JP6319122B2 - Sulfur-containing aminoorganoxysilane compound and method for producing the same - Google Patents
Sulfur-containing aminoorganoxysilane compound and method for producing the same Download PDFInfo
- Publication number
- JP6319122B2 JP6319122B2 JP2015016239A JP2015016239A JP6319122B2 JP 6319122 B2 JP6319122 B2 JP 6319122B2 JP 2015016239 A JP2015016239 A JP 2015016239A JP 2015016239 A JP2015016239 A JP 2015016239A JP 6319122 B2 JP6319122 B2 JP 6319122B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- thio
- carbon atoms
- methyl
- groups
- 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.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims description 41
- 229910052717 sulfur Inorganic materials 0.000 title claims description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 25
- 239000011593 sulfur Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- -1 amine compound Chemical class 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 10
- 150000002430 hydrocarbons Chemical group 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 12
- 125000003277 amino group Chemical group 0.000 description 11
- 125000002947 alkylene group Chemical group 0.000 description 10
- 125000005842 heteroatom Chemical group 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000003944 tolyl group Chemical group 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 125000000101 thioether group Chemical group 0.000 description 4
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000006410 propenylene group Chemical group 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 0 *C(*N(*)*)=C Chemical compound *C(*N(*)*)=C 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical group CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- ZWAQJGHGPPDZSF-UHFFFAOYSA-N 1-prop-2-enylpiperazine Chemical compound C=CCN1CCNCC1 ZWAQJGHGPPDZSF-UHFFFAOYSA-N 0.000 description 1
- FMRSVUHIKQTOFR-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(C)CCCS FMRSVUHIKQTOFR-UHFFFAOYSA-N 0.000 description 1
- DQMRXALBJIVORP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(C)CCCS DQMRXALBJIVORP-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- SUSANAYXICMXBL-UHFFFAOYSA-N 4-prop-2-enylmorpholine Chemical compound C=CCN1CCOCC1 SUSANAYXICMXBL-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- VXQOFNJETKUWLT-UHFFFAOYSA-N [dimethoxy(methyl)silyl]methanethiol Chemical compound CO[Si](C)(CS)OC VXQOFNJETKUWLT-UHFFFAOYSA-N 0.000 description 1
- KFXKOQKIAJLZNS-UHFFFAOYSA-N [ethoxy(dimethyl)silyl]methanethiol Chemical compound CCO[Si](C)(C)CS KFXKOQKIAJLZNS-UHFFFAOYSA-N 0.000 description 1
- ZHYGIFUMPWJZSI-UHFFFAOYSA-N [methoxy(dimethyl)silyl]methanethiol Chemical compound CO[Si](C)(C)CS ZHYGIFUMPWJZSI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JWAJUTZQGZBKFS-UHFFFAOYSA-N n,n-diethylprop-2-en-1-amine Chemical compound CCN(CC)CC=C JWAJUTZQGZBKFS-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- XSIGLRIVXRKQRA-UHFFFAOYSA-N triethoxysilylmethanethiol Chemical compound CCO[Si](CS)(OCC)OCC XSIGLRIVXRKQRA-UHFFFAOYSA-N 0.000 description 1
- QJOOZNCPHALTKK-UHFFFAOYSA-N trimethoxysilylmethanethiol Chemical compound CO[Si](CS)(OC)OC QJOOZNCPHALTKK-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、シランカップリング剤、表面処理剤、樹脂添加剤、塗料添加剤、接着剤等として有用な、含硫黄アミノオルガノキシシラン化合物及びその製造方法に関する。 The present invention relates to a sulfur-containing aminoorganoxysilane compound useful as a silane coupling agent, a surface treatment agent, a resin additive, a paint additive, an adhesive and the like, and a method for producing the same.
アミノアルコキシシラン化合物は、極性官能基のアミノ基と、加水分解性基であるアルコキシシリル基を有することからシランカップリング剤、表面処理剤、樹脂添加剤、塗料添加剤、接着剤等として使用した場合に有用である。このようなアミノアルコキシシラン化合物の具体例としては、３−アミノプロピルトリメトキシシランや３−エチレンジアミノプロピルトリメトキシシラン等が例示され、特に含硫黄アミノオルガノキシシラン化合物の具体例として、１−アミノ−４−チオ−ヘプチルトリメトキシシランが例示される（特許文献１：国際公開第２００９／０５６７７８号）。 Since the aminoalkoxysilane compound has an amino group of a polar functional group and an alkoxysilyl group that is a hydrolyzable group, it was used as a silane coupling agent, a surface treatment agent, a resin additive, a paint additive, an adhesive, and the like. Useful in cases. Specific examples of such an aminoalkoxysilane compound include 3-aminopropyltrimethoxysilane and 3-ethylenediaminopropyltrimethoxysilane. Particularly, specific examples of the sulfur-containing aminoorganoxysilane compound include 1-amino An example is -4-thio-heptyltrimethoxysilane (Patent Document 1: International Publication No. 2009/0567778).
しかし、上記含硫黄アミノオルガノキシシラン化合物は１級アミノ基を有しており、特定の官能基を含む樹脂、特にエポキシ樹脂やカーボネート樹脂に添加した場合、所望の効果を発揮できない可能性がある。例えば、エポキシ樹脂に添加した場合、エポキシ基がアミノ基によって開環重合し、樹脂が硬化してしまう可能性がある。また、カーボネート樹脂に添加した場合、含硫黄アミノオルガノキシシラン化合物のアミノ基がアミド基へと変換され、アミノ基の効果が十分に発揮されない可能性がある。このため、種々の官能基に対して安定である（一液型硬化性組成物に使用できる）アミノオルガノキシシラン化合物が望まれていた。 However, the sulfur-containing aminoorganoxysilane compound has a primary amino group, and when added to a resin containing a specific functional group, particularly an epoxy resin or a carbonate resin, the desired effect may not be exhibited. . For example, when added to an epoxy resin, the epoxy group may undergo ring-opening polymerization with an amino group, and the resin may be cured. Moreover, when added to a carbonate resin, the amino group of the sulfur-containing aminoorganoxysilane compound is converted to an amide group, and the effect of the amino group may not be sufficiently exhibited. For this reason, an aminoorganoxysilane compound that is stable with respect to various functional groups (can be used in a one-component curable composition) has been desired.
本発明は、上記事情に鑑みなされたもので、塗料添加剤、接着剤等として用いた場合にアミノ基及びアルコキシシリル基等のオルガノキシシリル基の効果が十分発揮でき、且つ一液型硬化性組成物とすることができる含硫黄アミノオルガノキシシラン化合物及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and when used as a coating additive, adhesive, etc., the effects of organoxysilyl groups such as amino groups and alkoxysilyl groups can be sufficiently exerted, and one-component curable It is an object of the present invention to provide a sulfur-containing aminoorganoxysilane compound that can be made into a composition and a method for producing the same.
本発明者らは、上記目的を達成するため、鋭意検討を重ねた結果、一般式（１）で示される含硫黄アミノオルガノキシシラン化合物は、分子の自由度が従来のアミノアルコキシシラン化合物よりも高く、塗料添加剤や接着剤等として使用した場合にアミノ基及びアルコキシシリル基等のオルガノキシシリル基の効果を十分に発揮でき、且つ一液型組成物とすることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the sulfur-containing aminoorganoxysilane compound represented by the general formula (1) has a molecular freedom higher than that of a conventional aminoalkoxysilane compound. It has been found that when used as a paint additive or adhesive, the effects of organoxysilyl groups such as amino groups and alkoxysilyl groups can be sufficiently exerted, and a one-component composition can be obtained. It came to complete.
従って、本発明は、下記に示す含硫黄アミノオルガノキシシラン化合物及びその製造方法を提供する。
［１］
下記一般式（１）
で示される含硫黄アミノオルガノキシシラン化合物。
［２］
前記Ｒ3が、
［−ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2−］又は
［−ＣＨ2ＣＨ2ＯＣＨ2ＣＨ（ＣＨ3）−］
で示される基である［１］記載の含硫黄アミノオルガノキシシラン化合物。
［３］
下記一般式（２）
で示されるアミン化合物と、下記一般式（３）
で示されるメルカプト基含有オルガノキシシラン化合物を反応させることを特徴とする下記一般式（１’）
で示される含硫黄アミノオルガノキシシラン化合物の製造方法。
［４］
得られる含硫黄アミノオルガノキシシラン化合物が、一般式（１’）におけるＲ3''が［−ＣＨ2ＣＨ2ＣＨ2−］で示される基を含むものと、［−ＣＨ2ＣＨ（ＣＨ3）−］で示される基を含むものとの混合物である［３］記載の含硫黄アミノオルガノキシシラン化合物の製造方法。
Accordingly, the present invention provides the following sulfur-containing aminoorganoxysilane compound and a method for producing the same.
[1]
The following general formula (1)
A sulfur-containing aminoorganoxysilane compound represented by:
[2]
R 3 is
[—CH 2 CH 2 OCH 2 CH 2 CH 2 —] or [—CH 2 CH 2 OCH 2 CH (CH 3 ) —]
The sulfur-containing aminoorganoxysilane compound according to [1], which is a group represented by:
[3]
The following general formula (2)
An amine compound represented by the following general formula (3)
Wherein the mercapto group-containing organoxysilane compound represented by the general formula (1 ′)
A process for producing a sulfur-containing aminoorganoxysilane compound represented by:
[4]
The obtained sulfur-containing aminoorganoxysilane compound includes those in which R 3 ″ in the general formula (1 ′) includes a group represented by [—CH 2 CH 2 CH 2 —], and [—CH 2 CH (CH 3 )-] The method for producing a sulfur-containing aminoorganoxysilane compound according to [3], which is a mixture containing the group represented by-].
本発明によれば、使用時にアミノ基の効果を従来以上に発揮でき、且つ一液型硬化性組成物とすることができ、シランカップリング剤、表面処理剤、樹脂添加剤、塗料添加剤、接着剤等として用いることができる含硫黄アミノオルガノキシシラン化合物を提供することができる。 According to the present invention, the amino group effect can be exhibited more than before when used, and a one-component curable composition can be obtained. A silane coupling agent, a surface treatment agent, a resin additive, a paint additive, A sulfur-containing aminoorganoxysilane compound that can be used as an adhesive or the like can be provided.
本発明の含硫黄アミノオルガノキシシラン化合物は、下記一般式（１）で示される化合物である。
ここで、Ｒ1，Ｒ2 は炭素数１〜２０、特に１〜１０の非置換の１価炭化水素基であり、各々同一又は異なっていてもよい。また、Ｒ1とＲ2が互いに結合してこれらが結合する窒素原子と共に環を形成してもよい。Ｒ1，Ｒ2としては、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基等の直鎖状アルキル基、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、テキシル基、２−エチルヘキシル基等の分岐状アルキル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、ビニル基、アリル基、プロペニル基等のアルケニル基、フェニル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基等が例示され、特に、原料の調達容易性及び生成物の有用性から、メチル基、エチル基が好ましい。また、これらの炭化水素基の水素原子の一部又は全部が置換されていてもよく、該置換基としては、具体的には、例えば、メトキシ基、エトキシ基、（イソ）プロポキシ基等のアルコキシ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；シアノ基；アミノ基；フェニル基、トリル基等の炭素数６〜１０のアリール基、ベンジル基、フェネチル基等の炭素数７〜１０のアラルキル基、炭素数２〜１０のアシル基；それぞれ各アルキル基、各アルコキシ基が炭素数１〜５であるトリアルキルシリル基、トリアルコキシシリル基、ジアルキルモノアルコキシシリル基、モノアルキルジアルコキシシリル基等が挙げられ、更にエステル基（−ＣＯＯ−）、エーテル基（−Ｏ−）、スルフィド基（−Ｓ−）等が介在していてもよく、これらを組み合わせて用いることもできる。 Wherein, R 1, R 2 is a carbon number of 1 to 20, in particular 1-10 unsubstituted monovalent hydrocarbon group, but it may also have each the same or different. R 1 and R 2 may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. Specific examples of R 1 and R 2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a linear alkyl group such as a decyl group, an isopropyl group, Branched alkyl groups such as isobutyl group, sec-butyl group, tert-butyl group, texyl group and 2-ethylhexyl group, cyclic alkyl groups such as cyclopentyl group and cyclohexyl group, alkenyl groups such as vinyl group, allyl group and propenyl group An aryl group such as a phenyl group, an aralkyl group such as a benzyl group and a phenethyl group are exemplified, and a methyl group and an ethyl group are particularly preferred from the viewpoint of easy procurement of raw materials and usefulness of the product. Further, some or all of the hydrogen atoms of these hydrocarbon groups may be substituted. Specific examples of the substituent include alkoxy groups such as methoxy group, ethoxy group, and (iso) propoxy group. Group: halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; amino group; carbon number 7 such as aryl group having 6 to 10 carbon atoms such as phenyl group and tolyl group, benzyl group and phenethyl group -10 aralkyl groups, C2-C10 acyl groups; each alkyl group, each alkoxy group having 1 to 5 carbon atoms, a trialkylsilyl group, a trialkoxysilyl group, a dialkylmonoalkoxysilyl group, a monoalkyldi Examples include alkoxysilyl groups, and ester groups (—COO—), ether groups (—O—), sulfide groups (—S—) and the like may be interposed. It may be used in combination.
また、Ｒ1，Ｒ2が結合して環構造を形成する場合には、下記式
Ｒ3は、酸素原子、窒素原子、硫黄原子等のヘテロ原子を含んでもよい炭素数１〜２０、特に１〜１０の直鎖状又は分岐状の２価炭化水素基であり、炭素数１〜２０の２価炭化水素基としては、具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキサメチレン基、オクタメチレン基、デシレン基等の直鎖状アルキレン基、メチルエチレン基、メチルプロピレン基等の分岐状アルキレン基、シクロヘキシレン基等の環状アルキレン基、プロペニレン基等のアルケニレン基、フェニレン基等のアリーレン基、メチレンフェニレン基、メチレンフェニレンメチレン基等のアラルキレン基等が例示され、特に原料の調達容易性からプロピレン基が望ましい。また、ヘテロ原子を含んでもよい炭素数１〜２０の２価炭化水素基としては、［−ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2−］、［−ＣＨ2ＣＨ2ＯＣＨ2ＣＨ（ＣＨ3）−］で示される基等が挙げられる。また、これらの炭化水素基の水素原子の一部又は全部が置換されていてもよく、該置換基としては、具体的には、例えば、メトキシ基、エトキシ基、（イソ）プロポキシ基等のアルコキシ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；シアノ基；アミノ基；フェニル基、トリル基等の炭素数６〜１０のアリール基、ベンジル基、フェネチル基等の炭素数７〜１０のアラルキル基、炭素数２〜１０のアシル基、それぞれ各アルキル基、各アルコキシ基が炭素数１〜５であるトリアルキルシリル基、トリアルコキシシリル基、ジアルキルモノアルコキシシリル基、モノアルキルジアルコキシシリル基等が挙げられ、更に、エステル基（−ＣＯＯ−）、エーテル基（−Ｏ−）、スルフィド基（−Ｓ−）等が介在していてもよく、これらを組み合わせて用いることもできる。
R 3 is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms which may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Specific examples of the 20 divalent hydrocarbon group include a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, an octamethylene group, and a decylene group, a methylethylene group, and a methyl group. Examples include branched alkylene groups such as propylene groups, cyclic alkylene groups such as cyclohexylene groups, alkenylene groups such as propenylene groups, arylene groups such as phenylene groups, aralkylene groups such as methylenephenylene groups and methylenephenylenemethylene groups, etc. Propylene groups are desirable because of the ease of procurement of raw materials. Further, the divalent hydrocarbon group which may having 1 to 20 carbon atoms include a
Ｒ4は炭素数１〜２０、特に１〜１０の直鎖状又は分岐状の２価炭化水素基であり、具体的には、Ｒ3として例示したもの（ヘテロ原子を含んでもよい２価炭化水素基として挙げたものを除く）と同様のものが挙げられる。 R 4 is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, and specifically, those exemplified as R 3 (divalent carbon atoms which may contain a hetero atom) The thing similar to the thing except the thing quoted as a hydrogen group is mentioned.
Ｒ5，Ｒ6は炭素数１〜１０、好ましくは１〜６、より好ましくは１〜３の１価炭化水素基であり、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基等の直鎖状アルキル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基等の分岐状アルキル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、ビニル基、アリル基、プロペニル基等のアルケニル基、フェニル基、トリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基等が例示され、目的物が比較的低沸点化合物となる点から、特にメチル基、エチル基が好ましい。 R 5 and R 6 are monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, Linear alkyl groups such as pentyl group, hexyl group, heptyl group, octyl group, decyl group, branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, Examples include alkenyl groups such as vinyl group, allyl group and propenyl group, aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group and phenethyl group, etc. In particular, a methyl group and an ethyl group are preferable.
上記一般式（１）で示される含硫黄アミノオルガノキシシラン化合物の具体例としては、
１−ジメチルアミノ−４−チオ−ヘプチルトリメトキシシラン、
１−ジメチルアミノ−４−チオ−ヘプチルメチルジメトキシシラン、
１−ジメチルアミノ−４−チオ−ヘプチルジメチルメトキシシラン、
１−ジメチルアミノ−４−チオ−ヘプチルトリエトキシシラン、
１−ジメチルアミノ−４−チオ−ヘプチルメチルジエトキシシラン、
１−ジメチルアミノ−４−チオ−ヘプチルジメチルエトキシシラン、
１−ジメチルアミノ−２−メチル−３−チオ−ヘキシルトリメトキシシラン、
１−ジメチルアミノ−２−メチル−３−チオ−ヘキシルメチルジメトキシシラン、
１−ジメチルアミノ−２−メチル−３−チオ−ヘキシルジメチルメトキシシラン、
１−ジメチルアミノ−２−メチル−３−チオ−ヘキシルトリエトキシシラン、
１−ジメチルアミノ−２−メチル−３−チオ−ヘキシルメチルジエトキシシラン、
１−ジメチルアミノ−２−メチル−３−チオ−ヘキシルジメチルエトキシシラン、
１−ジエチルアミノ−４−チオ−ヘプチルトリメトキシシラン、
１−ジエチルアミノ−４−チオ−ヘプチルメチルジメトキシシラン、
１−ジエチルアミノ−４−チオ−ヘプチルジメチルメトキシシラン、
１−ジエチルアミノ−４−チオ−ヘプチルトリエトキシシラン、
１−ジエチルアミノ−４−チオ−ヘプチルメチルジエトキシシラン、
１−ジエチルアミノ−４−チオ−ヘプチルジメチルエトキシシラン、
１−ジエチルアミノ−２−メチル−３−チオ−ヘキシルトリメトキシシラン、
１−ジエチルアミノ−２−メチル−３−チオ−ヘキシルメチルジメトキシシラン、
１−ジエチルアミノ−２−メチル−３−チオ−ヘキシルジメチルメトキシシラン、
１−ジエチルアミノ−２−メチル−３−チオ−ヘキシルトリエトキシシラン、
１−ジエチルアミノ−２−メチル−３−チオ−ヘキシルメチルジエトキシシラン、
１−ジエチルアミノ−２−メチル−３−チオ−ヘキシルジメチルエトキシシラン、
１−メチルピペラジノ−４−チオ−ヘプチルトリメトキシシラン、
１−メチルピペラジノ−４−チオ−ヘプチルメチルジメトキシシラン、
１−メチルピペラジノ−４−チオ−ヘプチルジメチルメトキシシラン、
１−メチルピペラジノ−４−チオ−ヘプチルトリエトキシシラン、
１−メチルピペラジノ−４−チオ−ヘプチルメチルジエトキシシラン、
１−メチルピペラジノ−４−チオ−ヘプチルジメチルエトキシシラン、
１−メチルピペラジノ−２−メチル−３−チオ−ヘキシルトリメトキシシラン、
１−メチルピペラジノ−２−メチル−３−チオ−ヘキシルメチルジメトキシシラン、
１−メチルピペラジノ−２−メチル−３−チオ−ヘキシルジメチルメトキシシラン、
１−メチルピペラジノ−２−メチル−３−チオ−ヘキシルトリエトキシシラン、
１−メチルピペラジノ−２−メチル−３−チオ−ヘキシルメチルジエトキシシラン、
１−メチルピペラジノ−２−メチル−３−チオ−ヘキシルジメチルエトキシシラン、
１−フェニルメチルアミノ−４−チオ−ヘプチルトリメトキシシラン、
１−フェニルメチルアミノ−４−チオ−ヘプチルメチルジメトキシシラン、
１−フェニルメチルアミノ−４−チオ−ヘプチルジメチルメトキシシラン、
１−フェニルメチルアミノ−４−チオ−ヘプチルトリエトキシシラン、
１−フェニルメチルアミノ−４−チオ−ヘプチルメチルジエトキシシラン、
１−フェニルメチルアミノ−４−チオ−ヘプチルジメチルエトキシシラン、
１−フェニルメチルアミノ−２−メチル−３−チオ−ヘキシルトリメトキシシラン、
１−フェニルメチルアミノ−２−メチル−３−チオ−ヘキシルメチルジメトキシシラン、
１−フェニルメチルアミノ−２−メチル−３−チオ−ヘキシルジメチルメトキシシラン、
１−フェニルメチルアミノ−２−メチル−３−チオ−ヘキシルトリエトキシシラン、
１−フェニルメチルアミノ−２−メチル−３−チオ−ヘキシルメチルジエトキシシラン、
１−フェニルメチルアミノ−２−メチル−３−チオ−ヘキシルジメチルエトキシシラン、
１−ジメチルアミノ−３−オキソ−７−チオ−デシルトリメトキシシラン、
１−ジメチルアミノ−３−オキソ−７−チオ−デシルメチルジメトキシシラン、
１−ジメチルアミノ−３−オキソ−７−チオ−デシルジメチルメトキシシラン、
１−ジメチルアミノ−３−オキソ−７−チオ−デシルトリエトキシシラン、
１−ジメチルアミノ−３−オキソ−７−チオ−デシルメチルジエトキシシラン、
１−ジメチルアミノ−３−オキソ−７−チオ−デシルジメチルエトキシシラン、
１−ジメチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルトリメトキシシラン、
１−ジメチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルメチルジメトキシシラン、
１−ジメチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルジメチルメトキシシラン、
１−ジメチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルトリエトキシシラン、
１−ジメチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルメチルジエトキシシラン、
１−ジメチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルジメチルエトキシシラン、
１−ジエチルアミノ−３−オキソ−７−チオ−デシルトリメトキシシラン、
１−ジエチルアミノ−３−オキソ−７−チオ−デシルメチルジメトキシシラン、
１−ジエチルアミノ−３−オキソ−７−チオ−デシルジメチルメトキシシラン、
１−ジエチルアミノ−３−オキソ−７−チオ−デシルトリエトキシシラン、
１−ジエチルアミノ−３−オキソ−７−チオ−デシルメチルジエトキシシラン、
１−ジエチルアミノ−３−オキソ−７−チオ−デシルジメチルエトキシシラン、
１−ジエチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルトリメトキシシラン、
１−ジエチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルメチルジメトキシシラン、
１−ジエチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルジメチルメトキシシラン、
１−ジエチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルトリエトキシシラン、
１−ジエチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルメチルジエトキシシラン、
１−ジエチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルジメチルエトキシシラン等が例示される。
Specific examples of the sulfur-containing aminoorganoxysilane compound represented by the general formula (1) include
1-dimethylamino-4-thio-heptyltrimethoxysilane,
1-dimethylamino-4-thio-heptylmethyldimethoxysilane,
1-dimethylamino-4-thio-heptyldimethylmethoxysilane,
1-dimethylamino-4-thio-heptyltriethoxysilane,
1-dimethylamino-4-thio-heptylmethyldiethoxysilane,
1-dimethylamino-4-thio-heptyldimethylethoxysilane,
1-dimethylamino-2-methyl-3-thio-hexyltrimethoxysilane,
1-dimethylamino-2-methyl-3-thio-hexylmethyldimethoxysilane,
1-dimethylamino-2-methyl-3-thio-hexyldimethylmethoxysilane,
1-dimethylamino-2-methyl-3-thio-hexyltriethoxysilane,
1-dimethylamino-2-methyl-3-thio-hexylmethyldiethoxysilane,
1-dimethylamino-2-methyl-3-thio-hexyldimethylethoxysilane,
1-diethylamino-4-thio-heptyltrimethoxysilane,
1-diethylamino-4-thio-heptylmethyldimethoxysilane,
1-diethylamino-4-thio-heptyldimethylmethoxysilane,
1-diethylamino-4-thio-heptyltriethoxysilane,
1-diethylamino-4-thio-heptylmethyldiethoxysilane,
1-diethylamino-4-thio-heptyldimethylethoxysilane,
1-diethylamino-2-methyl-3-thio-hexyltrimethoxysilane,
1-diethylamino-2-methyl-3-thio-hexylmethyldimethoxysilane,
1-diethylamino-2-methyl-3-thio-hexyldimethylmethoxysilane,
1-diethylamino-2-methyl-3-thio-hexyltriethoxysilane,
1-diethylamino-2-methyl-3-thio-hexylmethyldiethoxysilane,
1-diethylamino-2-methyl-3-thio-hexyldimethylethoxysilane,
1-methylpiperazino-4-thio-heptyltrimethoxysilane,
1-methylpiperazino-4-thio-heptylmethyldimethoxysilane,
1-methylpiperazino-4-thio-heptyldimethylmethoxysilane,
1-methylpiperazino-4-thio-heptyltriethoxysilane,
1-methylpiperazino-4-thio-heptylmethyldiethoxysilane,
1-methylpiperazino-4-thio-heptyldimethylethoxysilane,
1-methylpiperazino-2-methyl-3-thio-hexyltrimethoxysilane,
1-methylpiperazino-2-methyl-3-thio-hexylmethyldimethoxysilane,
1-methylpiperazino-2-methyl-3-thio-hexyldimethylmethoxysilane,
1-methylpiperazino-2-methyl-3-thio-hexyltriethoxysilane,
1-methylpiperazino-2-methyl-3-thio-hexylmethyldiethoxysilane,
1-methylpiperazino-2-methyl-3-thio-hexyldimethylethoxysilane,
1-phenylmethylamino-4-thio-heptyltrimethoxysilane,
1-phenylmethylamino-4-thio-heptylmethyldimethoxysilane,
1-phenylmethylamino-4-thio-heptyldimethylmethoxysilane,
1-phenylmethylamino-4-thio-heptyltriethoxysilane,
1-phenylmethylamino-4-thio-heptylmethyldiethoxysilane,
1-phenylmethylamino-4-thio-heptyldimethylethoxysilane,
1-phenylmethylamino-2-methyl-3-thio-hexyltrimethoxysilane,
1-phenylmethylamino-2-methyl-3-thio-hexylmethyldimethoxysilane,
1-phenylmethylamino-2-methyl-3-thio-hexyldimethylmethoxysilane,
1-phenylmethylamino-2-methyl-3-thio-hexyltriethoxysilane,
1-phenylmethylamino-2-methyl-3-thio-hexylmethyldiethoxysilane,
1-phenylmethylamino-2-methyl-3-thio-hexyldimethylethoxysilane,
1-dimethylamino-3-oxo-7-thio-decyltrimethoxysilane,
1-dimethylamino-3-oxo-7-thio-decylmethyldimethoxysilane,
1-dimethylamino-3-oxo-7-thio-decyldimethylmethoxysilane,
1-dimethylamino-3-oxo-7-thio-decyltriethoxysilane,
1-dimethylamino-3-oxo-7-thio-decylmethyldiethoxysilane,
1-dimethylamino-3-oxo-7-thio-decyldimethylethoxysilane,
1-dimethylamino-5-methyl-3-oxo-6-thio-nonyltrimethoxysilane,
1-dimethylamino-5-methyl-3-oxo-6-thio-nonylmethyldimethoxysilane,
1-dimethylamino-5-methyl-3-oxo-6-thio-nonyldimethylmethoxysilane,
1-dimethylamino-5-methyl-3-oxo-6-thio-nonyltriethoxysilane,
1-dimethylamino-5-methyl-3-oxo-6-thio-nonylmethyldiethoxysilane,
1-dimethylamino-5-methyl-3-oxo-6-thio-nonyldimethylethoxysilane,
1-diethylamino-3-oxo-7-thio-decyltrimethoxysilane,
1-diethylamino-3-oxo-7-thio-decylmethyldimethoxysilane,
1-diethylamino-3-oxo-7-thio-decyldimethylmethoxysilane,
1-diethylamino-3-oxo-7-thio-decyltriethoxysilane,
1-diethylamino-3-oxo-7-thio-decylmethyldiethoxysilane,
1-diethylamino-3-oxo-7-thio-decyldimethylethoxysilane,
1-diethylamino-5-methyl-3-oxo-6-thio-nonyltrimethoxysilane,
1-diethylamino-5-methyl-3-oxo-6-thio-nonylmethyldimethoxysilane,
1-diethylamino-5-methyl-3-oxo-6-thio-nonyldimethylmethoxysilane,
1-diethylamino-5-methyl-3-oxo-6-thio-nonyltriethoxysilane,
1-diethylamino-5-methyl-3-oxo-6-thio-nonylmethyldiethoxysilane,
Examples include 1-diethylamino-5-methyl-3-oxo-6-thio-nonyldimethylethoxysilane.
本発明における含硫黄アミノオルガノキシシラン化合物の製造方法としては、例えば、下記一般式（２）
で示されるアミン化合物と、下記一般式（３）
で示されるメルカプト基含有オルガノキシシラン化合物を反応させる方法が例示される。
Examples of the method for producing a sulfur-containing aminoorganoxysilane compound in the present invention include the following general formula (2):
An amine compound represented by the following general formula (3)
The method of making the mercapto group containing organoxysilane compound shown by these react is illustrated.
ここで、Ｒ3'は酸素原子、窒素原子、硫黄原子等のヘテロ原子を含んでもよい炭素数１〜１８、特に１〜８の直鎖状又は分岐状の２価炭化水素基であり、炭素数１〜１８の２価炭化水素基としては、具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキサメチレン基、オクタメチレン基等の直鎖状アルキレン基、メチルエチレン基、メチルプロピレン基等の分岐状アルキレン基、シクロヘキシレン基等の環状アルキレン基、プロペニレン基等のアルケニレン基、フェニレン基等のアリーレン基、メチレンフェニレン基、メチレンフェニレンメチレン基等のアラルキレン基等が例示され、特に原料の調達容易性からメチレン基が望ましい。また、ヘテロ原子を含んでもよい炭素数１〜１８の２価炭化水素基としては、［−ＣＨ2ＣＨ2ＯＣＨ2−］で示される基等が挙げられる。また、これらの炭化水素基の水素原子の一部又は全部が置換されていてもよく、該置換基としては、具体的には、例えば、メトキシ基、エトキシ基、（イソ）プロポキシ基等のアルコキシ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；シアノ基；アミノ基；フェニル基、トリル基等の炭素数６〜１０のアリール基、ベンジル基、フェネチル基等の炭素数７〜１０のアラルキル基等が挙げられ、更に、エステル基（−ＣＯＯ−）、エーテル基（−Ｏ−）、スルフィド基（−Ｓ−）等が介在してもよく、これらを組み合わせて用いることもできる。
Ｒ1，Ｒ2，Ｒ4，Ｒ5，Ｒ6，Ｒ7及びｎは上述した通りである。
Here, R 3 ′ is a linear or branched divalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 8 carbon atoms that may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, Specific examples of the divalent hydrocarbon group of 1 to 18 include a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, and an octamethylene group, a methylethylene group, and a methyl group. Examples include branched alkylene groups such as propylene groups, cyclic alkylene groups such as cyclohexylene groups, alkenylene groups such as propenylene groups, arylene groups such as phenylene groups, aralkylene groups such as methylenephenylene groups and methylenephenylenemethylene groups, etc. A methylene group is desirable from the viewpoint of easy procurement of raw materials. Further, the divalent hydrocarbon group having 1 to 18 carbon atoms which may contain a hetero atom, [- CH 2 CH 2 OCH 2 -] group represented by may be mentioned. Further, some or all of the hydrogen atoms of these hydrocarbon groups may be substituted. Specific examples of the substituent include alkoxy groups such as methoxy group, ethoxy group, and (iso) propoxy group. Group: halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; amino group; carbon number 7 such as aryl group having 6 to 10 carbon atoms such as phenyl group and tolyl group, benzyl group and phenethyl group -10 aralkyl groups and the like, and further an ester group (—COO—), an ether group (—O—), a sulfide group (—S—) and the like may be interposed, and these may be used in combination. it can.
R 1 , R 2 , R 4 , R 5 , R 6 , R 7 and n are as described above.
上記一般式（２）で示されるアミン化合物としては、具体的にはジメチルアリルアミン、ジエチルアリルアミン、アリルメチルアニリン、アリルピロリジン、アリルピペリジン、アリルピペラジン、メチルアリルピペラジン、アリルモルホリン等が例示される。 Specific examples of the amine compound represented by the general formula (2) include dimethylallylamine, diethylallylamine, allylmethylaniline, allylpyrrolidine, allylpiperidine, allylpiperazine, methylallylpiperazine, allylmorpholine and the like.
上記一般式（３）で示されるメルカプト基含有オルガノキシシラン化合物としては、具体的には、メルカプトメチルトリメトキシシラン、メルカプトメチルメチルジメトキシシラン、メルカプトメチルジメチルメトキシシラン、メルカプトメチルトリエトキシシラン、メルカプトメチルメチルジエトキシシラン、メルカプトメチルジメチルエトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルジメチルメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルメチルジエトキシシラン、３−メルカプトプロピルジメチルエトキシシラン等が例示される。 Specific examples of the mercapto group-containing organoxysilane compound represented by the general formula (3) include mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyldimethylmethoxysilane, mercaptomethyltriethoxysilane, and mercaptomethyl. Methyldiethoxysilane, mercaptomethyldimethylethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxy Examples thereof include silane and 3-mercaptopropyldimethylethoxysilane.
上記一般式（２）で示されるアミン化合物と、上記一般式（３）で示されるメルカプト基含有オルガノキシシラン化合物の配合比は特に限定されないが、反応性、生産性の点から、一般式（２）で示される化合物１モルに対し、一般式（３）で示される化合物を０．１〜４モル、特に０．２〜２モルの範囲が好ましい。 The compounding ratio of the amine compound represented by the general formula (2) and the mercapto group-containing organoxysilane compound represented by the general formula (3) is not particularly limited, but from the viewpoint of reactivity and productivity, the general formula ( The range of 0.1 to 4 mol, particularly 0.2 to 2 mol, of the compound represented by the general formula (3) is preferable with respect to 1 mol of the compound represented by 2).
上記反応の反応速度を向上させるために、ラジカル発生剤を触媒として用いることもできる。用いられるラジカル発生剤としては、ｔ−ブチルペルオキシド、ジｔ−ブチルペルオキシド、過酸化ベンゾイル等の過酸化物、アゾビスイソブチロニトリル、２，２’−アゾビス−（２−メチルブチロニトリル）等のアゾ化合物等が例示される。 In order to improve the reaction rate of the above reaction, a radical generator can also be used as a catalyst. Examples of the radical generator used include peroxides such as t-butyl peroxide, di-t-butyl peroxide and benzoyl peroxide, azobisisobutyronitrile, and 2,2′-azobis- (2-methylbutyronitrile). An azo compound such as
触媒の使用量は特に限定されないが、反応性、生産性の点から、上記一般式（２）で示されるアミン化合物１モルに対し、０．０００１〜０．２モル、特に０．００１〜０．１モルの範囲が好ましい。 The amount of the catalyst used is not particularly limited, but from the viewpoint of reactivity and productivity, 0.0001 to 0.2 mol, particularly 0.001 to 0, with respect to 1 mol of the amine compound represented by the general formula (2). A range of 1 mol is preferred.
上記反応の反応温度は特に限定されないが、０〜２００℃、特に２０〜１５０℃が好ましく、反応時間も特に限定されないが、１〜４０時間、特に１〜２０時間が好ましい。反応雰囲気は窒素、アルゴン等の不活性ガス雰囲気とすることが好ましい。 Although the reaction temperature of the said reaction is not specifically limited, 0-200 degreeC, especially 20-150 degreeC is preferable, Reaction time is also not specifically limited, However, 1-40 hours, Especially 1-20 hours are preferable. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen or argon.
なお、上記反応は無溶媒でも進行するが、溶媒を用いることもできる。用いられる溶媒としては、ペンタン、ヘキサン、シクロヘキサン、ヘプタン、イソオクタン、ベンゼン、トルエン、キシレン等の炭化水素系溶媒、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン等の非プロトン性極性溶媒、ジクロロメタン、クロロホルム等の塩素化炭化水素系溶媒等が例示される。これらの溶媒は１種を単独で使用してもよく、あるいは２種以上を混合して使用しても良い。 In addition, although the said reaction advances even without a solvent, a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ester solvents such as ethyl acetate and butyl acetate. And aprotic polar solvents such as acetonitrile, N, N-dimethylformamide and N-methylpyrrolidone, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.
上記反応により、例えば、下記一般式（１’）
で示される含硫黄アミノオルガノキシシラン化合物を得ることができる。
By the above reaction, for example, the following general formula (1 ′)
The sulfur-containing aminoorganoxysilane compound shown by these can be obtained.
Ｒ3''は酸素原子、窒素原子、硫黄原子等のヘテロ原子を含んでもよい炭素数３〜２０、特に３〜１０の直鎖状又は分岐状の２価炭化水素基であり、具体的には、プロピレン基、ブチレン基、ヘキサメチレン基、オクタメチレン基、デシレン基等の直鎖状アルキレン基、メチルプロピレン基等の分岐状アルキレン基、エチレン基、プロピレン基等の直鎖状アルキレン基とシクロヘキシレン基等の環状アルキレン基とを組み合わせた基、ブチレン基等のアルケニレン基、エチレンフェニレン基、メチレンフェニレンエチレン基等のアラルキレン基等が例示され、特に原料の調達容易性からプロピレン基が望ましい。また、ヘテロ原子を含んだものとしては、［−ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2−］、［−ＣＨ2ＣＨ2ＯＣＨ2ＣＨ（ＣＨ3）−］で示される基等が挙げられる。更に、これらの炭化水素基の水素原子の一部又は全部が置換されていてもよく、該置換基としては、具体的には、例えば、メトキシ基、エトキシ基、（イソ）プロポキシ基等のアルコキシ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；シアノ基；アミノ基；フェニル基、トリル基等の炭素数６〜１０のアリール基、ベンジル基、フェネチル基等の炭素数７〜１０のアラルキル基、炭素数２〜１０のアシル基、それぞれ各アルキル基、各アルコキシ基が炭素数１〜５であるトリアルキルシリル基、トリアルコキシシリル基、ジアルキルモノアルコキシシリル基もしくはモノアルキルジアルコキシシリル基が挙げられ、更に、エステル基（−ＣＯＯ−）、エーテル基（−Ｏ−）、スルフィド基（−Ｓ−）等が介在していてもよく、これらを組み合わせて用いることもできる。 R 3 ″ is a linear or branched divalent hydrocarbon group having 3 to 20 carbon atoms, particularly 3 to 10 carbon atoms, which may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Is a linear alkylene group such as a propylene group, butylene group, hexamethylene group, octamethylene group or decylene group; a branched alkylene group such as a methylpropylene group; a linear alkylene group such as an ethylene group or a propylene group; Examples include a group in combination with a cyclic alkylene group such as a silene group, an alkenylene group such as a butylene group, an aralkylene group such as an ethylenephenylene group and a methylenephenyleneethylene group, and a propylene group is particularly desirable from the viewpoint of easy procurement of raw materials. Examples of those containing a hetero atom include groups represented by [—CH 2 CH 2 OCH 2 CH 2 CH 2 —] and [—CH 2 CH 2 OCH 2 CH (CH 3 ) —]. Furthermore, some or all of the hydrogen atoms of these hydrocarbon groups may be substituted. Specific examples of the substituent include alkoxy groups such as a methoxy group, an ethoxy group, and an (iso) propoxy group. Group: halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; amino group; carbon number 7 such as aryl group having 6 to 10 carbon atoms such as phenyl group and tolyl group, benzyl group and phenethyl group -10 aralkyl group, acyl group having 2 to 10 carbon atoms, each alkyl group, trialkylsilyl group, trialkoxysilyl group, dialkylmonoalkoxysilyl group or monoalkyldi, each alkoxy group having 1 to 5 carbon atoms. An alkoxysilyl group, and an ester group (—COO—), an ether group (—O—), a sulfide group (—S—), etc. Good, it can also be used in combination.
上記反応によって得られる本発明の含硫黄アミノオルガノキシシラン化合物としては、具体的には、一般式（１）の具体例として挙げたものと同様なものを例示することができるが、特に、一般式（１’）におけるＲ3''が［−ＣＨ2ＣＨ2ＣＨ2−］で示される基を含むのものと、［−ＣＨ2ＣＨ（ＣＨ3）−］で示される基を含むものとの混合物として得ることができ、例えば、下記式（４）
この場合、一般式（１’）におけるＲ3''が［−ＣＨ2ＣＨ2ＣＨ2−］で示される基を含むのものと、［−ＣＨ2ＣＨ（ＣＨ3）−］で示される基を含むものとが生成する割合（質量％）は、通常５０：５０〜９５：５、特に６５：３５〜９０：１０である。 In this case, R 3 ″ in formula (1 ′) includes a group represented by [—CH 2 CH 2 CH 2 —] and a group represented by [—CH 2 CH (CH 3 ) —]. The ratio (mass%) of the product containing is usually 50:50 to 95: 5, particularly 65:35 to 90:10.
また、本発明における上記一般式（１）で示される含硫黄アミノオルガノキシシラン化合物において、Ｒ3が炭素数１又は２の炭化水素基である場合の製造方法は、例えば、３−メルカプトプロピルトリメトキシシラン及び炭酸カリウム等の塩基を混合して生じたチオラートとジアルキルアミノエチルクロリドとを反応させる方法が挙げられる。 In addition, in the sulfur-containing aminoorganoxysilane compound represented by the general formula (1) in the present invention, when R 3 is a hydrocarbon group having 1 or 2 carbon atoms, the production method is, for example, 3-mercaptopropyltri A method of reacting a thiolate produced by mixing a base such as methoxysilane and potassium carbonate with a dialkylaminoethyl chloride is mentioned.
以下、実施例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
［実施例１］
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−メルカプトプロピルトリメトキシシラン７８．５ｇ（０．４００モル）を仕込み、８０℃に加温した。内温が安定した後、ジメチルアリルアミン４２．５ｇ（０．４９９モル）と、２，２’−アゾビス（２−メチルブチロニトリル）３．９ｇ（０．０１９モル）の混合物を２時間で滴下し、８５℃で１時間撹拌した。反応液を蒸留し、沸点１２１−１２２℃／０．４ｋＰａの留分を１２．４ｇ得た。
[Example 1]
To a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 78.5 g (0.400 mol) of 3-mercaptopropyltrimethoxysilane was charged and heated to 80 ° C. After the internal temperature was stabilized, a mixture of 42.5 g (0.499 mol) of dimethylallylamine and 3.9 g (0.019 mol) of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 2 hours. And stirred at 85 ° C. for 1 hour. The reaction solution was distilled to obtain 12.4 g of a fraction having a boiling point of 121 to 122 ° C./0.4 kPa.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定した。
質量スペクトル
ｍ／ｚ ２０４，１７９，１２１，９１，５８
1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）
図１にチャートで示す。
ＩＲスペクトル
図２にチャートで示す。
以上の結果より、得られた化合物は１−ジメチルアミノ−４−チオ−ヘプチルトリメトキシシラン５５質量％と１−ジメチルアミノ−２−メチル−３−チオ−ヘキシルトリメトキシシラン４５質量％であることが確認された。
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m /
1 H-NMR spectrum (deuterated chloroform solvent)
A chart is shown in FIG.
IR spectrum FIG. 2 is a chart.
From the above results, the obtained compound was 55% by mass of 1-dimethylamino-4-thio-heptyltrimethoxysilane and 45% by mass of 1-dimethylamino-2-methyl-3-thio-hexyltrimethoxysilane. Was confirmed.
［実施例２］
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−メルカプトプロピルメチルジメトキシシラン７２．０ｇ（０．４００モル）を仕込み、８０℃に加温した。内温が安定した後、ジメチルアリルアミン３４．０ｇ（０．３９９モル）と、２，２’−アゾビス（２−メチルブチロニトリル）３．９ｇ（０．０１９モル）の混合物を１時間で滴下し、８５℃で２時間撹拌した。反応液を蒸留し、沸点１０７−１０８℃／０．４ｋＰａの留分を１５．９ｇ得た。
[Example 2]
A flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 72.0 g (0.400 mol) of 3-mercaptopropylmethyldimethoxysilane and heated to 80 ° C. After the internal temperature was stabilized, a mixture of 34.0 g (0.399 mol) of dimethylallylamine and 3.9 g (0.019 mol) of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 1 hour. And stirred at 85 ° C. for 2 hours. The reaction solution was distilled to obtain 15.9 g of a fraction having a boiling point of 107-108 ° C./0.4 kPa.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定した。
質量スペクトル
ｍ／ｚ １８８，１１９，１０５，７５，５８
1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）
図３にチャートで示す。
ＩＲスペクトル
図４にチャートで示す。
以上の結果より、得られた化合物は１−ジメチルアミノ−４−チオ−ヘプチルメチルジメトキシシラン５１質量％と１−ジメチルアミノ−２−メチル−３−チオ−ヘキシルメチルジメトキシシラン４９質量％であることが確認された。
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 188, 119, 105, 75, 58
1 H-NMR spectrum (deuterated chloroform solvent)
FIG. 3 shows a chart.
IR spectrum FIG. 4 is a chart.
From the above results, the obtained compound was 51% by mass of 1-dimethylamino-4-thio-heptylmethyldimethoxysilane and 49% by mass of 1-dimethylamino-2-methyl-3-thio-hexylmethyldimethoxysilane. Was confirmed.
［実施例３］
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−メルカプトプロピルトリメトキシシラン５６．０ｇ（０．２８５モル）を仕込み、８０℃に加温した。内温が安定した後、ジメチルアミノエチルアリルエーテル３６．６ｇ（０．２８３モル）と、２，２’−アゾビス（２−メチルブチロニトリル）０．５５６ｇ（０．００２８９モル）の混合物を１時間で滴下し、９５℃で２時間撹拌した。反応液を蒸留し、沸点１３５−１４０℃／０．４ｋＰａの留分を７０．１ｇ得た。
[Example 3]
In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 56.0 g (0.285 mol) of 3-mercaptopropyltrimethoxysilane was charged and heated to 80 ° C. After the internal temperature was stabilized, a mixture of 36.6 g (0.283 mol) of dimethylaminoethyl allyl ether and 0.556 g (0.00289 mol) of 2,2′-azobis (2-methylbutyronitrile) was added. The solution was added dropwise over time and stirred at 95 ° C. for 2 hours. The reaction solution was distilled to obtain 70.1 g of a fraction having a boiling point of 135 to 140 ° C./0.4 kPa.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定した。
質量スペクトル
ｍ／ｚ ２８０，１６２，１２１，９１，５８
1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）
図５にチャートで示す。
ＩＲスペクトル
図６にチャートで示す。
以上の結果より、得られた化合物は１−ジメチルアミノ−３−オキソ−７−チオ−デシルトリメトキシシラン８５質量％と１−ジメチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルトリメトキシシラン１５質量％であることが確認された。
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m /
1 H-NMR spectrum (deuterated chloroform solvent)
FIG. 5 shows a chart.
IR spectrum FIG. 6 is a chart.
From the above results, the obtained compound was 85% by mass of 1-dimethylamino-3-oxo-7-thio-decyltrimethoxysilane and 1-dimethylamino-5-methyl-3-oxo-6-thio-nonyltri. It was confirmed that it was 15% by mass of methoxysilane.
［実施例４］
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、３−メルカプトプロピルメチルジメトキシシラン５１．８ｇ（０．２８７モル）を仕込み、８０℃に加温した。内温が安定した後、ジメチルアミノエチルアリルエーテル３７．２ｇ（０．２８８モル）と、２，２’−アゾビス（２−メチルブチロニトリル）０．５８１４ｇ（０．００３０２２モル）の混合物を１時間で滴下し、９５℃で２時間撹拌した。反応液を蒸留し、沸点１５４−１５６℃／０．４ｋＰａの留分を６６．３ｇ得た。
[Example 4]
A flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 51.8 g (0.287 mol) of 3-mercaptopropylmethyldimethoxysilane and heated to 80 ° C. After the internal temperature was stabilized, a mixture of 37.2 g (0.288 mol) of dimethylaminoethyl allyl ether and 0.5814 g (0.003022 mol) of 2,2′-azobis (2-methylbutyronitrile) The solution was added dropwise over time and stirred at 95 ° C. for 2 hours. The reaction solution was distilled to obtain 66.3 g of a fraction having a boiling point of 154-156 ° C./0.4 kPa.
得られた留分の質量スペクトル、1Ｈ−ＮＭＲスペクトル、ＩＲスペクトルを測定した。
質量スペクトル
ｍ／ｚ ２６４，１６２，１３１，１０５，７５，５８
1Ｈ−ＮＭＲスペクトル（重クロロホルム溶媒）
図７にチャートで示す。
ＩＲスペクトル
図８にチャートで示す。
以上の結果より、得られた化合物は１−ジメチルアミノ−３−オキソ−７−チオ−デシルメチルジメトキシシラン（１０−ジメチルアミノ−４−チオ−８−オキソ−デシルメチルジメトキシシラン）８８質量％と１−ジメチルアミノ−５−メチル−３−オキソ−６−チオ−ノニルメチルジメトキシシラン１２質量％であることが確認された。
A mass spectrum, 1 H-NMR spectrum, and IR spectrum of the obtained fraction were measured.
Mass spectrum m / z 264, 162, 131, 105, 75, 58
1 H-NMR spectrum (deuterated chloroform solvent)
FIG. 7 shows a chart.
IR spectrum FIG. 8 is a chart.
From the above results, the obtained compound was 88% by mass of 1-dimethylamino-3-oxo-7-thio-decylmethyldimethoxysilane (10-dimethylamino-4-thio-8-oxo-decylmethyldimethoxysilane). It was confirmed to be 12% by mass of 1-dimethylamino-5-methyl-3-oxo-6-thio-nonylmethyldimethoxysilane.
Claims (4)
で示される含硫黄アミノオルガノキシシラン化合物。 The following general formula (1)
A sulfur-containing aminoorganoxysilane compound represented by:
［−ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2−］又は
［−ＣＨ2ＣＨ2ＯＣＨ2ＣＨ（ＣＨ3）−］
で示される基である請求項１記載の含硫黄アミノオルガノキシシラン化合物。 R 3 is
[—CH 2 CH 2 OCH 2 CH 2 CH 2 —] or [—CH 2 CH 2 OCH 2 CH (CH 3 ) —]
The sulfur-containing aminoorganoxysilane compound according to claim 1, which is a group represented by the formula:
で示されるアミン化合物と、下記一般式（３）
で示されるメルカプト基含有オルガノキシシラン化合物を反応させることを特徴とする下記一般式（１’）
で示される含硫黄アミノオルガノキシシラン化合物の製造方法。 The following general formula (2)
An amine compound represented by the following general formula (3)
Wherein the mercapto group-containing organoxysilane compound represented by the general formula (1 ′)
A process for producing a sulfur-containing aminoorganoxysilane compound represented by:
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015016239A JP6319122B2 (en) | 2015-01-30 | 2015-01-30 | Sulfur-containing aminoorganoxysilane compound and method for producing the same |
| CN201510908790.8A CN105837613A (en) | 2015-01-30 | 2015-12-10 | Sulfur-containing amino organoxysilane compound and production method thereof |
| KR1020160009944A KR102503405B1 (en) | 2015-01-30 | 2016-01-27 | Sulfur-containing amino organoxysilane compound and method for preparing the same |
| TW105102863A TWI680980B (en) | 2015-01-30 | 2016-01-29 | Sulfur-containing amine-based organic oxysilane compound and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015016239A JP6319122B2 (en) | 2015-01-30 | 2015-01-30 | Sulfur-containing aminoorganoxysilane compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016141623A JP2016141623A (en) | 2016-08-08 |
| JP6319122B2 true JP6319122B2 (en) | 2018-05-09 |
Family
ID=56569738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015016239A Active JP6319122B2 (en) | 2015-01-30 | 2015-01-30 | Sulfur-containing aminoorganoxysilane compound and method for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6319122B2 (en) |
| KR (1) | KR102503405B1 (en) |
| CN (1) | CN105837613A (en) |
| TW (1) | TWI680980B (en) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660454A (en) * | 1969-08-19 | 1972-05-02 | Dow Corning | Process of making amino substituted organosilicon compounds and the compounds made thereby |
| US3700715A (en) * | 1971-08-23 | 1972-10-24 | Gen Electric | Polyaminoalkylthioalkyl silanes |
| JPS57108159A (en) * | 1980-12-24 | 1982-07-06 | Toshiba Silicone Co Ltd | Self-bondable room temperature-curing polysiloxane composition |
| US4421893A (en) * | 1982-01-18 | 1983-12-20 | Dow Corning Corporation | Tintable, dyeable, curable coatings and coated articles |
| JPH0940680A (en) * | 1995-07-26 | 1997-02-10 | Pola Chem Ind Inc | New silicone having leaving group |
| AU729287B2 (en) * | 1996-11-22 | 2001-02-01 | Mona Industries, Inc. | Silicone monomers and oligomers having a carboxyl functional group thereon |
| FR2922760B1 (en) | 2007-10-31 | 2009-11-20 | Oreal | ENHANCING AND / OR COLORING HUMAN KERATINIC FIBERS USING A COMPOSITION COMPRISING A PARTICULAR AMINOSILICIE COMPOUND AND COMPOSITION AND DEVICE |
| WO2011102470A1 (en) * | 2010-02-19 | 2011-08-25 | 日産化学工業株式会社 | Composition for formation of resist underlayer film containing silicon having nitrogen-containing ring |
| US9175026B2 (en) * | 2011-03-23 | 2015-11-03 | The Regents Of The University Of California | Synthesis of thioether containing trialkoxysilanes |
| JP6141077B2 (en) * | 2013-04-08 | 2017-06-07 | 東洋ゴム工業株式会社 | Physical property improving agent, method for producing the same, and rubber composition |
| JP6011475B2 (en) * | 2013-06-25 | 2016-10-19 | 信越化学工業株式会社 | Sulfur-containing organoxysilane compound having bissilylamino group and process for producing the same |
-
2015
- 2015-01-30 JP JP2015016239A patent/JP6319122B2/en active Active
- 2015-12-10 CN CN201510908790.8A patent/CN105837613A/en active Pending
-
2016
- 2016-01-27 KR KR1020160009944A patent/KR102503405B1/en active IP Right Grant
- 2016-01-29 TW TW105102863A patent/TWI680980B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| KR102503405B1 (en) | 2023-02-24 |
| JP2016141623A (en) | 2016-08-08 |
| TWI680980B (en) | 2020-01-01 |
| TW201700483A (en) | 2017-01-01 |
| KR20160094300A (en) | 2016-08-09 |
| CN105837613A (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2011121906A (en) | Silane compound containing two or more amino groups and method for producing the same | |
| JP6365445B2 (en) | Aminoalkylalkoxydisiloxane compound and method for producing the same | |
| JP2011246392A (en) | Cyclic silazane compound having carboxylate group and method for producing the same | |
| JP5630458B2 (en) | Organoxysilane compound having secondary amino group protected by silyl group and method for producing the same | |
| JP6939706B2 (en) | Carbonate group-containing silane compound and its production method | |
| JP4453822B2 (en) | Silane compound having two or more protected functional groups and method for producing the same | |
| JP6319122B2 (en) | Sulfur-containing aminoorganoxysilane compound and method for producing the same | |
| JP2011251936A (en) | Ureido silane compound | |
| JP2014058480A (en) | Organoxysilane compound having carbonyl group and amino group, and method for producing the compound | |
| KR102458128B1 (en) | Nitrogen-containing organoxysilane compound and method for producing the same | |
| JP6011475B2 (en) | Sulfur-containing organoxysilane compound having bissilylamino group and process for producing the same | |
| EP3015471B1 (en) | Novel bisalkoxysilane compound and its production method | |
| JP2015098459A (en) | Nitrogen-containing organoxy silane compound-containing composition, and preparation method thereof | |
| JP5754272B2 (en) | Carboxylic acid silyl ester compound having bulky substituent and method for producing the same | |
| JP2016040233A (en) | Bicyclo amino organoxysilane compound and method for producing the same | |
| KR20190119525A (en) | Glycoluril ring-containing organosilicon compound and making method | |
| JP6720913B2 (en) | Unsaturated bond-containing bissilyl compound and method for producing the same | |
| JP4662042B2 (en) | Bisorganoxysilane compound having amino group protected by silyl group and method for producing the same | |
| JP2011246391A (en) | Silane compound having carboxylate ester group and amino group protected with silyl group, and method for producing the same | |
| EP3660025A1 (en) | Nitrogen-containing cyclic organoxysilane compound and method for producing the same | |
| JP5942868B2 (en) | Method for producing sulfide group-containing organosilicon compound | |
| JP5644515B2 (en) | Unsaturated bond-containing silyl group-protected amino acid compound and method for producing the same | |
| JP6207287B2 (en) | Silyl group-containing norbornene compound and method for producing the same | |
| FR2833958A1 (en) | New organosilicon compounds having hydroxy or hydrolyzable group and rubber-reactive aminopolysulfide group, useful as coupling agents in elastomer compositions containing white reinforcing fillers | |
| KR20140141483A (en) | Silyl-protected nitrogen-containing cyclic compounds and making method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170125 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20171012 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20171017 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171214 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20180116 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180131 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20180208 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180306 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180319 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6319122 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |