US2973323A - Lubricating oil composition containing heterocyclic polyamine salts of partial ester of phosphorodithioic acid as antiwear agent - Google Patents
Lubricating oil composition containing heterocyclic polyamine salts of partial ester of phosphorodithioic acid as antiwear agent Download PDFInfo
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- US2973323A US2973323A US631516A US63151656A US2973323A US 2973323 A US2973323 A US 2973323A US 631516 A US631516 A US 631516A US 63151656 A US63151656 A US 63151656A US 2973323 A US2973323 A US 2973323A
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- salt
- lubricating oil
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- oil
- phosphorodithioic acid
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- 150000003839 salts Chemical class 0.000 title claims description 34
- 229920000768 polyamine Polymers 0.000 title claims description 17
- 239000000203 mixture Substances 0.000 title claims description 11
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 title description 22
- 239000010687 lubricating oil Substances 0.000 title description 15
- 125000000623 heterocyclic group Chemical group 0.000 title description 10
- 150000002148 esters Chemical class 0.000 title description 5
- 239000003795 chemical substances by application Substances 0.000 title description 2
- 239000003921 oil Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000010688 mineral lubricating oil Substances 0.000 claims description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000003599 detergent Substances 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000004312 hexamethylene tetramine Substances 0.000 description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 150000004885 piperazines Chemical class 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000007866 anti-wear additive Substances 0.000 description 3
- -1 heterocyclic amines Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- DQNJHGSFNUDORY-UHFFFAOYSA-N bis(2-ethylhexoxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCC(CC)COP(S)(=S)OCC(CC)CCCC DQNJHGSFNUDORY-UHFFFAOYSA-N 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical class C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- QRJZGVVKGFIGLI-UHFFFAOYSA-N 2-phenylguanidine Chemical class NC(=N)NC1=CC=CC=C1 QRJZGVVKGFIGLI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- FQLUTPMTAXATHQ-UHFFFAOYSA-N calcium;7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical compound [Ca].C1=CC=CC2(O)C1S2 FQLUTPMTAXATHQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- ZYORFJZPPWUUCE-UHFFFAOYSA-N formaldehyde;piperazine Chemical compound O=C.C1CNCCN1 ZYORFJZPPWUUCE-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
- C10M137/105—Thio derivatives not containing metal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
Definitions
- This invention relates to lubricants and more particularly to lubricants containing small amounts of heterocyclic polyamine salts of partially esterified phosphorodithioic acids added to improve the load-carrying, antiwear and oxidation-resistance characteristics of the mineral oil.
- One of the objects of our invention is to provide a lubricating oil having improved anti-wear characteristics. Another object of our invention is to provide a lubricant having improved load-carrying, anti-wear and oxidationresistance characteristics. Other objects of the invention will become manifest from the following disclosure.
- a small amount of a salt of a heterocyclic polyamine containing at least one atom of nitrogen in the tri-coordinated state and partially esterified phosphorodithioic acid is added to mineral lubricating oil a small amount of a salt of a heterocyclic polyamine containing at least one atom of nitrogen in the tri-coordinated state and partially esterified phosphorodithioic acid.
- the heterocyclic polyamines which may be used in forming the salt useful in our invention include cyclo di-, triand tetramines.
- heterocyclic polyamines useful in forming the partially esterified phosphorodithioate salts are tetrarnines such as hexamethylenetetramine; triamines such as the trialkylcyclotrirnethylenetriamines.
- CH2 which may be prepared by reacting primary aliphatic amines and formaldehyde; piperazine and alkyl-substituted piperazines; and alkylisomelamines
- salts useful in our invention the following are given:
- heterocyclic polyamine salts of partial esters of dithiophosphoric acids may be added to the lubricating oil in amounts of approximately 0.05 to 0.5% by weight phosphorus equivalent. We have found that if the amount of salt is equal to about the equivalent of 0.1 weight percent of phosphorus, a very significant improvement in anti-wear characteristics of the oil is obtained.
- polyamine salts of our invention may be added to lubricating oils together with other well-known additives, such as detergents, pour point depressants and viscosity index improvers.
- the salts useful in our invention may be prepared by reacting the desired heterocyclic polyamine with the desired partially esterified phosphorodithioate.
- Another method of preparing heterocyclic amines falling within the scope of our invention is by reacting a partially esterified dithiophosphoric acid with an aldehyde and excess ammonia.
- the following are specific examples which are illustrative of the manner in which the compounds of our invention may be prepared.
- a crystallized product salts include alkyl, aryl, aralkyl and alkaryl dithiophosseparated from the filtrate on chilling to a temperature of 30 F. attained a yield of Upon recrystallizing the product from hexane, a white solid was obtained having a melting point of 69-70 C. and analyzing nitrogen 10.5%, phosphorus 6.1%, sulfur 12.8%. These values are close to the calculated values of 11.3% nitro- 3 gen, 6.3% phosphorus and 13% sulfur for hexamethylenetetrammonium di-2-ethylhexyldithiophosphate.
- solvent-refined neutral oil having an SUS viscosity of 170 at 100 F. and containing basic barium petroleum sulfohate as a detergent and sulfurized terpenes as corrosion inhibitor was tested in accordance with the Four-Ball Test briefly described on pages 13 and 14 of The Performance of Lubricating Oils, by Zuidema, published in 1952 by Reinhold Publishing Corporation, New York.
- the sulfurized terpene corrosion inhibitor is a product of 29.4 wt. percent sulfur which is available on the market.
- the basic barium sulfonate was prepared by sulfonating a mineral lubricating oil fraction with sulfur trioxide at a temperature of below 120 F. and neutralizing the resulting sulfonic acids with an excess of barium hydroxide octahydrate. This oil was tested with and without antiwear additives for purposes of comparison. The results are given in Table I.
- Mid-Continent refined neutral oil having an SUS viscosity of 170 at 100 F. containing phenol extract resulting from the solvent-refining of the oil, barium alkyl phenol sulfide-calcium sulfonate detergent available on the market, and mixed alcohols-methacrylate polymer pour point depressant and viscosity index improver, also available as a commercial product, was tested with and without various dithiophosphoric acid salts in which the amount of salt added was equivalent to 0.1 weight percent of phosphorus. The results of the tests are given in Table II. Further identification of the above commercial additives is as follows. Barium and calcium contents of the detergent additive were 8.1 and 0.6 wt. percent respectively. The average molecular weight of the methacrylate polymer was in the 10,000 to 20,000 range.
- the detergent, pour depressant and viscosity improver are not necessary ingredients of the oil insofar as the present invention is concerned but are added to the oil merely to 'give a balanced oil corresponding to one which would be used in actual commercial practice.
- a lubricant composition comprising a major portion of a mineral lubricating oil and a minor portion, sufiicient to enhance substantially the load-'carrying'properties of the oil, of at least one heterocyclic polyamine salt of a phosphorodithiotic acid ester of the formula where R is a C -C radical selected from the group consisting of alkyl, phenyl, alkylphenyl, and phenylakyl radicals, and where the hetcrocyclic polyamine is selected from the group consisting of hexamethylenetetramine, trilower alkyl cyclotrimethylene triamines, piperazine, lower alkyl-substituted piperazines, and lower alkyl isomelamines.
- a lubricating oil in accordance with claim 1 containing an amount of said salt equivalent to about 0.05 to 0.05% by weight of phosphorus.
- a lubricating oil in accordance with claim 7 containing an amount of said salt equivalent to about 0.05 to 0.5% by weight of phosphorus.
- a lubricating oil composition in accordance with claim 1 which contains a small amount of a detergent and a corrosion inhibitor.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
LUBRICATING OIL COMPOSITION CONTAINING HETEROCYCLIC POLYAMINE SALTS OF PAR= TIAL ESTER F PHOSPHORODITHIOIC ACID AS ANTIWEAR AGENT Allen F. Millikan, Crystal Lake, and Giiford W. Crosby, River Forest, lll., assignors to The Pure Oil Company, Chicago, 111., a corporation of Ohio No Drawing. Filed Dec. 31, 1956, Ser. No. 631,516
Claims. (Cl. 252-3237) I This invention relates to lubricants and more particularly to lubricants containing small amounts of heterocyclic polyamine salts of partially esterified phosphorodithioic acids added to improve the load-carrying, antiwear and oxidation-resistance characteristics of the mineral oil.
The addition of salts of alkyl dithiophosphoric acids such as the zinc salts, to mineral oils in order to improve the wear-resistance characteristics of such oils is well known. We have discovered that if a partially esterified phosphorodithioic acid is combined with a heterocyclic polyamine to form a salt, the resulting salt has substantially better anti-wear characteristics than other types of amine or metal salts.
One of the objects of our invention is to provide a lubricating oil having improved anti-wear characteristics. Another object of our invention is to provide a lubricant having improved load-carrying, anti-wear and oxidationresistance characteristics. Other objects of the invention will become manifest from the following disclosure.
In accordance with our invention there is added to mineral lubricating oil a small amount of a salt of a heterocyclic polyamine containing at least one atom of nitrogen in the tri-coordinated state and partially esterified phosphorodithioic acid. The heterocyclic polyamines which may be used in forming the salt useful in our invention include cyclo di-, triand tetramines. As examples of heterocyclic polyamines useful in forming the partially esterified phosphorodithioate salts are tetrarnines such as hexamethylenetetramine; triamines such as the trialkylcyclotrirnethylenetriamines.
CH2 which may be prepared by reacting primary aliphatic amines and formaldehyde; piperazine and alkyl-substituted piperazines; and alkylisomelamines The partial esters of phosphorodithioic acids with which the heterocyclic polyamines are combined to form 2,973,323 Patented Feb. 28, 1961 tain 4 to 20 carbon atoms and preferably those partial esters which contain two hydrocarbon groups. These groups may contain other substituents, such as oxygen, sulfur and nitrogen in the form of hydroxyl, thiol or amino radicals. As specific examples of salts useful in our invention the following are given:
(1) Piperazine salt of 0,0-di-2-ethylhexyl phosphorodithioic acid (2) N,N-dibutylpiperazine salt of 0,0-di-(octylphenyl) phosphorodithioic acid (3) Eethylisomelamine salt of 0,0-didecyl phosphorodithioic acid (4) Hexamethylenetetramine salt of 0,0-didodecyl phosphorodithioic acid (5) Piperazine salt of S,S-didodecyl phosphorodithioic acid (6) Hexamethylenetetramine salt of 0,0-di-2-ethylbutyl phosphorodithioic acid (7) N,N-dioctylpiperazine salt of 0,0-diphenyl phosphorodithioic acid (8) Hexamethylenetetramine salt of 0,0-di(phenylpropyl) phosphorodithioic acid (9) N,N,N-trimethyltrirnethylenetriamine salt of 0,0- di-2-ethylhexyl phosphorodithioic acid.
The heterocyclic polyamine salts of partial esters of dithiophosphoric acids may be added to the lubricating oil in amounts of approximately 0.05 to 0.5% by weight phosphorus equivalent. We have found that if the amount of salt is equal to about the equivalent of 0.1 weight percent of phosphorus, a very significant improvement in anti-wear characteristics of the oil is obtained.
The above-described compounds are disclosed and claimedv as novel compounds in our copending application Serial No. 655,011, filed April 25, 1957, now Patent 2,894,951.
The polyamine salts of our invention may be added to lubricating oils together with other well-known additives, such as detergents, pour point depressants and viscosity index improvers.
The salts useful in our invention may be prepared by reacting the desired heterocyclic polyamine with the desired partially esterified phosphorodithioate. Another method of preparing heterocyclic amines falling within the scope of our invention is by reacting a partially esterified dithiophosphoric acid with an aldehyde and excess ammonia. The following are specific examples which are illustrative of the manner in which the compounds of our invention may be prepared.
EXAMPLE I To 195 grams of 2-ethylhexyl alcohol, 195 grams of toluene and 195 grams of solvent-refined neutral oil having an SUS viscosity of 85 at 100 F. there was added 83.5 grams of phosphorus pentasuliide-so that the mixture contained 1.5 mols of the alcohol to 0.38 mol of phosphorus pentasulfide. The mixture was stirred for four hours on the steam bath and the resulting acid solution then filtered and treated with 133 grams (0.94
mol) of hexamethylenetetramine at room temperature. After the mixture was allowed to react for 16 hours it was diluted with hexane and excess hexamethylenetetramine separated by filtration. A crystallized product salts include alkyl, aryl, aralkyl and alkaryl dithiophosseparated from the filtrate on chilling to a temperature of 30 F. attained a yield of Upon recrystallizing the product from hexane, a white solid was obtained having a melting point of 69-70 C. and analyzing nitrogen 10.5%, phosphorus 6.1%, sulfur 12.8%. These values are close to the calculated values of 11.3% nitro- 3 gen, 6.3% phosphorus and 13% sulfur for hexamethylenetetrammonium di-2-ethylhexyldithiophosphate.
EXAMPLE 'II Di-Z-ethylhexyl dithiophosphoric acid prepared as in the previous example was reacted with one eq ivalent of paraformaldehyde and an excess of anhydrous ammonia at room temperature for a period of one hour. The solvent (toluene) and excess ammonia was then removed by vacuum stripping in the presence of nitrogen and the liquid product was clarified by filtration through celite. Analysis of the resulting liquid product gave a ratio of nitrogen to phosphorus of 1.6, which would correspond to a mixture of hexamethylenetetramine or cyclotrimethylenetriamine salts of the partially esterified thiophosphoric acid with ammonium salts of the same acid.
Table I Four-Ball Transition Point to High Wear Rate Load in Kg.
Anti-wear Additive Mireral. Oil-94.1 pts. by
W Basic Ba pet. sulionate 5.3 pts. by Wt. Suliurized terpene 65 pts. by W Mineral Oi194.1 pts. by
Basic Ba pet. Sultanate- 5.3 pts. by Wt.
Sulfurized terpene0.65
M by wt. Minteral Oil-94.1 pts. by
W Basic Ba pet. su1tonate 5.3 pts. by wt. Sulfurized terpene0.65
pts. by w Mirieral Oil-94.1 pts. by
w 4 Basic Ba pct. sulfonate- 5.3 pts. by wt.
Sulfurized terpene0.0 pts. by wt.
1--- None 60 Ammonium di-2-ethyl hexyl dithiophos- 90 phate. 1
Complex salt of Example 100 Salt of Example 1 Q 130 1 Contained in composition (1) in amount of equivalent to 0.1% by weight of phosphorus.
In order to demonstrate the wear-resisting characteristics of compounds within the scope of our invention, solvent-refined neutral oil having an SUS viscosity of 170 at 100 F. and containing basic barium petroleum sulfohate as a detergent and sulfurized terpenes as corrosion inhibitor was tested in accordance with the Four-Ball Test briefly described on pages 13 and 14 of The Performance of Lubricating Oils, by Zuidema, published in 1952 by Reinhold Publishing Corporation, New York. The sulfurized terpene corrosion inhibitor is a product of 29.4 wt. percent sulfur which is available on the market. The basic barium sulfonate was prepared by sulfonating a mineral lubricating oil fraction with sulfur trioxide at a temperature of below 120 F. and neutralizing the resulting sulfonic acids with an excess of barium hydroxide octahydrate. This oil was tested with and without antiwear additives for purposes of comparison. The results are given in Table I.
From an examination of Table I it is apparent that the oil to which the inhibitor prepared in accordance with Example I was added improved the load at which transition to high Wear took place by over 100%. The complex salt made in accordance with Example II increased the load at which transition to high Wear occurred by almost Whereas the ammonium di-Z-ethylhexyl dithiophosphate only improved the transition point by 50%.
In order to further demonstrate the superiority of salts falling Within the scope of our invention over other types of amine or metal salts, Mid-Continent refined neutral oil having an SUS viscosity of 170 at 100 F., containing phenol extract resulting from the solvent-refining of the oil, barium alkyl phenol sulfide-calcium sulfonate detergent available on the market, and mixed alcohols-methacrylate polymer pour point depressant and viscosity index improver, also available as a commercial product, was tested with and without various dithiophosphoric acid salts in which the amount of salt added was equivalent to 0.1 weight percent of phosphorus. The results of the tests are given in Table II. Further identification of the above commercial additives is as follows. Barium and calcium contents of the detergent additive were 8.1 and 0.6 wt. percent respectively. The average molecular weight of the methacrylate polymer was in the 10,000 to 20,000 range.
Table II Transition Point to High Wear Rate Load in Kg.
Anti-wear Additive Mineral oil84.2 parts by vol Phenol extract4.5 parts by vol Ba alkylphenolsulfide Ca sulfonat Mineral oil-84.2 parts by VOL--. Phenol extract-4.5 parts by vol Baalkylphenolsulfide Ca sulfonat Mineral oil-84.2 parts by vol Phenol extract-4.5 parts by vol. Ba alkylphenolsulfide 0a sulfonat Mineral oil84.2 parts by vol Phenol ext-raet4.5 parts by vol Ba alkylphenolsulfide Ca sulfonate Mineral oil-84.2 parts by vol Phenol extract-4.5 parts by vol Ba alkylphenolsulfide Ga sulfonate- Methacrylate polymer-6.3 parts by vbl Methacrylate polymer-6.3 parts by vol Mineral nib-84.2 parts by vol Phenol extract4.5 parts by vol Ba alkylphenolsulf de .Ca sulf0nate -5.0 parts by v0 Methacrylate polymer-6.3 parts by vol parts by v0 parts by vo Methaerylate polymer-6.3 parts by vol parts by v0 e parts by vol Methacrylate polymer6.3 parts by vol parts by vol Methacrylatc polymer6.3 parts by vol .0 parts by vol Methacryiate polymer-6.3 parts by vol None 50 +Salt'of Example I +Aniline salt of 'di-2-ethylhexyl phosphorodithioic acid.
+Tripheny1guanidine salt of di-2-ethylhexyl s0 phosphorodlthioic acid.
+Phenylguanidine salt of di-2-ethylhexyl phosphorodithioic acid.
+Piperidine salt of di2-ethylhexyl phospho- 80 rodithioic acid.
lllltllllllll +Zinc salt of di-2-ethy1hexy1 phosphorodi- 100 thioic acid.
From an inspection of Table II it will be seen that while amine salts and zinc salts in general increased the load point at which transition to high rate occurred, the hexamethylenetetramine salt (the only salt in Table II falling within the scope of the present invention) is superior to any of the other compounds tested and raised the loadcarrying ability of the oil by 140%.
In the foregoing examples the detergent, pour depressant and viscosity improver are not necessary ingredients of the oil insofar as the present invention is concerned but are added to the oil merely to 'give a balanced oil corresponding to one which would be used in actual commercial practice.
It will be seen, therefore, that we have found a select group of amine salts which have unusual ability in improving the anti-wear characteristics of mineral lubricating oils.
We claim as our invention:
1. A lubricant composition comprising a major portion of a mineral lubricating oil and a minor portion, sufiicient to enhance substantially the load-'carrying'properties of the oil, of at least one heterocyclic polyamine salt of a phosphorodithiotic acid ester of the formula where R is a C -C radical selected from the group consisting of alkyl, phenyl, alkylphenyl, and phenylakyl radicals, and where the hetcrocyclic polyamine is selected from the group consisting of hexamethylenetetramine, trilower alkyl cyclotrimethylene triamines, piperazine, lower alkyl-substituted piperazines, and lower alkyl isomelamines.
2. A lubricating oil in accordance with claim 1 in which the polyamine is a trialkylcyclotrimethylenetriamine.
3. A lubricating oil in accordance with claim 1 in which the polyamine is a piperazine.
4. A lubricating oil in accordance with claim 1 in which the polyamine is an alkylisomelamine.
5. A lubricating oil in accordance with claim 1 containing an amount of said salt equivalent to about 0.05 to 0.05% by weight of phosphorus.
6. A lubricating oil in accordance with claim 1 in which the salt is a hexamethylenetetramine salt of a dialkyl phosphorodithioic acid.
7. A lubricating oil in accordance with claim 6 in which the salt is hexamethylenetetrammonium di-Z-ethylhexyl phosphorodithioate.
8. A lubricating oil in accordance with claim 7 containing an amount of said salt equivalent to about 0.05 to 0.5% by weight of phosphorus.
9. A lubricating oil composition in accordance with claim 1 which contains a small amount of a detergent and a corrosion inhibitor.
10. A lubricating oil composition in accordance with claim 9 in which the detergent is a basic barium petroleum sulfonate and the corrosion inhibitor is a sulfurized terpene.
References Cited in the file of this patent UNITED STATES PATENTS 2,167,867 Benning Aug. 1, 1939 2,316,587 Irigai Apr. 13, 1943 2,447,288 Smith et a1 Apr. 17, 1948 2,640,209 Blair et a1. May 26, 1953 2,676,150 Loughran et al. Apr. 20, 1954 2,679,481 Norris et al. May 25, 1954 2,683,691 Thorpe et al. July 13, 1954 2,712,526 McDermott July 5, 1955 2,767,165 Smith et al. Oct. 16, 1956 2,773,861 Musselman Dec. 11, 1956 2,773,862 Musselman Dec. 11, 1956 2,798,045 Buck et al. July 2, 1957 UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No., 2,973,323 February 28, 1961 Allen F. Millikan et a1.
It is hereby oertified'that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 6 line 5 for "0,05%" read 05 (SEAL) Attest:
ERNEST W. SWIDER Attesting Officer DAVID L. LADD Commissioner of Patents
Claims (1)
1. A LUBRICANT COMPOSITION COMPRISING A MAJOR PORTION OF A MINERAL LUBRICATING OIL AND A MINOR PORTION, SUFFICIENT TO ENHANCE SUBSTANTIALLY THE LOAD-CARRYING PROPERTIES OF THE OIL, OF AT LEAST ONE HETEROCYCLIC POLYAMINE SALT OF A PHOSPHORODITHIOTIC ACID ESTER OF THE FORMULA
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US631516A US2973323A (en) | 1956-12-31 | 1956-12-31 | Lubricating oil composition containing heterocyclic polyamine salts of partial ester of phosphorodithioic acid as antiwear agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US631516A US2973323A (en) | 1956-12-31 | 1956-12-31 | Lubricating oil composition containing heterocyclic polyamine salts of partial ester of phosphorodithioic acid as antiwear agent |
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| US2973323A true US2973323A (en) | 1961-02-28 |
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|---|---|---|---|
| US631516A Expired - Lifetime US2973323A (en) | 1956-12-31 | 1956-12-31 | Lubricating oil composition containing heterocyclic polyamine salts of partial ester of phosphorodithioic acid as antiwear agent |
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| US (1) | US2973323A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3116249A (en) * | 1960-12-23 | 1963-12-31 | Shell Oil Co | Lubricating oil compositions |
| US3129699A (en) * | 1961-11-24 | 1964-04-21 | Pure Oil Co | Diesel fuel containing a heterocyclic polyamine salt |
| US3159578A (en) * | 1960-02-26 | 1964-12-01 | Shell Oil Co | Organic functional fluids and polymeric amine salt additives therefor |
| US3184412A (en) * | 1962-09-28 | 1965-05-18 | California Research Corp | Lubricants inhibited against oxidation |
| US3185643A (en) * | 1962-09-28 | 1965-05-25 | California Reserach Corp | Oxidation resistant lubricants |
| US3185645A (en) * | 1962-09-28 | 1965-05-25 | California Research Corp | Oxidation inhibited lubricants |
| US3201447A (en) * | 1962-11-29 | 1965-08-17 | Universal Oil Prod Co | Ether amine salts of dithiophosphoric acid mono and diesters |
| US3238132A (en) * | 1962-11-29 | 1966-03-01 | Universal Oil Prod Co | Stabilization of organic substances with dithiophosphate salts |
| US3290246A (en) * | 1962-09-07 | 1966-12-06 | Snam Spa | Lubricants containing zinc dithiophosphates |
| US3519563A (en) * | 1967-10-31 | 1970-07-07 | Chevron Res | Thiophosphate salts of aralkylene diamines as antiwear,extreme pressure and oxidation inhibitor agents |
| DE2221646A1 (en) * | 1971-05-05 | 1972-11-09 | Esso Res And Engineering Co | Lubricating oil preparations |
| DE3223794A1 (en) * | 1981-06-26 | 1983-01-13 | Agip Petroli S.P.A., Roma | LUBRICANT ADDITIVES |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2167867A (en) * | 1936-05-07 | 1939-08-01 | Du Pont | Lubricant |
| US2316587A (en) * | 1940-02-20 | 1943-04-13 | Gen Electric | Stabilized oil |
| US2447288A (en) * | 1946-03-06 | 1948-08-17 | Gulf Oil Corp | Primary aliphatic amine salts of dialiphatic substituted mono-thiophosphoric acids |
| US2640209A (en) * | 1946-09-09 | 1953-06-02 | Johnson Co Gordon | Egg washing machine |
| US2676150A (en) * | 1952-04-09 | 1954-04-20 | American Cyanamid Co | Corrosion inhibitors for lubricating oils |
| US2679481A (en) * | 1952-02-07 | 1954-05-25 | Socony Vacuum Oil Co Inc | Antioxidants |
| US2683691A (en) * | 1951-08-18 | 1954-07-13 | Shell Dev | Extreme pressure lubricants |
| US2712526A (en) * | 1951-12-22 | 1955-07-05 | Exxon Research Engineering Co | Hydrocarbon oil additive |
| US2767165A (en) * | 1952-07-03 | 1956-10-16 | Gulf Oil Corp | Addition agents |
| US2773861A (en) * | 1955-12-30 | 1956-12-11 | Standard Oil Co | Process of stabilizing phosphorus sulfide-oxygen containing organic compound reaction products against hydrogen sulfide evolution |
| US2773862A (en) * | 1955-12-30 | 1956-12-11 | Standard Oil Co | Process of stabilizing phosphorus sulfide-oxygen-containing organic compound reaction products |
| US2798045A (en) * | 1954-09-27 | 1957-07-02 | Shell Dev | Lubricating compositions |
-
1956
- 1956-12-31 US US631516A patent/US2973323A/en not_active Expired - Lifetime
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2167867A (en) * | 1936-05-07 | 1939-08-01 | Du Pont | Lubricant |
| US2316587A (en) * | 1940-02-20 | 1943-04-13 | Gen Electric | Stabilized oil |
| US2447288A (en) * | 1946-03-06 | 1948-08-17 | Gulf Oil Corp | Primary aliphatic amine salts of dialiphatic substituted mono-thiophosphoric acids |
| US2640209A (en) * | 1946-09-09 | 1953-06-02 | Johnson Co Gordon | Egg washing machine |
| US2683691A (en) * | 1951-08-18 | 1954-07-13 | Shell Dev | Extreme pressure lubricants |
| US2712526A (en) * | 1951-12-22 | 1955-07-05 | Exxon Research Engineering Co | Hydrocarbon oil additive |
| US2679481A (en) * | 1952-02-07 | 1954-05-25 | Socony Vacuum Oil Co Inc | Antioxidants |
| US2676150A (en) * | 1952-04-09 | 1954-04-20 | American Cyanamid Co | Corrosion inhibitors for lubricating oils |
| US2767165A (en) * | 1952-07-03 | 1956-10-16 | Gulf Oil Corp | Addition agents |
| US2798045A (en) * | 1954-09-27 | 1957-07-02 | Shell Dev | Lubricating compositions |
| US2773861A (en) * | 1955-12-30 | 1956-12-11 | Standard Oil Co | Process of stabilizing phosphorus sulfide-oxygen containing organic compound reaction products against hydrogen sulfide evolution |
| US2773862A (en) * | 1955-12-30 | 1956-12-11 | Standard Oil Co | Process of stabilizing phosphorus sulfide-oxygen-containing organic compound reaction products |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3159578A (en) * | 1960-02-26 | 1964-12-01 | Shell Oil Co | Organic functional fluids and polymeric amine salt additives therefor |
| US3116249A (en) * | 1960-12-23 | 1963-12-31 | Shell Oil Co | Lubricating oil compositions |
| US3129699A (en) * | 1961-11-24 | 1964-04-21 | Pure Oil Co | Diesel fuel containing a heterocyclic polyamine salt |
| US3290246A (en) * | 1962-09-07 | 1966-12-06 | Snam Spa | Lubricants containing zinc dithiophosphates |
| US3184412A (en) * | 1962-09-28 | 1965-05-18 | California Research Corp | Lubricants inhibited against oxidation |
| US3185643A (en) * | 1962-09-28 | 1965-05-25 | California Reserach Corp | Oxidation resistant lubricants |
| US3185645A (en) * | 1962-09-28 | 1965-05-25 | California Research Corp | Oxidation inhibited lubricants |
| US3201447A (en) * | 1962-11-29 | 1965-08-17 | Universal Oil Prod Co | Ether amine salts of dithiophosphoric acid mono and diesters |
| US3238132A (en) * | 1962-11-29 | 1966-03-01 | Universal Oil Prod Co | Stabilization of organic substances with dithiophosphate salts |
| US3519563A (en) * | 1967-10-31 | 1970-07-07 | Chevron Res | Thiophosphate salts of aralkylene diamines as antiwear,extreme pressure and oxidation inhibitor agents |
| DE2221646A1 (en) * | 1971-05-05 | 1972-11-09 | Esso Res And Engineering Co | Lubricating oil preparations |
| DE3223794A1 (en) * | 1981-06-26 | 1983-01-13 | Agip Petroli S.P.A., Roma | LUBRICANT ADDITIVES |
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