JP6583050B2 - Method for producing organopolysiloxane - Google Patents
Method for producing organopolysiloxane Download PDFInfo
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- JP6583050B2 JP6583050B2 JP2016034535A JP2016034535A JP6583050B2 JP 6583050 B2 JP6583050 B2 JP 6583050B2 JP 2016034535 A JP2016034535 A JP 2016034535A JP 2016034535 A JP2016034535 A JP 2016034535A JP 6583050 B2 JP6583050 B2 JP 6583050B2
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- 229920001296 polysiloxane Polymers 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 125000000962 organic group Chemical group 0.000 claims description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 125000003277 amino group Chemical group 0.000 claims description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 229940014800 succinic anhydride Drugs 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011968 lewis acid catalyst Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 150000003752 zinc compounds Chemical class 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000002736 metal compounds Chemical group 0.000 claims description 3
- ZJHUBLNWMCWUOV-UHFFFAOYSA-N oxocane-2,8-dione Chemical compound O=C1CCCCCC(=O)O1 ZJHUBLNWMCWUOV-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 6
- 150000002430 hydrocarbons Chemical group 0.000 description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- -1 3,3,3-trifluoropropyl group Chemical group 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 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 9
- 150000003949 imides Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 125000001931 aliphatic group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 125000000101 thioether group Chemical group 0.000 description 3
- 229940102001 zinc bromide Drugs 0.000 description 3
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000005749 Copper compound Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-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
- 239000002841 Lewis acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010702 perfluoropolyether Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000570 polyether Chemical group 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003326 scandium compounds Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
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- Silicon Polymers (AREA)
Description
本発明は、新規なオルガノポリシロキサンに関するものであり、特に優れた耐熱性を有するオルガノポリシロキサン及びその製造方法に関するものである。 The present invention relates to a novel organopolysiloxane, and particularly to an organopolysiloxane having excellent heat resistance and a method for producing the same.
オルガノポリシロキサンは、主鎖がシロキサン結合で側鎖に有機基を有する、有機−無機複合高分子である。耐熱性、耐候性、摺動性、耐薬品性、電気絶縁性などの優れた特徴をもつ材料であり、オイル状、ゴム状、レジン状などの形態がある。オルガノポリシロキサンのオイルはシリコーンオイルとも呼ばれ、他の有機系のオイルよりも耐熱性や耐候性が高く、またさらさらとした独特の感触を有するという特徴がある。耐熱性に優れることから、工業用の熱媒などに使用される。 Organopolysiloxane is an organic-inorganic composite polymer having a main chain having a siloxane bond and an organic group in a side chain. It is a material with excellent characteristics such as heat resistance, weather resistance, slidability, chemical resistance and electrical insulation, and there are forms such as oil, rubber and resin. Organopolysiloxane oils are also called silicone oils, and are characterized by higher heat resistance and weather resistance than other organic oils, and also have a smooth and unique feel. Because of its excellent heat resistance, it is used as an industrial heating medium.
シリコーンオイルの有機基には様々なものが使用される。非反応性の有機基としては、アルキル基、フェニル基、ポリエーテル基、フルオロアルキル基、パーフルオロポリエーテル基などがあり、反応性の有機基としては、ビニル基、エポキシ基、アミノ基、ヒドロキシル基、メルカプト基、カルボキシル基などがある。用途によってそれぞれのシリコーンオイルを使い分ける。 Various organic groups of silicone oil are used. Non-reactive organic groups include alkyl groups, phenyl groups, polyether groups, fluoroalkyl groups, perfluoropolyether groups, and reactive organic groups include vinyl groups, epoxy groups, amino groups, hydroxyl groups. Groups, mercapto groups, carboxyl groups and the like. Use different silicone oils depending on the application.
一方、イミドは、一級アミンとカルボン酸の無水物を反応させて得られ、Ｒa−ＣＯ−ＮＲb−ＣＯ−Ｒc（Ｒa，Ｒb，Ｒcは有機基を示す）のような一般式で表される窒素と２つのＣ＝Ｏ結合を有する化合物の総称である。この構造は化学的に重要であり、医薬や農薬の中間体、塗料、有機樹脂など産業のあらゆる分野に利用されるものである。一般によく知られているものとして、イミド構造が連続している高分子であるポリイミド樹脂があり、耐熱性、電気絶縁性、耐薬品性、機械的強度などが優れており、スーパーエンジニアリングプラスチックの１つとして知られている。特に耐熱性については、あらゆる樹脂の中でも最高水準の耐熱性を示す材料である。 On the other hand, an imide is obtained by reacting a primary amine with an anhydride of carboxylic acid, such as R a —CO—NR b —CO—R c (where R a , R b , R c represents an organic group). It is a general term for compounds represented by the general formula and having two C═O bonds. This structure is chemically important and is used in all industrial fields such as pharmaceutical and agrochemical intermediates, paints, and organic resins. As a well-known one, there is a polyimide resin which is a polymer having a continuous imide structure, which has excellent heat resistance, electrical insulation, chemical resistance, mechanical strength, etc. Known as one. In particular, with respect to heat resistance, it is a material that exhibits the highest level of heat resistance among all resins.
イミドとオルガノポリシロキサンを組み合わせることで、それぞれの特長を併せ持つ優れた材料を作製することが可能になる。例えば、特許文献１〜４（特許第４２１８２８２号公報、特開２００４−２６３０５８号公報、特許第５３１４８５６号公報、特許第４２０４４３５号公報）では、ジアミノポリシロキサンを原料としたシロキサン−ポリイミド共重合体について記述されており、様々な特長を有することで工業的に重要な材料であることが示されている。しかし、イミドの繰り返し構造が存在することで生成物は固体となり、用途によってはハンドリングが困難であるという欠点がある。 By combining imide and organopolysiloxane, it becomes possible to produce excellent materials having both characteristics. For example, in Patent Documents 1 to 4 (Japanese Patent No. 4218282, Japanese Patent Application Laid-Open No. 2004-263058, Japanese Patent No. 5314856, and Japanese Patent No. 4204435), a siloxane-polyimide copolymer using diaminopolysiloxane as a raw material is disclosed. It has been described and shown to be an industrially important material with various features. However, due to the presence of the imide repeating structure, the product becomes solid, and there is a drawback that handling is difficult depending on the application.
イミドとオルガノポリシロキサンの複合材料で、溶剤希釈をしないで液状であるものはほとんどないが、これは高分子の主鎖に剛直なイミドが存在するためである。主鎖をオルガノポリシロキサンだけにして、側鎖にイミド構造を有する有機基を変性したイミド変性オルガノポリシロキサンを合成することで、２つの材料の特長を兼ね備える液状材料ができるものと考えられるが、現在までにそのような材料はない。 Almost no composite material of imide and organopolysiloxane is in liquid form without solvent dilution, because there is a rigid imide in the main chain of the polymer. By synthesizing an imide-modified organopolysiloxane in which the main chain is only an organopolysiloxane and the side chain is modified with an organic group having an imide structure, it is considered that a liquid material having the characteristics of the two materials can be produced. To date there is no such material.
本発明は、上記事情に鑑みなされたもので、優れた耐熱性を有する液状の新規なイミド変性オルガノポリシロキサン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 an object thereof is to provide a novel liquid imide-modified organopolysiloxane having excellent heat resistance.
本発明者は、上記目的を達成するため鋭意検討を重ねた結果、後述する式（４）で表されるアミノ基含有有機基を有するオルガノポリシロキサンと式（５）又は（６）で表される有機化合物とを反応させた後、さらにルイス酸触媒存在下でシリル化剤と反応させることにより、式（１）で表される新規なイミド変性オルガノポリシロキサンが得られ、該オルガノポリシロキサンは液状であり、優れた耐熱性を有することを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventor is represented by an organopolysiloxane having an amino group-containing organic group represented by the following formula (4) and a formula (5) or (6). Is reacted with a silylating agent in the presence of a Lewis acid catalyst to obtain a novel imide-modified organopolysiloxane represented by the formula (1). It has been found that it is liquid and has excellent heat resistance, and has led to the present invention.
従って、本発明は、下記のオルガノポリシロキサンの製造方法を提供する。
［１］
（Ａ）下記平均組成式（４）で表され、１分子中に炭素数１〜１０のアミノ基含有有機基を少なくとも１個有するオルガノポリシロキサン：１００質量部、
（Ｂ）下記一般式（５）又は（６）で表される有機化合物：（Ａ）成分中のアミノ基に対しモル比で１〜３倍となる量、
（Ｃ）ルイス酸触媒：（Ａ）成分のアミノ基に対しモル比で０．１〜２倍となる量、
（Ｄ）シリル化剤：（Ａ）成分のアミノ基に対しモル比で１〜３倍となる量、
（Ｅ）有機溶剤：（Ａ）成分を１００質量部としたときに０〜５，０００質量部
を用いて、
（Ｉ）上記（Ａ）成分と（Ｂ）成分とを、必要により（Ｅ）成分の存在下で反応させ、下記平均組成式（７）で表されるオルガノポリシロキサン（Ｆ）を形成させる工程と、
（ＩＩ）得られた（Ｆ）成分と（Ｃ）成分及び（Ｄ）成分とを混合して、（Ｆ）成分中のカルボキシル基をシリル化し、加熱して（Ｆ）成分中のアミド基とシリル化したカルボキシル基とを縮合反応させる工程、及び
（ＩＩＩ）上記縮合反応させる工程後、酸性物質を添加し、生成した塩をろ別する工程
を含む、
下記平均組成式（１）
で表され、１分子中に下記一般式（２）又は（３）
で表される構造の有機基を少なくとも１個含むオルガノポリシロキサンを製造する製造方法（但し、上記一般式（６）中の有機化合物Ｎ、一般式（９）中の有機基ｙ、及び上記一般式（３）中の有機基ｎがいずれも０である場合を除く。）。
［２］
（Ａ）成分のアミン当量が２００〜５，０００ｇ／ｍｏｌである［１］に記載のオルガノポリシロキサンの製造方法。
［３］
（Ｂ）成分が、無水コハク酸、無水マレイン酸、無水グルタル酸、無水アジピン酸、無水ピメリン酸又は無水フタル酸である［１］又は［２］に記載のオルガノポリシロキサンの製造方法。
［４］
（Ｃ）成分が金属化合物である［１］〜［３］のいずれか１項に記載のオルガノポリシロキサンの製造方法。
［５］
（Ｃ）成分が亜鉛化合物である［４］に記載のオルガノポリシロキサンの製造方法。
［６］
（Ｄ）成分がジシラザン化合物である［１］〜［５］のいずれかに記載のオルガノポリシロキサンの製造方法。
Therefore, this invention provides the manufacturing method of the following organopolysiloxane.
[1]
(A) Organopolysiloxane represented by the following average composition formula (4) and having at least one amino group-containing organic group having 1 to 10 carbon atoms in one molecule: 100 parts by mass
(B) an organic compound represented by the following general formula (5) or (6): an amount that is 1 to 3 times in molar ratio to the amino group in the component (A);
(C) Lewis acid catalyst: an amount that is 0.1 to 2 times in molar ratio to the amino group of component (A),
(D) Silylating agent: an amount that is 1 to 3 times in molar ratio to the amino group of component (A),
(E) Organic solvent: When the component (A) is 100 parts by mass, 0 to 5,000 parts by mass are used,
(I) The process of making the said (A) component and (B) component react in presence of (E) component as needed, and forming the organopolysiloxane (F) represented by the following average compositional formula (7) When,
(II) The obtained component (F) is mixed with the components (C) and (D) to silylate the carboxyl group in the component (F) and heated to form the amide group in the component (F). A step of subjecting a silylated carboxyl group to a condensation reaction, and ( III ) after the step of causing the condensation reaction, adding an acidic substance and filtering out the generated salt,
The following average composition formula (1)
Represented by the following general formula (2) or (3)
A production method for producing an organopolysiloxane containing at least one organic group having a structure represented by the formula (However, the organic compound N in the general formula (6), the organic group y in the general formula (9), and the general Except when all the organic groups n in the formula (3) are 0) .
[2]
(A) The manufacturing method of the organopolysiloxane as described in [1] whose amine equivalent of a component is 200-5,000 g / mol.
[3]
(B) The method for producing an organopolysiloxane according to [1] or [2], wherein the component is succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride or phthalic anhydride.
[4]
(C) The method for producing an organopolysiloxane according to any one of [1] to [3], wherein the component is a metal compound.
[5]
(C) The manufacturing method of organopolysiloxane as described in [4] whose component is a zinc compound.
[6]
(D) The manufacturing method of organopolysiloxane in any one of [1]-[5] whose component is a disilazane compound.
本発明の新規なオルガノポリシロキサンは、イミド構造を有する液体であり、高耐熱の材料として使用できる。 The novel organopolysiloxane of the present invention is a liquid having an imide structure and can be used as a material having high heat resistance.
以下、本発明についての詳細を記す。 Details of the present invention will be described below.
［オルガノポリシロキサン］
本発明のオルガノポリシロキサンは、イミド構造が含まれる有機基が変性されているものであり、下記平均組成式（１）で示される。
The organopolysiloxane of the present invention has a modified organic group containing an imide structure, and is represented by the following average composition formula (1).
上記式（１）中、Ｒ1は同一又は異種の炭素数１〜１０の非置換もしくは置換の１価炭化水素基又は上記一般式（２）もしくは（３）で表される構造の有機基であり、Ｒ1のうち少なくとも１個は上記一般式（２）又は（３）で表される構造の有機基を含む。１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基などが挙げられ、さらに、これらの基の炭素原子に結合した水素原子の一部又は全部がハロゲン原子又はその他の基で置換されていてもよく、置換基としては、トリフルオロメチル基、３，３，３−トリフルオロプロピル基等が例示される。中でも、飽和の脂肪族基又は芳香族基が好ましく、メチル基、フェニル基が好ましい。 In the above formula (1), R 1 is the same or different, unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or an organic group having a structure represented by the above general formula (2) or (3). And at least one of R 1 includes an organic group having a structure represented by the general formula (2) or (3). Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and the like. A part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom or other group, and examples of the substituent include a trifluoromethyl group, a 3,3,3-trifluoropropyl group, and the like. Illustrated. Among them, a saturated aliphatic group or an aromatic group is preferable, and a methyl group or a phenyl group is preferable.
本発明においては、Ｒ1のうち少なくとも１個、好ましくは２〜２００個、より好ましくは２〜１５０個は一般式（２）又は（３）で表される構造の有機基を含むものである。 In the present invention, at least one of R 1 , preferably 2 to 200, more preferably 2 to 150 contains an organic group having a structure represented by the general formula (2) or (3).
上記式（２）、（３）中、Ｒ2〜Ｒ7は互いに同一又は異種の水素原子又は炭素数１〜１０の非置換もしくは置換の１価炭化水素基である。１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基などが挙げられ、さらに、これらの基の炭素原子に結合した水素原子の一部又は全部がハロゲン原子又はその他の基で置換されていてもよく、置換基としては、トリフルオロメチル基、３，３，３−トリフルオロプロピル基等が例示され、水素原子、メチル基が好ましい。また、Ｒ2又はＲ3とＲ4又はＲ5、Ｒ6とＲ7が結合して環を形成してもよく、該環としては、シクロプロパン環、シクロブタン環、シクロペンタン環、シクロヘキサン環、ベンゼン環等が例示され、ベンゼン環が好ましい。 In the above formulas (2) and (3), R 2 to R 7 are the same or different hydrogen atoms or unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and the like. A part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom or other group, and examples of the substituent include a trifluoromethyl group, a 3,3,3-trifluoropropyl group, and the like. Examples thereof include a hydrogen atom and a methyl group. R 2 or R 3 and R 4 or R 5 , R 6 and R 7 may combine to form a ring, such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, A benzene ring etc. are illustrated and a benzene ring is preferable.
ｍ，ｎは０〜３の整数であり、好ましくは０〜２の整数であり、より好ましくは０又は１である。 m and n are integers of 0 to 3, preferably integers of 0 to 2, and more preferably 0 or 1.
Ｘ，Ｙはそれぞれ炭素数１〜１０のヘテロ原子を介在してもよい非置換もしくは置換の２価炭化水素基であり、ＣＨ2、Ｃ2Ｈ4、Ｃ3Ｈ6、Ｃ4Ｈ8、Ｃ5Ｈ10、Ｃ6Ｈ12などのアルキレン基が挙げられ、エーテル基やチオエーテル基などを介在していてもよい。また、フェニレン基、シクロヘキシレン基等の環状構造を形成してもよく、炭素原子に結合した水素原子の一部又は全部がハロゲン原子又はその他の基で置換されていてもよい。 X and Y are each an unsubstituted or substituted divalent hydrocarbon group that may intervene with a heteroatom having 1 to 10 carbon atoms, CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , Examples include alkylene groups such as C 5 H 10 and C 6 H 12 , and ether groups or thioether groups may be interposed. Moreover, you may form cyclic structures, such as a phenylene group and a cyclohexylene group, and one part or all part of the hydrogen atom couple | bonded with the carbon atom may be substituted by the halogen atom or other groups.
一般式（２）、（３）の具体的な構造を以下に示すが、これらに限定されるものではない。
上記式（１）中、ａは２以上、好ましくは２〜１２の整数、ｂは０以上、好ましくは１〜９９８、より好ましくは５〜５００の整数、ｃは０以上、好ましくは０〜１０の整数、ｄは０以上、好ましくは０〜５の整数で、２≦ａ＋ｂ＋ｃ＋ｄ≦１，０００であり、２≦ａ＋ｂ＋ｃ＋ｄ≦８００が好ましい。ａ＋ｂ＋ｃ＋ｄが１，０００より大きいと、粘度が高くなり、作業性が悪くなる場合がある。 In the above formula (1), a is 2 or more, preferably an integer of 2 to 12, b is 0 or more, preferably 1 to 998, more preferably an integer of 5 to 500, and c is 0 or more, preferably 0 to 10 And d is 0 or more, preferably an integer of 0 to 5, 2 ≦ a + b + c + d ≦ 1,000, and 2 ≦ a + b + c + d ≦ 800 is preferable. If a + b + c + d is greater than 1,000, the viscosity may increase and workability may deteriorate.
式（１）で表されるオルガノポリシロキサンの具体的な構造としては、下記一般式で表されるものが挙げられるが、これらに限定されない。なお、下記式中のＭｅ，Ｐｈ，Ｉはそれぞれメチル基、フェニル基を示し、ＩはＮ−スクシンイミドプロピル基を代表して示すが、式（２）、（３）で表される構造の有機基であればいずれのものでもよい。
［オルガノポリシロキサンの製造方法］
本発明のオルガノポリシロキサンは、（Ａ）下記平均組成式（４）で表され、１分子中にアミノ基含有有機基を少なくとも１個有するオルガノポリシロキサンと、（Ｂ）下記一般式（５）又は（６）で表される有機化合物とを、必要により（Ｅ）有機溶剤の存在下で付加反応させ、さらに、（Ｃ）ルイス酸触媒、（Ｄ）シリル化剤を混合して縮合反応（イミド化反応）させることにより得ることができる。
以下、本発明のオルガノポリシロキサンの原料となる成分及び製造方法について詳細を記す。
[Method for producing organopolysiloxane]
The organopolysiloxane of the present invention is represented by (A) the following average composition formula (4), an organopolysiloxane having at least one amino group-containing organic group in one molecule, and (B) the following general formula (5). Alternatively, the organic compound represented by (6) is subjected to an addition reaction in the presence of (E) an organic solvent, if necessary, and (C) a Lewis acid catalyst and (D) a silylating agent are mixed to perform a condensation reaction ( (Imidation reaction).
Hereinafter, the component used as the raw material of the organopolysiloxane of this invention and a manufacturing method are described in detail.
［（Ａ）成分］
（Ａ）成分は、下記平均組成式（４）で表され、１分子中にアミノ基含有有機基を少なくとも１個有するオルガノポリシロキサンである。
The component (A) is an organopolysiloxane represented by the following average composition formula (4) and having at least one amino group-containing organic group in one molecule.
上記式（４）中、Ｒ8は同一又は異種の炭素数１〜１０の非置換もしくは置換の１価炭化水素基又は炭素数１〜１０のアミノ基含有有機基であり、Ｒ8のうち少なくとも１個、好ましくは２〜２００個はアミノ基含有有機基を含む。１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基などが挙げられ、さらに、これらの基の炭素原子に結合した水素原子の一部又は全部がハロゲン原子又はその他の基で置換されていてもよく、置換基としては、トリフルオロメチル基、３，３，３−トリフルオロプロピル基等が例示される。中でも、飽和の脂肪族基又は芳香族基が好ましく、メチル基、フェニル基が好ましい。 In said formula (4), R < 8 > is the same or different C1-C10 unsubstituted or substituted monovalent | monohydric hydrocarbon group or a C1-C10 amino group containing organic group, At least among R < 8 >. One, preferably 2 to 200, contains an amino group-containing organic group. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and the like. A part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom or other group, and examples of the substituent include a trifluoromethyl group, a 3,3,3-trifluoropropyl group, and the like. Illustrated. Among them, a saturated aliphatic group or an aromatic group is preferable, and a methyl group or a phenyl group is preferable.
アミノ基含有有機基中のアミノ基は、一級アミンであることが好ましい。アミノ基含有有機基としては、例えば、エーテル基やチオエーテル基などを介在していてもよい炭素数１〜１０のアミノアルキル基が好ましく、特にアミノプロピル基が好ましい。アミノ基含有有機基の具体的な構造を以下に示すが、これらに限定されるものではない。
（Ａ）成分のアミン当量は、２００〜５，０００ｇ／ｍｏｌが好ましく、３００〜４，８００ｇ／ｍｏｌがより好ましく、４００〜４，５００ｇ／ｍｏｌがさらに好ましい。２００ｇ／ｍｏｌよりも少ないと、生成物の分子量が小さくなることにより耐熱性が低くなる場合があり、５，０００ｇ／ｍｏｌよりも多いと、導入する官能基量が少なくなることにより耐熱性が低くなる場合がある。 The amine equivalent of the component (A) is preferably 200 to 5,000 g / mol, more preferably 300 to 4,800 g / mol, and still more preferably 400 to 4,500 g / mol. If it is less than 200 g / mol, the heat resistance may be lowered due to the molecular weight of the product being reduced, and if it is more than 5,000 g / mol, the heat resistance is lowered due to the reduced amount of functional groups to be introduced. There is a case.
（Ａ）成分の具体的な構造としては、下記一般式で表されるものが挙げられるが、これらに限定されない。なお、下記式中のＭｅ，Ｐｈはそれぞれメチル基、フェニル基であり、Ａはアミノプロピル基を代表して示すが、炭素数１〜１０のアミノ基含有有機基であればいずれのものでもよい。
［（Ｂ）成分］
（Ｂ）成分は、下記一般式（５）又は（６）で表される有機化合物である。
The component (B) is an organic compound represented by the following general formula (5) or (6).
上記式（５）、（６）中、Ｒ9〜Ｒ14は互いに同一又は異種の水素原子又は炭素数１〜１０の非置換もしくは置換の１価炭化水素基である。１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基などが挙げられ、さらに、これらの基の炭素原子に結合した水素原子の一部又は全部がハロゲン原子又はその他の基で置換されていてもよく、置換基としては、トリフルオロメチル基、３，３，３−トリフルオロプロピル基等が例示され、水素原子、メチル基が好ましい。
また、Ｒ9又はＲ10とＲ11又はＲ12、Ｒ13とＲ14が結合して環を形成してもよく、該環としては、シクロプロパン環、シクロブタン環、シクロペンタン環、シクロヘキサン環、ベンゼン環等が例示され、ベンゼン環が好ましい。
Ｍ，Ｎは０〜３の整数であり、好ましくは０〜２の整数であり、より好ましくは０又は１である。
In the above formulas (5) and (6), R 9 to R 14 are the same or different hydrogen atoms or unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and the like. A part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom or other group, and examples of the substituent include a trifluoromethyl group, a 3,3,3-trifluoropropyl group, and the like. Examples thereof include a hydrogen atom and a methyl group.
R 9 or R 10 and R 11 or R 12 , R 13 and R 14 may be combined to form a ring, and examples of the ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, A benzene ring etc. are illustrated and a benzene ring is preferable.
M and N are integers of 0 to 3, preferably integers of 0 to 2, and more preferably 0 or 1.
（Ｂ）成分の具体的な構造を以下に示すが、これらに限定されるものではない。
（Ｂ）成分としては、無水コハク酸、無水マレイン酸、無水グルタル酸、無水アジピン酸、無水ピメリン酸、無水フタル酸であることが好ましく、無水コハク酸、無水マレイン酸が特に好ましい。 As the component (B), succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, and phthalic anhydride are preferable, and succinic anhydride and maleic anhydride are particularly preferable.
（Ｂ）成分は、（Ａ）成分のアミノ基に対しモル比で１〜３倍となる量を使用するが、好ましくは１〜２．５倍、より好ましくは１〜２倍である。１倍より少ないと未反応のアミノ基が残存するため耐熱性が悪くなる場合があり、３倍より多くなると、精製時に未反応の（Ｂ）成分を除去するために効率が悪くなる場合がある。 The component (B) is used in an amount of 1 to 3 times in molar ratio with respect to the amino group of the component (A), preferably 1 to 2.5 times, more preferably 1 to 2 times. If it is less than 1 time, unreacted amino groups remain and heat resistance may be deteriorated. If it is more than 3 times, efficiency may be deteriorated because unreacted component (B) is removed during purification. .
［（Ｃ）成分］
（Ｃ）成分はルイス酸触媒であり、ルイス酸としては様々のものが挙げられ、ホウ素化合物、アルミニウム化合物、スカンジウム化合物、チタン化合物、バナジウム化合物、鉄化合物、コバルト化合物、ニッケル化合物、銅化合物、亜鉛化合物、ランタン化合物、セリウム化合物などがあり、金属化合物が好ましく、特に亜鉛化合物が好ましい。
[Component (C)]
Component (C) is a Lewis acid catalyst, and various examples of Lewis acids include boron compounds, aluminum compounds, scandium compounds, titanium compounds, vanadium compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds, and zinc. There are compounds, lanthanum compounds, cerium compounds and the like, metal compounds are preferable, and zinc compounds are particularly preferable.
亜鉛化合物としては、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛などのハロゲン化亜鉛化合物や、硝酸亜鉛、硫酸亜鉛、炭酸亜鉛、トリフルオロメタンスルホン酸亜鉛などの亜鉛塩といった無機亜鉛化合物が好適に用いられ、塩化亜鉛、臭化亜鉛が好ましい。 As the zinc compound, inorganic zinc compounds such as zinc halide compounds such as zinc chloride, zinc bromide and zinc iodide, and zinc salts such as zinc nitrate, zinc sulfate, zinc carbonate and zinc trifluoromethanesulfonate are preferably used. Zinc chloride and zinc bromide are preferred.
（Ｃ）成分は、（Ａ）成分のアミノ基に対しモル比で０．１〜２倍となる量を使用し、好ましくは０．２〜１．８倍、より好ましくは０．５〜１．５倍である。０．１倍よりも少ないと反応が遅く長時間要する場合があり、２倍よりも多いと反応系から除去するために効率が悪くなる場合がある。 The component (C) is used in an amount of 0.1 to 2 times in molar ratio to the amino group of the component (A), preferably 0.2 to 1.8 times, more preferably 0.5 to 1 times. .5 times. If it is less than 0.1 times, the reaction may be slow and take a long time, and if it is more than 2 times, it may be inefficient because it is removed from the reaction system.
［（Ｄ）成分］
（Ｄ）成分はシリル化剤であり、シリル化剤としては、クロロシラン化合物やジシラザン化合物などが挙げられるが、ジシラザン化合物が好ましい。
ジシラザン化合物としては、ヘキサメチルジシラザン、１，１，３，３−テトラメチルジシラザン、１，３−ジビニル−１，１，３，３−テトラメチルジシラザン、１，３−ジフェニル−１，１，３，３−テトラメチルジシラザンなどが挙げられるが、ヘキサメチルジシラザンが好ましい。
[(D) component]
Component (D) is a silylating agent, and examples of the silylating agent include chlorosilane compounds and disilazane compounds, but disilazan compounds are preferred.
Examples of the disilazane compound include hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-diphenyl-1, Examples include 1,3,3-tetramethyldisilazane, and hexamethyldisilazane is preferable.
（Ｄ）成分は、（Ａ）成分のアミノ基に対しモル比で１〜３倍となる量を使用し、好ましくは１．１〜２．８倍、より好ましくは１．２〜２．５倍である。１倍より少ないと反応が十分に進行しない場合があり、３倍よりも多いと反応系から除去するために効率が悪くなる場合がある。 The component (D) is used in an amount of 1 to 3 times in molar ratio to the amino group of the component (A), preferably 1.1 to 2.8 times, more preferably 1.2 to 2.5. Is double. If it is less than 1 time, the reaction may not proceed sufficiently, and if it is more than 3 times, it may be inefficient because it is removed from the reaction system.
［（Ｅ）成分］
（Ｅ）成分は有機溶剤であり、基質（（Ａ）、（Ｂ）成分）を溶解させるための反応溶剤である。（Ｅ）成分としては、トルエン、キシレン等の芳香族炭化水素系溶剤、ヘキサン、ヘプタン、オクタン、イソオクタン、デカン、シクロヘキサン、メチルシクロヘキサン、イソパラフィン等の脂肪族炭化水素系溶剤、工業用ガソリン、石油ベンジン、ソルベントナフサ等の炭化水素系溶剤、アセトン、メチルエチルケトン、２−ペンタノン、３−ペンタノン、２−ヘキサノン、２−ヘプタノン、４−ヘプタノン、メチルイソブチルケトン、ジイソブチルケトン、アセトニルアセトン、シクロヘキサノン等のケトン系溶剤、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル等のエステル系溶剤、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、１，２−ジメトキシエタン、１，４−ジオキサン等のエーテル系溶剤、２−メトキシエチルアセタート、２−エトキシエチルアセタート、プロピレングリコールモノメチルエーテルアセタート、２−ブトキシエチルアセタート等のエステルとエーテル部分を有する溶剤、又はこれらの混合溶剤などが挙げられる。これらは１種単独で又は２種以上を適宜組み合わせて用いることができる。
[(E) component]
The component (E) is an organic solvent and is a reaction solvent for dissolving the substrate (components (A) and (B)). (E) Component includes aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane and isoparaffin, industrial gasoline, petroleum benzine , Hydrocarbon solvents such as solvent naphtha, ketones such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, cyclohexanone Solvent, ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, 1 Ether solvents such as 4-dioxane, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, solvents having an ester moiety such as 2-butoxyethyl acetate, or a mixture thereof A solvent etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.
（Ｅ）成分は、（Ａ）成分と（Ｄ）成分を溶解し、（Ｃ）成分を溶解しない溶剤であることが好ましい。これは、反応終了後に（Ｃ）成分を容易に除去することが可能となるためであり、（Ｃ）成分が溶解しない場合はろ過により除去できるのに対し、（Ｃ）成分が溶解する場合は洗浄操作が必要であり効率と収率が悪くなるからである。（Ｂ）成分は（Ｅ）成分に溶解してもしなくてもよいが、溶解する方が反応の進行が速いため、溶解する方が好ましい。 The component (E) is preferably a solvent that dissolves the components (A) and (D) and does not dissolve the component (C). This is because the component (C) can be easily removed after completion of the reaction. When the component (C) does not dissolve, it can be removed by filtration, whereas when the component (C) dissolves. This is because a washing operation is necessary, and the efficiency and yield are deteriorated. The component (B) may or may not be dissolved in the component (E), but it is preferable that the component is dissolved because the reaction proceeds faster.
（Ｅ）成分の配合量としては、（Ａ）成分を１００質量部としたときに、０〜５，０００質量部であり、０〜４，０００質量部が好ましく、０〜３，０００質量部がより好ましい。５，０００質量部よりも多いと、反応の進行が遅くなる場合がある。なお、配合する場合は、５００質量部以上とすることが好ましい。 (E) As a compounding quantity of a component, when (A) component is 100 mass parts, it is 0-5,000 mass parts, 0-4,000 mass parts are preferable, and 0-3,000 mass parts. Is more preferable. When it is more than 5,000 parts by mass, the progress of the reaction may be slow. In addition, when mix | blending, it is preferable to set it as 500 mass parts or more.
上記平均組成式（１）のオルガノポリシロキサンは、前記（Ａ）〜（Ｅ）成分を使用することにより製造される。 The organopolysiloxane of the above average composition formula (1) is produced by using the components (A) to (E).
［（Ａ）成分と（Ｂ）成分の付加反応］
（Ａ）成分及び（Ｂ）成分は反応基質であり、より詳しく説明すると（Ａ）成分が主剤で（Ｂ）成分が反応剤である。（Ａ）成分と（Ｂ）成分を、必要により（Ｅ）成分の存在下で混合すると、室温（２５℃）でも発熱しながら反応し、下記平均組成式（７）で表されるオルガノポリシロキサン（Ｆ）を形成する。
The component (A) and the component (B) are reaction substrates. More specifically, the component (A) is the main agent and the component (B) is the reactant. When the component (A) and the component (B) are mixed in the presence of the component (E) if necessary, the reaction occurs while generating heat even at room temperature (25 ° C.), and the organopolysiloxane represented by the following average composition formula (7) (F) is formed.
上記式（７）中、Ｒ15は同一又は異種の炭素数１〜１０の非置換もしくは置換の１価炭化水素基又は上記一般式（８）もしくは（９）で表される構造の有機基であり、Ｒ15のうち少なくとも１個は上記一般式（８）又は（９）で表される構造の有機基を含む。１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基などが挙げられ、さらに、これらの基の炭素原子に結合した水素原子の一部又は全部がハロゲン原子又はその他の基で置換されていてもよく、置換基としては、トリフルオロメチル基、３，３，３−トリフルオロプロピル基等が例示される。中でも、飽和の脂肪族基又は芳香族基が好ましく、メチル基、フェニル基が好ましい。
Ｒ15のうち少なくとも１個、好ましくは２〜２００個、より好ましくは２〜１５０個は一般式（８）又は（９）で表される構造の有機基を含む。
In the above formula (7), R 15 is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or an organic group having a structure represented by the above general formula (8) or (9). And at least one of R 15 includes an organic group having a structure represented by the general formula (8) or (9). Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and the like. A part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom or other group, and examples of the substituent include a trifluoromethyl group, a 3,3,3-trifluoropropyl group, and the like. Illustrated. Among them, a saturated aliphatic group or an aromatic group is preferable, and a methyl group or a phenyl group is preferable.
At least 1, preferably 2 to 200, more preferably 2 to 150, of R 15 include an organic group having a structure represented by the general formula (8) or (9).
上記式（８）、（９）中、Ｒ16〜Ｒ21は互いに同一又は異種の水素原子又は炭素数１〜１０の非置換もしくは置換の１価炭化水素基である。１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基などが挙げられ、さらに、これらの基の炭素原子に結合した水素原子の一部又は全部がハロゲン原子又はその他の基で置換されていてもよく、置換基としては、トリフルオロメチル基、３，３，３−トリフルオロプロピル基等が例示され、水素原子、メチル基が好ましい。
また、Ｒ16又はＲ17とＲ18又はＲ19、Ｒ20とＲ21が結合して環を形成してもよく、該環としては、シクロプロパン環、シクロブタン環、シクロペンタン環、シクロヘキサン環、ベンゼン環等が例示され、ベンゼン環が好ましい。
ｘ，ｙは０〜３の整数であり、好ましくは０〜２の整数であり、より好ましくは０又は１である。
In the above formulas (8) and (9), R 16 to R 21 are the same or different hydrogen atoms or unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and the like. A part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom or other group, and examples of the substituent include a trifluoromethyl group, a 3,3,3-trifluoropropyl group, and the like. Examples thereof include a hydrogen atom and a methyl group.
R 16 or R 17 and R 18 or R 19 , R 20 and R 21 may be combined to form a ring, such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, A benzene ring etc. are illustrated and a benzene ring is preferable.
x and y are integers of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.
Ｚ，Ｗはそれぞれ炭素数１〜１０のヘテロ原子を介在してもよい非置換もしくは置換の２価炭化水素基であり、ＣＨ2、Ｃ2Ｈ4、Ｃ3Ｈ6、Ｃ4Ｈ8、Ｃ5Ｈ10、Ｃ6Ｈ12などのアルキレン基が挙げられ、エーテル基やチオエーテル基などを介在していてもよい。また、フェニレン基、シクロヘキシレン基等の環状構造を形成してもよく、炭素原子に結合した水素原子の一部又は全部がハロゲン原子又はその他の基で置換されていてもよい。 Z and W are each an unsubstituted or substituted divalent hydrocarbon group that may intervene with a heteroatom having 1 to 10 carbon atoms, CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , Examples include alkylene groups such as C 5 H 10 and C 6 H 12 , and ether groups or thioether groups may be interposed. Moreover, you may form cyclic structures, such as a phenylene group and a cyclohexylene group, and one part or all part of the hydrogen atom couple | bonded with the carbon atom may be substituted by the halogen atom or other groups.
一般式（８）、（９）の具体的な構造を以下に示すが、これらに限定されるものではない。
上記式（７）中、ｉは２以上、好ましくは２〜１２の整数、ｊは０以上、好ましくは１〜９９８、より好ましくは５〜５００の整数、ｋは０以上、好ましくは０〜１０の整数、ｌは０以上、好ましくは０〜５の整数で、２≦ｉ＋ｊ＋ｋ＋ｌ≦１，０００であり、２≦ｉ＋ｊ＋ｋ＋ｌ≦８００が好ましい。ｉ＋ｊ＋ｋ＋ｌが１，０００より大きいと、粘度が高くなり、作業性が悪くなる場合がある。 In the above formula (7), i is 2 or more, preferably an integer of 2 to 12, j is 0 or more, preferably 1 to 998, more preferably an integer of 5 to 500, and k is 0 or more, preferably 0 to 10 And l is an integer of 0 or more, preferably an integer of 0 to 5, 2 ≦ i + j + k + l ≦ 1,000, and preferably 2 ≦ i + j + k + l ≦ 800. If i + j + k + l is greater than 1,000, the viscosity may increase and workability may deteriorate.
（Ｆ）成分の具体的な構造としては、下記一般式で表されるものが挙げられるが、これらに限定されない。なお、下記式中のＭｅ，Ｐｈはそれぞれメチル基、フェニル基を示し、Ｂは下記に示す構造を代表して示すが、式（８）又は（９）で表される構造の有機基であればいずれのものでもよい。
［触媒的イミド化反応］
（Ｆ）成分中のアミド基とカルボキシル基の間で縮合反応が起こると、目的となる平均組成式（１）のオルガノポリシロキサンを得ることができる。しかし、加熱のみで反応を進行させることは難しく、反応温度も２００℃前後あるいはそれ以上を必要とするためエネルギー的に不利である。そのため、上述した（Ｃ）成分と（Ｄ）成分が必要である。
[Catalytic imidization reaction]
When a condensation reaction occurs between the amide group and carboxyl group in component (F), the desired organopolysiloxane of average composition formula (1) can be obtained. However, it is difficult to advance the reaction only by heating, and the reaction temperature is about 200 ° C. or higher, which is disadvantageous in terms of energy. Therefore, the component (C) and the component (D) described above are necessary.
（Ｆ）成分から平均組成式（１）のオルガノポリシロキサンを得るためには、縮合反応により閉環してイミド化する必要があり、そのために（Ｃ）成分と（Ｄ）成分を使用する。
（Ｃ）成分は触媒であり、（Ｄ）成分は（Ｆ）成分中のカルボキシル基をシリルキャップするための反応試剤である。（Ｆ）成分と（Ｃ）成分を混合し、そこへ（Ｄ）成分を加えると（Ｆ）成分中のカルボキシル基がシリル化され、加熱することによりシリル化されたカルボキシル基とアミド基が縮合することで式（１）のオルガノポリシロキサンを得ることができる。カルボキシル基では縮合が起こりにくいが、シリル化することにより縮合が進行しやすくなる。このとき、（Ｃ）成分は（Ｄ）成分と反応することでシリル化のための活性種を生成する、また詳細な機構については確かではないが縮合反応を触媒するという２つの役割を担っているものと推測される。
In order to obtain the organopolysiloxane of the average composition formula (1) from the component (F), it is necessary to cyclize and imidize by a condensation reaction, and therefore the components (C) and (D) are used.
The component (C) is a catalyst, and the component (D) is a reaction reagent for silyl-capping the carboxyl group in the component (F). When component (F) and component (C) are mixed and component (D) is added thereto, the carboxyl group in component (F) is silylated and the silylated carboxyl group and amide group are condensed by heating. By doing so, the organopolysiloxane of the formula (1) can be obtained. Condensation is unlikely to occur with a carboxyl group, but condensation tends to proceed by silylation. At this time, the component (C) plays the two roles of reacting with the component (D) to generate active species for silylation and catalyzing the condensation reaction, although the detailed mechanism is not certain. Presumed to be.
［生成物の精製］
イミド化終了後は、（Ｄ）成分から発生したアンモニアが系中に存在するため、これを除去する必要がある。アンモニアの除去方法について特に制限はないが、酸性物質と反応させて中和してから生成した塩をろ別する方法などが挙げられる。酸性物質としては塩酸、硫酸、硝酸、リン酸、ホウ酸、ギ酸、酢酸、クエン酸、乳酸、酪酸等が挙げられる。反応性の観点から酸性物質は液体が好ましく、酢酸やリン酸が好ましい。
[Product purification]
After the imidization is completed, ammonia generated from the component (D) is present in the system, and thus needs to be removed. Although there is no restriction | limiting in particular about the removal method of ammonia, The method etc. which filter the salt produced | generated after making it react with an acidic substance and neutralizing are mentioned. Examples of the acidic substance include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, formic acid, acetic acid, citric acid, lactic acid, and butyric acid. From the viewpoint of reactivity, the acidic substance is preferably a liquid, and acetic acid and phosphoric acid are preferred.
（Ｃ）成分は、（Ｅ）成分に不溶であればろ過により取り除くことができる。（Ｅ）成分に溶解している場合には、液−液抽出により洗浄して系外に排出する必要がある。
未反応の（Ｂ）成分及び（Ｄ）成分と（Ｅ）成分は、減圧留去により取り除くことができる。
If the component (C) is insoluble in the component (E), it can be removed by filtration. When it is dissolved in the component (E), it must be washed by liquid-liquid extraction and discharged out of the system.
Unreacted components (B) and (D) and (E) can be removed by distillation under reduced pressure.
以上の工程を経て、目的とする本発明のオルガノポリシロキサンを製造することができる。 Through the above steps, the target organopolysiloxane of the present invention can be produced.
本発明のオルガノポリシロキサンは、優れた耐熱性を有するものであり、工業用の熱媒や潤滑剤などのオイル、耐熱性コーティング材料、耐熱性ゴム材料、樹脂への添加剤等の用途に好適に使用し得る。 The organopolysiloxane of the present invention has excellent heat resistance, and is suitable for applications such as industrial heat transfer oils and lubricants, heat resistant coating materials, heat resistant rubber materials, additives to resins, etc. Can be used for
以下、実施例及び比較例を示し、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。また、下記例において、Ｍｅはメチル基を表す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, Me represents a methyl group.
［実施例１］
撹拌装置、温度計、滴下ロート、還流冷却管を取り付けた３００ｍＬの３つ口フラスコに、（Ｂ）成分として無水コハク酸を３．２０ｇ（０．０３２ｍｏｌ）、（Ｅ）成分としてトルエンを８１．７４ｇ（７０質量％）仕込み、室温（２５℃）にて混合撹拌しているところに、（Ａ）成分として滴下ロートに仕込んだ下記式（Ａ−１）のオルガノポリシロキサン１３．７６ｇ（アミノ基として０．０３２ｍｏｌ）を滴下した。滴下終了後、室温（２５℃）にて４時間撹拌し、フラスコに（Ｃ）成分として臭化亜鉛を７．２０ｇ（０．０３２ｍｏｌ）投入し、５０℃まで加熱した。そこへ、（Ｄ）成分として滴下ロートに仕込んだヘキサメチルジシラザン７．７６ｇ（０．０４８ｍｏｌ）を滴下し、滴下終了後８０℃で１時間熟成し、放冷して４０℃以下にしたところで、酢酸３．１７ｇ（０．０５３ｍｏｌ）を滴下してさらに３０分熟成した。反応溶液中の固体をろ過により取り除き、７０℃／１時間減圧留去した後、１２０℃／１時間さらに減圧留去することで黄色透明の液体を得た。分析の結果、下記式（Ｉ）のオルガノポリシロキサンであることを確認した。
In a 300 mL three-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 3.20 g (0.032 mol) of succinic anhydride as component (B) and 81. of toluene as component (E). In a place where 74 g (70% by mass) is charged and mixed and stirred at room temperature (25 ° C.), 13.76 g of an organopolysiloxane of the following formula (A-1) charged to the dropping funnel as the component (A) (amino group) As 0.032 mol). After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 4 hours, and 7.20 g (0.032 mol) of zinc bromide as a component (C) was charged into the flask and heated to 50 ° C. To this, 7.76 g (0.048 mol) of hexamethyldisilazane charged in the dropping funnel as component (D) was dropped, and after completion of dropping, the mixture was aged at 80 ° C. for 1 hour, allowed to cool to 40 ° C. or less. Then, 3.17 g (0.053 mol) of acetic acid was added dropwise, followed by further aging for 30 minutes. The solid in the reaction solution was removed by filtration and distilled under reduced pressure at 70 ° C./1 hour, and then further distilled under reduced pressure at 120 ° C./1 hour to obtain a yellow transparent liquid. As a result of analysis, it was confirmed that it was an organopolysiloxane of the following formula (I).
［実施例２］
（Ｂ）成分として無水コハク酸の代わりに無水マレイン酸を３．１４ｇ（０．０３２ｍｏｌ）使用した以外は実施例１と同様にして製造し、黄色透明の液体を得た。分析の結果、下記式（II）のオルガノポリシロキサンであることを確認した。
A yellow transparent liquid was obtained in the same manner as in Example 1 except that 3.14 g (0.032 mol) of maleic anhydride was used as the component (B) instead of succinic anhydride. As a result of analysis, it was confirmed that it was an organopolysiloxane of the following formula (II).
［実施例３］
（Ｂ）成分として無水コハク酸の代わりに無水グルタル酸を３．６５ｇ（０．０３２ｍｏｌ）使用した以外は実施例１と同様にして製造し、黒色の液体を得た。分析の結果、下記式（III）のオルガノポリシロキサンであることを確認した。
A black liquid was obtained in the same manner as in Example 1 except that 3.65 g (0.032 mol) of glutaric anhydride was used as the component (B) instead of succinic anhydride. As a result of analysis, it was confirmed that it was an organopolysiloxane of the following formula (III).
［実施例４］
（Ｂ）成分として無水コハク酸の代わりに無水フタル酸を４．７４ｇ（０．０３２ｍｏｌ）使用した以外は実施例１と同様にして製造し、黄色透明の液体を得た。分析の結果、下記式（IV）のオルガノポリシロキサンであることを確認した。
A yellow transparent liquid was obtained in the same manner as in Example 1 except that 4.74 g (0.032 mol) of phthalic anhydride was used as the component (B) instead of succinic anhydride. As a result of analysis, it was confirmed that it was an organopolysiloxane of the following formula (IV).
＜耐熱性＞
上記で得られたオルガノポリシロキサンの耐熱性を熱質量分析で評価した。具体的には、試料１０ｍｇを装置に入れた後、空気中で室温（２５℃）から１０℃／分の昇温速度で４００℃まで加熱し、質量損失率が５％となった温度を測定した。測定装置にはＴｈｅｒｍｏ ｐｌｕｓ ＴＧ８１２０（リガク製）を用いた。なお、比較例１として、上記式（Ａ−１）のオルガノポリシロキサンの耐熱性を評価した。これらの結果を表１に示す。
<Heat resistance>
The heat resistance of the organopolysiloxane obtained above was evaluated by thermal mass spectrometry. Specifically, after 10 mg of a sample is placed in the apparatus, it is heated from room temperature (25 ° C.) to 400 ° C. at a rate of temperature increase of 10 ° C./min in air, and the temperature at which the mass loss rate becomes 5% is measured. did. Thermo plus TG8120 (manufactured by Rigaku) was used as a measuring device. In addition, as Comparative Example 1, the heat resistance of the organopolysiloxane of the above formula (A-1) was evaluated. These results are shown in Table 1.
表１の結果より、本発明のオルガノポリシロキサンは、原料となるアミノ変性ポリシロキサンよりも、同じ質量を損失するときの温度が高いことから、耐熱性に優れていることがわかる。 From the results shown in Table 1, it can be seen that the organopolysiloxane of the present invention is superior in heat resistance since the temperature when the same mass is lost is higher than that of the amino-modified polysiloxane as a raw material.
Claims (6)
（Ｂ）下記一般式（５）又は（６）で表される有機化合物：（Ａ）成分中のアミノ基に対しモル比で１〜３倍となる量、
（Ｃ）ルイス酸触媒：（Ａ）成分のアミノ基に対しモル比で０．１〜２倍となる量、
（Ｄ）シリル化剤：（Ａ）成分のアミノ基に対しモル比で１〜３倍となる量、
（Ｅ）有機溶剤：（Ａ）成分を１００質量部としたときに０〜５，０００質量部
を用いて、
（Ｉ）上記（Ａ）成分と（Ｂ）成分とを、必要により（Ｅ）成分の存在下で反応させ、下記平均組成式（７）で表されるオルガノポリシロキサン（Ｆ）を形成させる工程と、
（ＩＩ）得られた（Ｆ）成分と（Ｃ）成分及び（Ｄ）成分とを混合して、（Ｆ）成分中のカルボキシル基をシリル化し、加熱して（Ｆ）成分中のアミド基とシリル化したカルボキシル基とを縮合反応させる工程、及び
（ＩＩＩ）上記縮合反応させる工程後、酸性物質を添加し、生成した塩をろ別する工程
を含む、
下記平均組成式（１）
で表され、１分子中に下記一般式（２）又は（３）
で表される構造の有機基を少なくとも１個含むオルガノポリシロキサンを製造する製造方法（但し、上記一般式（６）中の有機化合物Ｎ、一般式（９）中の有機基ｙ、及び上記一般式（３）中の有機基ｎがいずれも０である場合を除く。）。 (A) Organopolysiloxane represented by the following average composition formula (4) and having at least one amino group-containing organic group having 1 to 10 carbon atoms in one molecule: 100 parts by mass
(B) an organic compound represented by the following general formula (5) or (6): an amount that is 1 to 3 times in molar ratio to the amino group in the component (A);
(C) Lewis acid catalyst: an amount that is 0.1 to 2 times in molar ratio to the amino group of component (A),
(D) Silylating agent: an amount that is 1 to 3 times in molar ratio to the amino group of component (A),
(E) Organic solvent: When the component (A) is 100 parts by mass, 0 to 5,000 parts by mass are used,
(I) The process of making the said (A) component and (B) component react in presence of (E) component as needed, and forming the organopolysiloxane (F) represented by the following average compositional formula (7) When,
(II) The obtained component (F) is mixed with the components (C) and (D) to silylate the carboxyl group in the component (F) and heated to form the amide group in the component (F). A step of subjecting a silylated carboxyl group to a condensation reaction, and ( III ) after the step of causing the condensation reaction, adding an acidic substance and filtering out the generated salt,
The following average composition formula (1)
Represented by the following general formula (2) or (3)
A production method for producing an organopolysiloxane containing at least one organic group having a structure represented by the formula (However, the organic compound N in the general formula (6), the organic group y in the general formula (9), and the general Except when all the organic groups n in the formula (3) are 0) .
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