene, naphthylene and the liXe.
The long chain hydrocarbon R21 substituents are olefin poly~ers as described above for those olefin polymers useful informing reactants.
Representative hydrocarbyl substituted hydroxy aromatic compounds contemplated for use in the present invention include, but are not limited to, 2-polypropylene phenol, 3-polypropylene phenol, 4-polypropylene phenol, 2-polybutylene phenol, 3-polyisobutylene phenol, 4-polyisobutylene phenol, 4-polyisobutylene-2-chlorophenol, 4-polyisobutylene-2-methylphenol, and the like.
Suitable hydrocarbyl-substitued polyhydroxy aromatic compounds include the polyolefin catechols, the polyolefin resorcinols, and the polyolefin hydroquinones, e. g., 4-polyisobutylene-l, 2-dihydroxybenzene, 3-polypropylene-l, 2-dihydroxybenzene, 5-polyisobutylene-l, 3-dihydroxybenzene, 4-polyamylene-1,3-dihydroxybenzene, and the like.
Suitable hydrocarbyl-substituted naphthols include 1 - p o l y i s o b u t y l e n e - 5 - h y d r o x y n a E~ h t h a l e n e, l-polypropylene-3-hydroxynaphthalene and the like.
2al~022 (D) Still another class of long chain hydrocarbyl reactants to form the improved dispersants of this invention are the Mannich base aminophenol-type condensation products as they are known in the art. Such Mannich condensation products generally are prepared by reacting about 1 mole of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides (e.g., polyisobutylene-substituted succinic anhydride~ with an about 1 mole of amine-substituted hydroxy aromatic compound (e.g., aminophenol), which aromatic compound can also be halogen- or hydrocarbyl-sustituted, to form a long chain hydrocarbon substituted amide or imide-containing phenol intermediate adduct (generally having a number average molecular weiqht of 700 or greater), and condensing about a molar proportion of the long chain hydrocarbon substituted amide- or imide-containing phenol intermediate adduct with about 1 to 2.5 moles o~ formaldehyde and about 0.5 to 2 moles of the second adduct of this invention.
Suitable aminophenols include 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-3-chlorophenol, 4-amino~2-bromophenol and 4-amino-3-ethylphenol.
The preparation and use of the hydroxy aromatic compounds and amino-substituted hydroxy aromatic compounds, and methods useful for reaction thereof with an aldehyde and the selected second adduct of this invention are as described in U.S. Patents 4,820,432 and 4,828,742, the disclosures of which are hereby incorporated her~in in their entirety.
PREPARATION OF THE DISPERSANT
(A) The second adduct (e.g., the branched amido-amine oligomers) is readily reacted with the selected polymer substituted mono- or dicarboxylic acid material, e.g. alkenyl succinic anhydride, by heating an oil 2 ~ 2 ~
solution containing 5 to 95 wt. % of the polymer substitu~ed dicarboxylic acid material to about 100 to 250~C., preferably 125 to 175-C. I generally for 1 to 10, e . g. ~ to 6 hours until the desired amount of water is removed. The heating i8 preferably carried out to favor forDIation of imides and/or amides, rather than salts.
Generally from 1 to 5, preferably from about 1. 5 to 3 moles of mono- or dicarboxylic acid ~noiety content (e . g., grafted maleic anhydride or grafted acrylic acid content) is used per reactive nitrogen equivalent (preferably per equivalent of primary nitrogen) of the second adduct.
An example of the reaction of a second adduct with a polymer-substituted dicarboxylic acid producing reactant is the reaction of polyisobutylene (PIB)-substituted succinic anhydride (PIBSA) with a second addllct having three terminal -NH2 groups, which can be illustrated as follows:
PIB
~i + [H2N Link-]3N
o r~ PIB
O Link-N
PIB --~ / ~~
N-Link - NO
J \ O\
O\ rl~PIB
Link-N~¦
o where "Link" is the moiety:
( 2 4 H) xC(O) C2H4 (NHC2H4) x~~ wherein x is an integer of from O to 10, preferably from 2 to 6.
An example of the reaction of a second adduct with a polymer-substituted monocarboxylic acid producing reactant is the reaction of polyisobutylene propionic acid (PI~A) with a second adduct having 3 terminal -NH2 groups~ which can be illustrated as follows:
3 PIB- CH2C-OH + [H2N-Link-]3~ _ pl _~ Link-NH-O~C-CH2-PIB
PIB-CH2C-~N-Link-N \
Link-NH-O-I-CH2-PIB
wherein 'ILink" and x are as defined above.
It will be understood that the second adduct can be employed alone or in admixture with any of the above described amines, such ~s the polyalkylene polyamines, useful in preparing the second adduct.
Preferably, the polymer substituted mono- or dicarboxylic acid producinq material and amido-amine will be contacted for a time and under conditions sufficient to react substantially all of the primary nitrogens in the second adduct reactant. The progress of this reaction can be followed by infra-red analysis.
The dispersant-forming reaction can be conducted in a polar or non-polar solvent (e.g., xylene, toluene, benzene and the like), and is preferably conducted in the presence of a mineral or synthetic lubricating oil.
2016~22 The nitrogen-containing dispersant materials of the instant invention as described above can be post-treated by contacting said nitrogen-containing dispersant materials with one or more post-treating reagents selected from the grsup consisting of carbon disulfide, sulfur, sulfur chlorides, alkenyl cyanides, aldehydes, ketones, urea, thio-urea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphi~es, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothio yantes, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds plus phenols, and sulfur plus phenols, and Cl to C30 hydrocarbyl substituted succinic acids and anhydrides (e.g., succinic anhydride, dode~yl succinic anhydride and the like~, fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyl (e.g., C1 to C4 alkyl) acid esters of the foregoing, e.g., meth l maleate, ethyl fumarate, methyl fumarate, and the like.
Since post-treating processes involving the use of these post-treating reagents is known insofar as application to high molecular weight nitrogen containing diseprsants of the prior art, further descriptions of these processes herein is unnecessary. In order to apply the prior art processes to the compositions of this invention, all that is necessary is that reaction conditions, ratio of reactants, and the like as described in the prior art, be applied to the novel compositions of this invention. The following U.S. patents are expressly incorporated herein by reference for their disclosure of post-treating processes and post-treating reagents applicable to the compositions of this invention: U.S. Pat. Nos. 3,087,936; 3,200,107;
2 ~ 2 3,254,025; 3,256,185; 3,278~550; 3,281,428; 3,282,955;
3,284,410: 3,338,832, 3,344,069; 3,366,569; 3,373,111;
3,367,943; 3,403,102; 3,428,561; 3,502,677; 3,513,093;
3,533,945; 3,541,012; 3,63g,242; 3,708,522; 3,859,318;
3,865,813; 3,470,09~; 3,369,021; 3,184,411; 3,185,645;
3,245,908; 3,24~,909; 3,245,910; 3,573,205; 3,692,681;
3,749,695; 3,865,740; 3,954,639; 3,458,530; 3,390,086;
3,367~943; 3,185,704, 3,551,466; 3,4~5,750; 3,312,619;
3,280,034; 3,71~,663; 3,652,516; UK Pat. No. 1,085,g03; UK
Pat. No. 1,162,436; U.S. Pat. No. 3,558,743.
The nitrogen containing dispersant materials of this invention can also be treated with polymerizable lactones (such as epsilon-caprolactone) to form dispersant adducts having the moiety -[C(O)(CH2)zO]mH, whexein z is a number of from 4 to 8 (e.g., 5 to 7) and m has an average value of from about 0 to 100 ~e.g., 0.2 to 20).
The dispersants of this invention can be post-treated with a C5 to C9 lactone, (e.g., C6 to Cg lactone, such as epsilon-caprolactone) by heating a mixture of the dispersant material and lactone in a reaction vessel in the absence of a solvent at a temperature of about 50C to about 200C, more preferably from about 75C to about 180C, and most preferably from about 90DC to about 160C, for a sufficient period of time to effect reaction.
Optionally, a solvent for the lactone~ dispersant material and/or he resulting adduct may be employed to control viscosity and/or the reaction rates.
- In one preferred embodiment, the C5 to Cg lactone, e.g., epsilon-caprolactone, is reacted with a dispersant material in a 1:1 mole ratio of lactone to dispersant material. In practice, the ratio of lactone to dispersant material may vary considerably as a means of controlling the length of the sequence of the lactone units in the adduct. For example, the mole ratio of the lactone to the dispersant material may vary from about 10:1 to ~016~2~
about 0.1:1, more preferably from about 5:1 to about 0.2:1, and most preferably from about 2:1 to about 0.4:1. It is preferable to maintain the average degree of polymerization of the lactone monomer below about 100, with a degree of polymerization on the order of from about 0.2 to about 50 being preferred, and fro~ about 0.2 to about 20 being more preferred. For optimum dispersant p~rformance, sequences of from about 1 to about 5 lactone units in a row are preferred.
Catalysts useful in the promotion of the lactone-dispersant material reactions are selected from the group consisting of stannous octanoate, stannous hexanoate, tetrabutyl titanate, a variety of organic based acid catalysts and amine catalysts, as described on page 266, and forward, in a book chapter authored by R.D. Lundberg and E. F. Cox, entitled "Kinetics and Mechanisms of Polymerization: Ring Opening Polymerization", edited by Frisch and Reegen, published by Marcel Dekker in 1969, wherein stannous octanoate is an especially preferred catalyst. The catalyst is added to the reac:tion mixture at a concentration level of about 50 to about 10,000 parts per weight of catalyst per olle million parts of the total reaction mixture.
The reactions of such lactones with dispersant materials containing nitrogen or ester groups is more completely described in copending applications Serial Numbers 916,108; 916,217: 916,218; 916,287; 916,303;
916,113; and 916,114, all filed on October 7, 1986; and co-pending Serial Number 178,099 filed on April 6, 1988;
the disclosure of each of which is hereby incorporated by reference in its entirety.
The nitrogen-containing dispersant materials of this invention can also be post-treated by reaction with an alkyl acetoacetate or alkyl thioacetate of the formula:
~016~22 ~a _ c - CH2 - C - Xa - Rb O O
wherein Xa is 0 or S, Rb is H or Ra, and Ra is in each instance in which it appears independently selected from the group consisting of substituted and unsubstituted alkyl or aryl (preferably alkyl o~ 1 to 6 carbon atoms, e.g., methyl, ethyl, etc.) to form an amino compound N-substituted by at least one tautomeric substituent of the formula:
C--CH2--C--Ra ~_~ C--CH--C Ra wherein R9 is as defined above.
The reaction is preferably effected at a temperature sufficiently high so as to substantially minimize the production of the enaminone and produce, instead r the keto-enol tautomer. Temperatures of at l~ast about 150C are preferred to meet this goal although proper choice of temperature depends on many factors, including reactants, concentration, reaction solvent choice, etc.
Temperatures of from about 120~C to 220C, preferably from about 150~C to 180C will generally be used. The reaction of the nitrogen-containinq dispersant material and the alkyl acetonate and the alXyl thioacetate will liberate the corresponding HORb and HSRb by-products, respectively.
Preferably, such by-products are substantially removed, as by distilltion or stripping with an inert gas (such as N2), prior to use of the thus prepared dispersant adduct. Such distillation and stripping steps are conveniently performed at elevated temperature, e.g., at the selected reaction temperature (for example, at 150C or higher~. A neutral diluent such as mineral oil may be used for the reaction.
The amount of alkyl aceto-acetate and/or alkyl thioacetate reactants used can vary widely, and is preferably selected so as to avoid substantial excesses of these reactants. Generally, these reactants are used in a reactant:amine nitrogen-equivalent molar ratio of from about 0.1 to 1:1, and preferably from about 0.5 to 1:1, whsrein the moles of amine nitrogen-equivalent is the moles of econdary nitrogens plus twice the moles of primary nitrogens in the nitrogen-containing dispersant material (e.g., polyisobutenyl succinimide) which is thus contacted with the alkylacetonate or alkyl thioacetate. The reaction should also be conducted in the substantial absence of strong acids (e.g., mineral acids, such as HCl, HB2, H2S04, H3P03 and the like, and sulfonic acids, such as para-toluene sulfonic acids) to avoid the undesired side-reactions and decrease in yield to the adducts of this invention.
The reactions of such alkyl acetoacetates and thioacetoacetates with nitrogen-containing dispersant materials is more completely described in copending application Serial No. 51,276, filed May 18, 1987, the disclosure of which is hereby incorporated by reference in its entirety.
Further aspects of the present invention reside in the formation of metal complexes of the novel dispersant additives prepared in accordance with this invention.
Suitable metal complexes may be formed in accordance with known techniques of employing a reactive metal ion species during or after the formation of the present dispersant materials. Complex forming metal reactants include the metal nitrates, thiocyanates, halides, carboxylatPs, phosphates, thio-phosphates, sulfates, and borates of transition metals such as iron, cobalt, nickel, copper, chromium, manganese, molybdenum, tungsten, ruthenium, -5~-palladium, platinum, cadmium, lead, silver, mercury, antimony and the like. Prior art disclosures of these complexing reactions may be also found in U.S. Patents 3,306,908 and Re. 26,433, the disclosures of which are hereby incorporated by reference in their entirety.
The processes of these incorporated patents, as applied to the compositions of this invention, and the post-treated composition~ thus produced constitute a further aspect of this invention.
The dispersant-forming reaction can be conducted in a polar or non-polar solvent (e.g., xylene, toluene, benzene and the like), and is preferably conducted in th~
presence of a mineral or synthetic lubricating oil.
The nitrogen containing dispersants can be further treated by boration as generally taught in U.S. Patent Nos. 3,087,936 and 3,254,025 (incorporated herein by reference thereto). This is readily accomplished by treating the selected acyl nitrogen dispersant with a boron compound selected from the class consisting of boron oxide, boron halides, boron acids and esters of boron acids in an amount to provide from about 0.1 atomic proportion of boron for each mole of said acylated nitrogen composition to about 20 atomic proportions of boron for each atomic proportion of nitrogen of said acylated nitrogen composition. Usefully the di-cpersants of the inventive combination contain from about 0.05 to 2.0 wt. %, e.g. 0.05 to 0.7 wt. % boron based on the total weight of said borated acyl nitrogen compound. The boron, which appears to be in the product as dehydrated boric acid polymers (primarily (HB02)3), is believed to attach to the dispersant imides and diimides as amine salts, e.g., the metaborate salt of said diimide.
Treating is readily carried out by adding from about 0.05 to 4, e.g. 1 to 3 wt. % tbased on the weight of said acyl nitrogen compound) of caid boron compound, ~16~22 ~-59-preferably boric acid which is most usually added as a slurry to said acyl nitrogen compound and heating with stirring at from about 135^C. to 190, e.g. 140-1709C , for from 1 to 5 hours followed by nitrogen stripping at said temperature ranges. Or, the boron treatment can be carried out by adding boric acid to the hot reaction mixture of the monocarboxylic acid material and amine while removing water.
The ashless dispersants of this invention can be used alone or in admixture with other dispersants such as esters derived from the aforesaid long chain hydrocarbon substituted dicarboxylic acid material and from hydroxy compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols, etc. The polyhydric alcohols are the most preferred hydroxy compound and preferably contain from 2 to about 10 hydroxy radicals, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycoll and other alkylene glycols in which the alkylene radical contains from 2 to about 8 carbon atoms. Other useful polyhydric alcohols include glycerol, mono-oleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof.
The ester dispersant may also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, l-cyclohexane-3-ol, and oleyl alcohol. Still other classes of the alcohols capable of yielding the esters of this invention comprise the ether-alcohols and amino-alcohols including, for example, the oxy-alkylene, oxy-arylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxy-alkylene, amino-alkylene or amino-arylene oxy-arylene radicals. They are exemplified by Cellosolve, Carbitol, N,N,N',N'-tetrahydroxy-trimethylene di-amine, and 201~322 ether-alcohols having up to about 150 oxy-alkylene radicals in which the alkylene radical contains from 1 to about 8 carbon atoms.
The ester dispersant may he di-esters of succinic acids or acidic esters, i.e., partially esterified succinic acids; as well as partially esterified polyhydric alcohols or phenols, i.e., esters having free alcohols or phenolic hydroxyl radicals. Mixtures of the above illustrated esters liXewise are contemplated within the scope of this invention.
The ester dispersant may be prepared by one of several known methods as illustrated for example in U.S.
Patent 3,381,022. The ester dispersants may also be borated, similar to the nitrogen containing dispersants, as described above.
Hydroxyamines which can be reacted with the aforesaid long chain hydrocarbon substituted dicarboxylic acid materials to form dispersants include 2-amino-1-bu-tanol, 2-amino-2-methyl-1-propanol, p-(beta-hydroxy-ethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1, 3-propane-diol, 2-amino-2-ethyl-1, 3-propanediol, N-(beta-hydroxy-propyl)-N'-(beta-amino-ethyl)-piperazine, tris(hydroxymethyl) amino-methane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine, beta-(beta-hydroxyethoxy)ethylamine, and the like. Mixtures of these or similar amines can also be employed. The above description of nucleophilic reactants suitable for reaction with the hydrocarbyl substituted dicarboxylic acid or anhydride includes amines, alcohols, and compounds of mixed amine and hydroxy containing reactive functional groups, i.e., amino-alcohols.
The tris(hydroxymethyl) amino methane (THAM) can be reacted with the aforesaid acid material to form amides, imides or ester type additives as taught by U.K. 984,409, or to form oxazoline compounds and borated oxazoline 2~1 6~22 compounds as described, for example, in U.S. 4,102,798;
4,116,876 and 4,113,639.
Other dispersants which can be employed in admixture with the novel diEpersants of this invention are those derived from the aforesaid long chain hydrocarbyl substituted dicarboxylic acid material and the aforesaid amines, such as polyalkylene polyamines, e.g., long chain hydrocarbyl suhstituted succinimides. Exemplary of such other dispersants are those described in co-pending Serial No. 95,056, filed September 9, 1987.
A preferred group of ashless dispersants are those derived from polyisobutylene substituted with succinic anhydride groups and reacted with second adducts, containing on average at leas~ 6 (e.g., from 6 to 30) reactiva nitrogen moieties and from 2 to 4 primary nitrogen groups per molecule, formed by reacting polyethylane amines, e.g., tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof, with a branched first adduct prepared by reacting ammonia or a diprimary amine having from 2 to 12 total nitrogen atoms and from 2 to 30 carbon atoms per molecule with an acrylate-type compound of formula (IX) above, and most preferably with an acrylate-type reactant selected from the group consisting of lower alkyl alky-asrylates (e.g., methyl, ethyl, iso-propyl, propyl, iso-butyl, n-butyl, tert-butyl, etc., esters of methacrylic acid, acrylic acid, and the like).
The dispersants of the present invention can be incorporated into a lubricating oil (or a fuel in any convenient way. Thus, these mixtures can be added directly to the lubricating oil (or fuel) by dispersing or dissolving the same in the lubricating oil (or fuel) at the desired level of concentration of the dispersant. Such 20~6~2~
blending into the additional lubricating oil (or fuel) can occur at room temperature or elevated temperatures.
Alternatively, the disper~ants can be blended with a suitable oil-soluble solvent/diluent (such as benzene, xylene, toluene, lubricating base oils and petroleum distillates, including the various normally liquid fuels described in detail below) to fsrm a concentrate, and then blending the concentrate with a lubricating oil (or fuel) to obtain the final formulation. Such dispersant concentrates will typically contain (on an active ingredient (A.I.) basis) from about 3 to about 45 wt.%, and preferably from about 10 to about 35 wt.%, dispersant additive, and typically from about 30 to 90 wt.%, preferably from about 40 to 60 wt.%, base oil, based on the concentrate weight.
OLEAGINOUS COMPOSITIONS
The additive mixtures of the present invention possess very good dispersant properties as measured herein in a wide variety of environments. Accordingly, the additive mixtures are used by incorporation and dissolution into an oleaginous material such as fuels and lubricating oils. When the additive mixtures of this invention are used in normally liquid petroleum fuels such as middle distillates boiling fro~ about 65~ to 430~C, including kerosene, diesel fuels, home heating fuel oil, jet fuels, etc., a concentration of the additives in the fuel in the range of typically from about 0.001 to about 0.5, and preferably 0.005 to about 0.15 weight percent, based on the total weight of the composition, will usually be employed.
The properties of such fuels are well known as illustrated, for example, by ASTM Specifications D #396-73 (Fuel Oils) and D #439-73 (Gasolines) available from the American Society for Testing Materials ("ASTM"), 1916 Race Street, Philadelphia, Pennsylvania 19103.
201~22 The fuel compositions of this invention can contain, in addition to the products of this invention, other additives which are well known to those of skill in the art. These can include anti-knock agen~s such as tetraalkyl lead compounds, lead scavengers such as haloalkanes, deposit preventers or modifiers such as triaryl phosphates, dyes, cetane improvers, anitoxidants such as 2,6-ditertiary-butyl-4-methylphenol, rust inhibitors, bacteriostatic agents, gum inhibitors, metal deactivators, upper cylinder lubricants and the like.
The additive mixtures of the present invention find their primary utility in lubricating oil compositions which employ a base oil in which the additives re dissolved or dispersed. Such base oils may be natural sr synthetic.
Base oils suitable for US2 in preparing the lubricating oil compositions of the present invention include those conventionally employed as cranXcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like. Advantageous results are also achieved by employing the additive mixtures of the present invention in base oils conventionally employed in and/or adapted for use as power transmitting fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and the like. Gear lubricants, industrial oils, pump oils and other lubricating oil compositions can also benefit from the incorporation therein of the additive mixtures of the present invention.
These lubricating oil formulations conventionally contain several different types of additives that will supply the characteristics that are required in the formulations. Among these types of additives are included viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point 2~6~22 depressant~, antiwear agents, friction modifiers, etc. as described in U. S. Patent 4,797,219, the disclosure of which is hereby incorporated by reference in its entirety.
Some of these numerous additives can provide a multiplicity of effects, e.g. a dispersant-oxidation inhibitor. This approach is well known and need not be further elaboratPd herein.
In the preparation of lubricating oil formulations it is common practice to introduce the additives in the form of 10 to 80 wt. %, e.g., 20 to 80 wt. ~ active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent. Usually these concentrates may be diluted with 3 to 100, e.g., 5 to 40 parts by weight of lubricating oil, per part by weight of the additive package, in forming finished lubricants, e.g.
crankcase motor oils. The purpose of concentrates, of course, is to make the handl ing of the various ~aterials less difficult and awkward as well as to facilitate solution or dispersion in the final blend. Thus, a dispersant would be usually employed in the form of a 40 to 50 wt. % concentrate, for example, in a lubricating oil fraction.
The ashless dispersants of the present invention will bP generally used in admixture with a lube oil basestock, comprising an oil of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
Natural oils include animal oils and vegetable oils (e.g., castor, lard oil) liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have ~016022 been modified by esterification, etherification, etc., constitute another class of known ~ynthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-poly isopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of poly-ethylene glycol having a molecular weight of 50Q-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid ester~ and C13 Oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, ~aleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diissoctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
201~022 Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butylphenyl)silicate, hexa-~4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polvmeric tetrahydrofurans.
Unrefined, refined and rerefined oils can be used in the lubricants of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art. Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
Compositions when containing these conventional additives are typically blended into the base oil in amounts effective to provide their normal attendant ~016022 function. Representative effective amounts of such additives (as the respective active ingredients) in the fully formulated oil are illustratad as follows:
~t.% A.I. Wt.% AoI~
Compositions ~Çfg~Y~L (Broad~_ Viscosity Modifier .01-4 0.01-12 De~ergents 0.01-3 0.01-20 Corrosion Inhibitor 0.01-1.5 .01-5 Oxidation Inhibitor 0.01-1.5 .01-5 Dispersant 0.1-8 .1-20 Pour Point Depressant 0.01-1.5 .01-5 Anti-Foaming Agents 0.001-0.15 .001-3 Anti-Wear Agents 0.001-1.5 .001-5 FrictiQn Modifiers 0.01-1.5 .01-5 Mineral Oil Base Balance Balance When other additives are employed, it may be desirable, although not necessary, to prepare additive concentrates comprising concentrated solutions or disper-sions of the novel dispersants of this invention (in concentrate amounts hsreinabove described), together with one or more of said other additives (said concentrate when constituting an additive mixture being referred to herein as an additive-package) whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing acrompanied with mild heating, but this is not essential. The concentrate or additive-package will typically be formulated to contain the additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base lubricant. Thus, the dispersants of the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive-packages ~160~2 containing active ingredients in collective amounts of typically from about 2.5 to about 90%, and preferably from about 15 to about 75%, and mo8t preferably from about 25 to about 60~ by weight additive~ in the appropriate proportions with the remainder being base oil.
The final formulations may employ typically about 10 wt. ~ of the additive-package with the remainder being base oil.
All of said weight percents expressed herein (unless otherwise indicated) are based on active ingredient (A.I.) content of the additive, and/or upon ths total weight of any additive-package, or formulation which will be the sum of the A.I. weight of each additive plus the weight of total oil or diluent.
This invention will be further understood by reference to the following examples, wherein all parts are parts by weight, unless otherwise noted and which include preferred embodiments of the invention.
~nl6022 EXAMP~E_~. Preparation of NH3-Methyl Acryla~e First Adduct.
8.2 g of ammonia is bubbled into 100 ml of anhydrous methanol at -lO C. This cooled ammonia-methanol solution is added ts 296 g of methyl acrylate (MeAc) dropwise under a nitrogen atmosphere with external cooling to keep the liquid reaction mixture at a temperature of from about 20-25C. After the addition is completed, the reaction mixture is allowed to stir at room temperature overnite. The reaction mixture is then stripped with N2 gas to remove the excess methylacrylate and methanol until constant weight. The product analyzes for 52.3 wt.% C, 7.89 wt.% H and 4.5 wt.% N (theoretical 52.~ wt.% C, 7.6.
wt.% H, 5.1 wt.% N).
XAMPLE 2. Preparation of NH3-MeAc + TETA Second Adduct.
55 g (0.2 mole) of the product of Example 1 is charged into a reaction flask and diluted with 100 ml of anhydrous isopropanolO ~hile stirring and under N2 atmosphere, ~7.6 g (0.6 mole) of triethylenetetramine (TETA) is added and heated to 100C while nitrogen sparging for about 10 hours. When the infrared analysis indicates complete disappearance of the ester band, the reaction mixture is stripped at 100C for one half hour and the product collected. It analyzes for 27.2 wt.% N and 4.21 milliequivalents of primary nitrogen per gram of sample.
EXAMPLE 3. Preparation of NH3-MeAc + PAM Second Adduct.
The procedure of Example 2 i5 followed except that 27.5 g (0.1 mole) of the ammonia-methyl acrylate first adduct and 70.6 g (0.6 milliequivalent of primary nitrogen) ~016~22 of poly(ethyleneamine) having an average of 5 to 7 nitrogen atoms per molecule (PAM) are used. The product analyzes for z7.6 wt.% N and 3.38 milliequivalents of primary nitrogen per gram of sample.
XAMPI,E 4. Preparation of NH3-MeAc-TETA + PIBSA
Dispersant.
About 300 g (0.1 mole) of a polyisobutenyl succinic anhydride derived from a l~n 2225 polyisobutylene ~w/Fln = 2 . 5) and having a saponification number of 37.4 (67.7% active ingredient) is charged into a reaction flask with 127 g S150N and heated to 150C while stirring under nitrogen blanket.
Then 23.2 g (0.1 equivalents of primary nitrogen) of the second adduct prepared in Example 2 is added slowly for about one half hour. The reactic n mixture is heat soaked while stirring and nitrogen stripping for 3 hours. The oil solution containing the dispersant is filtered while hot and evaluated. It is found to have a kinematic visco~ity of 341 cSt at 100C and contains 1.52 wt.% N.
X~PLE_5. Preparation of NH3-MeAc-PAM + PIBSA
Dispersant.
The procedure of Example 4 is repeated except that 29.6 g (0.1 equivalents of primary nitrogen) of the adduct of Example 3 and 300 g of the PIBSA are used. The filtered oil solution is found to have a kinematic viscosity of 490 cSt at 100C and 1.81 wt.% N.
XAMPLE 6. Preparation of DETA-Methylacrylate First Adduct.
Using the procedure of Example 1, 51.5 g (0.5 mole) of diethylene triamine (DETA) is charged into a reaction flask and diluted with 100 ml of anhydrous i s o p r o p a n o 1 .
Then 258 g (3 mole) of methyl acrylate is added at a rate to keep the reaction temperature below 30C. When the addition is completed, the reaction mixture is stirred at room temperature overnight. The reaction mixture is stripped with a N2 ga~ stream until constant weight and the product analyzes for 54.17 wt.% C, 8.67 wt.% H and 7.74 wt.% N (theoretical 54.0 wt.~ C, 8.1 wt.% H, 7.8 wt.% N).
EXAMPLE 7. Preparation of MeAc-DETA + TETA Second Adduct.
The procedure of Example 2 is repeated except that 53.3 g (O.1 mole) of the methyl-acrylate-DETA adduct of Example 6 and 73 g (0.5 mole) of triethylenetetramine ~TETA) are used. Th~ product analyzes for 28 wt.% N and 3.88 milliequivalents of primary nitrogen per gram of sample.
EXAMPLE 8. Preparation of MeAc-DETA + PAM Second Adduct.
The procedure of Example 7 is followed except that 53.3 g of the adduct of Example 6 and 117 g of PAM are used. The product analyzes for 28.2 wt.% N and 3.33 milliequivalent of primary nitrogen per gram of sample.
XAMPLE 9. Preparation of MeAc-DETA-TETA + PIBSA
Dispersant.
The procedure of Example 4 is carried out except that 12.9 g (0.05 equivale~ts of primary nitrogen) of the product of Example 7, 150 g of PIBSA and 64.5 g of S150N
are used. The filtered oil solution has a kinematic viscosity of 300 cSt at 100C and 1.5~ wt.% N.
XAMPLE 10. Preparation of MeAc-DETA-PAM + PIBSA
Dispersant.
The procedure of Example 4 is repeated except that 15 g (O.05 equivalents of primary nitrogen) of the product ~01 6~22 of Example 8, 150 g of PIBSA and 67 g of S150N are used.
The filtered oil solutio~ analyzes for a kinematic viscosity of 592 cSt at 100C and 1.83 wt.% N.
OMPARATIVE EXAMPLE A. Preparation of PIBSA-TETA
Dispersant.
The procedure of Example 4 is repeated except that 150 g (.05 mole) of PIBSA, 3.65 g ~0.025 mole) of triethylenetetramine and 56 g of S150N are used. I'he filtered oil solution analyzes for 0.67 %wt. N and has a kinematic viscosity of 381 cSt at 100C.
OMPARATIVE EXAMPLE B. Preparation of PIBSA-PAM
Dispersant.
The procedure of Example 4 is repeated except that 150 g (0.05 mole) of PIBSA, 5.85 g of PAM (0.05 equivalents of primary nitrogen) and 58 g of S150N are used. The filtered oil solution analyzes for 0.91 wt.% N and a kinematic viscosity of 450 cSt at 100C.
The product dispersants thereby obtained are summarized as set forth in Table I below.
TABLE I
Example VIS 100C, No. PIB Mn Amine wt% NcSt(1) 4 2225 Ex. 2 Product 1.52 341 " Ex. 3 Product 1.81 490 9 " Ex. 4 Product 1.59 300 " Ex. 8 Product 1.83 592 Comp. A " TETA 0.67 381 Comp. B " PAM 0.91 450 (1) kinematic viscosity.
2016~22 The following lubricating oil compositions are prepared using the dispersants of Examples 4, 5, 9, 10, and Comparative Examples A - B. The resulting compositions are then tested for sludge inhibition (via the SIB test) and varnish inhibition (via the VIB test), as described below.
The SIB test has been found, after a large number of evaluations, to be an excellent test for assessing the dispersing power of lubricating oil dispersant additives.
The ~edium chosen for the SI~ test is a used cranXcase mineral lubricating oil composition having an original viscosity of about 325 SUS at 38C that had been used in a taxicab that is driven yenerally for short trips only, thereby causing a buildup of a high concentration of sludge precursors. The oil that is used contained only a refined base mineral lubricating oil, a viscosity index improvar, a pour point depressant and zinc dialkyl-dithiophosphate anti-wear additive. The oil contained no sludge dispersant. A quantity of such used oil is acquired by draining and refilling the taxicab crankcase at 1000-2000 mile intervals.
The SIB test is conducted in the following manner: the aforesaid used crankcase oil, which is milky brown in color, is freed of sludge by centrifuging for one hour at about 39,000 gravities (gs.). The resulting clear bright red supernatant oil is then decanted from the insoluble sludge particles thereby separated out. However, the supernatant oil still contains oil-soluble sludge precursors which on heating under the conditions employed by this test will tend to form additional oil-insoluble deposits of sludge. The sludge inhibiting properties of the additives being tested are determined by adding to portions of the supernatant used oil, a small amount, such 2016~22 as 0.5, 1 or 2 weight percent, of the particular additive being tested. Ten grams of each blend being tested are placed in a stainless steel centrifuge tube and are heated at 135C for 16 hours in the presence of air. Following the heating, the tube containing the oil being tested is cooled and then centrifuged for about 30 minutes at room temperature at about 39,000 gs. Any deposits of new sludge tat form in this step are separated from ~he oil by decanting the supernatant oil and then carefully ishing the sludge deposits with 25 ml of heptane to remove all remaining oil from the sludge and further centrifuging.
The weight of the new solid sludge that has been formed in the test, in milligrams, is determined by drying the residue and weighing it. The results are reported as amount of precipitated sludge in comparison with the precipitated sludge of a blank not containing any additional additive, which blank is normalized to a rating of 10. The less new sludge precipitated in the presence of the additivej the lower the SIB value and the more effective is the additive as a sludge dispersant. In other words, if the additive gives half as much precipitated sludge as the blank, then it would be rated 5.0 since the blank will be normalized to 10.
The VIB test is used to determine varnish inhibition. Here, each test sample consisted of 10 grams of lubricating oil containing a small amount of the additive being tested. The test oil to which the additive is admixed is of the same type as used in the above-described SIB test. Each ten gram sample i9 heat soaked overnight at about 140C and thereafter centrifuged to remove the sludge. The supernatant fluid of each sample is subjected to heat cycling from about 150C to room temperature over a period of 3.5 hours at a frequency of about 2 cycles per minute. During the heating phase, gas ~0~ 6~22 which is a mixture of about O.7 volume percent S02, 1.4 ~olume percent NO and balance air is bubbled through the test samples. During the cooling phase, water vapor is bubbled through the test samples. At the end of the test period, which testing cycle can be repeated as necessary to determine the inhibiting effect of any additive, the wall surfaces of the test flasks in which the samples are contained are visually evaluated as to the varnish inhibition. The amount of varnish imposed on the walls is rated to values of from 1 to 11 with the hiyher number being the greater amount of varnish, in comparison with a blank with no additive that is rated 11.
10.00 grams of SIB test oil are mixed with 0.05 grams of the products of the Examples as described in Table I and tested in the aforedescribed SIB and VIB tests. The data thereby obtained are summarized in Table II below.
TABLE II
Dispersant Example Wt.%
No. AmL~e N SIB VIB
4 NH3-MeAc + TETA 1.52 1.3 3 NH3-MeAc ~ PAM 1.81 1.58 3 9 DET~-MeAC + TETA 1.59 0.22 3 DETA-MeAc + PAM 1.83 1.63 3 Comp. A TETA 0.67 3.59 7 Comp. B P~M O.91 1.79 7 The above data thereby obtained show that the dispersants of this invention have excellent SIB/VIB
performance and sludge and varnish inhibiting properties.
A series of lubricating formulations were prepared which contained ~ vol% of the novel branched dispersants ~01~022 formed in Examples 4~ 5, 9 and 10, respectively. Each lubricating composition also contained mineral lubricating oil, a mixture of overbased Mg sulfonate detergent inhibitor and overbased Ca sulfonate detergent inhibitor, zinc dialkyl dithiophosphate antiwear agent, antioxidant and ethylene propylene vi5c05ity index improver.
The following Table illustrates preparation of additional first and second adducts employing the present invention.
2~1 6~22 _ ~ O C:~ o Q OO O O O O O
O ~ I O
E~-F
C ~_ P~
a ~
Y ~ ¦ ~ N t~ N ~~ N t`~
_ X
~ O o ~ C~
_ C~, ~ O O O ~ O
~ _~ 11~ ~ ~ O ~ O-- O O
U~ t~ ~ ~ CO O ~ _ _ ~
C ~ ~ V _ .~ ~ ~ O ~ O ~ Il O~ ) o ~ ~ U 5:
-O~ ~ C) ~ S~
P. ~ V U
Z~ ^ Z
-4~ S
Z Z C~ Z ~ Z; ~ ~ Z
X~ 1 Ul W ~
20~6~22 (1) Exs. 11, 12, 14, 16, 1~ and 19--repeat procedure of Example 1 (with 80% molar excess of polyfunctional reactant).
Exs. 13, 15, 17 and 20 --repeat procedure of Example 6 (with 80% molar excess of polyfunctional reactant).
(2) Degree of branching of first adduct.
(3) First adduct product ~ixture stripped of excess poly-~unctional reactant. Exq. 11 20--repeat procedure of Example 2.
( 4 ) TEPA = tetraethylene pentamine: DETA = diethylene triamine; TETA a triethylene tetramine; HPHA =
hexapropylene heptamine; EDA - ethylene diamine.
The principles, preferred embodiments, and modes of operation of the present invention have been described in the foregoing specification~ The invention which is intended to be pro~ec~ed herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
This invention relates to improved oil soluble dispersant additives useful in fuel and lubricating compositions, and to concentrates containing said additives.
BACKGROUND OF TH~ INVENTION
U.S. Patent 2,921,085 relates to the preparation of beta-aminopropionamides by reaction of an alkyl amine with an acrylate to form an alkyl aminopropionate and reaction of the latter compound with an amine. The resulting compounds are disclosed to have utility as surface active agents, specifically as emulsifying, wetting, foaming and detergent agents.
U.S. Patent 3,337,60~ relates to adducts of hydroxyalkyl alkylene polyamines and acrylates. The resulting adducts are added to polyepoxides to provide compositions which are suitable for use as a barrier coating for polyethylene surfaces, and for additional end uses, such as in molding. In addition, the adducts are disclosed to be useful as catalysts in resin preparation and as corrosion inhibitors in water systems for ferrous metals.
U.S. Patent 3,417,140 relates to the preparation of amido-amine compositions, which are useful as epoxy resin curing agents, by reacting a polyalkylene polyamine and a fatty amine (comprising a mono- or diamine having as one of the substituents on a nitrogen atom a hydrocarbyl radical having 8 to 24 carbon atoms) with an alpha-beta unsaturated carbonylic compound. It is disclosed that this ~016~22 reaction occurs through the Michael addition of an amine group across the unsaturated group of the carbonylic compound and through the condensation of an amine group with the carbonylic group.
U.S. Patent 3,247,163 also relates to curing agents for polyepoxide compositions, which curing agents are prepared by reacting an organic amine and an acrylate.
U.S. Patent 3,445,441 relates to amino-amido polymers characterized by being a reaction product of at least a polyamine and an acrylate type compound, such as methyl or ethyl acrylate, and methyl or ethyl methacrylate. The patent states that the polymers are useful in a wide variety of applications, such as floculating agents, water clarifying additives, corrosion inhibitors in oil and gas wells, and as lube oil additives. The patent further discloses that the polymers may be derivitized, including acylation with monocarboxylic acids and polycarboxylic acids, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, for example, diglycolic, phthalic, succinic, etc., acids.
U.S. Patent 3,~03,003 relates to lubricating compositions containing an amido-amine reaction product of a terminally carboxylated isoprene polymer which is formed by reacting a terminally carboxylated substantially completely hydrogenated polyisoprene having an average molecular weight between about 20,000 and 250,000 and a nitrogen compound of the group consisting of polyalkylene amines and hydroxyl polyalkylene amines.
U.S. Patent 4,493,771 relates to scale inhibiting with compounds containing quaternary ammonium and methylene phosphonic acid groups. These compounds are derivatives of polyamines in which the amine hydrogens have been substituted with both methylene phosphonic acid groups or their salts and hydroxypropyl quaternary ammonium halide groups. The patent discloses that any amine that contains ~16022 reactive amino hydrogens can be utilized, for example, polyglycol amines, amido-amines, oxyacylated amines, and others.
U.S. Patent 4,459,241 contains a similar disclosure to U.S. Patent 4,493,771.
SUMMARY OF THE INVENTION
A process for forming a nitrogen-containing lubricating oil dispersant additive which comprises: (a) contacting in a first liquid reaction mixture a first nitrogen-containing compound having at least two reactive nitrogen moieties with a polyfunctional reactant having within its structure a first functional group reactive with a -NH- group, and at least one additional functional group reactive with a -NH- group, in an amount and under conditions sufficient to selectively react the first functional groups in the polyfunctional reactant with the reactive nitrogen moieties to form a first reaction mixture containing a first adduct; (b) contacting the first adduct with a second nitrogen-containing compound having at least two -NH- groups in an amount and under conditions sufficient to react the additional functional groups in the first adduct with said -NH- groups in the second nitrogen-containing compound to form a second adduct characterized by having within its structure on average (i) at least two nitrogen-containing moieties derived from the second nitrogen-containing compound per nitrogen-containing moiety derived from the first nitrogen-containing compound and (ii) at least two unreacted primary or secondary amine groups per molecule; and (c) contacting the second adduct in a second liquid reaction mixture with at least one long chain hydrocarbon-substituted reactant in an amount and under conditions sufficient to form the nitrogen-containng dispersant, said long chain hydrocarbon-substituted reactant comprising at least one member selected from the group consisting of;
tA) long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups;
(B~ halogenated long chain hydrocarbons;
(C) mixtures of formaldehyde and a long chain hydrocarbyl substituted phenol; and (D) mixtures of formaldehyde and a reaction product formed by reaction of long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups and an amino-substituted, optionally hydrocarbyl-sub-stituted phenol.
In one preferred embodiment, the present invention is directed to a branched amido-amine dispersant additive, and more preferably to a star branched amido-amine dispersant additive, useful in oleaglnous compositions formed by (a) reacting a first nitrogen- containing compound (e.g., ammonia or an organic amine) with an alpAa, beta-unsaturated compound of the formula:
~2 R3 wl R - C = C - C - Y
wherein W1 i5 sulfur or oxygen, Y is -oR4, -SR4, or ~R4 (R5) and Rl R2 R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstitut2d hydrocarbyl, to form a first adduct containing unreacted -C(Wl)-Y groups; (b) reacting the first adduct with a polyamine (e.g., a polyalkylene polyamine) to form a second adduct containing unreacted -NH- groups (preferably primary amine groups) and comprising a branched amido-amine oligomer, and (c) reacting said second adduct with a long chain hydrocarbyl substituted mono- or dicalboxylic acid material comprising a polyolefin of 300 to 10,000 number average molecular weight substituted with at least 0.3 (e.g., from about 1 to 4) mono- or dicarboxylic acid producing moieties ~0~22 (preferably acid or anhydrlde moieties) per polyolefin molecule.
The materials of the invention are different from the prior art because of their effectiveness and their ability to provide enhanced dispersancy. In fuels, the additives serve to minimize the degree of carburetor and fuel iniector fouling from deposits. In addition, the additives of this invention possess superior viscometric properties.
Therefore, the present invention is also directed to novel processes for preparing the dispersant fuel adducts of this invention.
DETAILED ~ESCRIPTION OF THE INVENTION
FIRST NITROGEN-CONTAINING COMPOUND
As described above, the first adduct employed in the present invention is prepared by contacting a polyfunctional reactant with a first nitrogen-containing compound containing at least two (e.g., from 2 to 20), preferably at least 3 te.g., from 3 to 15), and most preferably from 3 to 8, reactive nitrogen moieties (that is, the total of the nitrogen-bonded H atoms) per molecule of the first nitrogen-containing compound. The first nitrogen-containing compound will generally comprise at least on~ member selected from the group consisting of ammonia, organic primary monoamines and organic polyamines containing at least one primary amine group or at least two secondary amine groups per molecule. Generally, the organic amines will contain from about 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total carbon atoms and about 2 to 12, preferably 3 to 12, and most preferably from 3 to 8 (e.g., 5 to 9) total nitroyen atoms in the molecule. These amines may be hydrocarbyl amines or may be hydrocarbyl ~mines including other groups, e.g, hydroxy groups, alkoxy ~0~ ~022 groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularly useful. Preferred amines are aliphatic saturated amines, including those of the general formulas:
R-N-R', and R-N-(CH2)s ~ N-(CH2)s ~ N-R
R" R' L R''' R' t (I) (II~
wherein R, R', R'' and R''' are independently selected from the group consisting of hydrogen; Cl to C~5 straiqht or branched chain alkyl radicals; C1 to C12 alkoxy C2 to C6 alkylene radicals; C2 to C12 hydroxy amino alkylene radicals; and Cl to C12 alkylamino C2 to C6 alkylene radicals; and wherein R"' can additionally comprise a moiety of the formula:
~CH2)s' -N ~ H (III~
I t~
R' wherein R' is as defined above, and wherein s and s' can be the same or a different number of from 2 to 6, preferably 2 to 4; and t and t' can be the same or different and are numbers of from O to 10, preferably 2 to 7, and most preferably about 3 to 7, with the proviso that the sum of t and t' is not greater than 15. To assure a facile reaction, it is preferred that R, R', R'', R''', s, s', t and t' be selected in a manner sufficient to provide the compounds of Formulas I and II with typically at least one primary or secondary amine group, preferably at least two primary or secondary amine groups. This can be achieved by selecting at least one of said R, R', R" or R''' groups to be hydrogen or by letting t in Formula II he at least one when R"' is H or when the III moiety possesses a secondary amino group.
20~6~22 Non-limitinq examples of suitable organic amine compounds include~ 1,2-diaminoethane; 1,3-diaminopropane;
1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such as diethylene triamine; triethylene tetra;
tetraethylene pentamine; polypropylene amines such as 1,2-propylene diamine; di-(1,2-propylene)triamine;
d i - (1, 3 -p r op yl e n e) t ri am i ne ;
N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);
diisopropanol amine; diethanol amine; trie~hanol amine;
mono-, di-, and tri-tallow amines; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof.
Other useful amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl piperazines of the general formula (IV~:
H ~ -(C~)p ~ ~ 2 2~
wherein P1 and P2 are the same or different and are each integers of from 1 to 4, and nl, n2 and n3 are the same or different and are each integers of from 1 to 3. Non-limiting examples of such amines include 2~pentadecyl imidazoline: N-(2-aminoethyl) piperazine; etc.
Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines invol~es the reaction of an involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylen~ dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, ~16~22 triethylenetetra, tetraethylene pentamine and isomeric piperazines. Low cost poly~ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.
Useful amines also include polyoxyalkylene polyamines such as those of the formulae:
NH2 alkylene ~ O-alkylene ~ NH2 (V~
m where m has a value of about 3 to 70 and preferably 10 to 35; and R ~ alkylenef ~ -alkylen ~ NH2 n P (VI) where "n" has a value of about 1 to 40 with the provision that the sum of all the n's is from about 3 to about 70 and preferably from about 6 to about 35, and R is a polyvalent saturated hydrocarbon radical of up to ten carbon atoms wherein the number of substituents on the R group is represented by the value of "p", which is a number of from 3 to 6. The alkylene groups in either formula (V) or (VI~
may be straight or branched chains containing about 2 to 7, and preferably about 2 to 4 carbon atoms.
The polyoxyalkylene polyamines of formulas (V) or (VI) above, preferably polyoxyalkylene diamines and polyoxyalkylene triamines, may have average molecular weights ranging from about 200 to about 4000 and preferably from about 400 to about 2000. The preferred polyoxyal-kylene polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2000. The polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc.
~6~22 under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.
Additional amines useful in the present invention are described in U.S. Patent 3,445,441, the disclosure of which is hereby incorporated by reference in its entirety.
Most preferred as the first nitrogen-containing compound are members selected from the group consisting of ammonia and organic diprimary amines having fxom 2 to 12 carbon atoms and from 2 to 8 nitrogen atoms per molecule.
Examples of such preferred organic diprimary amines are ethylene diamine, propylene diamine, diethylene triamine, dipropylene triamine, triethylene tetraamine, tripropylene tetraamine, tetraethylene pentaamine, tetrapropylene pentaamine, polyhexamethylene diamine, phenyl diamine.
POLYFUNCTIONAL REACTANT
Polyfunctional reactants useful in this invention include compounds having the formula (VII):
~1 w2 x ~ c ~ (T)a ~ [ (C)b- Y]c wherein Wl and w2 are the same or different and are O
or S, X and Y are the same or different, and preferably are each groups reactive with a ~NH- group (i.e., with NH3 or with primary or secondary amine groups), T is a substituted or unsubstituted hydrocarbon moiety, "a" is 0 or 1, "b" is 0 or 1, and "c" is an integer of at least 1, with the provisos that c = 1 when a = 0 and b = 1 when a = 1 , and with the further proviso that at least two of X, Y and T
are reactive with a -NH- group.
The X and ~ functional groups are the same or different and include groups selected from the group consisting of: halide, -oR4, -SR4, -N(R4)(R5) _ z 1 C (O) oR4, - C (O) R4 , --(R3) C = C (R 1) (R2) -zl-nitrlle, -Zl-cyano, -Zl-thiocyano, -Z1-isothiocyano, and -Z1-isocyano, wherein Rl, R2, R3, R4 and R5 are the same or different and are H or substituted or unsubstituted hydrocarbyl and wherein zl is Cl to C20 (preferably Cl to C10) bivalent hydrocarbylene (preferably alkylene or arylene). If a = b = 1, and T contains at least one >C=C< group, X and Y can together further comprise -O- or -S-, to provide as reactants a class of ethylenically unsaturated and aromatic anhydrides and sulfo~anhydrides. Preferably the X and Y
groups in the selected polyfunctional reactant are different, and the reactivity of the X moiety with -N~-groups, under the selected reaction conditions, is greater than the reactivity of the Y moieties with such -NH- groups to permit a substantially selective reaction of the X
groups with the first nitrogen-containing compound as described below. The relative reactivity of these groups on a polyfunctional reactant can be readily determined by conventional methods.
Wh en R 1 R 2 R3, R4 or R 5 a r e hydrocarbyl, these groups can comprise alkyl, cycloalkyl, aryl, alkaryl r aralkyl or heterocyclic, which can be substituted with groups which are substantially inert to any component of the reaction mixture under conditions selected for preparation of the amido-amine. Such substituent groups include hydroxy, halide (e.g., Cl, Fl, I, Br), -SH and alkylthio. When one or more of R1 through R5 are alkyl, such alkyl groups can be straight or branched chain, and will generally contain from 1 to 20, more usually from 1 to 10, and preferably from 1 to 4, carbon atoms. Illustrative of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and the like. When one or more of Rl through R5 are aryl, the aryl group will generally contain from 6 to 10 carbon atoms (e.g., phenyl, naphthyl).
2~1 6~22 When one or more of Rl through R5 are alkaryl, the alkaryl group will generally contain from about 7 to 20 carbon atoms, and preferably from 7 to 12 carbon atoms.
Illustrative of such alkaryl groups are tolyl, m-ethyl-phenyl, o-ethyltolyl, and m-hexyltolyl. When one or more of R through R5 are aralkyl, the aryl component generally consists of phenyl or (Cl to C6) alkyl-sub-stituted phenol and the alkyl component generally contains from 1 to 12 carbon atoms, and preferably from 1 to 6 carbon atoms. Examples of such aralkyl groups are benzyl, o-ethylbenzyl, and 4-isobutylbenzyl. When one or more of Rl and R5 are cycloalkyl, the cycloalkyl group will generally contain from 3 to 12 carbon atoms, and preferably from 3 to 6 carbon atoms. Illustrative of such cycloalkyl groups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, and cyclododecyl. When one or more of Rl through R5 are heterocyclic, the heterocyclic group generally consists of a compound having at least one ring of 6 to 12 members in which on one more ring carbon atoms is replaced by oxygen or nitrogen. Examples of such heterocyclic groups are furyl, pyranyl, pyridyl, piperidyl, dioxanyl, tetra-hydrofuryl, pyrazinyl and 1,4-oxazinyl.
T is a polyvalent organic radical whose valence is equal to c + 1, wherein "c" is an integer of at least 1, preferably 1 to 3. Ordinarily T will not contain more than 20 carbon atoms and preferably not more than 10 carbon atoms. T can therefore include divalent groups such as as saturated and unsaturated hydrocarbylene (e.g., alkylene, alkenylene, arylene, and the like). When T ;s substituted, it can contain one or more substituents selected from the class consisting of halo, lower alkoxy, lower alkyl mercapto, nitro, lower alkyl, carboxy and oxo. It also may contain interrupting groups such as -O-, -S-, -S(O)-, -S(O)2-, -NH-, -C(O)- and the like.
Exemplary O f zl groups are Cl to C10 branched and straight chained alkylene such as -(CH2)f-wherein "f" is an integer of from 1 to 10 (e.g., -CH2-, C H ~ -C3 H7 -, - C4 H8 ~, - C 5H 1 o ~ a n like), and C6 to C20 arylene, and alkyl-substituted arylene such as -Ar-, -Ar-((CH2)f)-, -((CH2)f)-Ar-, -Ar-~(CH2)f)-~r- and the like, wherein Ar is phenylene, methylphenylene, naphthylene, methylnaphthylene and the like and wherein f is as defined above.
Examples of polyfunctional reactants of formula VII wherein X is (Rl)(R2)C=C(R3)-, a = b = O and c =
1 are difunctional reactants comprising alpha, beta-ethylenically unsaturated compounds selected from the group consisting of compounds of the formula:
R2 R3 wl R - C = C - C - Y (VIII) wherein Wl is sulfur or oxygen, Y is as defined above, and is preferably -oR4, -SR4, or -NR4(R5), wherein Rl, R2, R3, R4 and R5 are as defined above.
The alpha, beta-ethylenically unsaturated carboxylate compounds employed herein have the following formula:
R2 R3 o Rl- C = C - ~C - oR4 (IX) w h erein Rl, R2, R3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of such alpha, beta-ethylenically unsaturated carboxylate compounds of formula IX are acrylic acid, methacrylic acid, the methyl, ethyl, isopropyl, n-butyl, and isobutyl esters of acrylic and methacrylic acids, 2-butenoic acid, 2-hexenoic acid, 2-decenoic acid, 3-methyl-2-heptenoic acid, 3-methyl-2-butenoic acid, 3-phenyl-2-propenoic acid, 3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid, 2-propyl-2-propenoic acid, 2-isopropyl-2-hexenoic acid, 2,3-dimethyl ~Ot6022 -2-butenoic acid, 3-cyclohexyl-~-methyl-2-pentenoic acid, 2-propenoic acid, methyl 2-propenoate, methyl 2-methyl 2-propenoate, methyl 2-butenoate, ethyl 2-hexenoate, isopropyl 2-decenoate, phenyl 2-pentenoate, tertiary butyl 2-propenoate, octadecyl 2-propenoate, dodecyl 2-decenoate, cyclopropyl 2,3-dimethyl-2-butenoate, methyl 3-phenyl-2-propenoate, and the like.
The alpha, beta-ethylenically unsaturated reactants of formula IX wherein -oR4 is instead -R4 are aldehydes and ketones of the formula:
R2 R3 o Rl- C = C - C - R4 (IXa) wh erein R1, R2, R3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined abo~e. Examples of such alpha, beta-ethylenically unsaturated aldehydes and ketones of formula IXa are:
H2c=cH-c(o)-cH3 H2C=CH-C (O) -C2H5 H2C=CH-C~O)-C3H7 H2C=CH-C(O)-C~cH3)3 H2c=cH--c ()--C5~11 H2C=C(CH3)-C(O)-CH(cH3)2 H2C=C(CH3)-c(O)-c2H5 H(cH3)c=cH-c(o)-cH3 H(CH3)C=CH-C(O)-CH(CH3)2 H(CH3)C=CH-C()~C2H5 H(CH3)c=cH-c(o)-c3H7 H(C2H5)C=CH-C(O)-c(cH3)3 H(CH3)C=CH-c(O)-csHll (CH3)(c2Hs)c=c(cH3)-c(o)-cH3 H(CH3)C=C(cH3)-c(O)-c2H5 ~016~22 The alphal beta-ethylenically unsaturated carboxylate thioester compounds employed herein have the following formula:
Rl- C = C _ll _ SR4 (X) w h erein Rl, R2, ~3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of such alpha, beta-ethylenically unsaturated carboxylate thioesters of formula X are methylmercapto 2-butenoate, ethylmercapto 2-hexenoate, isopropylmercapto 2-decenoate, phenylmercapto 2-pentenoate, tertiary butylmercapto 2-propenoate, octa-decylmercapto 2-propenoate, dodecylmercapto 2-decenoate, cyclopropylmercapto 2,3-dimethyl-2-butenoate, methyl-mercapto 3-phenyl-2-propenoate, methylmercapto 2-pro-penoate, methylmercapto 2-methyl-2-propenoate, and the like.
The alpha, beta-ethylenically unsaturated carboxyamide compounds employed herein have the following formula:
R - C = C - C - NR4(R5) (XI~
wherein Rl, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated carboxyamides of formula XI
are 2-butenamide, 2-hexenamide, 2-decenamide, 3-methyl-2-heptenamide, 3-methyl-2-butenamide, 3-phenyl-2-propenamide, 3-cyclohexyl-2-butenamide, 2-methyl-2-butenamide, 2-propyl-2-propenamide, 2-isopropyl-2-hexenamide, 2,3-dimethyl-2-butenamide, 3-cyclohexyl-2-methyl-2-pentenamide, N-methyl 2-butenamide, N,N-diethyl 2-hexenamide, N-isopropyl 2-decenamide, N-phenyl 2-pentenamide, N-tertiary butyl 2-propenamide, ~01~22 N-octadecyl 2-propenamide, N,N-didodecyl 2-decenamide, N-cyclopropyl 2,3-dimethyl-2-butenamide, N-methyl 3-phenyl-2-propenamide, 2-propenamide, 2-methyl-2-pro-penamide, 2-ethyl-2-propenamide and the like.
The alpha, beta-ethylenically unsaturated thiocarboxylate compounds employed herein have the following formula:
R~ - oR4 (XII) wherein Rl, R2, R3 and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated thiocarboxylate compounds of formula XII are 2-butenthioic acid, 2-hexenthioic acid, 2-decenthioic acid, 3-methyl-2-heptenthioic acid, 3-methyl-2-butenthioic acid, 3-phenyl-2-propenthioic acid, 3-cyclohexyl-2-butenthioic acid, 2-methyl-2-butenthioic acid, 2-propyl-2-propenthioic acid, 2-isopropyl-2-hex-enthioic acid, 2,3-dimethyl-2-butenthioic acid, 3-cyclo-hexyl-2-methyl-2-pententhioic acid, 2-propenthioic acid, methyl 2-propenthioate, methyl 2-methyl 2-propenthioate, methyl 2-hutenthioate, ethyl 2-hexenthioate, isopropyl 2-decenthioate, phenyl 2-pententhioate, tertiary butyl 2-propenthioate, octadecyl 2-propenthioate, dodecyl 2-decenthioate, cyclopropyl 2,3-dimethyl-2-butenthioate, methyl 3-phenyl-2-propenthioate, and the like.
The alpha, beta-ethylenically unsaturated dithioic acid and acid ester compounds employed herein have the following formula:
R1- C = C - C - SR4 (XIII) wn erein R1, R2, R3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated dithioic acids and acid 20~ 6~22 esters of formula XIII are 2-butendithioic acid, 2-hexendithioic acid, 2-decendithioic acid, 3-methyl-2-hep-tendithioic acid, 3-methyl-2~butendithioic acid, 3-phenyl-2-propendithioic acid, 3-cyclohexyl-2-buten-dithioic acid, 2-methyl-2-butendithioic acid, 2-propyl-2-propendithioic acid, 2-isopropyl-2-hexendithioic acid, 2,3-dimethyl-2-butendithioic acid, 3-cyclohexyl-2-methyl-2-pentendithioic acid, 2-propendithioic acid, methyl 2-propendithioate, methyl 2-methyl 2-propendithioate, methyl 2-butendithioate, ethyl 2-hexendithioate, isopropyl 2-decendithioate, phenyl 2-pentendithioate, tertiary butyl 2-propendithioate, octadecyl 2-propendithioate, dodecyl 2-decendithioate, cyclopropyl 2,3-dimethyl-2-butendithioate, methyl 3-phenyl-2-propendithioate, and the like.
The alpha, beta-ethylenically unsaturated thiocarboxyamide compounds employed herein have the following formu:la:
R - C = C - C - NR4(R5) (XIV) wherein Rl, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated thiocarboxyamides of formula XIV are 2-butenthioamide, 2-hexenthioamide, 2-decen-thioamide, 3-methyl-2-heptenthioamide, 3-methyl-2-buten-thioamide, 3-phenyl-2-propenthioamide, 3-cyclohexyl-2-buten-thioamide, 2-methyl-2-butenthioamide, 2-propyl-2-propen-thioamide, 2-isopropyl-2-hexenthioamide, 2,3-di-methyl-2-butenthioamide, 3-cyclohexyl-2-methyl-2-penten-thioamide, N-methyl 2-butenthioamide, N,N-diethyl 2 hexenthioamide, N-isopropyl 2-decenthioamide, N-phenyl 2-pententhioamide, N-tertiary butyl 2-propenthioamide, N-octadecyl 2-propenthioamide, N,N-didodecyl 2-decen-thioamide, N-cyclopropyl ~,3-dimethyl-2-butenthioamide, ~016022 ~ 17 -N-methyl 3-phenyl-2-propenthioamide, 2-propenthioamide, 2-methyl-2-propenthioamide, 2-ethyl-2-propenthioamide and the liXe.
Exemplary of polyfunctional reactants of formula VII wherein a = b = c = 1 ar~ compounds of the formula (XV):
wl w2 X - C ~ T - C - Y
wherein Wl, W2, X, ~ and T are as defined above and wherein X and Y are different. Preferred members of this class of reactants are compounds of the formula (XVI):
O O
li \l X - C - T' - C - Y
wherein X and Y are as defined above, wherein X and Y are different and wherein T' is substituted or unsubstituted divalent Cl to C20 (preferably, Cl to C10) y or alkenylene e.g -C2H5-, -(CH2~3-' -(~H2)4-~
-CH=CH-, -C~CH2)-CH2-, and the like, or C6 to C20 ~preferably, C6 to C14) divalent substituted or unsubstituted arylene such as phenylene, naphthylene, bisphenylene, -phenyl-O-phenyl- and the like. Illustrative of bisfunctional reactants of formula XVI are:
H2C=CH-C(O)-CH-C(O)-OCH3 H2C=CH-C(O)-C2H4-C(O)-OCH3 2 CH C(O) C2H4-C(O)-OC2H5 H2C=CH-C (O) -C3H6-C (O) -Cl H2C=CH-c(o)-c2H4-c(o)-sH
2 CH C(O) C5H1o~C(O)~SCH3 H2c=c(CH3)-c(o)-c2H4-c(o)-OcH3 H2c=c~CH3)-c(o)-c2H4-c~o)-oc2H5 H2C=C~-C(O)-CH-C(O)-CH
H2C=CH-C(O)-C2H4-C(O)-CH3 20~6022 H2C=CH-C (O) -C2H4-C (O) -C2H5 H(CH3)C=CH-C(O)-CH2-C(O)-OCH3 H(cH3)c=cH-c(o)-c2H4-c(o)-ocH3 H(CH3)C=CH-C(O)-c2H4-c(O)-oc H
H(CH3)C=CH-C(O)-C3H6-C(O~-Cl H(C2H5)C=CH~C(O)-C2H4-C(O)-SH
H(cH3)c=cH-c(o)-c5Hlo-c(o)-sc~3 (CH3)(c2H5)c=c(cH3)-c(o)-c2H4-c(o~-OCH3 H(cH3)c=c(cH3)-c(o)-~2H4-c(o)-oc2H5 H(CH3)C=CH-C(O)-CH2-C(O)-CH3 H(CH3)C=CH-C(O)-C2H4-C(O)-CH3 H(cH3)c=cH-c(o)-c2H4-c(o)-c2H5 Cl-C(O)-C'H2-C(O)-OCH3 Cl-c(o)-c2H4-c(o)-OcH3 Cl C () C2H4 C (O) -OC2H5 Cl-C(o)-c3H6-c(o)-OH
Cl-C(O)-C2H4-C(O)-sH
Cl-C(o)-c5Hlo-c(o)-scH3 Cl-C(o)-c2H4-c(o)-OcH3 Cl-C(O)-C2H4-C(a)-oc2H5 Cl-C(O)-CH2-C(O)-CH3 Cl-c(o)-c2H4-c(o)-cH3 Cl-C (O) -C2H4-C (O) -C2H5 CH30-C(O)-CH2-C(O)-OH
CH3o-c(o)-c2H4-c(o)-oH
CH30 C(O) C2H4 C(O) SH
CH30 C(O) C3H6 C(O) Cl C2H5o-c(o)-c2H4-c(o)-sH
CH3o-c(o)-c5Hlo-c(o)-scH3 CH3s-c(o)-cH2-c(o)-ocH3 CH3-c(o)-cH2-c(o)-OH
CH3 C(O) C2H4 C(O) OH
~16~22 H3 C(O~ C2H4 C(O)-SH
Exemplary of reactants of fo~mula VII wherein a =
b = c - 1, Wl and w2 are O, T contains a >C=C< group and wherein X and Y togeth~r comprise O- or -S~ are:
Il~o ~ ~ b chloromaleic anhydride, and the like.
Exemplary of polyfunctional reactants of formula VII wherein a = b = 1 and c > 1 are compounds of the formula (XVII):
wl w2 ~1 11 X - C - T - [ (C)- Y]c wherein Wl, W2, X, Y, T and "c" are as defined above and wherein X and Y are different. Illustrative of compounds of formula XVII above are:
H~C=CH-C(O)-CH2--[C(O)-OCH3~2 H2c=cH-c(o)-c2H3-[c(o)-OCH3]2 H2C=CH-C(O)-ARYL-~C(O)-OCH3]2 H2C=CH-C(O)-ARYL-[C(O)-OCH3]2 2 H C(O) C2H3 [C(O)-OC2H5]2 C2C=CH-C(O)-NAPTHYL-[C(O)-OCH3]2 C2C=CH-C(O)-NA~HTHYL-~C(O)-OCH3]2 H2C=CH-C(O)-c2H3-[c(o)-oc2H5]2 H2C=CH-C(O)-C3H5-[C~O)-cl]2 H2C=CH-[C() -C2H3-[C(O) -SH]2 H2C=CH-C(O)-C5Hg-[~(O)-scH3]2 H2C=C(CH3) -C(O) -C2H3-[C(O) -OCH3]2 2~16~2 H2C=C(CH3) -C(O) -C2H3-[C(O) -OC2H5]2 H2c=cH-c(o)-cH2-[c(o)-cH3]2 H2C=CH-C(O)-C2H3-[C(O)-CH3]2 H2C=CH-C(O)-ARYL-[C(O)-CH3]2 H(CH3)C=CH-C(O)-CH-[C(O)-OCH3]2 H(CH3)C=CH-C(O) C2H3-[C(O)-OCH3]2 H(CH3)C=CH-C(O)-C2H3-[C(O)-OC2H5]2 H(CH3)C=CH-C(O)-c3H5-[c(Q)-cl]2 H(c2H5)c=cH-c(o)-c2H3-[c(o)-sH]2 H(CH3)C=CH-C(O)-C5H9-[C(O)-SCH3]2 (cH3)(c2H5)c=c(cH3)-c(o)-c2H3-[c(o)-OcH3]2 H(CH3)C=C(CH3)-C()-C2H3-[C()-C2H5]2 H(cH3)c=cH-c(o)-cH-[c(o3-cH3]2 H(cH3)c=cH-c(o)-c2H3-[c(o)-cH3]2 H(CH3)C=CH-C()-C2H3-[C()-C2H5]2 Cl-C(O)-CH-[C(O)-OCH3]2 Cl-C(O)-C2H3-[C(O)-OcH3]2 Cl-C(O)-C2H3-[c(o)-oc2H5]2 Cl-C(O)-C3H5-[c(O)-oH]2 Cl-C(O)-C2H3-[C(O)-sH]2 Cl-C(O)-C5Hg-[C(O)-scH3]2 Cl-C(O)-C2H3-[C(O)-OcH3]2 Cl-C(o)-c2H3-[c(o)-oc2H5]2 Cl-C(O)-CH-[C(O)-cH3]2 Cl-C(O)-C2H3-[C(O)-cH3]2 cl-C(o)-c2H3-[c(o)-c2H5]2 CH30-C(O)-CH-[c(O)-OH]2 CH30-C(O)-C2H3-[C(O)-OH]2 CH30-C(O)-C2H3-[C(O)-sH]2 CH30-C(O)-C3H5-[c(O)-cl]2 C2H5-C()-C2H3-[C()-SH]2 CH30-C(O)-C5Hg-[C(O)-SCH3]2 201~02~
CH3S-C(O)-CH-[C(O)-OcH3]2 CH3-C(O)-CH-[c(O)-oH]2 CH3-C(O)-C2H3-[c(o)-OH~2 CH3-CtO)-C2H3-[c(o)-sH]2 Exemplary of the polyfunctional reactants of formula VII wherein a = O and b = c = 1 are bisfunctional compounds of the formula (XIX):
~ W2 X -- C -- C -- Y
wherein Wl, W2, X and Y are as defined above and wherein X and Y are different. Illustrative of compounds of formula XIX above are:
C2c=cH-c(o)-c(o)-ocH3 C2C=CH-C(O)-C(O)-OCH3 H2C=C~-C (O)--C (O) -OC2H5 ~I2C=CH-C (O) -C (O) -Cl H2C=CH-C(O)-C(O)-SH
H2c=cH-c(o)-c(o)-scH3 H2C=C(CH3)~C()~C()~CH3 H2C=C(CH3)~C()~Ct)~C2H5 C2C=CH-C(O)-C(O)-CH3 C2c=cH-c(o)-c(o)-cH3 H2C=CH-C (O) -C (O) -C2H5 H(CH3)C=CH-C(O)-C(O)-OCH3 H(CH3)C=CH-C(O)-C(O)-OCH3 H(CH3)C=cH-c(o)-c(o)-oc2H5 H(CH3)C=CH-C(O)-c(O)-cl H(c2Hs)c=cH-c(o)-c(o)~sH
H(~H3)C=CH-C(O)-C(O)-SCH3 (CH3)(c2~s)c=c(cH3)-c(o)-c(o)-ocH3 H(CH3~C=C(CH3)_c(o)-c(o)-oc2H5 ~016~22 ~ 22 -H(CH3)C=CH-C~O)-C(O)-C~3 H(CH3)C=CH-C(O)-C(O)-CH3 H(CH3)C=CH-C(O)-C(O)-c2H5 Cl-C(O)-C(O)-OCH3 Cl-C(O)-C(O)-OCH3 Cl C (O~ -C (O) -OC2H5 Cl-C(O)-C(O)-OH
Cl-C(O)-C(O)-SH
Cl-C(O)-C(O)-SCH3 Cl-C(O)-C(O)-OCH3 Cl-C (O) -C (O) -OC2H5 Cl-C(O)-C(O)-CH3 Cl-C(O)-C(O)-CH3 Cl--C (O) -C (O) -C2H5 CH30-C(O)-C(O)-OH
C2H5-C(O)-C(O)-OH
CH30-C(O)-C(O)-SH
CH30-C(O)-C(O)-Cl C2Hso-c(o)~c(o)-sH
CH30-C(O)-C(O)-SCH
CH30-C(O)-C(O)-OCH3 CH3-C(O)-C(O)-OH
C2H5-C(O)-C(O)-OH
CH30-C(O)-C(O)-SH
Also useful as polyfunctional reactants in the present invention are compounds of the formula (XX):
wl O
1~ 11 RlOC -(CH2)dlS((cH2)d2 CH C \
~
o ~6022 wherein Rl and Wl are as defined above, and wherein "dl" and "d2" are each integers of from 1 to 10;
compounds of the formula (XXI):
~ 1 R l - C = C - S - Y "
wherein Rl, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above, and wherein Y" comprises a reactive functional group selected from the group consisting of:
halide, -oR4, -SR4, -N(R4)(R5), -ZlC(o)oR4 and -(R3)C=C(R1)(R2), wherein R4 is H or substituted or unsubstituted hydrocarbyl as defined above, and compound~ of the formula (XXIa):
Rl- C = C - CN
wherein Rl, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
Examples of such compounds of formula XX are:
CH30C(O)C2H4SCH2 ANHY
CH30C(O)CH2SCH2-ANHY
CH30C(O)C3H6SCH2-ANHy CH30C(0)C(CH3)2SCH2-ANHY
CH3oc(o)cH(cH3)scH2-ANHy C2H50C(O)C2H4SCH2 ANHY
C2H50C(O)CH2SCH2-ANHy C2H50C(O)C3H6SCH2 ANHY
C2H50C(0)C(CH3)2SCH2 ANHY
C2H50C(O)CH(CH3)SCH2 ANHY
wherein ANHY is thP moiety:
~016022 ~, O
-- C~ -- C
~o ~0 Examples of such compounds of formula XXI are:
H2C=CH-S () 2-0C113 H2C=CH--S(~)2-C~3 H2C=CH-S (O) 2-OC2H5 H2C=CH 'S (~)) 2-Cl H2c=c~-s~o)2-sH
H2C=C~-S () 2-SCH3 H2C=C(CH3)-s~o)2-ocH3 H2c=c(cH3)-s(o)2-oc2H5 H2C=CH-S(0)2-OCH(CH3)2 H(CH3)C=CH-S(o)2-OCH3 H(cH3)c=cH-s(o)-2-ocH3 H(CH3)c=cH-s(o)2-oc2H5 H(CH3)~=CH-S(o)2-cl H(c2H5)c=CH-S(o)2-sH
H(CH3)C=CH-S(o)2-scH3 (cH3)(c2Hs)c=c(cH3)-s(o)2 OCH3 H(CH3)C=C(CH3)-S(0)2-oc2H5 Examples of such compounds of formula XXIa are:
H2C=CH-CN
H2c=c(cH3)-cN
H(CH3)C=CH-CN
H(C2H5)C=CH-CN
H(cH3)c=c(cH3)-cN
(cH3)(c2H5)c=c(CH3)-CN
2Q~6~22 Preferred compounds for reaction with the first nitrogen-containing compound in accordance with this invention are lower alkyl esters of acrylic and lower alkyl alpha-substituted acrylic acid. Illustrative of suh preferred compounds are compounds of the formula:
CH2 = C ~ CoR4 (XXII) where R3 is hydrogen or a C1 to C4 alkyl group, such as methyl, and R4 is hydrogen or a C1 to C4 alkyl group, capable of being removed so as to form an amido group, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tart-butyl, aryl, hexyl, etc. e.g., propyl acrylate and propyl methacrylate. In the most preferred embodiments these compounds are acrylic and methacrylic esters such as methyl or ethyl acrylate, methyl or ethyl methacrylate.
The polyfunctional reactants useful in this invention are known materials and can be prepared by conventional methods known to those skilled in the art, which need not be decribed herein.
PREPARATION OF_THE FIRST ADDUCT
The selected first nitrogen-containing compound and polyfunctional reactant are contacted in a first reaction mixture in an amount and under conditions sufficient to react the X functional groups of the latter with at least a portion of, and preferably substantially all of, the reactive nitrogen moieties in the first nitrogen-containing compound.
In preparing the first adduct, it is preferred that the moles of the polyfunctional reactant employed be at least equal to the equivalents of the reactive nitrogen moieties in the first nitrogen-containing compound (that is, the sum of the nitrogen-bonded H atoms in the first nitrogen containing compound). Preferably, a molar excess 2016~22 of the polyfunctional reactant of about at least 10%, such as 10-300%, or greater, for example, 25-200%, is employed.
Larger excess can be employed if desired. For example, NH3 is herein considered to have three reactive nitrogen moieties per molecule, and preferably at least 3 (e.g., from 3.3-10) moles of the polyfunctional reactant are employed in the first reaction mixture per mole of N~3, to form a first adduct having, on average, three N-bonded moieties derived from the polyfunctional reactant, each such moiety containing the group (XXI~
wl w2 Il il - C - (T)a - [(C)b-(Y)Jc wherein W1, W2, Y, T, "a", "b" and "c" are as defined above. Preferably, the first adduct contains on average at least 3 groups, more preferably from 3 to 20, and most preferably from 3 to 8, groups of formula XXIII.
The polyfunctional reactant and first nitrogen compound are preferably admixed by introducing the first nitrogen compound into the liquid reaction mixture containing the polyfunctional reactant, with mixing, to provide an excess of the polyfunctional reactant during the charging of the first nitrogen compound.
The conditions of the temperature and pressure employed for employPd for contacting of the first nitrogen-containing compound and the polyfunctional reactant can vary widely but will be generally from about -lO to 40C (preferably from about 10 to 20C). The progress of the reaction can be followed by IR to observe the disappearance of -N-H- bondsO Lower temperatures can be used, although longer reaction times may be required.
Higher temperatures can also be employed but will tend to increase the amount of the less reactive Y functional groups which react with the reactive nitrogen moieties of the first nitrogen-containing compound, thereby decreasing ~0~ ~22 the desired selectivity for the reaction with the more reactive X functional groups.
The reaction time involved can vary widely depending on a wide variety of factors. For example, there is a relationship between time and temperature. In general, lower temperature demands longer times. Usually, reaction times of from about 2 to 30 hours, such as 5 to 25 hours, and preferably 3 to lO hours will be employed.
Although one can employ a solvent, the reaction can be run without the use of any solvent. It is preferred to avoid the use of an aqueous solvent such as water.
However, taking into consideration the effect of solvent on the reaction, where desired, any suitable solvent can be employed, whether organic or inorganic, polar or non-polar. Suitable solvents include alkanols (e.g., C1 to C6 alkanols such as methanol, isopropanol, ethanol and the like), ethers, xylene, benzene, toluene, tretrahydrofuran, methlyene chloride, chloroform, chlorobenzene, and the like.
The resulting first adduct product mixture is then preferably treated, as by stripping or sparging (with, e.g, nitrogen gas) (e.g., from about 20 to about 100C~
optionally under vacuum to remove any volatile reaction by-products and unreacted polyfunctional reactant to minimize the reaction of the second nitrogen-containing compound therewith in the second stage of the process of the present invention. Therefore, the second liquid reaction mixture, wherin the second adduct is formed, is preferably substantially free of unreacted polyfunctional reactant, e.g. contains less than about l wt%, and more preferably about 0.1 wt% unreacted polyfunctional reactant.
The reaction of the polyfunctional reactants of formula VII with a first nitrogen-containing compound can be illustrated as follows:
20~60~2 monoamines ( Eq . 1 ) O
NH3 + 3 H2C=CH-C-OCH3 --o N [C2H4C-Oc~3 ] 3 (Eq. 2) NH2Rl + 2 H2C=C(C~3)-C-Oc~3 -l Rl -N [ CH2 C ( CH3 ) C-OCH3 ] 2 polyamines l ~Eq- 3 ) H2NC2H4NH2 ~ 4 H2C=CH-C-OCH
o NC2H4N- [ C2H4C-CH3 ] 2 1l [ C2H4C--OCH3 ] 2 (Eq- 4 ) ~N (C2H4NH) 4C2~4NH2 + 8 H2c=cH-c-ocH
o k~
N[C2H4NH]4C2Ho,N~[C2H4(~~CH3]2 l ll [ C2H4C--OCH3 ]
[ C2H4C-OCH3 ] 2 Eq. 5) H2N(c2H4NH)c2~NH2 + 6 H2C=C~I-C-~3 - ~~
~16022 N [ C2H4NH] 2C~4N- [ C2H4C-ocH3 ~ 2 I O
[ C2H4C-CH3 ]
[C2H4C-OCH3 ] 2 (Eq- 6~ H2NC2H4NH2 + 4 H2C=CH-C-Cl NC2H4N- [ C2H4C~Cl ] 2 l ll [ C2H4 C-Cl ] 2 (Eq- 7 ) H2NC2H4NH2 + 4 H2C=CH-C-CH3 NC2H4N--[ C2H4C~CH3 ] 2 l O
[C2H4c-cH3 ] 2 O O
Il 11 (Eq- 8 ) H2NC2H4NH2 + 4 CH30-C-CH2CCH
O O
NC2H4N-[CcH2ccH3]2 t- 4 CH30H
[ ICl CH2~1CI CH3 ] 2 O O
The selective reaction of the first nitrogen-containing compound with an alpha- beta ethylenically unsaturated compound of formula VII results 2~16~22 in the addition of the reactive nitrogen equivalents across the double bond of these polyfunctional reactants.
The average degree of branching in the first adduct is increased as the number of reactive nitrogen moieties in the first nitrogen-containing compound increases.
The average degree of branching ("DBl") of the first adduct can be calculated from the expression:
DB1 = [3(na~ + 2(np) + (ns)] x c wherein "na" is 1 when ammonia is employed as the first nitrogen~containing compound and is zero when ammonia is not used, and wherein "np" and "nS" are the number of primary and secondary amine groups, respectively, in the organic amine, if employed as the first nitrogen-containing compound, and wherein "c" is an integer of at least 1 (and is equal to (r - 1), wherein "r" is the number of functional groups in each molecule of the polyfunctional reactant which are reactive with a -NH- group, as defined in formula VII above). DBl in the first adduct is at least 2 (e.g., from 2 to 30), preferably at least 3 (e.g., from 3 to 20), and more preferably from 3 to 15. When the first nitrogen-containing compound comprises a mixture of ammonia and an organic amine the average degree of branching can be determined by giving each of the factors in the above expression their weighted average of each such nitrogen-containing compound incorporated into the first adduct.
For example, ammonia provides a 3-branch first adduct (DBl = 3) ~ ~ ~y Y - N
~ ~ ~y ~16~22 whereas diethylene triamine provides a 5-branch first adduct (DB1 = 5) Y
~ N '¦~ N /~ N ~
wherein ...Y represents a difunctional reactant which has been bonded to the r~active nitrogen moieties. The degree of branching will be increased still further if a trifunctional reactant is employed. For example, ammonia preferably provides a first adduct of the structure (DB
- 6):
Y\ /\ Y
... N
/ \ Y
\ y and diethylene triamine provides a first adduct of the structure (DBl = 10~:
Y~ Y
N ~ N 3 N
Y/ ~ Y
. . .
2 ~
wherein .../ represent~ a trifunctional reactant which has been bonded to the reac~ive nitrogen moieties.
SECOND NITROGEN-CONTA~N~NG ~OMPOUND
The second nitrogen-containing compound will comprise at least one polyamine containing at least 2 (e.g.
from 2 to 20), preferably at least 3 (e.g. from 3 to 15), and most preferably from 3 to 10, reactive nitrogen moieties, that is the total of the nitrogen-bonded H atoms per molecule of the second nitrogen-containing compound.
The second nitrogen-containing compound will generally comprise at least one member selected from the group consisting of organic primary and secondary polyamines containing at least one primary amine group (and preferably containing at least two (e.g., 2 to 6, preferably 2 to 4) primary amine groups) or at least two secondary amine groups per molecule. Generally, the organic polyamines will contain from about 2 to 60, preferably 2 to 40 ~e.g. 3 to 20), total carbon atoms and about 2 to 12, preferably 3 to 12, and most preferably from 3 to 8 (e.g., 5 to 9) total nitrogen atoms in the molecule. These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularly useful. Preferred amines are aliphatic saturated amines, including those of the general formulas: .
R-N-(CH2)s- ~ p-(CH2)s ~ N R
R' l R''' J R' t (XXIV) 20~ 6~2 wherein R, R' and R' ' ' are independently selected from the group consisting of hydrogen; Cl to C25 straight or branched chain alkyl radicals; C1 to C12 alkoxy C2 to C6 alkylene radicals; C2 to C12 hydroxy amino alkylene radicals; and Cl to C~2 alkylamino C2 to C6 alkylene radicals: and wherein R" ' can additionally comprise a moiety of the formula:
_ ( C~2 ) s '--N~H ( XXV) IJt~
R' wherein R' is as defined abo~re, and wherein s and s' can be the same or a different number of from 2 to 6, preferably 2 to 4; and t and t' can be the same or different and are numbers of from O l:o 10, preferably 2 to 7, and most preferably about 3 to 7, with the proviso that the sum of t and t ' is not greater than 15 . To assure a facile reaction, it is preferred that R, R', R' ' ', s, s', t and t' be selected in a manner sufficient to provide the compounds of Formula XXIV with typically at least two primary or secondary amine group, preferably a total of from 2 to 8 primary and secondary amine groups. This can be achieved by selecting at least one of said R, R' or R' ' ' groups to be hydrogen or by letting t in Formula XXIV be at least one when R" ' is H or when the XXV moiety possesses a secondary amino group.
Non-limiting examples of suitable organic amine compounds include: 1, 2-diaminoethane; 1, 3-diaminopropane 1, 4-diaminobutane; 1, 6-diaminohexane; polyethylene amines such as diethylene triamine; triethylene tetra;
tetraethylene pentamine; polypropylene amines such as 1, 2-propylene diamine; di-(1,2-propylene)triamine;
di- ( 1, 3 -propylene) triamine;
N,N-di~nethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine; N-dodecyl-l, 3-propane ~01~022 diamine; tris hydroxymethylaminomethane (THAM);
diisopropanol amine; diethanol amine; triethanol amine;
mono-, di-, and tri-tallow amines; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof.
Other useful amine compounds include those d i s cu ss a d ab ov e w it h res p ect to the first nitrogen~containing adduct in formulae IV - VI.
Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines involves the reaction of an involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride~ with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylenetetra, tetraethylene pentamine and isomeric piperazines. Low cost poly(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.
The second nitrogen~containing compound can comprise an amido-amine formed by reacting a polyamine with an alpha, beta-ethylenically unsaturated compound ~e.g., of formula XXII), e.g. by reacting polyethylene amines (e.g., tetraethylene pentaamine, pentaethylene hexamine, and the like), polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof, with with an acrylate-type compound of formula (XXII) above, and most preferably with an acrylate-type reactant selected from the group consisting of lower alkyl alky-acrylates (e.g., methyl, ethyl, iso-propyl, propyl, iso-butyl, n-butyl, tert-butyl, etc., esters of methacrylic acid, acrylic acid, and the like).
~0~6~2~
Exemplary of such amido-amines are compounds of the formula:
NH2[ (CH2)zNH]xC(O)C2H4[NH(cH2)zJxNH2 wherein x is an integer of from 1 to 10, and z is an integer of from 2 to 6.
Most preferred as the second nitrogen-containing compound are members selected from the group consisting of organic diprimary amines having from ~ to 30 carbon atoms, from 2 to 12 total nitrogen atoms and from O to 10 secondary nitrogen atoms per molecule. Examples of such preferred organic diprimary amines are ethylene diamine, propylene diamine, diethylene triamine, dipropylene triamine, triethylene tetraamine, tripropylene tetraamine, tetraethylene pentaamine, tetrapropylene pentaamine, polyamino cyclohexylmethane and the like.
PREPARATION OF SECOND ADDUCT
The first adduct, containing an average of at least 2 (e.g., 2 to 10), and preferably at least 3 (e.g.
from 3 to 8), unreacted functional Y groups per molecule, is contacted with the second nitrogen-containing compound in an amount and under conditions sufficient to react the remaining functional groups with the reactive nitrogen moieties of the second nitrogen-containing compound to form a second adduct characterized by having within its structure on average (i) at least two, (e.g., 2 to 30), preferably at least 3 (e.g., 3 to 20), nitrogen-containing moieties derived from the second nitrogen-containing compound per nitrogen-containing moiety derived from the first compound and (ii) at least two (e.g., 2 to 6;
preferably 2 to 4) unreacted primary or secondary amine groups.
The reaction of a polyamine with the first adduct can be illustrated as followc:
2Q~6~2 ~ 36 -N--~C2H4C(O)OCH3]3 + 3 NH2C2H4NH2 (Eq. 9) N -~C2H4c(O)-NH-c2H4NH2]3 + 3 CH30H
o NC2H4N-[C2H4c--OcH3]2 i lC~ + 4 NH2C2H4NH2 [C2H4C-oCH3]2 ~
~ (Eq. lO) Nc2H4N-[c2H4c-NH-c2H4NH2]2 + 4 CH30 O
[C2H4C-NH-C2H~NH2]2 N--~2H4C(~C)CH3]3 + 3 NH2(C2H4NH)4C2 ~
(Eq. 11) N t C~H4c(o)-NH-(c2H4NH)4c2H4NH2]3 + 3 CH3OH
C
NC2H4N-[C2H4c-OcH3]2 + 4 NH2(C2H4N~)3C2H4NH2 [C 2H4C-OCH3]2 ~
(Eq. 12) NC2H4N-[C2H4C-NH-(C2H4NH)3C2H4NH2]2 + ~ CH30H
[C2H4c-NH-(c2H4NH)3c2H4NH2]2 ~016~22 C2H4N [C2H4C-CH3]2 + NH2(c2H4NH)3c2H4NH2 7 I I /
[C2H4c~cH3]2 ~
(Eq. 13) Nc2~4N-[c2H4~=N-(c2H4NH~3c2H4NH2~2 ¦ IH3 ~C2H4C=N-(C2H4N~)3c2H4NH2]2 The reaction between the selected polyamine and the first adduct is carried out at any suitable temperature. Temperatures up to the decomposition points of reactants and products can be employed. In practice, one generally carries out the reaction by heating the reactants below 100C, such as 80-90C, for a suitable p~riod of time, such as a few hours. Where the first adduct was formed using an acrylic-type ester is employed, the prograss of the reaction can be judged by the removal of the alcohol in forming the amide. During the early part of the reaction alcohol is removed quite readily below 100C in the case of low boiliny alcohols such as methanol or ethanol. As the reaction slows, the temperature is raised to push the reaction to completion and the temperature may be raised to 150C toward the end of the reaction. Removal of alcohol is a convenient method of judging the progress and completion of the reaction which is generally continued until no more alcohol is evolved.
Based on removal of alcohol, the yields are generally stoichiometric. In more difficult reactions, yields of at least 95% are generally obtained.
Similarly, it will be understood that the reaction of a polyamine with a first adduct prepared using an ethylenically unsaturated carboxylate thioester of formula ~16~22 IX liberates the corresponding HSX4 compound (e.g., H2S
when R4 is hydrogen) as a by-product, and the reaction of a polyamine with a first adduct prepared using an ethylenically unsaturated carboxyamide of formula X
liberates the corresponding HNR4(R5) compound (e.g., ammonia when R4 and R5 are each hydrogen) as by-product in forming the second adduct.
The reaction time involved can vary widely depending on a wide variety of factors. For example, there is a relationship between time and temperature. In general, lower temperature (e.g., at about 25~C) demands longer times. Usually, reaction times of from about 2 to 30 hours, such as 5 to 25 hours, and preferably 3 to 10 hours will be employed.
Although one can employ a solvent, the reaction can be run without the use of any solvent. I~ is preferred to avoid the use of an aqueous solvent such as water.
However, taking into consideration the effect of solvent on the reaction, where desired, any suitable solvent can be employed, whether organic or inorganic, polar or non-polar. Suitable solvents include alkanols (e.g., Cl to C6 alkanols such as methanol, isopropanol, ethanol and the like), ethers, xylene, benzene, toluene, tretrahydrofuran, methlyene chloride, chloroform, chlorobenzene, and the like.
When the selected polyfunctional reactant comprises an alpha, beta-unsaturated compound of formula VII wherein Wl is oxygen, the resulting first adduct reaction product contains at least one amido linkage (-C(O)N<) and such materials are herein termed "amido amines." Similarly, when the selected alpha, beta unsaturated compound of formula VII comprises a compound wherein W is sulfur, the resulting reaction product with the polyamine contains thioamide linkage (-C(S)N<) and these materials are herein termed "thioamido-amines." For convenience, the following discussion is directed to the preparation and use of amido-amines, although it will be understood that such discussion is also applicable to the thioamido-amines.
These amido-a~ine adducts so formed are characterized by both amido and amino groups. In their simplest embodiments they may be represented by units of the following idealized formula:
- N - A ~ ~ H2 ~H - C -wherein the R's, which may be the same or different, are hydrogen or a substituted group, such as a hydrocarbon group, for example, alkyl, alkenyl, alkynyl, aryl, etc., and A is a moiety of the polyamine which, for example, may be aryl, cycloalkyl, alkyl, etc., and n is an integer such as 1-10 or greater. The amido-amine adducts preferably contain an average of from 1 to 3 amido groups per molecule of the amido-amine adduct.
Preferably, however, the amido-amines of this invention are not cross-linked to any substantial degree, and more preferably are substantially branched.
Steps (a) and (b~ in the process of this invention can be repeated if desired to form more highly branched adducts. For example, a second adduct formed as described above can comprise the "first nitrogen-containing compound"
passed to the repeated step (a) and can be therein contacted with additional polyfunctional reactant (e.g., an alpha, beta-ethylenically unsaturated carboxylate~, preferably in a molar excess to the reactive nitrogen moieties in the second adduct (that is, the total number of -N-H- bonds remaining unreacted in the second adduct), to form a more highly branched "first" adduct which can then be treated to remove the excess unreacted polyfunctional 201 ~22 reactant and contacted in a separate step with an additional second nitrogen-containing compound, such as a polyalkylene polyamine, as described above. Such more highly branched nitrogen-containing adduct will be characterized as indicated above for the second adducts (that is, on average, will contain in its structure at least two unreacted primary or secondary amine groups, and at least two nitrogen-containing moieties derived from the additional second nitrogen-containing compound per nitrogen-containing moiety derived from the nitrogen-containing adduct so contacted in the repeat of step (a)) and can be employed in the subsequent reaction with the selected reactants A - D to for~ a dispersant of this invention.
~0~ 6~22 PR~PAR~aION OF LONG CHAIN HY~ROCAR~YL SUBSTITUTED REACTANT
(A) As indicated above, the dispersant materials of this invention can be prepared by reacting the second adduct with a hydrocarbyl-substituted acid, anhydride or ester material. The long chain hydrocarbyl polymer-substituted mono- or dicarboxylic acid material, i.e., acid, anhydride or acid ester used in this invention, includes the reaction product of a long chain hydrocarbon polymer, generally a polyolefin, with a monounsaturated carboxylic reactant comprising at least one member selected from the group consisting of (i) monounsaturated C4 to C10 dicarboxylic acid (preferably wherein (a) the carboxyl groups are vicinyl, ~i.e. located on adjacent carbon atoms) and (b)- at least one, preferably both, of said adjacent carbon atoms are part of said mono unsaturation); (ii) derivatives of (i) such as anhydrides or Cl to C5 alcohol derived mono- or di-esters of (i);
(iii) monounsaturated C3 to C10 monocarboxylic acid wherein the carbon-carbon double bond is conjugated to the carboxy group, i.e, of the structure 10~
--C=C--C-- ;
and (iv) derivatives of (iii) such as Cl to C5 alcohol derived monoesters of (iii). Upon reaction with the polymer, the monounsaturation of the monounsaturated carboxylic reactant becomes saturated. Thus, for example, maleic anhydride becomes a polymer substituted succinic anhydride, and acrylic acid becomes a polymer substituted propionic acid.
Typically, from about 0.7 to about 4.0 (e.g., 0.8 to 2.6), preferably from about 1.0 to about 2.0, and most preferably from about 1.1 to about 1.7 moles of said ~16~22 monounsaturated carboxylic reactant are charged to the reactor per mole of polymer charged.
Normally, not all of the polymer reacts with the monounsaturated carboxylic reactant and the reaction mixture will contain non-acid substituted polymer. The polymer-substituted mono- or dicarboxylic acid material (also referred to herein as "functionalized" polymer or polyolefin), non-acid substituted polyolefin, and any other polymeric by-products, e.g. chlorinated polyolefin, (also referred to herein as "unfunctionalized" polymer) are collectively referred to herein as "product residue" or "product mixture". The non-acid substituted polymer is typically not removed from the reaction mixture (because such removal is difficult and would be commercially infeasible) and the product mixture, stripped of any monounsaturated carboxylic reactant is employed for further reaction with the amine or alcohol as described hereinafter to make the dispersant.
Characterization of the average number of moles of monounsaturated carboxylic reactant which have reacted per mole of polymer charged to the reaction (whether it has undergone reaction or not) is defined herein as functionality. Said functionality is based upon (i~
determination of the saponification number of the resulting product mixture using potassium hydroxide; and (ii) the number average molecular weight of the polymer charged, using techniques well known in the art. Functionality is defined solely with reference to the resulting product mixture. Although the amount of said reacted polymer contained in the resulting product mixture can be subsequently modified, i.e. increased or d~creased by techniques known in the art, such modifications do not alter functionality as defined above. The terms "polymer substituted monocarboxylic acid material" and "polymer substituted dicarboxylic acid material" as used herein are 20~ 6~2 intended to refer to the product mixture whether it has undergone such modification or not.
Accordingly, the functionality of the polymer substituted mono- and dicarboxylic acid materiai will be typically at least a~out 0.5, preferably at least about 0.8, and most preferably at least about 0.9 and will vary typically from about 0.~ to about 2.8 (e.g., 0.6 to 2), preferably from about 0.8 to about 1.4, and most preferably from about 0.9 to about 1.3.
Exemplary of such monounsaturated carboxylic reactants are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyl (e.g., Cl to C4 alkyl) acid esters of the foregoing, e.g., methyl maleate, ethyl fumarate, methyl fumarate, etc.
Preferred olefin polymers for reaction with the monounsaturated carboxylic reactants to form reactant A are polymers comprising a major molar amount of C2 to C10, e.g. C2 to C5 monoolefin. Such olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-l, styrene, etc. The polymers can be homopolymers such as polyisobutylene, as well as copolymers of two sr more of such olefins such as copolymers of: ethylene and propylene; butylene and isobutylene; propylene and isobutylene; etc. Mixtures of polymers prepared by polymerization of mixtures of isobutylene, butene-1 and butene-2, e.g., polyisobutylene wherein up to about 40% of the monomer units are derived from butene-l and butene-2, is an exemplary, and preferred, olefin polymer. Other copolymers include those in which a minor molar amount of the copolymer monomers, e.g., 1 to 10 mole %, is a C4 to C18 non-conjugated diolefin, e.g., a copolymer of isobutylene and butadiene; or a copolymer of ethylene, propylene and 1,4-hexadiene: ~tc.
2~6~22 In some cases, the olefin polymer may be com-pletely saturated, for example an ethylene-propylene copolymer made by a Ziegler-Natta synthesis using hydrogen as a moderator to control molecular weight.
The olefin poly~ers used in the formation of reactant A will have number average molecular weights within the range of about 300 to 10,000, generally from about 700 and about S,000, preferably from about 1000 to 4,000, more preferably between about 1300 and about 3,000.
Particularly useful olefin polymers have number average molecular weights within the range of about 1500 and about 3000 with approximately one terminal double bond per polymer chain. An especially useful starting material for highly potent dispersant additives useful in ac~ordance with this invsntion is polyisobutylene, wherein up to about 40% of the monomer units are derived from butene-l and/or butene-2. The number average molecular weight for such polymers can be determined by several known techniques. A
convenient method for such determination is by gel permeation chromatography (GPC) which additionally provides molecular weight distribution information, see W. W. Yau, J.J. Kirkland and D.D. Bly, I'Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.
The olefin polymers will generally have a molecular weight distribution (the ratio of the weight average molecular weight to number average molecular w e i g ht~ i-e- ~w/~n) f from about 1. 0 t~
4.5, and more typically from about 1.5 to 3Ø
T h e p ol y m e r c a n b e reacted with the monounsaturated carboxylic reactant by a variety of methods. For example, the polymer can be first halogenated, chlorinat~d or brominated to about 1 to 8 wt.
%, preferably 3 to 7 wt. % chlorine, or bromine, based on the weight of polymer, by passing the chlorine or bromine through the polymer at a temperature of 60 to 250C, 2016~22 preferably 110 to 160 C, e.g. 120 to 140-C, for about 0.5 to 10, preferably 1 to 7 hours. The halogenated polymer may then be reacted with sufficient monounsaturated carboxylic reactant at 109 to 250~C, usually about 180 to 235-C, for about 0.5 to 10, e.g. 3 to 8 hours, so the product obtained will contain the desired number of moles of the monounsaturated carboxylic reactant per mole of the halogenated polymer. Processes of this general type are taught in U.S. Patents 3,087,436: 3,172,89~; 3,272,74~ and others. Alternatively, the polymer and the monounsaturated carboxylic reactant are mixed and heated while adding chlorine to the hot material. Processes of this type are disclosed in U.S. Patents 3,215,707; 3,231,587; 3,912,764;
4,110,349; 4,234,435; and in U.R. 1,440,219.
Alternately, the polymer and the monounsaturated carboxylic reactant can be contacted at elevated temperature to cause a thermal "ene" reaction to take place. Thermal "ene" reactions have been heretofore described in U.S. Patents 3,361,673 and 3,401,118, the disclosures of which are hereby incorporated by reference in their entirety.
Preferably, the polymers used in this invention contain less than 5 wt~, more preferably less than 2 wt%, and most preferably less than 1 wt% of a polymer fraction comprising polymer molecules having a molecular weight of less than about 300, as determined by high temperature gel premeation chromatography employing the corresponding pol~mer calibration curve. Such preferred polymers have been found to permit the preparation of reaction products, particularly when employing maleic anhydride as the unsaturated acid reactant, with decreased sediment. In the event the polymer produced as described above contains greater than about 5 wt% of such a low molecular weight polymer fraction, the polymer can be first treated by conventional means to remove the low molecular weight 2016~22 fraction to the desired level prior to initiating the ene reaction, and preferably prior to contacing the polymer with the selected unsaturated carboxylic reactant(s). For example, the polymer can be heated, preferably with inert gas (e.g., nitrogen) stripping, at elevated temperature under a reduced pressure to volatilize the low molecular weight polymer component3 which can then be removed from the heat treatment ves-~el. The precise temperature, pressure and time for such heat treatment can vary widely depending on such factors as as the polymer number average molecular weight, the amount of the low molecular weight fraction to be removed, the particular monomers employed and other factors. Generally, a temperature of from about 60 to 100C and a pressure of from about 0.1 to 0.9 atmospheres and a time of from about 0.5 to 20 hours (e.g., 2 to 8 hours) will be sufficient.
In this process, the selected polymer and monounsaturated carboxylic reactant and halogen (e.g., chlorine gas), where employed, are contacted for a time and under conditions effective to form the desired polymer substituted mono- or dicarboxylic acid material.
Generally, the polymer and monounsaturated carboxylic reactant will be contacted in a unsaturated carboxylic reactant to polymer mole ratio usually from about 0.7:1 to 4:1, and preferably from about l:l to 2:1, at an elevated temperature, generally from about 120 to 260C, preferably from about 160 to 240C. The mole ratio of halogen to monounsaturated carboxylic reactant charged will also vary and will generally range from about 0.5:1 to 4:1, and more typically from about 0.7:1 to 2:1 (e.g., from about 0.9 to 1.4:1). The reaction will be generally carried out, with stirring for a time of from about 1 to 20 hours, preferably from about 2 to 6 hours.
By the use of halogen, about 65 to 95 wt. % of the polyolefin, e.g. polyisobutylene will normally react with ~016022 the monounsaturated carboxylic acid reactant. Upon carrying out a thermal reaction without the use of halogen or a catalyst, then usually only about 50 to 75 wt. ~ of the polyisobutylene will react. Chlorination helps increase the reactivity. For ~onvenience, the aforesaid functionality ratios of mono- or dicarboxylic acid producing units to polyolefin, e.g., 1.1 to 1.~, etc. are based upon the total amount of polyolefin, that is, the total of both the reacted and unreacted polyolefin, used to make the product.
The reaction is preferably conducted in the substantial absence of 2 and water (to avoid competing side reactions), and to this end can be conducted in an atmosphere of dry N2 gas or other gas inert under the reaction conditions. The reactants can be charged separately or together as a mixture to the reaction zone, and the reaction can be carried out continuously, semi-continuously or batchwise. Although not generally necessary, the reaction can be carried out in the presence of a liquid diluent or solvent, e.g., a hydrocarbon diluent such as mineral lubricating oil, toluene, xylene, dichlorobenzene and the like. The polymer substituted mono- or dicarboxylic acid material thus formed can be recovered from the liquid reaction mixture, e.g., after stripping the reaction mixture, if desired, with an inert gas such as N2 to remove unreacted unsaturated carboxylic reactant.
If desired, a catalyst or promoter for reaction of the olefin polymer and monounsaturated carboxylic reactant (whether the olefin polymer and monounsaturated carboxylic reactant are contacted in the presence or absence of halogen (e.g., chlorine)) can be employed in the reaction zone. Such catalyst of promoters include alkoxides o f Ti, Zr, V and Al, and nickel salts (e.g., Ni acetoacetonate and Ni iodide) which catalysts or promoters will be generally 20~6022 employed in an amount of from about 1 to 5,000 ppm by weight, based on the mass of the reaction medium.
(B) Also useful as long chain hydrocarhyl reactants to form the improved dispersants of this invention are halogenated long chain aliphatic hydrocarbons (as shown in U.S. Patents 3,275,554 and 3,565,804, the disclosures of which are hereby incorporated by reference in their entirety~ where the halogen group on the halogenated hydrocarbon is displaced with the second adduct in the subsequent reaction therewith.
(C) Another class of long chain hydrocarbyl reactants to form the improved dispersants of this invention are any of the long chain hydrocarbyl-substituted hydroxy aromatic compounds which are known in the art as useful for forming Mannich condensation products. Such Mannich condensation products generally are prepared by condensing about 1 mole of a high molecular weight hydrocarbyl substituted hydroxy aromatic compound (e.g., having a number average molecular weight of 700 or greater) with about 1 to 2.5 moles of an aldehyde such as formaldehyde or paraformald4hyde and about 0.5 to 2 moles of the second adduct, using the condensation conditions as disclosed, e.g., in U~S. Patents 3,442,808; 3,649,229; and 3,798,165 (the clisclosures which are hereby incorporated by reference in their entirety). Such Mannich condensation products may include a long chain, high molecular weight hydrocarbon on the phenol group or may be reacted with a compound containing such a hydrocarbon, e.g., polyalkenyl succinic anhydride as shown in said aforementioned U.S.
Patent 3,442,808.
The optionally substituted hydroxy aromatic compounds used in the preparation of the Mannich base products include those compounds having the formula R21y - Ar - (OH)z 2~16~22 wherein Ar represents R2 x R2 x ~ or ~
wherein q is 1 or 2, R21 is a long chain hydrocarbon, R~ is a hydrocarbon or substituted hydrocarbon radical having from 1 to about 3 carbon atom2~ or a halogen radical such as the bromide or chloride radical, y is an integer from 1 to 2, x is an integer from O to 2, and z is an integer from 1 to 2.
Illustrative of such Ar groups are phenylene, biphenylene, naphthylene and the liXe.
The long chain hydrocarbon R21 substituents are olefin poly~ers as described above for those olefin polymers useful informing reactants.
Representative hydrocarbyl substituted hydroxy aromatic compounds contemplated for use in the present invention include, but are not limited to, 2-polypropylene phenol, 3-polypropylene phenol, 4-polypropylene phenol, 2-polybutylene phenol, 3-polyisobutylene phenol, 4-polyisobutylene phenol, 4-polyisobutylene-2-chlorophenol, 4-polyisobutylene-2-methylphenol, and the like.
Suitable hydrocarbyl-substitued polyhydroxy aromatic compounds include the polyolefin catechols, the polyolefin resorcinols, and the polyolefin hydroquinones, e. g., 4-polyisobutylene-l, 2-dihydroxybenzene, 3-polypropylene-l, 2-dihydroxybenzene, 5-polyisobutylene-l, 3-dihydroxybenzene, 4-polyamylene-1,3-dihydroxybenzene, and the like.
Suitable hydrocarbyl-substituted naphthols include 1 - p o l y i s o b u t y l e n e - 5 - h y d r o x y n a E~ h t h a l e n e, l-polypropylene-3-hydroxynaphthalene and the like.
2al~022 (D) Still another class of long chain hydrocarbyl reactants to form the improved dispersants of this invention are the Mannich base aminophenol-type condensation products as they are known in the art. Such Mannich condensation products generally are prepared by reacting about 1 mole of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides (e.g., polyisobutylene-substituted succinic anhydride~ with an about 1 mole of amine-substituted hydroxy aromatic compound (e.g., aminophenol), which aromatic compound can also be halogen- or hydrocarbyl-sustituted, to form a long chain hydrocarbon substituted amide or imide-containing phenol intermediate adduct (generally having a number average molecular weiqht of 700 or greater), and condensing about a molar proportion of the long chain hydrocarbon substituted amide- or imide-containing phenol intermediate adduct with about 1 to 2.5 moles o~ formaldehyde and about 0.5 to 2 moles of the second adduct of this invention.
Suitable aminophenols include 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-3-chlorophenol, 4-amino~2-bromophenol and 4-amino-3-ethylphenol.
The preparation and use of the hydroxy aromatic compounds and amino-substituted hydroxy aromatic compounds, and methods useful for reaction thereof with an aldehyde and the selected second adduct of this invention are as described in U.S. Patents 4,820,432 and 4,828,742, the disclosures of which are hereby incorporated her~in in their entirety.
PREPARATION OF THE DISPERSANT
(A) The second adduct (e.g., the branched amido-amine oligomers) is readily reacted with the selected polymer substituted mono- or dicarboxylic acid material, e.g. alkenyl succinic anhydride, by heating an oil 2 ~ 2 ~
solution containing 5 to 95 wt. % of the polymer substitu~ed dicarboxylic acid material to about 100 to 250~C., preferably 125 to 175-C. I generally for 1 to 10, e . g. ~ to 6 hours until the desired amount of water is removed. The heating i8 preferably carried out to favor forDIation of imides and/or amides, rather than salts.
Generally from 1 to 5, preferably from about 1. 5 to 3 moles of mono- or dicarboxylic acid ~noiety content (e . g., grafted maleic anhydride or grafted acrylic acid content) is used per reactive nitrogen equivalent (preferably per equivalent of primary nitrogen) of the second adduct.
An example of the reaction of a second adduct with a polymer-substituted dicarboxylic acid producing reactant is the reaction of polyisobutylene (PIB)-substituted succinic anhydride (PIBSA) with a second addllct having three terminal -NH2 groups, which can be illustrated as follows:
PIB
~i + [H2N Link-]3N
o r~ PIB
O Link-N
PIB --~ / ~~
N-Link - NO
J \ O\
O\ rl~PIB
Link-N~¦
o where "Link" is the moiety:
( 2 4 H) xC(O) C2H4 (NHC2H4) x~~ wherein x is an integer of from O to 10, preferably from 2 to 6.
An example of the reaction of a second adduct with a polymer-substituted monocarboxylic acid producing reactant is the reaction of polyisobutylene propionic acid (PI~A) with a second adduct having 3 terminal -NH2 groups~ which can be illustrated as follows:
3 PIB- CH2C-OH + [H2N-Link-]3~ _ pl _~ Link-NH-O~C-CH2-PIB
PIB-CH2C-~N-Link-N \
Link-NH-O-I-CH2-PIB
wherein 'ILink" and x are as defined above.
It will be understood that the second adduct can be employed alone or in admixture with any of the above described amines, such ~s the polyalkylene polyamines, useful in preparing the second adduct.
Preferably, the polymer substituted mono- or dicarboxylic acid producinq material and amido-amine will be contacted for a time and under conditions sufficient to react substantially all of the primary nitrogens in the second adduct reactant. The progress of this reaction can be followed by infra-red analysis.
The dispersant-forming reaction can be conducted in a polar or non-polar solvent (e.g., xylene, toluene, benzene and the like), and is preferably conducted in the presence of a mineral or synthetic lubricating oil.
2016~22 The nitrogen-containing dispersant materials of the instant invention as described above can be post-treated by contacting said nitrogen-containing dispersant materials with one or more post-treating reagents selected from the grsup consisting of carbon disulfide, sulfur, sulfur chlorides, alkenyl cyanides, aldehydes, ketones, urea, thio-urea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphi~es, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothio yantes, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds plus phenols, and sulfur plus phenols, and Cl to C30 hydrocarbyl substituted succinic acids and anhydrides (e.g., succinic anhydride, dode~yl succinic anhydride and the like~, fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyl (e.g., C1 to C4 alkyl) acid esters of the foregoing, e.g., meth l maleate, ethyl fumarate, methyl fumarate, and the like.
Since post-treating processes involving the use of these post-treating reagents is known insofar as application to high molecular weight nitrogen containing diseprsants of the prior art, further descriptions of these processes herein is unnecessary. In order to apply the prior art processes to the compositions of this invention, all that is necessary is that reaction conditions, ratio of reactants, and the like as described in the prior art, be applied to the novel compositions of this invention. The following U.S. patents are expressly incorporated herein by reference for their disclosure of post-treating processes and post-treating reagents applicable to the compositions of this invention: U.S. Pat. Nos. 3,087,936; 3,200,107;
2 ~ 2 3,254,025; 3,256,185; 3,278~550; 3,281,428; 3,282,955;
3,284,410: 3,338,832, 3,344,069; 3,366,569; 3,373,111;
3,367,943; 3,403,102; 3,428,561; 3,502,677; 3,513,093;
3,533,945; 3,541,012; 3,63g,242; 3,708,522; 3,859,318;
3,865,813; 3,470,09~; 3,369,021; 3,184,411; 3,185,645;
3,245,908; 3,24~,909; 3,245,910; 3,573,205; 3,692,681;
3,749,695; 3,865,740; 3,954,639; 3,458,530; 3,390,086;
3,367~943; 3,185,704, 3,551,466; 3,4~5,750; 3,312,619;
3,280,034; 3,71~,663; 3,652,516; UK Pat. No. 1,085,g03; UK
Pat. No. 1,162,436; U.S. Pat. No. 3,558,743.
The nitrogen containing dispersant materials of this invention can also be treated with polymerizable lactones (such as epsilon-caprolactone) to form dispersant adducts having the moiety -[C(O)(CH2)zO]mH, whexein z is a number of from 4 to 8 (e.g., 5 to 7) and m has an average value of from about 0 to 100 ~e.g., 0.2 to 20).
The dispersants of this invention can be post-treated with a C5 to C9 lactone, (e.g., C6 to Cg lactone, such as epsilon-caprolactone) by heating a mixture of the dispersant material and lactone in a reaction vessel in the absence of a solvent at a temperature of about 50C to about 200C, more preferably from about 75C to about 180C, and most preferably from about 90DC to about 160C, for a sufficient period of time to effect reaction.
Optionally, a solvent for the lactone~ dispersant material and/or he resulting adduct may be employed to control viscosity and/or the reaction rates.
- In one preferred embodiment, the C5 to Cg lactone, e.g., epsilon-caprolactone, is reacted with a dispersant material in a 1:1 mole ratio of lactone to dispersant material. In practice, the ratio of lactone to dispersant material may vary considerably as a means of controlling the length of the sequence of the lactone units in the adduct. For example, the mole ratio of the lactone to the dispersant material may vary from about 10:1 to ~016~2~
about 0.1:1, more preferably from about 5:1 to about 0.2:1, and most preferably from about 2:1 to about 0.4:1. It is preferable to maintain the average degree of polymerization of the lactone monomer below about 100, with a degree of polymerization on the order of from about 0.2 to about 50 being preferred, and fro~ about 0.2 to about 20 being more preferred. For optimum dispersant p~rformance, sequences of from about 1 to about 5 lactone units in a row are preferred.
Catalysts useful in the promotion of the lactone-dispersant material reactions are selected from the group consisting of stannous octanoate, stannous hexanoate, tetrabutyl titanate, a variety of organic based acid catalysts and amine catalysts, as described on page 266, and forward, in a book chapter authored by R.D. Lundberg and E. F. Cox, entitled "Kinetics and Mechanisms of Polymerization: Ring Opening Polymerization", edited by Frisch and Reegen, published by Marcel Dekker in 1969, wherein stannous octanoate is an especially preferred catalyst. The catalyst is added to the reac:tion mixture at a concentration level of about 50 to about 10,000 parts per weight of catalyst per olle million parts of the total reaction mixture.
The reactions of such lactones with dispersant materials containing nitrogen or ester groups is more completely described in copending applications Serial Numbers 916,108; 916,217: 916,218; 916,287; 916,303;
916,113; and 916,114, all filed on October 7, 1986; and co-pending Serial Number 178,099 filed on April 6, 1988;
the disclosure of each of which is hereby incorporated by reference in its entirety.
The nitrogen-containing dispersant materials of this invention can also be post-treated by reaction with an alkyl acetoacetate or alkyl thioacetate of the formula:
~016~22 ~a _ c - CH2 - C - Xa - Rb O O
wherein Xa is 0 or S, Rb is H or Ra, and Ra is in each instance in which it appears independently selected from the group consisting of substituted and unsubstituted alkyl or aryl (preferably alkyl o~ 1 to 6 carbon atoms, e.g., methyl, ethyl, etc.) to form an amino compound N-substituted by at least one tautomeric substituent of the formula:
C--CH2--C--Ra ~_~ C--CH--C Ra wherein R9 is as defined above.
The reaction is preferably effected at a temperature sufficiently high so as to substantially minimize the production of the enaminone and produce, instead r the keto-enol tautomer. Temperatures of at l~ast about 150C are preferred to meet this goal although proper choice of temperature depends on many factors, including reactants, concentration, reaction solvent choice, etc.
Temperatures of from about 120~C to 220C, preferably from about 150~C to 180C will generally be used. The reaction of the nitrogen-containinq dispersant material and the alkyl acetonate and the alXyl thioacetate will liberate the corresponding HORb and HSRb by-products, respectively.
Preferably, such by-products are substantially removed, as by distilltion or stripping with an inert gas (such as N2), prior to use of the thus prepared dispersant adduct. Such distillation and stripping steps are conveniently performed at elevated temperature, e.g., at the selected reaction temperature (for example, at 150C or higher~. A neutral diluent such as mineral oil may be used for the reaction.
The amount of alkyl aceto-acetate and/or alkyl thioacetate reactants used can vary widely, and is preferably selected so as to avoid substantial excesses of these reactants. Generally, these reactants are used in a reactant:amine nitrogen-equivalent molar ratio of from about 0.1 to 1:1, and preferably from about 0.5 to 1:1, whsrein the moles of amine nitrogen-equivalent is the moles of econdary nitrogens plus twice the moles of primary nitrogens in the nitrogen-containing dispersant material (e.g., polyisobutenyl succinimide) which is thus contacted with the alkylacetonate or alkyl thioacetate. The reaction should also be conducted in the substantial absence of strong acids (e.g., mineral acids, such as HCl, HB2, H2S04, H3P03 and the like, and sulfonic acids, such as para-toluene sulfonic acids) to avoid the undesired side-reactions and decrease in yield to the adducts of this invention.
The reactions of such alkyl acetoacetates and thioacetoacetates with nitrogen-containing dispersant materials is more completely described in copending application Serial No. 51,276, filed May 18, 1987, the disclosure of which is hereby incorporated by reference in its entirety.
Further aspects of the present invention reside in the formation of metal complexes of the novel dispersant additives prepared in accordance with this invention.
Suitable metal complexes may be formed in accordance with known techniques of employing a reactive metal ion species during or after the formation of the present dispersant materials. Complex forming metal reactants include the metal nitrates, thiocyanates, halides, carboxylatPs, phosphates, thio-phosphates, sulfates, and borates of transition metals such as iron, cobalt, nickel, copper, chromium, manganese, molybdenum, tungsten, ruthenium, -5~-palladium, platinum, cadmium, lead, silver, mercury, antimony and the like. Prior art disclosures of these complexing reactions may be also found in U.S. Patents 3,306,908 and Re. 26,433, the disclosures of which are hereby incorporated by reference in their entirety.
The processes of these incorporated patents, as applied to the compositions of this invention, and the post-treated composition~ thus produced constitute a further aspect of this invention.
The dispersant-forming reaction can be conducted in a polar or non-polar solvent (e.g., xylene, toluene, benzene and the like), and is preferably conducted in th~
presence of a mineral or synthetic lubricating oil.
The nitrogen containing dispersants can be further treated by boration as generally taught in U.S. Patent Nos. 3,087,936 and 3,254,025 (incorporated herein by reference thereto). This is readily accomplished by treating the selected acyl nitrogen dispersant with a boron compound selected from the class consisting of boron oxide, boron halides, boron acids and esters of boron acids in an amount to provide from about 0.1 atomic proportion of boron for each mole of said acylated nitrogen composition to about 20 atomic proportions of boron for each atomic proportion of nitrogen of said acylated nitrogen composition. Usefully the di-cpersants of the inventive combination contain from about 0.05 to 2.0 wt. %, e.g. 0.05 to 0.7 wt. % boron based on the total weight of said borated acyl nitrogen compound. The boron, which appears to be in the product as dehydrated boric acid polymers (primarily (HB02)3), is believed to attach to the dispersant imides and diimides as amine salts, e.g., the metaborate salt of said diimide.
Treating is readily carried out by adding from about 0.05 to 4, e.g. 1 to 3 wt. % tbased on the weight of said acyl nitrogen compound) of caid boron compound, ~16~22 ~-59-preferably boric acid which is most usually added as a slurry to said acyl nitrogen compound and heating with stirring at from about 135^C. to 190, e.g. 140-1709C , for from 1 to 5 hours followed by nitrogen stripping at said temperature ranges. Or, the boron treatment can be carried out by adding boric acid to the hot reaction mixture of the monocarboxylic acid material and amine while removing water.
The ashless dispersants of this invention can be used alone or in admixture with other dispersants such as esters derived from the aforesaid long chain hydrocarbon substituted dicarboxylic acid material and from hydroxy compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols, etc. The polyhydric alcohols are the most preferred hydroxy compound and preferably contain from 2 to about 10 hydroxy radicals, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycoll and other alkylene glycols in which the alkylene radical contains from 2 to about 8 carbon atoms. Other useful polyhydric alcohols include glycerol, mono-oleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof.
The ester dispersant may also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, l-cyclohexane-3-ol, and oleyl alcohol. Still other classes of the alcohols capable of yielding the esters of this invention comprise the ether-alcohols and amino-alcohols including, for example, the oxy-alkylene, oxy-arylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxy-alkylene, amino-alkylene or amino-arylene oxy-arylene radicals. They are exemplified by Cellosolve, Carbitol, N,N,N',N'-tetrahydroxy-trimethylene di-amine, and 201~322 ether-alcohols having up to about 150 oxy-alkylene radicals in which the alkylene radical contains from 1 to about 8 carbon atoms.
The ester dispersant may he di-esters of succinic acids or acidic esters, i.e., partially esterified succinic acids; as well as partially esterified polyhydric alcohols or phenols, i.e., esters having free alcohols or phenolic hydroxyl radicals. Mixtures of the above illustrated esters liXewise are contemplated within the scope of this invention.
The ester dispersant may be prepared by one of several known methods as illustrated for example in U.S.
Patent 3,381,022. The ester dispersants may also be borated, similar to the nitrogen containing dispersants, as described above.
Hydroxyamines which can be reacted with the aforesaid long chain hydrocarbon substituted dicarboxylic acid materials to form dispersants include 2-amino-1-bu-tanol, 2-amino-2-methyl-1-propanol, p-(beta-hydroxy-ethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1, 3-propane-diol, 2-amino-2-ethyl-1, 3-propanediol, N-(beta-hydroxy-propyl)-N'-(beta-amino-ethyl)-piperazine, tris(hydroxymethyl) amino-methane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine, beta-(beta-hydroxyethoxy)ethylamine, and the like. Mixtures of these or similar amines can also be employed. The above description of nucleophilic reactants suitable for reaction with the hydrocarbyl substituted dicarboxylic acid or anhydride includes amines, alcohols, and compounds of mixed amine and hydroxy containing reactive functional groups, i.e., amino-alcohols.
The tris(hydroxymethyl) amino methane (THAM) can be reacted with the aforesaid acid material to form amides, imides or ester type additives as taught by U.K. 984,409, or to form oxazoline compounds and borated oxazoline 2~1 6~22 compounds as described, for example, in U.S. 4,102,798;
4,116,876 and 4,113,639.
Other dispersants which can be employed in admixture with the novel diEpersants of this invention are those derived from the aforesaid long chain hydrocarbyl substituted dicarboxylic acid material and the aforesaid amines, such as polyalkylene polyamines, e.g., long chain hydrocarbyl suhstituted succinimides. Exemplary of such other dispersants are those described in co-pending Serial No. 95,056, filed September 9, 1987.
A preferred group of ashless dispersants are those derived from polyisobutylene substituted with succinic anhydride groups and reacted with second adducts, containing on average at leas~ 6 (e.g., from 6 to 30) reactiva nitrogen moieties and from 2 to 4 primary nitrogen groups per molecule, formed by reacting polyethylane amines, e.g., tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof, with a branched first adduct prepared by reacting ammonia or a diprimary amine having from 2 to 12 total nitrogen atoms and from 2 to 30 carbon atoms per molecule with an acrylate-type compound of formula (IX) above, and most preferably with an acrylate-type reactant selected from the group consisting of lower alkyl alky-asrylates (e.g., methyl, ethyl, iso-propyl, propyl, iso-butyl, n-butyl, tert-butyl, etc., esters of methacrylic acid, acrylic acid, and the like).
The dispersants of the present invention can be incorporated into a lubricating oil (or a fuel in any convenient way. Thus, these mixtures can be added directly to the lubricating oil (or fuel) by dispersing or dissolving the same in the lubricating oil (or fuel) at the desired level of concentration of the dispersant. Such 20~6~2~
blending into the additional lubricating oil (or fuel) can occur at room temperature or elevated temperatures.
Alternatively, the disper~ants can be blended with a suitable oil-soluble solvent/diluent (such as benzene, xylene, toluene, lubricating base oils and petroleum distillates, including the various normally liquid fuels described in detail below) to fsrm a concentrate, and then blending the concentrate with a lubricating oil (or fuel) to obtain the final formulation. Such dispersant concentrates will typically contain (on an active ingredient (A.I.) basis) from about 3 to about 45 wt.%, and preferably from about 10 to about 35 wt.%, dispersant additive, and typically from about 30 to 90 wt.%, preferably from about 40 to 60 wt.%, base oil, based on the concentrate weight.
OLEAGINOUS COMPOSITIONS
The additive mixtures of the present invention possess very good dispersant properties as measured herein in a wide variety of environments. Accordingly, the additive mixtures are used by incorporation and dissolution into an oleaginous material such as fuels and lubricating oils. When the additive mixtures of this invention are used in normally liquid petroleum fuels such as middle distillates boiling fro~ about 65~ to 430~C, including kerosene, diesel fuels, home heating fuel oil, jet fuels, etc., a concentration of the additives in the fuel in the range of typically from about 0.001 to about 0.5, and preferably 0.005 to about 0.15 weight percent, based on the total weight of the composition, will usually be employed.
The properties of such fuels are well known as illustrated, for example, by ASTM Specifications D #396-73 (Fuel Oils) and D #439-73 (Gasolines) available from the American Society for Testing Materials ("ASTM"), 1916 Race Street, Philadelphia, Pennsylvania 19103.
201~22 The fuel compositions of this invention can contain, in addition to the products of this invention, other additives which are well known to those of skill in the art. These can include anti-knock agen~s such as tetraalkyl lead compounds, lead scavengers such as haloalkanes, deposit preventers or modifiers such as triaryl phosphates, dyes, cetane improvers, anitoxidants such as 2,6-ditertiary-butyl-4-methylphenol, rust inhibitors, bacteriostatic agents, gum inhibitors, metal deactivators, upper cylinder lubricants and the like.
The additive mixtures of the present invention find their primary utility in lubricating oil compositions which employ a base oil in which the additives re dissolved or dispersed. Such base oils may be natural sr synthetic.
Base oils suitable for US2 in preparing the lubricating oil compositions of the present invention include those conventionally employed as cranXcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like. Advantageous results are also achieved by employing the additive mixtures of the present invention in base oils conventionally employed in and/or adapted for use as power transmitting fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and the like. Gear lubricants, industrial oils, pump oils and other lubricating oil compositions can also benefit from the incorporation therein of the additive mixtures of the present invention.
These lubricating oil formulations conventionally contain several different types of additives that will supply the characteristics that are required in the formulations. Among these types of additives are included viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point 2~6~22 depressant~, antiwear agents, friction modifiers, etc. as described in U. S. Patent 4,797,219, the disclosure of which is hereby incorporated by reference in its entirety.
Some of these numerous additives can provide a multiplicity of effects, e.g. a dispersant-oxidation inhibitor. This approach is well known and need not be further elaboratPd herein.
In the preparation of lubricating oil formulations it is common practice to introduce the additives in the form of 10 to 80 wt. %, e.g., 20 to 80 wt. ~ active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent. Usually these concentrates may be diluted with 3 to 100, e.g., 5 to 40 parts by weight of lubricating oil, per part by weight of the additive package, in forming finished lubricants, e.g.
crankcase motor oils. The purpose of concentrates, of course, is to make the handl ing of the various ~aterials less difficult and awkward as well as to facilitate solution or dispersion in the final blend. Thus, a dispersant would be usually employed in the form of a 40 to 50 wt. % concentrate, for example, in a lubricating oil fraction.
The ashless dispersants of the present invention will bP generally used in admixture with a lube oil basestock, comprising an oil of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
Natural oils include animal oils and vegetable oils (e.g., castor, lard oil) liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have ~016022 been modified by esterification, etherification, etc., constitute another class of known ~ynthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-poly isopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of poly-ethylene glycol having a molecular weight of 50Q-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid ester~ and C13 Oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, ~aleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diissoctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
201~022 Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butylphenyl)silicate, hexa-~4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polvmeric tetrahydrofurans.
Unrefined, refined and rerefined oils can be used in the lubricants of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art. Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
Compositions when containing these conventional additives are typically blended into the base oil in amounts effective to provide their normal attendant ~016022 function. Representative effective amounts of such additives (as the respective active ingredients) in the fully formulated oil are illustratad as follows:
~t.% A.I. Wt.% AoI~
Compositions ~Çfg~Y~L (Broad~_ Viscosity Modifier .01-4 0.01-12 De~ergents 0.01-3 0.01-20 Corrosion Inhibitor 0.01-1.5 .01-5 Oxidation Inhibitor 0.01-1.5 .01-5 Dispersant 0.1-8 .1-20 Pour Point Depressant 0.01-1.5 .01-5 Anti-Foaming Agents 0.001-0.15 .001-3 Anti-Wear Agents 0.001-1.5 .001-5 FrictiQn Modifiers 0.01-1.5 .01-5 Mineral Oil Base Balance Balance When other additives are employed, it may be desirable, although not necessary, to prepare additive concentrates comprising concentrated solutions or disper-sions of the novel dispersants of this invention (in concentrate amounts hsreinabove described), together with one or more of said other additives (said concentrate when constituting an additive mixture being referred to herein as an additive-package) whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing acrompanied with mild heating, but this is not essential. The concentrate or additive-package will typically be formulated to contain the additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base lubricant. Thus, the dispersants of the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive-packages ~160~2 containing active ingredients in collective amounts of typically from about 2.5 to about 90%, and preferably from about 15 to about 75%, and mo8t preferably from about 25 to about 60~ by weight additive~ in the appropriate proportions with the remainder being base oil.
The final formulations may employ typically about 10 wt. ~ of the additive-package with the remainder being base oil.
All of said weight percents expressed herein (unless otherwise indicated) are based on active ingredient (A.I.) content of the additive, and/or upon ths total weight of any additive-package, or formulation which will be the sum of the A.I. weight of each additive plus the weight of total oil or diluent.
This invention will be further understood by reference to the following examples, wherein all parts are parts by weight, unless otherwise noted and which include preferred embodiments of the invention.
~nl6022 EXAMP~E_~. Preparation of NH3-Methyl Acryla~e First Adduct.
8.2 g of ammonia is bubbled into 100 ml of anhydrous methanol at -lO C. This cooled ammonia-methanol solution is added ts 296 g of methyl acrylate (MeAc) dropwise under a nitrogen atmosphere with external cooling to keep the liquid reaction mixture at a temperature of from about 20-25C. After the addition is completed, the reaction mixture is allowed to stir at room temperature overnite. The reaction mixture is then stripped with N2 gas to remove the excess methylacrylate and methanol until constant weight. The product analyzes for 52.3 wt.% C, 7.89 wt.% H and 4.5 wt.% N (theoretical 52.~ wt.% C, 7.6.
wt.% H, 5.1 wt.% N).
XAMPLE 2. Preparation of NH3-MeAc + TETA Second Adduct.
55 g (0.2 mole) of the product of Example 1 is charged into a reaction flask and diluted with 100 ml of anhydrous isopropanolO ~hile stirring and under N2 atmosphere, ~7.6 g (0.6 mole) of triethylenetetramine (TETA) is added and heated to 100C while nitrogen sparging for about 10 hours. When the infrared analysis indicates complete disappearance of the ester band, the reaction mixture is stripped at 100C for one half hour and the product collected. It analyzes for 27.2 wt.% N and 4.21 milliequivalents of primary nitrogen per gram of sample.
EXAMPLE 3. Preparation of NH3-MeAc + PAM Second Adduct.
The procedure of Example 2 i5 followed except that 27.5 g (0.1 mole) of the ammonia-methyl acrylate first adduct and 70.6 g (0.6 milliequivalent of primary nitrogen) ~016~22 of poly(ethyleneamine) having an average of 5 to 7 nitrogen atoms per molecule (PAM) are used. The product analyzes for z7.6 wt.% N and 3.38 milliequivalents of primary nitrogen per gram of sample.
XAMPI,E 4. Preparation of NH3-MeAc-TETA + PIBSA
Dispersant.
About 300 g (0.1 mole) of a polyisobutenyl succinic anhydride derived from a l~n 2225 polyisobutylene ~w/Fln = 2 . 5) and having a saponification number of 37.4 (67.7% active ingredient) is charged into a reaction flask with 127 g S150N and heated to 150C while stirring under nitrogen blanket.
Then 23.2 g (0.1 equivalents of primary nitrogen) of the second adduct prepared in Example 2 is added slowly for about one half hour. The reactic n mixture is heat soaked while stirring and nitrogen stripping for 3 hours. The oil solution containing the dispersant is filtered while hot and evaluated. It is found to have a kinematic visco~ity of 341 cSt at 100C and contains 1.52 wt.% N.
X~PLE_5. Preparation of NH3-MeAc-PAM + PIBSA
Dispersant.
The procedure of Example 4 is repeated except that 29.6 g (0.1 equivalents of primary nitrogen) of the adduct of Example 3 and 300 g of the PIBSA are used. The filtered oil solution is found to have a kinematic viscosity of 490 cSt at 100C and 1.81 wt.% N.
XAMPLE 6. Preparation of DETA-Methylacrylate First Adduct.
Using the procedure of Example 1, 51.5 g (0.5 mole) of diethylene triamine (DETA) is charged into a reaction flask and diluted with 100 ml of anhydrous i s o p r o p a n o 1 .
Then 258 g (3 mole) of methyl acrylate is added at a rate to keep the reaction temperature below 30C. When the addition is completed, the reaction mixture is stirred at room temperature overnight. The reaction mixture is stripped with a N2 ga~ stream until constant weight and the product analyzes for 54.17 wt.% C, 8.67 wt.% H and 7.74 wt.% N (theoretical 54.0 wt.~ C, 8.1 wt.% H, 7.8 wt.% N).
EXAMPLE 7. Preparation of MeAc-DETA + TETA Second Adduct.
The procedure of Example 2 is repeated except that 53.3 g (O.1 mole) of the methyl-acrylate-DETA adduct of Example 6 and 73 g (0.5 mole) of triethylenetetramine ~TETA) are used. Th~ product analyzes for 28 wt.% N and 3.88 milliequivalents of primary nitrogen per gram of sample.
EXAMPLE 8. Preparation of MeAc-DETA + PAM Second Adduct.
The procedure of Example 7 is followed except that 53.3 g of the adduct of Example 6 and 117 g of PAM are used. The product analyzes for 28.2 wt.% N and 3.33 milliequivalent of primary nitrogen per gram of sample.
XAMPLE 9. Preparation of MeAc-DETA-TETA + PIBSA
Dispersant.
The procedure of Example 4 is carried out except that 12.9 g (0.05 equivale~ts of primary nitrogen) of the product of Example 7, 150 g of PIBSA and 64.5 g of S150N
are used. The filtered oil solution has a kinematic viscosity of 300 cSt at 100C and 1.5~ wt.% N.
XAMPLE 10. Preparation of MeAc-DETA-PAM + PIBSA
Dispersant.
The procedure of Example 4 is repeated except that 15 g (O.05 equivalents of primary nitrogen) of the product ~01 6~22 of Example 8, 150 g of PIBSA and 67 g of S150N are used.
The filtered oil solutio~ analyzes for a kinematic viscosity of 592 cSt at 100C and 1.83 wt.% N.
OMPARATIVE EXAMPLE A. Preparation of PIBSA-TETA
Dispersant.
The procedure of Example 4 is repeated except that 150 g (.05 mole) of PIBSA, 3.65 g ~0.025 mole) of triethylenetetramine and 56 g of S150N are used. I'he filtered oil solution analyzes for 0.67 %wt. N and has a kinematic viscosity of 381 cSt at 100C.
OMPARATIVE EXAMPLE B. Preparation of PIBSA-PAM
Dispersant.
The procedure of Example 4 is repeated except that 150 g (0.05 mole) of PIBSA, 5.85 g of PAM (0.05 equivalents of primary nitrogen) and 58 g of S150N are used. The filtered oil solution analyzes for 0.91 wt.% N and a kinematic viscosity of 450 cSt at 100C.
The product dispersants thereby obtained are summarized as set forth in Table I below.
TABLE I
Example VIS 100C, No. PIB Mn Amine wt% NcSt(1) 4 2225 Ex. 2 Product 1.52 341 " Ex. 3 Product 1.81 490 9 " Ex. 4 Product 1.59 300 " Ex. 8 Product 1.83 592 Comp. A " TETA 0.67 381 Comp. B " PAM 0.91 450 (1) kinematic viscosity.
2016~22 The following lubricating oil compositions are prepared using the dispersants of Examples 4, 5, 9, 10, and Comparative Examples A - B. The resulting compositions are then tested for sludge inhibition (via the SIB test) and varnish inhibition (via the VIB test), as described below.
The SIB test has been found, after a large number of evaluations, to be an excellent test for assessing the dispersing power of lubricating oil dispersant additives.
The ~edium chosen for the SI~ test is a used cranXcase mineral lubricating oil composition having an original viscosity of about 325 SUS at 38C that had been used in a taxicab that is driven yenerally for short trips only, thereby causing a buildup of a high concentration of sludge precursors. The oil that is used contained only a refined base mineral lubricating oil, a viscosity index improvar, a pour point depressant and zinc dialkyl-dithiophosphate anti-wear additive. The oil contained no sludge dispersant. A quantity of such used oil is acquired by draining and refilling the taxicab crankcase at 1000-2000 mile intervals.
The SIB test is conducted in the following manner: the aforesaid used crankcase oil, which is milky brown in color, is freed of sludge by centrifuging for one hour at about 39,000 gravities (gs.). The resulting clear bright red supernatant oil is then decanted from the insoluble sludge particles thereby separated out. However, the supernatant oil still contains oil-soluble sludge precursors which on heating under the conditions employed by this test will tend to form additional oil-insoluble deposits of sludge. The sludge inhibiting properties of the additives being tested are determined by adding to portions of the supernatant used oil, a small amount, such 2016~22 as 0.5, 1 or 2 weight percent, of the particular additive being tested. Ten grams of each blend being tested are placed in a stainless steel centrifuge tube and are heated at 135C for 16 hours in the presence of air. Following the heating, the tube containing the oil being tested is cooled and then centrifuged for about 30 minutes at room temperature at about 39,000 gs. Any deposits of new sludge tat form in this step are separated from ~he oil by decanting the supernatant oil and then carefully ishing the sludge deposits with 25 ml of heptane to remove all remaining oil from the sludge and further centrifuging.
The weight of the new solid sludge that has been formed in the test, in milligrams, is determined by drying the residue and weighing it. The results are reported as amount of precipitated sludge in comparison with the precipitated sludge of a blank not containing any additional additive, which blank is normalized to a rating of 10. The less new sludge precipitated in the presence of the additivej the lower the SIB value and the more effective is the additive as a sludge dispersant. In other words, if the additive gives half as much precipitated sludge as the blank, then it would be rated 5.0 since the blank will be normalized to 10.
The VIB test is used to determine varnish inhibition. Here, each test sample consisted of 10 grams of lubricating oil containing a small amount of the additive being tested. The test oil to which the additive is admixed is of the same type as used in the above-described SIB test. Each ten gram sample i9 heat soaked overnight at about 140C and thereafter centrifuged to remove the sludge. The supernatant fluid of each sample is subjected to heat cycling from about 150C to room temperature over a period of 3.5 hours at a frequency of about 2 cycles per minute. During the heating phase, gas ~0~ 6~22 which is a mixture of about O.7 volume percent S02, 1.4 ~olume percent NO and balance air is bubbled through the test samples. During the cooling phase, water vapor is bubbled through the test samples. At the end of the test period, which testing cycle can be repeated as necessary to determine the inhibiting effect of any additive, the wall surfaces of the test flasks in which the samples are contained are visually evaluated as to the varnish inhibition. The amount of varnish imposed on the walls is rated to values of from 1 to 11 with the hiyher number being the greater amount of varnish, in comparison with a blank with no additive that is rated 11.
10.00 grams of SIB test oil are mixed with 0.05 grams of the products of the Examples as described in Table I and tested in the aforedescribed SIB and VIB tests. The data thereby obtained are summarized in Table II below.
TABLE II
Dispersant Example Wt.%
No. AmL~e N SIB VIB
4 NH3-MeAc + TETA 1.52 1.3 3 NH3-MeAc ~ PAM 1.81 1.58 3 9 DET~-MeAC + TETA 1.59 0.22 3 DETA-MeAc + PAM 1.83 1.63 3 Comp. A TETA 0.67 3.59 7 Comp. B P~M O.91 1.79 7 The above data thereby obtained show that the dispersants of this invention have excellent SIB/VIB
performance and sludge and varnish inhibiting properties.
A series of lubricating formulations were prepared which contained ~ vol% of the novel branched dispersants ~01~022 formed in Examples 4~ 5, 9 and 10, respectively. Each lubricating composition also contained mineral lubricating oil, a mixture of overbased Mg sulfonate detergent inhibitor and overbased Ca sulfonate detergent inhibitor, zinc dialkyl dithiophosphate antiwear agent, antioxidant and ethylene propylene vi5c05ity index improver.
The following Table illustrates preparation of additional first and second adducts employing the present invention.
2~1 6~22 _ ~ O C:~ o Q OO O O O O O
O ~ I O
E~-F
C ~_ P~
a ~
Y ~ ¦ ~ N t~ N ~~ N t`~
_ X
~ O o ~ C~
_ C~, ~ O O O ~ O
~ _~ 11~ ~ ~ O ~ O-- O O
U~ t~ ~ ~ CO O ~ _ _ ~
C ~ ~ V _ .~ ~ ~ O ~ O ~ Il O~ ) o ~ ~ U 5:
-O~ ~ C) ~ S~
P. ~ V U
Z~ ^ Z
-4~ S
Z Z C~ Z ~ Z; ~ ~ Z
X~ 1 Ul W ~
20~6~22 (1) Exs. 11, 12, 14, 16, 1~ and 19--repeat procedure of Example 1 (with 80% molar excess of polyfunctional reactant).
Exs. 13, 15, 17 and 20 --repeat procedure of Example 6 (with 80% molar excess of polyfunctional reactant).
(2) Degree of branching of first adduct.
(3) First adduct product ~ixture stripped of excess poly-~unctional reactant. Exq. 11 20--repeat procedure of Example 2.
( 4 ) TEPA = tetraethylene pentamine: DETA = diethylene triamine; TETA a triethylene tetramine; HPHA =
hexapropylene heptamine; EDA - ethylene diamine.
The principles, preferred embodiments, and modes of operation of the present invention have been described in the foregoing specification~ The invention which is intended to be pro~ec~ed herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
Claims (41)
1. A process for forming a lubricating oil nitrogen-containing dispersant additive which comprises:
(a) contacting in a first liquid reaction mixture a first nitrogen-containing compound having at least two reactive nitrogen moieties with a polyfunctional reactant having within its structure a first functional group reactive with a -NH- group, and at least one additional functional group reactive with a -NH- group, in an amount and under conditions sufficient to selectively react at least a portion of said first functional groups in said polyfunctional reactant with said reactive nitrogen moieties to form a first adduct;
(b) contacting said first adduct with a second nitrogen-containing compound having at least two -NH-groups in an amount and under conditions sufficient to react said additional functional groups in said first adduct with said -NH- groups in said second nitrogen-containing compound to form a second adduct characterized by having within its structure on average (i) at least two nitrogen-containing moieties derived from said second nitrogen-containing compound per nitrogen-containing moiety derived from said first nitrogen-containing compound and (ii) at least two unreacted primary or secondary amine groups per molecule; and (c) contacting said second adduct in a second liquid reaction mixture with at least one member selected from the group consisting of;
(A) long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups;
(B) halogenated long chain hydrocarbons;
(C) mixtures of an aldehyde and a long chain hydrocarbyl substituted phenol; and (D) mixtures of an aldehyde and a reaction product formed by reaction of long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups and an amino-substituted, optionally hydrocarbyl-sub-stituted phenol.
(a) contacting in a first liquid reaction mixture a first nitrogen-containing compound having at least two reactive nitrogen moieties with a polyfunctional reactant having within its structure a first functional group reactive with a -NH- group, and at least one additional functional group reactive with a -NH- group, in an amount and under conditions sufficient to selectively react at least a portion of said first functional groups in said polyfunctional reactant with said reactive nitrogen moieties to form a first adduct;
(b) contacting said first adduct with a second nitrogen-containing compound having at least two -NH-groups in an amount and under conditions sufficient to react said additional functional groups in said first adduct with said -NH- groups in said second nitrogen-containing compound to form a second adduct characterized by having within its structure on average (i) at least two nitrogen-containing moieties derived from said second nitrogen-containing compound per nitrogen-containing moiety derived from said first nitrogen-containing compound and (ii) at least two unreacted primary or secondary amine groups per molecule; and (c) contacting said second adduct in a second liquid reaction mixture with at least one member selected from the group consisting of;
(A) long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups;
(B) halogenated long chain hydrocarbons;
(C) mixtures of an aldehyde and a long chain hydrocarbyl substituted phenol; and (D) mixtures of an aldehyde and a reaction product formed by reaction of long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups and an amino-substituted, optionally hydrocarbyl-sub-stituted phenol.
2. The dispersant additive according to claim 1 wherein said long chain hydrocarbyl reactant comprises at least one long chain hydrocarbyl substituted mono- or dicarboxylic acid producing material formed by reacting an olefin polymer of C2 to C10 monoolefin having a number average molecular weight of about 300 to 10,000 and at least one of a C4 to C10 monounsaturated dicarboxylic acid material and a C3 to C10 monounsaturated moncarboxylic acid material, said acid producing material having an average of at least about 0.5 dicarboxylic acid producing moieties, per molecule of said olefin polymer present in the reaction mixture used to form said acid producing material.
3. The oil additive according to claim 1 wherein said polyfunctional reactant comprises at least one of:
(i) compounds having the formula:
X - ? - (T)a - [(?)b - Y]c wherein W1 and w2 are the same or different and are O
or S, X and Y are the same or different and comprise members selected from the group consisting of: halide, - OR4, -SR4, -N(R4) (R5), -Z1C(O)OR4, -C(O) R4, -(R3)C=C(R1) (R2), -Z1-nitrile, -Z1-cyano, -Z1-thiocyano, -Z1-isothiocyano, and -Z1-isocyano, wherein R1, R2, R3, R4 and R5 are the same or different and are H or substituted or unsubstituted hydrocarbyl and wherein Z1 is C1 to C20 bivalent hydrocarbylene, T is a substituted or unsubstituted hydrocarbon moiety, "a" is 0 or 1, "b" is 0 or 1, and "c" is an integer of at least 1, and wherein X
and Y can together comprise -O- or -S- when "a" is 1 and T
contains a >C=C< group, wherein at least two of X, Y and T
are groups reactive with a -NH- group, with the provisos that c = 1 when a = 0 and b = 1 when a = 1;
(ii) compounds of the formula:
wherein W1 is as defined above, and wherein R1 is H or substituted or unsubstituted hydrocarbyl, and "d1" and "d2" are each integers of from 1 to 10;
(iii) compounds of the formula:
wherein R1, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above, and wherein Y" comprises a reactive functional group selected from the group consisting of:
halide, -OR4, -SR4, -N(R4) (R5), -Z1C(O)OR4, and -(R3)C=C(R1)(R2), wherein R4 is as defined above; and (iv) compounds of the formula:
wherein R1, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
3. The disperant additive according to claim 1 wherein said polyfunctional reactant comprises at least one alpha, beta-unsaturated compound of the formula:
wherein X is sulfur or oxygen, Y is -OR4, -SR4, or -NR4 (R5), and R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl.
(i) compounds having the formula:
X - ? - (T)a - [(?)b - Y]c wherein W1 and w2 are the same or different and are O
or S, X and Y are the same or different and comprise members selected from the group consisting of: halide, - OR4, -SR4, -N(R4) (R5), -Z1C(O)OR4, -C(O) R4, -(R3)C=C(R1) (R2), -Z1-nitrile, -Z1-cyano, -Z1-thiocyano, -Z1-isothiocyano, and -Z1-isocyano, wherein R1, R2, R3, R4 and R5 are the same or different and are H or substituted or unsubstituted hydrocarbyl and wherein Z1 is C1 to C20 bivalent hydrocarbylene, T is a substituted or unsubstituted hydrocarbon moiety, "a" is 0 or 1, "b" is 0 or 1, and "c" is an integer of at least 1, and wherein X
and Y can together comprise -O- or -S- when "a" is 1 and T
contains a >C=C< group, wherein at least two of X, Y and T
are groups reactive with a -NH- group, with the provisos that c = 1 when a = 0 and b = 1 when a = 1;
(ii) compounds of the formula:
wherein W1 is as defined above, and wherein R1 is H or substituted or unsubstituted hydrocarbyl, and "d1" and "d2" are each integers of from 1 to 10;
(iii) compounds of the formula:
wherein R1, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above, and wherein Y" comprises a reactive functional group selected from the group consisting of:
halide, -OR4, -SR4, -N(R4) (R5), -Z1C(O)OR4, and -(R3)C=C(R1)(R2), wherein R4 is as defined above; and (iv) compounds of the formula:
wherein R1, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
3. The disperant additive according to claim 1 wherein said polyfunctional reactant comprises at least one alpha, beta-unsaturated compound of the formula:
wherein X is sulfur or oxygen, Y is -OR4, -SR4, or -NR4 (R5), and R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl.
4. The dispersant additive according to claim 1, wherein said second nitrogen-containing compound comprises at least one polyamine containing from 2 to 60 carbon atoms and from 2 to 12 nitrogen atoms per molecule.
5. The dispersant additive according to claim 4, wherein said polyamine comprises a polyalkylenepolyamine wherein each said alkylene group contains from 2 to 6 carbons and said polyalkylenepolyamine contains from 5 to about 9 nitrogen atoms per molecule.
6. The dispersant additive according to claim 2, wherein said hydrocarbyl substituted monounsaturated acid producing material comprises hydrocarbyl substituted C4 to C10 monounsaturated dicarboxylic acid producing material which comprises polyisobutylene of about 700 to 5000 number average molecular weight substituted with succinic anhydride moieties, said first nitrogen-containing compound comprises ammonia, said second nitrogen-containing compound comprises polyalkylenepolyamine wherein each said alkylene group contains from 2 to 6 carbons and said polyalkylenepolyamine contains from 5 to 9 nitrogen atoms per molecule, and said alpha, beta-unsaturated compound comprises at least one member selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
7. The dispersant additive according to claim 1 wherein said second nitrogen-containing compound comprises polyethylenepolyamine or polypropyleneamine.
8. The dispersant additive according to claim 4 wherein each dispersant additive is borated to provide from about 0.05 to 2.0 weight percent boron in said borated dispersant additive.
9. The dispersant additive according to claim 1 wherein said olefin polymer comprises polyisobutylene.
10. The dispersant additive according to claim 2 wherein the ratio of acid producing moieties per molecule of olefin polymer in said dispersant additive is from about 0.9 to 1.3.
11. The dispersant additive of claim 10, wherein said number average molecular weight of said olefin polymer is from about 1,300 to 3,000.
12. The dispersant additive of claim 2, wherein said monounsaturated acid material comprises maleic anhydride.
13. The dispersant additive according to claim 2 wherein about 1 to 5 moles of said acid producing material per primary nitrogen equivalent of said second adduct are present in said step (c) liquid reaction mixture.
14. The dispersant additive according to claim 4 wherein said second nitrogen-containing compound comprises a polyamine containing an average of at least 2 primary nitrogen atoms per molecule, said polyfunctional reactant comprises at least one alpha, beta-unsaturated compound and said first nitrogen-containing compound and said alpha, beta-unsaturated compound are contacted in an amount of from about 1.1 to 3 moles of said alpha, beta-unsaturated compound per equivalent of said reactive nitrogen moieties in said first nitrogen-containing compound.
15. The dispersant additive according to claim 14 wherein said first adduct is characterized by an average degree of branching of from 3 to 18.
16. The dispersant additive according to claim 15 wherein said second nitrogen-containing reactant comprises a polyamine which contains an average of at least 2 primary nitrogen atoms per molecule, said second adduct contains an average of from 2 to 4 unreacted primary amine and from 0 to 8 unreacted secondary amine groups per molecule.
17. The dispersant additive according to claim 16 wherein said amido-amine contains an average of from 1 to 3 amido groups per molecule of said amido amine.
18. A process for producing a dispersant additive useful as an oil additive which comprises:
(a) providing a nitrogen-containing branched adduct characterized by having within its structure on average at least two unreacted primary or secondary amine groups per molecule, said branched adduct being obtained by a process which comprises:
(i) contacting in a first reaction mixture a first nitrogen-containing compound having at least two reactive nitrogen moieties with a polyfunctional reactant having within its structure a first functional group reactive with a -NH- group, and at least one additional functional group reactive with a -NH- group, in an amount and under conditions sufficient to selectively react said first functional groups in said polyfunctional reactant with said reactive nitrogen moieties to form a first adduct;
(ii) contacting said first adduct in a second liquid reaction mixture with a second nitrogen-containing compound having at least two -NH- groups in an amount and under conditions sufficient to react said additional functional groups in said first adduct with said -NH-groups in said second nitrogen-containing compound to form a second adduct comprising said branched adduct, said branched adduct being further characterized by having within its structure on average (i) at least two nitrogen-containing moieties derived from said second nitrogen-containing compound per nitrogen-containing moiety derived from said first nitrogen-containing compound; and (b) providing a long chain hydrocarbyl substituted mono- or dicarboxylic acid producing material formed by reacting an olefin polymer of C2 to C10 monoolefin having a number average molecular weight of about 300 to 10,000 and at least one of a C4 to C10 monounsaturated dicarboxylic acid material and a C3 to C10 monounsaturated moncarboxylic acid material, said acid producing material having an average of at least about 0.5 dicarboxylic acid producing moieties, per molecule of said olefin polymer present in the reaction mixture used to form said acid producing material: and (c) contacting the said acid producing material with said branched nitrogen-containing adduct in an amount and under conditions sufficient to effect reaction of at least a portion of the primary amino groups on said branched nitrogen-containing adduct with at least a portion of the acid-producing groups in said acid producing material, to form said dispersant additive.
(a) providing a nitrogen-containing branched adduct characterized by having within its structure on average at least two unreacted primary or secondary amine groups per molecule, said branched adduct being obtained by a process which comprises:
(i) contacting in a first reaction mixture a first nitrogen-containing compound having at least two reactive nitrogen moieties with a polyfunctional reactant having within its structure a first functional group reactive with a -NH- group, and at least one additional functional group reactive with a -NH- group, in an amount and under conditions sufficient to selectively react said first functional groups in said polyfunctional reactant with said reactive nitrogen moieties to form a first adduct;
(ii) contacting said first adduct in a second liquid reaction mixture with a second nitrogen-containing compound having at least two -NH- groups in an amount and under conditions sufficient to react said additional functional groups in said first adduct with said -NH-groups in said second nitrogen-containing compound to form a second adduct comprising said branched adduct, said branched adduct being further characterized by having within its structure on average (i) at least two nitrogen-containing moieties derived from said second nitrogen-containing compound per nitrogen-containing moiety derived from said first nitrogen-containing compound; and (b) providing a long chain hydrocarbyl substituted mono- or dicarboxylic acid producing material formed by reacting an olefin polymer of C2 to C10 monoolefin having a number average molecular weight of about 300 to 10,000 and at least one of a C4 to C10 monounsaturated dicarboxylic acid material and a C3 to C10 monounsaturated moncarboxylic acid material, said acid producing material having an average of at least about 0.5 dicarboxylic acid producing moieties, per molecule of said olefin polymer present in the reaction mixture used to form said acid producing material: and (c) contacting the said acid producing material with said branched nitrogen-containing adduct in an amount and under conditions sufficient to effect reaction of at least a portion of the primary amino groups on said branched nitrogen-containing adduct with at least a portion of the acid-producing groups in said acid producing material, to form said dispersant additive.
19. The process according to claim 18 wherein said olefin polymer comprises polyisobutylene having a number average molecular weight of about 700 to 5,000, said monounsaturated acid material comprises maleic anhydride, and said acid producing material having an average of at least about 0.8 succinic anhydride producing moieties, per molecule of said olefin polymer present in the reaction mixture used to form said acid producing material.
20. The oil additive according to claim 1 wherein said polyfunctional reactant comprises at least one of:
(i) compounds having the formula:
wherein W1 and W2 are the same or different and are O
or S, X and Y are the same or different and comprise members selected from the group consisting of: halide, -OR4 , -SR4, -N(R4) (R5), - Z1C(O)OR4, -C(O)R4 , - (R3) C = C (R1) (R2), -Z1-nitrile, -Z1-cyano, -Z1-thiocyano, -Z1-isothiocyano, and -Z1-isocyano, wherein R1, R2, R3, R4 and R5 are the same or different and are H or substituted or unsubstituted hydrocarbyl and wherein Z1 is C1 to C20 bivalent hydrocarbylene, T is a substituted or unsubstituted hydrocarbon moiety, "a" is 0 or 1, "b" is 0 or 1, and "c" is an integer of at least 1, and wherein X
and Y can together comprise -O- or -S- when "a" is 1 and T
contains a >C=C< group, wherein at least two of X, Y and T
are groups reactive with a -NH- group, with the provisos that c = 1 when a = 0 and b = 1 when a = 1;
(ii) compounds of the formula:
wherein W1 is as defined above, and wherein R1 is H or substituted or unsubstituted hydrocarbyl, and "d1" and "d2" are each integers of from 1 to 10;
(iii) compounds of the formula:
wherein R1, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above, and wherein Y" comprises a reactive functional group selected from the group consisting of:
halide, -OR4, -SR4, -N(R4) (R5), -Z1C(O)OR4, and -(R3)C=C(R1)(R2), wherein R4 is as defined above; and (iv) compounds of the formula:
wherein R1, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
(i) compounds having the formula:
wherein W1 and W2 are the same or different and are O
or S, X and Y are the same or different and comprise members selected from the group consisting of: halide, -OR4 , -SR4, -N(R4) (R5), - Z1C(O)OR4, -C(O)R4 , - (R3) C = C (R1) (R2), -Z1-nitrile, -Z1-cyano, -Z1-thiocyano, -Z1-isothiocyano, and -Z1-isocyano, wherein R1, R2, R3, R4 and R5 are the same or different and are H or substituted or unsubstituted hydrocarbyl and wherein Z1 is C1 to C20 bivalent hydrocarbylene, T is a substituted or unsubstituted hydrocarbon moiety, "a" is 0 or 1, "b" is 0 or 1, and "c" is an integer of at least 1, and wherein X
and Y can together comprise -O- or -S- when "a" is 1 and T
contains a >C=C< group, wherein at least two of X, Y and T
are groups reactive with a -NH- group, with the provisos that c = 1 when a = 0 and b = 1 when a = 1;
(ii) compounds of the formula:
wherein W1 is as defined above, and wherein R1 is H or substituted or unsubstituted hydrocarbyl, and "d1" and "d2" are each integers of from 1 to 10;
(iii) compounds of the formula:
wherein R1, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above, and wherein Y" comprises a reactive functional group selected from the group consisting of:
halide, -OR4, -SR4, -N(R4) (R5), -Z1C(O)OR4, and -(R3)C=C(R1)(R2), wherein R4 is as defined above; and (iv) compounds of the formula:
wherein R1, R2, and R3 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
21. The process according to claim 19 wherein said polyfunctional reactant comprises at least one alpha, beta-unsaturated compound of the formula:
wherein X is sulfur or oxygen, Y is -OR4 -SR4, or -NR4 (R5), and R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl.
wherein X is sulfur or oxygen, Y is -OR4 -SR4, or -NR4 (R5), and R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl.
22. The process according to claim 21, wherein said second nitrogen-containing compound comprises at least one polyamine containing from 2 to 60 carbon atoms and from 2 to 12 nitrogen atoms per molecule.
23. The process according to claim 22, wherein said polyamine comprises a polyalkylenepolyamine wherein each said alkylene group contains from 2 to 6 carbons and said polyalkylenepolyamine contains from 5 to about 9 nitrogen atoms per molecule.
24. The process according to claim 23, wherein said first nitrogen-containing compound comprises ammonia, and said alpha, beta-unsaturated compound comprises at least one member selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
25. The process according to claim 24 wherein said second nitrogen-containing compound comprises polyethylenepolyamine or polypropyleneamine.
26. The process according to claim 25 wherein said olefin polymer comprises polyisobutylene.
27. The process according to claim 26 wherein each dispersant additive is borated to provide from about 0.05 to 2.0 weight percent boron in said borated dispersant additive.
28. The process according to claim 26 wherein the ratio of acid producing moieties per molecule of olefin polymer in said dispersant additive is from about 0.8 to 1.3.
29. The process of claim 28, wherein said number average molecular weight of said olefin polymer is from about 1,300 to 3,000, and wherein said second liquid reaction mixture is substantially free of said polyfunctional reactant.
30. The process of claim 18, wherein said said first liquid reaction mixture is treated to remove unreacted polyfunctional reactant before contacting said first adduct with said polyamine.
31. The process according to claim 18 wherein about 1 to 5 moles of said acid producing material per primary nitrogen equivalent of said second adduct are present in said step (c) liquid reaction mixture.
32. The process according to claim 19 wherein said second nitrogen-containing compound comprises a polyamine containing an average of at least 2 primary nitrogen atoms per molecule, said polyfunctional reactant comprises at least one alpha, beta unsaturated compound and said first nitrogen-containing compound and said alpha, beta-unsaturated compound are contacted in an amount of from about 1.1 to 3 moles of said alpha, beta-unsaturated compound per equivalent of said reactive nitrogen moieties in said first nitrogen-containing compound.
33. The process according to claims 32 or 34 wherein said first adduct is characterized by an average degree of branching of from 3 to 18.
34. The process according to claim 33 wherein said second nitrogen-containing reactant comprises a polyamine which contains an average of at least 2 primary nitrogen atoms per molecule, said second adduct contains an average of from 2 to 4 unreacted primary amine and from 0 to 8 unreacted secondary amine groups per molecule.
35. The process according to claim 34 wherein said amido-amine contains an average of from 1 to 3 amido groups per molecule of said amido-amine.
36. The process according to claim 18 wherein steps (a) and (b) are repeated at least once to provide a nitrogen-containing adduct of increased branching, before contacting with said acid producing material prepare said dispersant material.
37. A fuel oil composition containing from about 0.001 to 0.5 wt. % of the dispersant additive of claim 1.
38. A lubricating oil composition containing from about 0.1 to 20 wt. % of the dispersant additive of claim 1.
39. A lubricating oil composition containing from about 0.1 to 8 wt. % of the dispersant additive of claim 6.
40. The dispersant additive according to claim 1 wherein said polyolefin comprises ethylene-propylene copolymer.
41. The process according to claim 18 wherein said polyolefin comprises ethylene-propylene copolymer.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US35890389A | 1989-05-30 | 1989-05-30 | |
US358,903 | 1989-05-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2016022A1 true CA2016022A1 (en) | 1990-11-30 |
Family
ID=23411513
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002016022A Abandoned CA2016022A1 (en) | 1989-05-30 | 1990-05-03 | Branched amido-amine dispersant additives |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0400864A3 (en) |
JP (1) | JPH0362891A (en) |
KR (1) | KR900018345A (en) |
BR (1) | BR9002569A (en) |
CA (1) | CA2016022A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN117567912A (en) * | 2023-11-22 | 2024-02-20 | 江西科技师范大学 | Recyclable polyacrylate emulsion coating and preparation method and application thereof |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE69310644T2 (en) * | 1992-09-11 | 1997-09-04 | Shell Int Research | Gasoline compositions |
JP2002306365A (en) * | 2001-04-16 | 2002-10-22 | Worldtop Co Ltd | Steamed towel rolling-up device |
EP1858634A1 (en) * | 2005-02-03 | 2007-11-28 | The Lubrizol Corporation | Dispersants from condensed polyamines |
JP4757053B2 (en) * | 2006-02-17 | 2011-08-24 | 株式会社パイロットコーポレーション | Knock-type writing instrument with clip |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1068133A (en) * | 1965-02-04 | 1967-05-10 | Lubrizol Corp | Nitrogen-containing derivatives of substituted succinic acids |
US3445441A (en) * | 1965-03-25 | 1969-05-20 | Petrolite Corp | Amino-amido polymers |
US3718663A (en) * | 1967-11-24 | 1973-02-27 | Standard Oil Co | Preparation of oil-soluble boron derivatives of an alkylene polyamine-urea or thiourea-succinic anhydride addition product |
ZA771959B (en) * | 1976-04-01 | 1978-03-29 | Orogil | Compositions based on alkenylsuccinimides |
US4855116A (en) * | 1985-04-03 | 1989-08-08 | Bergwerksverband Gmbh | Activated coke method of removing nitrogen oxides from exhaust gases |
US4857217A (en) * | 1987-11-30 | 1989-08-15 | Exxon Chemical Patents Inc. | Dispersant additives derived from amido-amines |
-
1990
- 1990-05-03 CA CA002016022A patent/CA2016022A1/en not_active Abandoned
- 1990-05-22 EP EP19900305560 patent/EP0400864A3/en not_active Withdrawn
- 1990-05-29 JP JP2137310A patent/JPH0362891A/en active Pending
- 1990-05-30 KR KR1019900007836A patent/KR900018345A/en not_active Application Discontinuation
- 1990-05-30 BR BR909002569A patent/BR9002569A/en not_active Application Discontinuation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117567912A (en) * | 2023-11-22 | 2024-02-20 | 江西科技师范大学 | Recyclable polyacrylate emulsion coating and preparation method and application thereof |
CN117567912B (en) * | 2023-11-22 | 2024-05-28 | 江西科技师范大学 | Recyclable polyacrylate emulsion coating and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
KR900018345A (en) | 1990-12-21 |
JPH0362891A (en) | 1991-03-18 |
EP0400864A3 (en) | 1991-08-14 |
BR9002569A (en) | 1991-08-20 |
EP0400864A2 (en) | 1990-12-05 |
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