JP2011213868A - Organopolysiloxane and method for producing the same - Google Patents
Organopolysiloxane and method for producing the same Download PDFInfo
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- JP2011213868A JP2011213868A JP2010083488A JP2010083488A JP2011213868A JP 2011213868 A JP2011213868 A JP 2011213868A JP 2010083488 A JP2010083488 A JP 2010083488A JP 2010083488 A JP2010083488 A JP 2010083488A JP 2011213868 A JP2011213868 A JP 2011213868A
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- -1 acryloxy group Chemical group 0.000 claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- 238000007259 addition reaction Methods 0.000 claims description 30
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 27
- 125000003342 alkenyl group Chemical group 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- KLKRGCUPZROPPO-UHFFFAOYSA-N 2,2,6-trimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)(C)C KLKRGCUPZROPPO-UHFFFAOYSA-N 0.000 claims description 3
- CEGGECULKVTYMM-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)C CEGGECULKVTYMM-UHFFFAOYSA-N 0.000 claims description 3
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000001879 gelation Methods 0.000 abstract description 20
- 238000007086 side reaction Methods 0.000 abstract description 7
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 37
- 238000001816 cooling Methods 0.000 description 22
- 239000007795 chemical reaction product Substances 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 17
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 12
- 125000005641 methacryl group Chemical group 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 238000009413 insulation Methods 0.000 description 11
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003247 decreasing effect Effects 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZIFLDVXQTMSDJE-UHFFFAOYSA-N 3-[[dimethyl-[3-(2-methylprop-2-enoyloxy)propyl]silyl]oxy-dimethylsilyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)O[Si](C)(C)CCCOC(=O)C(C)=C ZIFLDVXQTMSDJE-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
- 229910008045 Si-Si Inorganic materials 0.000 description 3
- 229910006411 Si—Si Inorganic materials 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- OKQXCDUCLYWRHA-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)Cl OKQXCDUCLYWRHA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 238000004364 calculation method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 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 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000012676 equilibrium polymerization Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 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 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-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
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- PJEPOHXMGDEIMR-UHFFFAOYSA-N octane-3,5-dione Chemical compound CCCC(=O)CC(=O)CC PJEPOHXMGDEIMR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 125000005023 xylyl group Chemical group 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
Description
本発明は、アクリロキシ基又はメタアクリロキシ基（以下、場合により「（メタ）アクリロキシ基」と総称する。）を有するオルガノポリシロキサン及びその工業的有用な製造方法に関する。 The present invention relates to an organopolysiloxane having an acryloxy group or a methacryloxy group (hereinafter sometimes collectively referred to as “(meth) acryloxy group”) and an industrially useful production method thereof.
（メタ）アクリロキシ基を有するオルガノポリシロキサンは、メタクリル酸メチル及びスチレンのようなラジカル重合性モノマーと反応し易く、これらのモノマーから誘導される共重合体の出発原料、又はこれらのモノマーから得られるポリマーの改質剤として多用されている。 Organopolysiloxanes having (meth) acryloxy groups are easily reacted with radically polymerizable monomers such as methyl methacrylate and styrene, and are obtained from starting materials for copolymers derived from these monomers, or from these monomers. It is frequently used as a polymer modifier.
（メタ）アクリロキシ基を有するオルガノポリシロキサンの製造方法として、末端封鎖剤として１，３−ジ（メタクリロキシプロピル）テトラメチルジシロキサンを用い、酸触媒存在下でオクタメチルシクロテトラシロキサンを平衡重合することにより両末端が（メタ）アクリロキシプロピル基で封鎖されたジオルガノポリシロキサンを生成させる方法が知られている（例えば、非特許文献１参照。）。 As a method for producing an organopolysiloxane having a (meth) acryloxy group, 1,3-di (methacryloxypropyl) tetramethyldisiloxane is used as a terminal blocking agent and octamethylcyclotetrasiloxane is subjected to equilibrium polymerization in the presence of an acid catalyst. Thus, a method for producing a diorganopolysiloxane having both ends blocked with (meth) acryloxypropyl groups is known (for example, see Non-Patent Document 1).
また、ＯＨ基を有する（メタ）アクリレート化合物とＳｉＸ基（Ｘはハロゲン原子）を有するオルガノポリシロキサンとを、塩基の存在下で脱ＨＸ反応させることにより、（メタ）アクリロキシ基をオルガノポリシロキサンに導入する方法が知られている（例えば、特許文献１参照）。 In addition, a (meth) acryloxy group is converted into an organopolysiloxane by de-HXing a (meth) acrylate compound having an OH group and an organopolysiloxane having a SiX group (X is a halogen atom) in the presence of a base. A method of introduction is known (see, for example, Patent Document 1).
一方、ポリシロキサン鎖と（メタ）アクリロキシ基とがＳｉ−Ｏ−Ｃ結合ではなくＳｉ−Ｃ結合を介して結合した化合物の製造方法として、エポキシ基を有するオルガノポリシロキサンのエポキシ基と（メタ）アクリル酸とを開環付加反応させ、（メタ）アクリロキシ基を導入する方法が知られている（例えば、特許文献２、３参照。）。 On the other hand, as a method for producing a compound in which a polysiloxane chain and a (meth) acryloxy group are bonded through a Si-C bond instead of a Si-O-C bond, an epoxy group of an organopolysiloxane having an epoxy group and (meth) A method of introducing a (meth) acryloxy group by ring-opening addition reaction with acrylic acid is known (for example, see Patent Documents 2 and 3).
別の製造方法として、アルケニル基を有する（メタ）アクリル化合物とオルガノハイドロジェンポリシロキサンとを白金触媒存在下でヒドロシリル化反応させる方法が知られている（例えば、特許文献４、５参照。）。 As another production method, a method in which a (meth) acrylic compound having an alkenyl group and an organohydrogenpolysiloxane are subjected to a hydrosilylation reaction in the presence of a platinum catalyst is known (for example, see Patent Documents 4 and 5).
非特許文献１に記載の製造方法で使用する１，３−ジ（メタクリロキシプロピル）テトラメチルジシロキサンは、通常、メタクリロキシプロピルジメチルクロロシランの加水分解によって製造される。メタクリロキシプロピルジメチルクロロシランは、メタクリル酸アリルとジメチルハイドロジェンクロロシランとのヒドロシリル化反応によって製造されるが、この反応は極めてゲル化が起こりやすいという製造上の問題点があった。また、高純度品を得るには蒸留精製が必須であるが、蒸留時にも極めてゲル化が起こりやすいため、１，３−ジ（メタクリロキシプロピル）テトラメチルジシロキサンを工業的に大量生産するには困難が伴っていた。 1,3-di (methacryloxypropyl) tetramethyldisiloxane used in the production method described in Non-Patent Document 1 is usually produced by hydrolysis of methacryloxypropyldimethylchlorosilane. Methacryloxypropyldimethylchlorosilane is produced by a hydrosilylation reaction between allyl methacrylate and dimethylhydrogenchlorosilane, but this reaction has a problem in production that gelation easily occurs. Also, distillation purification is essential to obtain a high-purity product, but since gelation is very likely to occur during distillation, 1,3-di (methacryloxypropyl) tetramethyldisiloxane is industrially mass-produced. Was accompanied by difficulties.
特許文献１に記載の方法により製造された（メタ）アクリロキシ基を有するオルガノポリシロキサンは、シロキサン鎖と（メタ）アクリロキシ基とがＳｉ−Ｏ−Ｃ結合によって結合しているが、Ｓｉ−Ｏ−Ｃ結合は水分、酸性不純物、塩基性不純物等の影響で加水分解することがあり、このオルガノポリシロキサンの安定性には問題があった。 In the organopolysiloxane having a (meth) acryloxy group produced by the method described in Patent Document 1, a siloxane chain and a (meth) acryloxy group are bonded by a Si—O—C bond. The C bond may hydrolyze due to the influence of moisture, acidic impurities, basic impurities, etc., and this organopolysiloxane has a problem in stability.
特許文献２、３に記載の方法は、エポキシ基を有するオルガノポリシロキサンを得るために、オルガノハイドロジェンポリシロキサンを合成し、これとアルケニル基を有するエポキシ化合物とを白金触媒存在下ヒドロシリル化反応させることが予め必要で、反応が多段階になるという点で不利であった。 In the methods described in Patent Documents 2 and 3, in order to obtain an organopolysiloxane having an epoxy group, an organohydrogenpolysiloxane is synthesized, and this and an epoxy compound having an alkenyl group are subjected to a hydrosilylation reaction in the presence of a platinum catalyst. This is disadvantageous in that the reaction is multi-staged.
特許文献４、５に記載の方法は、アルケニル基を有する（メタ）アクリル化合物のアルケニル基と（メタ）アクリロキシ基のヒドロシリル化反応の選択性が問題となる場合がある。つまり、アルケニル基のみが選択的にヒドロシリル化反応する場合は問題ないが、アルケニル基と（メタ）アクリロキシ基の両方がオルガノハイドロジェンポリシロキサンのＳｉＨ基と反応した場合、反応混合物がゲル化してしまうことがある。また、アルケニル基と（メタ）アクリロキシ基の組み合わせによっては、アルケニル基よりも（メタ）アクリロキシ基の反応性の方が優位であることがあり、この場合、所望の（メタ）アクリロキシ基を有するオルガノポリシロキサンが得られないことがある。 In the methods described in Patent Documents 4 and 5, the selectivity of the hydrosilylation reaction between the alkenyl group and (meth) acryloxy group of the (meth) acrylic compound having an alkenyl group may be a problem. That is, there is no problem when only the alkenyl group selectively hydrosilylates, but when both the alkenyl group and the (meth) acryloxy group react with the SiH group of the organohydrogenpolysiloxane, the reaction mixture gels. Sometimes. Depending on the combination of an alkenyl group and a (meth) acryloxy group, the reactivity of the (meth) acryloxy group may be superior to the alkenyl group. In this case, the organo group having the desired (meth) acryloxy group may be used. Polysiloxane may not be obtained.
更に、白金触媒に対するアルケニル基の配位力が小さいために、副反応としてＳｉＨ基の脱水素によるＳｉ−Ｓｉ結合が生成する場合があり、このこともゲル化の原因となる。 Furthermore, since the coordinating power of the alkenyl group to the platinum catalyst is small, a Si—Si bond may be generated by dehydrogenation of the SiH group as a side reaction, which also causes gelation.
このように、Ｓｉ−Ｃ結合を介してポリシロキサン鎖に結合した（メタ）アクリロキシ基を有するオルガノポリシロキサンを製造する従来の方法は、多段階の反応が必要であり、又、反応中ゲル化及び副反応が生じることによって、所望の重合度及び所望の量の（メタ）アクリロキシ基を有するオルガノポリシロキサンを簡便に得ることができず、改善が望まれていた。 As described above, the conventional method for producing an organopolysiloxane having a (meth) acryloxy group bonded to a polysiloxane chain via a Si-C bond requires a multi-step reaction, and the gelation is performed during the reaction. As a result of the occurrence of side reactions, organopolysiloxanes having a desired degree of polymerization and a desired amount of (meth) acryloxy groups cannot be easily obtained, and improvements have been desired.
本発明は、上記事情に鑑みてなされたものであり、（メタ）アクリロキシ基を有するオルガノポリシロキサンを、一つの反応容器内においてワンポットで簡便に、ゲル化等の副反応を伴うことなく容易に製造することを可能にする方法、及び係る方法により得ることのできる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 organopolysiloxane having a (meth) acryloxy group can be easily prepared in one pot in one pot without any side reactions such as gelation. It is an object of the present invention to provide a method that enables production and an organopolysiloxane that can be obtained by such a method.
本発明者は、上記課題を解決するために鋭意検討した結果、（メタ）アクリロキシ基を有するオルガノポリシロキサンを製造する方法において、ＳｉＨ基を有するハイドロジェンポリシロキサンと、アルケニル基を有する（メタ）アクリレート化合物とをヒドロシリル化反応触媒を用いて付加反応させる際に、付加反応を所定量のβ−ジケトン化合物の存在下で行うことにより、その目的が達成されることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventor has found that in a method for producing an organopolysiloxane having a (meth) acryloxy group, a hydrogen polysiloxane having a SiH group and a (meth) having an alkenyl group. When an addition reaction of an acrylate compound with a hydrosilylation reaction catalyst is carried out in the presence of a predetermined amount of a β-diketone compound, the object is achieved and the present invention is completed. It came to.
すなわち、本発明は、以下のオルガノポリシロキサン及びその製造方法に関する。
１．下記一般式（１）：
（式中Ｒ1は置換若しくは非置換の炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基又はアラルキル基を示し、Ｒ２はアクリロキシ基又はメタアクリロキシ基を示し、Ｘは炭素数１〜１０の二価の炭化水素基を示し、ａは１以上の整数、ｂ及びｃはそれぞれ独立に０以上の整数を示し、ｂ／（ａ＋ｂ）の平均値は０．０５〜０．２５であり、ａ＋ｂ＋ｃは３〜２０の整数であり、同一分子中の複数のＲ１及びＲ２はそれぞれ同一でも異なっていてもよい。）で表されるオルガノポリシロキサン。
That is, this invention relates to the following organopolysiloxane and its manufacturing method.
1. The following general formula (1):
(Wherein R 1 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group or an aralkyl group; R 2 represents an acryloxy group or a methacryloxy group; Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, a is an integer of 1 or more, b and c each independently represents an integer of 0 or more, and the average value of b / (a + b) is 0.05 to And a + b + c is an integer of 3 to 20, and a plurality of R 1 and R 2 in the same molecule may be the same or different.)
２．下記一般式（２）：
（式中Ｒ1は置換若しくは非置換の炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基又はアラルキル基を示し、ｄは１以上の整数を示し、ｅは０以上の整数を示し、ｄ＋ｅは３〜２０の整数である。）で表されるハイドロジェンポリシロキサン（Ａ）と、アルケニル基を有する（メタ）アクリレート化合物（Ｂ）との付加反応を、ヒドロシリル化反応触媒（Ｃ）の存在下で行う工程を備え、付加反応が、ハイドロジェンポリシロキサン（Ａ）のＳｉＨ基に対するモル比が１．２〜１０．０の量のβ−ジケトン化合物（Ｄ）の存在下において行われ、上記ヒドロシリル化反応触媒（Ｃ）が白金又は白金錯体である、１．のオルガノポリシロキサンの製造方法。
2. The following general formula (2):
(Wherein R 1 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group or an aralkyl group, d represents an integer of 1 or more, and e represents 0 The above-mentioned integer is represented, and d + e is an integer of 3 to 20.) The hydrosilylation reaction of the hydrogen polysiloxane (A) represented by (A) and the (meth) acrylate compound (B) having an alkenyl group is performed. Comprising the step of performing the reaction in the presence of a reaction catalyst (C), wherein the addition reaction is performed in such a manner that the molar ratio of hydrogenpolysiloxane (A) to SiH groups is 1.2 to 10.0 in the amount of β-diketone compound (D). 1. The hydrosilylation reaction catalyst (C) is carried out in the presence of platinum or a platinum complex; The manufacturing method of organopolysiloxane of this.
３．付加反応を行う工程が、ハイドロジェンポリシロキサン（Ａ）、（メタ）アクリレート化合物（Ｂ）及びβ−ジケトン化合物（Ｄ）を含有する反応液を準備する工程と、反応液にヒドロシリル化反応触媒（Ｃ）を加える工程とを含む、２．の製造方法。 3. The step of performing the addition reaction includes a step of preparing a reaction solution containing the hydrogen polysiloxane (A), the (meth) acrylate compound (B) and the β-diketone compound (D), and a hydrosilylation reaction catalyst ( C), and 2. Manufacturing method.
４．β−ジケトン化合物（Ｄ）が、アセチルアセトン、ベンゾイルアセトン、ジベンゾイルメタンジピバロイルメタン、ジイソブチリルメタン、イソブチリルピバロイルメタン及び２，２，６，６−テトラメチル−３，５−オクタンジオンからなる群より選ばれる少なくとも１種の化合物である、２．又は３．の製造方法。 4). β-diketone compound (D) is acetylacetone, benzoylacetone, dibenzoylmethane dipivaloylmethane, diisobutyrylmethane, isobutyrylpivaloylmethane and 2,2,6,6-tetramethyl-3,5- 1. at least one compound selected from the group consisting of octanedione; Or 3. Manufacturing method.
本発明によれば、（メタ）アクリロキシ基を有するオルガノポリシロキサンを、一つの反応容器内においてワンポットで簡便に、ゲル化などの副反応を伴うことなく容易に製造することが可能である。 According to the present invention, it is possible to easily produce an organopolysiloxane having a (meth) acryloxy group in a single reaction vessel in a single pot without side reactions such as gelation.
以下、本発明を実施するための形態について詳細に説明する。本発明は以下に示す実施形態に限定されるものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the embodiments shown below.
本実施形態に係るオルガノポリシロキサンは、下記一般式（１）で表される構造を有する。 The organopolysiloxane according to this embodiment has a structure represented by the following general formula (1).
一般式（１）中、ａは１以上の整数を示し、ｂ及びｃはそれぞれ独立に０以上の整数を示し、ａ＋ｂ＋ｃは３〜２０の整数である。ｂ／（ａ＋ｂ）の平均値は、０．０５〜０．２５であることが好ましい。 In general formula (1), a represents an integer of 1 or more, b and c each independently represents an integer of 0 or more, and a + b + c is an integer of 3 to 20. The average value of b / (a + b) is preferably 0.05 to 0.25.
上記オルガノポリシロキサンは、下記一般式（２）で表されるハイドロジェンポリシロキサン（Ａ）と、アルケニル基を有する（メタ）アクリレート化合物（Ｂ）との付加反応によって得られる。上記付加反応は、ヒドロシリル化反応触媒（Ｃ）及びβ−ジケトン化合物（Ｄ）の存在下で行われる。ハイドロジェンポリシロキサン（Ａ）のＳｉＨ基に対するβ−ジケトン化合物（Ｅ）のモル比は１．２〜１０．０である。 The organopolysiloxane is obtained by an addition reaction between a hydrogen polysiloxane (A) represented by the following general formula (2) and a (meth) acrylate compound (B) having an alkenyl group. The addition reaction is performed in the presence of a hydrosilylation reaction catalyst (C) and a β-diketone compound (D). The molar ratio of β-diketone compound (E) to SiH groups of hydrogen polysiloxane (A) is 1.2 to 10.0.
式（１）及び（２）におけるＲ１は置換若しくは非置換の炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基又はアラルキル基を示す。炭素数が１０以下のＲ１としては、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基、及びオクチル基等のアルキル基；フェニル基、トリル基、キシリル基、クメニル基、及びメシチル基等のアリール基；ベンジル基、フェネチル基、及びフェニルプロピル基等のアラルキル基；又は、これらの基の炭素原子に結合している水素原子の１部若しくは全部をヒドロキシ基、シアノ基、及びハロゲン原子等で置換したヒドロキシプロピル基、シアノエチル基、１−クロロプロピル基、及び３，３，３−トリフルオロピル基等が挙げられる。これらの中でメチル基、フェニル基は耐熱性、耐光性が高い点でより好ましく、耐光性が特に優れている点でメチル基が最も好ましい。 R 1 in the formulas (1) and (2) represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group. Examples of R 1 having 10 or less carbon atoms include methyl group, ethyl group, propyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, cyclopentyl group, cyclohexyl group, and octyl group. An aryl group such as a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a mesityl group; an aralkyl group such as a benzyl group, a phenethyl group, and a phenylpropyl group; or a bond to a carbon atom of these groups A hydroxypropyl group, a cyanoethyl group, a 1-chloropropyl group, a 3,3,3-trifluoropyr group, etc., in which part or all of the hydrogen atoms are substituted with a hydroxy group, a cyano group, a halogen atom, etc. It is done. Among these, a methyl group and a phenyl group are more preferable in view of high heat resistance and light resistance, and a methyl group is most preferable in view of particularly excellent light resistance.
式（１）におけるＲ２は、下記式（３）で表されるアクリロキシ基又は下記式（４）で表されるメタアクリロキシ基である。
式（１）におけるＸは炭素数１〜１０の二価の炭化水素基を示す。この二価の炭化水素基を例示すると、−（ＣＨ２）−、−（ＣＨ２）２−、−（ＣＨ２）３−、−（ＣＨ２）４−、−（ＣＨ２）５−、−（ＣＨ２）６−、−（ＣＨ２）８−、−（ＣＨ２）１０−、−ＣＨ（ＣＨ３）ＣＨ２−、−Ｃ（ＣＨ３）２−等が挙げられ、特に−（ＣＨ２）２−、−（ＣＨ２）３−、−（ＣＨ２）４−、−ＣＨ（ＣＨ３）ＣＨ２−が好ましい。 X in Formula (1) shows a C1-C10 bivalent hydrocarbon group. Examples of this divalent hydrocarbon group include — (CH 2 ) —, — (CH 2 ) 2 —, — (CH 2 ) 3 —, — (CH 2 ) 4 —, — (CH 2 ) 5 —, -(CH 2 ) 6 -,-(CH 2 ) 8 -,-(CH 2 ) 10- , -CH (CH 3 ) CH 2- , -C (CH 3 ) 2- and the like, especially-( CH 2 ) 2 —, — (CH 2 ) 3 —, — (CH 2 ) 4 —, and —CH (CH 3 ) CH 2 — are preferred.
式（２）において、ｄ＋ｅは３〜２０の整数である。式（２）で表される１分子中に少なくとも１個のＳｉＨ基を持つハイドロジェンポリシロキサン（Ａ）は、例えば、以下の式（５）、（６）又は（７）で表されるものが挙げられる。 In Formula (2), d + e is an integer of 3-20. The hydrogen polysiloxane (A) having at least one SiH group in one molecule represented by the formula (2) is, for example, one represented by the following formula (5), (6) or (7) Is mentioned.
上記ハイドロジェンポリシロキサン（Ａ）は、２種類以上の組合せでもよく、１種単独であってもよい。 The hydrogenpolysiloxane (A) may be a combination of two or more types, or may be a single type.
アルケニル基含有（メタ）アクリレート化合物（Ｂ）は特に制限はないが、例えば、（メタ）アクリル酸アリル、（メタ）アクリル酸イソブテニル、（メタ）アクリル酸ヘキセニル、（メタ）アクリル酸アリロキシエチルが挙げられる。これらのアルケニル基含有（メタ）アクリレート化合物（Ｂ）は、２種類以上の組合せでもよく、１種単独であってもよい。 The alkenyl group-containing (meth) acrylate compound (B) is not particularly limited, and examples thereof include allyl (meth) acrylate, isobutenyl (meth) acrylate, hexenyl (meth) acrylate, and allyloxyethyl (meth) acrylate. Can be mentioned. These alkenyl group-containing (meth) acrylate compounds (B) may be a combination of two or more types, or may be a single type.
アルケニル基含有（メタ）アクリレート化合物（Ｂ）の量は、ＳｉＨ基を残さず最後まで反応させる観点からハイドロジェンポリシロキサン（Ａ）に由来するＳｉＨ基のモル量に対し余剰に添加することが好ましく、具体的には、［アルケニル基含有（メタ）アクリレート化合物のモル量］／［ＳｉＨ基のモル量］＝１．２〜３．０が好ましい。 The amount of the alkenyl group-containing (meth) acrylate compound (B) is preferably added in excess relative to the molar amount of SiH groups derived from the hydrogen polysiloxane (A) from the viewpoint of reacting to the end without leaving any SiH groups. Specifically, [Mole amount of alkenyl group-containing (meth) acrylate compound] / [Mole amount of SiH group] = 1.2 to 3.0 is preferable.
ヒドロシリル化反応触媒（Ｃ）は、周期律表第ＶＩＩＩ族遷移金属錯体触媒が好ましく、白金又は白金錯体のような白金系触媒が最も好ましい。このような触媒としては、例えば、塩化白金酸、塩化白金酸のアルコール溶液、塩化白金酸とアルコールとの反応物、塩化白金酸とオレフィン化合物との反応物、塩化白金酸とビニル基含有シロキサンとの反応物、及び白金のアセチルアセトン錯体が挙げられる。 The hydrosilylation reaction catalyst (C) is preferably a Group VIII transition metal complex catalyst of the periodic table, and most preferably a platinum-based catalyst such as platinum or a platinum complex. Examples of such a catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, chloroplatinic acid and a vinyl group-containing siloxane, and the like. And acetylacetone complexes of platinum.
上記反応触媒の量には特に制限はないが、ハイドロジェンポリシロキサン（Ａ）とアルケニル基含有（メタ）アクリレート化合物（Ｂ）との付加反応生成物であるオルガノポリシロキサンの重量に対して０．０１〜１００ｐｐｍが好ましい。上記反応触媒の量は、その添加効果を得るという観点から０．０１ｐｐｍ以上が好ましく、安全に合成反応を行い、且つコストの観点から１００ｐｐｍ以下が好ましい。 The amount of the reaction catalyst is not particularly limited, but is preferably about 0.1% relative to the weight of the organopolysiloxane which is an addition reaction product of the hydrogen polysiloxane (A) and the alkenyl group-containing (meth) acrylate compound (B). 01-100 ppm is preferable. The amount of the reaction catalyst is preferably 0.01 ppm or more from the viewpoint of obtaining the effect of the addition, preferably 100 ppm or less from the viewpoint of performing the synthesis reaction safely and cost.
β−ジケトン化合物（Ｄ）はＳｉＨ基同士の脱水素反応に伴うＳｉ−Ｓｉ結合の生成を防止する効果を有する。特に上記式（５）、（６）又は（７）で表したようなハイドロジェンポリシロキサン（Ａ）においてＳｉ−Ｓｉ結合が生成した場合、三次元的な網目構造を形成してしまうため、反応中にゲル化する傾向がある。 The β-diketone compound (D) has an effect of preventing the formation of Si—Si bonds accompanying the dehydrogenation reaction between SiH groups. In particular, when a Si—Si bond is generated in the hydrogen polysiloxane (A) as represented by the above formula (5), (6) or (7), a three-dimensional network structure is formed. There is a tendency to gel inside.
β−ジケトン化合物（Ｄ）の量は、ハイドロジェンポリシロキサン（Ａ）に由来するＳｉＨ基のモル量に対し１．２〜１０．０倍のモル量であることが好ましい。ＳｉＨ基同士の脱水素反応を抑制するという観点から１．２倍のモル量以上が好ましく、反応速度を速める観点から１０．０倍のモル量以下が好ましい。 The amount of the β-diketone compound (D) is preferably 1.2 to 10.0 times the molar amount of the SiH group derived from the hydrogen polysiloxane (A). From the viewpoint of suppressing the dehydrogenation reaction between SiH groups, the molar amount is preferably 1.2 times or more, and from the viewpoint of increasing the reaction rate, it is preferably 10.0 times or less.
上記β−ジケトン化合物（Ｄ）は、例えば、アセチルアセトン、ベンゾイルアセトン、ジベンゾイルメタンジピバロイルメタン、ジイソブチリルメタン、イソブチリルピバロイルメタン、及び２，２，６，６−テトラメチル−３，５−オクタンジオンからなる群より選ばれる少なくとも１種である。 Examples of the β-diketone compound (D) include acetylacetone, benzoylacetone, dibenzoylmethane dipivaloylmethane, diisobutyrylmethane, isobutyrylpivaloylmethane, and 2,2,6,6-tetramethyl- It is at least one selected from the group consisting of 3,5-octanedione.
本実施形態に係る製造方法は、上記一般式（２）のような１分子中に少なくとも１個のＳｉＨ基を持つハイドロジェンポリシロキサン（Ａ）とアルケニル基含有（メタ）アクリレート化合物（Ｂ）とを、ヒドロシリル化反応触媒（Ｃ）及び、β−ジケトン化合物（Ｄ）をハイドロジェンポリシロキサン（Ａ）に由来するＳｉＨ基のモル量に対し１．２〜１０．０倍のモル量の存在下において付加反応させることを特徴とするが、この付加反応は、通常、室温〜１００℃で行うことができる。（メタ）アクリロキシ基は高温で反応し易くゲル化する可能性があるため、反応温度は４０℃〜６０℃が好ましい。 The production method according to this embodiment includes a hydrogen polysiloxane (A) having at least one SiH group in one molecule as in the general formula (2), an alkenyl group-containing (meth) acrylate compound (B), In the presence of 1.2 to 10.0 times the molar amount of the hydrosilylation catalyst (C) and the β-diketone compound (D) relative to the molar amount of SiH groups derived from the hydrogen polysiloxane (A). The addition reaction is usually carried out at room temperature to 100 ° C. Since the (meth) acryloxy group easily reacts at high temperatures and may be gelled, the reaction temperature is preferably 40 ° C to 60 ° C.
上記付加反応は、必要に応じて溶剤中で行うことができる。溶剤としては、トルエン、及びキシレン等の芳香族系溶剤、ヘキサン、及びオクタン等の脂肪族系溶剤、メチルエチルケトン、及びメチルイソブチルケトン等のケトン系溶剤、酢酸エチル、及び酢酸イソブチル等のエステル系溶剤、ジイソプロピルエーテル、１，４−ジオキサン、ジエチルエーテル、テトラヒドロフラン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、及びプロピレングリコールモノメチルエーテルアセテート等のエーテル系溶剤、並びにイソプロパノール等のアルコール系溶剤、又はこれらの混合溶剤を使用することができる。 The above addition reaction can be performed in a solvent as necessary. Solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane and octane, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and isobutyl acetate, Use ether solvents such as diisopropyl ether, 1,4-dioxane, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate, and alcohol solvents such as isopropanol, or a mixed solvent thereof. can do.
また、反応の雰囲気としては空気中、不活性気体中のいずれでもよい。得られたオルガノヒドロポリシロキサンの着色が少ない点で、窒素、アルゴン、及びヘリウム等の不活性気体中が好ましいが、（メタ）アクリロキシ基の重合反応を防止する目的で少量の酸素を導入することもできる。 The reaction atmosphere may be either air or inert gas. The obtained organohydropolysiloxane is preferably in an inert gas such as nitrogen, argon, and helium because it is less colored, but a small amount of oxygen should be introduced for the purpose of preventing the polymerization reaction of the (meth) acryloxy group. You can also.
付加反応を行う工程は、ハイドロジェンポリシロキサン（Ａ）、（メタ）アクリレート化合物（Ｂ）及びβ−ジケトン化合物（Ｄ）を含有する反応液を準備する工程と、反応液にヒドロシリル化反応触媒（Ｃ）を加える工程とから構成されていてもよい。 The step of performing the addition reaction includes a step of preparing a reaction solution containing the hydrogen polysiloxane (A), the (meth) acrylate compound (B) and the β-diketone compound (D), and a hydrosilylation reaction catalyst ( And C).
（メタ）アクリロキシ基の重合反応を防止する目的で、反応系に、フェノチアジン，ヒンダードフェノール系化合物、アミン系化合物、キノン系化合物等の重合禁止剤を添加しておくことが好ましい。このような重合禁止剤の種類と量は、それらの添加によってヒドロシリル化反応の進行を妨げることなく、（メタ）アクリロキシ基、すなわち、アクリロキシ基又はメタアクリロキシ基の重合反応を防止することができれば特に限定されない。 For the purpose of preventing the polymerization reaction of the (meth) acryloxy group, it is preferable to add a polymerization inhibitor such as phenothiazine, a hindered phenol compound, an amine compound or a quinone compound to the reaction system. The type and amount of such a polymerization inhibitor are particularly limited as long as the addition of them can prevent the polymerization reaction of (meth) acryloxy groups, that is, acryloxy groups or methacryloxy groups, without hindering the progress of the hydrosilylation reaction. Not.
付加反応終了後、反応混合物を水洗や活性炭処理等の一般的な方法によって付加反応触媒を除去することができる。余剰のアルケニル基含有（メタ）アクリレート化合物（Ｂ）及びβ−ジケトン化合物（Ｄ）、溶剤を使用した場合の溶剤等は、加熱及び／又は減圧下で留去して、上記一般式（１）のオルガノポリシロキサンを得ることができる。 After completion of the addition reaction, the addition reaction catalyst can be removed from the reaction mixture by a common method such as washing with water or activated carbon treatment. The surplus alkenyl group-containing (meth) acrylate compound (B) and β-diketone compound (D), the solvent in the case of using a solvent, etc. are distilled off under heating and / or reduced pressure, and the above general formula (1) The organopolysiloxane can be obtained.
以下、実施例を挙げて本発明についてより具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。実施例、比較例においては以下の方法によって測定及び評価を行った。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In Examples and Comparative Examples, measurement and evaluation were performed by the following methods.
（１）ＳｉＨの反応率の算出
サンプリングした反応溶液０．０５ｇを重水素化クロロホルム溶媒１ｇに溶解して測定試料とした。この測定試料を用いて、４００ＭＨｚ（日本分光社製α−４００）の１Ｈ ＮＭＲの測定を積算回数１００回にて行い、得られた結果を解析した。ＳｉＨの反応率は、反応前と反応後のＳｉ−ＣＨ３に由来する０．２ｐｐｍのピークとＳｉＨに由来する４．６ｐｐｍのピークの面積比を求め、下記式に従い、算出した。ＳｉＨの反応率が９８％以上である場合をＡ、９０％以上９８％未満である場合をＢ、９０％未満である場合をＣと評価した。
ＳｉＨの反応率（％）＝［（Ａ１−Ｂ１）／Ａ１］×１００
Ａ１：反応前のピーク面積比
（反応前のＳｉＨのピーク面積）／（反応前のＳｉ−ＣＨ３のピーク面積）
Ｂ１：反応後のピーク面積比
（反応後のＳｉＨのピーク面積）／（反応後のＳｉ−ＣＨ３のピーク面積）
(1) Calculation of reaction rate of SiH 0.05 g of sampled reaction solution was dissolved in 1 g of deuterated chloroform solvent to prepare a measurement sample. Using this measurement sample, 1 H NMR measurement at 400 MHz (manufactured by JASCO Corporation α-400) was performed at 100 integration times, and the obtained results were analyzed. The reaction rate of SiH was calculated according to the following formula by obtaining the area ratio of the peak of 0.2 ppm derived from Si—CH 3 before the reaction and the peak of 4.6 ppm derived from SiH. The case where the reaction rate of SiH was 98% or more was evaluated as A, the case where it was 90% or more and less than 98% was evaluated as B, and the case where it was less than 90% was evaluated as C.
SiH reaction rate (%) = [(A1-B1) / A1] × 100
A1: Peak area ratio before reaction (peak area of SiH before reaction) / (peak area of Si—CH 3 before reaction)
B1: Peak area ratio after reaction (peak area of SiH after reaction) / (peak area of Si—CH 3 after reaction)
（２）ゲル化
サンプリングした反応溶液１ｇを０．２μｍ径のフィルターを取り付けたシリンジに入れ、溶液がフィルターを通過したらＡ、溶液がフィルターを通過しなかったらＣと評価した。
(2) Gelation 1 g of the sampled reaction solution was put into a syringe equipped with a 0.2 μm filter, and A was evaluated when the solution passed through the filter, and C was evaluated when the solution did not pass through the filter.
（３）反応選択性の算出
サンプリングした反応溶液０．０５ｇを重水素化クロロホルム溶媒１ｇに溶解して測定試料とした。この測定試料を用いて、４００ＭＨｚ（日本分光社製α−４００）の１Ｈ ＮＭＲの測定を積算回数１００回にて行い、得られた結果を解析した。アリルメタクリレートのメタクリル基の反応率は、反応前と反応後のＳｉ−ＣＨ３に由来する０．２ｐｐｍのピークとアリルメタクリレートのメタクリル基の二重結合に由来する５．５ｐｐｍのピークの面積比を求め、下記式に従い、算出した。アリルメタクリレートのメタクリル基の反応率が２％未満である場合をＡ、２％以上１０％未満である場合をＢ、１０％以上である場合をＣと評価した。なお、副反応であるメタクリル基の反応率が低いほど、反応選択性が優れていることを意味する。
アリルメタクリレートのメタクリル基の反応率（％）＝［（Ａ２−Ｂ２）／Ａ２］×１００
Ａ２：反応前のピーク面積比
（反応前のメタクリル基のピーク面積）／（反応前のＳｉ−ＣＨ３のピーク面積）
Ｂ２：反応後のピーク面積比
（反応後のメタクリル基のピーク面積）／（反応後のＳｉ−ＣＨ３のピーク面積）
(3) Calculation of reaction selectivity 0.05 g of the sampled reaction solution was dissolved in 1 g of deuterated chloroform solvent to prepare a measurement sample. Using this measurement sample, 1 H NMR measurement at 400 MHz (manufactured by JASCO Corporation α-400) was performed at 100 integration times, and the obtained results were analyzed. The reaction rate of the methacrylic group of allyl methacrylate is the area ratio of the peak of 0.2 ppm derived from Si—CH 3 before and after the reaction and the peak of 5.5 ppm derived from the double bond of the methacrylic group of allyl methacrylate. Obtained and calculated according to the following formula. The case where the reaction rate of the methacryl group of allyl methacrylate was less than 2% was evaluated as A, the case where it was 2% or more but less than 10%, and the case where it was 10% or more as C. In addition, it means that reaction selectivity is excellent, so that the reaction rate of the methacryl group which is a side reaction is low.
Reaction rate of methacryl group of allyl methacrylate (%) = [(A2-B2) / A2] × 100
A2: Peak area ratio before reaction (peak area of methacryl group before reaction) / (peak area of Si—CH 3 before reaction)
B2: Peak area ratio after reaction (peak area of methacryl group after reaction) / (peak area of Si—CH 3 after reaction)
［実施例１］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート（メタクリル酸アリル）１３０ｇ（１．０モル）及び、アセチルアセトン５２ｇ（０．５モル、［アセチルアセトン］／［ＳｉＨ］のモル比＝１．２５）、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して４．０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。フラスコ内容物の分析を行ったところ、ＳｉＨ基の赤外吸光（ＦＴ−ＩＲ）による２１３０ｃｍ−１の特性吸収及び１Ｈ ＮＭＲによる４．６ｐｐｍのピークは、ほぼ消失していた（ＳｉＨの反応率＞９９％）。また、反応系のゲル化も確認されなかった。１Ｈ ＮＭＲによる解析の結果、アリルメタクリレートのメタクリル基の二重結合に由来する５．５ｐｐｍのピークは減少せず、アリルメタクリレートのアリル基の二重結合に由来する５．２ｐｐｍのピークのみが減少していた（アリルメタクリレートのメタクリル基の反応率＜２％）。
[Example 1]
In a 0.5 L three-necked flask equipped with a stirrer, thermometer, reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol), allyl methacrylate (methacrylic acid) Allyl) 130 g (1.0 mol) and acetylacetone 52 g (0.5 mol, [acetylacetone] / [SiH] molar ratio = 1.25), hydroquinone monomethyl ether 0.05 g (polymerization inhibitor), The mixture was heated to 40 ° C. with stirring under a nitrogen gas atmosphere. Thereafter, platinum 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex is added in an amount such that the platinum metal is 4.0 ppm based on the weight of the organopolysiloxane which is an addition reaction product. Added. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm −1 by infrared absorption (FT-IR) of SiH group and the peak at 4.6 ppm by 1 H NMR almost disappeared (reaction rate of SiH > 99%). In addition, gelation of the reaction system was not confirmed. As a result of analysis by 1 H NMR, the 5.5 ppm peak derived from the methacrylic double bond of allyl methacrylate did not decrease, but only the 5.2 ppm peak derived from the allyl double bond of allyl methacrylate decreased. (Reaction rate of methacryl group of allyl methacrylate <2%).
その後、揮発成分を留去して、上記一般式（１）で表され、Ｒ１がメチル基、Ｒ２がメタアクリロキシ基、Ｘが−（ＣＨ２）３−であり、ａ、ｂ及びｃが、それぞれ、３〜４、０〜１及び０であり、ｂ／（ａ＋ｂ）の平均値が０．２０である付加反応生成物のオルガノポリシロキサン７７ｇを得た。 Thereafter, the volatile component is distilled off, represented by the general formula (1), wherein R 1 is a methyl group, R 2 is a methacryloxy group, X is — (CH 2 ) 3 —, and a, b and c are The addition reaction product organopolysiloxane 77g was 3-4, 0-1 and 0, respectively, and the average value of b / (a + b) was 0.20.
［実施例２］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）及び、アセチルアセトン３８３ｇ（３．８モル、［アセチルアセトン］／［ＳｉＨ］のモル比＝９．５）、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して４．０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。フラスコ内容物の分析を行ったところ、ＳｉＨ基の赤外吸光（ＦＴ−ＩＲ）による２１３０ｃｍ−１の特性吸収及び１Ｈ ＮＭＲによる４．６ｐｐｍのピークは減少していた（ＳｉＨの反応率：９２％）。また、反応系のゲル化も確認されなかった。１Ｈ ＮＭＲによる解析の結果、アリルメタクリレートのメタクリル基の二重結合に由来する５．５ｐｐｍのピークは減少せず、アリルメタクリレートのアリル基の二重結合に由来する５．２ｐｐｍのピークのみが減少していた（アリルメタクリレートのメタクリル基の反応率＜２％）。
[Example 2]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol), 383 g of acetylacetone (3.8 mol, [acetylacetone] / [SiH] molar ratio = 9.5), and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were added under a nitrogen gas atmosphere. Warm to 40 ° C. with stirring. Thereafter, platinum 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex is added in an amount such that the platinum metal is 4.0 ppm based on the weight of the organopolysiloxane which is an addition reaction product. Added. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm −1 by infrared absorption (FT-IR) of SiH group and the peak at 4.6 ppm by 1 H NMR were decreased (reaction rate of SiH: 92 %). In addition, gelation of the reaction system was not confirmed. As a result of analysis by 1 H NMR, the 5.5 ppm peak derived from the methacrylic double bond of allyl methacrylate did not decrease, but only the 5.2 ppm peak derived from the allyl double bond of allyl methacrylate decreased. (Reaction rate of methacryl group of allyl methacrylate <2%).
その後、揮発成分を留去して、上記一般式（１）で表され、Ｒ１がメチル基、Ｒ２がメタアクリロキシ基、Ｘが−（ＣＨ２）３−であり、ａ、ｂ及びｃが、それぞれ、３〜４、０〜１及び０であり、ｂ／（ａ＋ｂ）の平均値が０．１６である付加反応生成物のオルガノポリシロキサン６５ｇを得た。 Thereafter, the volatile component is distilled off, represented by the general formula (1), wherein R 1 is a methyl group, R 2 is a methacryloxy group, X is — (CH 2 ) 3 —, and a, b and c are The addition reaction product organopolysiloxane 65g was 3-4, 0-1 and 0, respectively, and the average value of b / (a + b) was 0.16.
［実施例３］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）及び、アセチルアセトン５２ｇ（０．５モル、［アセチルアセトン］／［ＳｉＨ］のモル比＝１．２５）、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、塩化白金酸のイソプロパノール溶液を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して４．０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。フラスコ内容物の分析を行ったところ、ＳｉＨ基の赤外吸光（ＦＴ−ＩＲ）による２１３０ｃｍ−１の特性吸収及び１Ｈ ＮＭＲによる４．６ｐｐｍのピークはほぼ消失していた（ＳｉＨの反応率＞９９％）。また、反応系のゲル化も確認されなかった。１Ｈ ＮＭＲによる解析の結果、アリルメタクリレートのメタクリル基の二重結合に由来する５．５ｐｐｍのピークは若干減少し、アリルメタクリレートのアリル基の二重結合に由来する５．２ｐｐｍのピークも減少していた（アリルメタクリレートのメタクリル基の反応率：７．８％）。
[Example 3]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol) and 52 g of acetylacetone (0.5 mol, [acetylacetone] / [SiH] molar ratio = 1.25) and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were added under nitrogen gas atmosphere. Warm to 40 ° C. with stirring. Thereafter, an isopropanol solution of chloroplatinic acid was added in an amount such that platinum metal was 4.0 ppm based on the weight of the organopolysiloxane as an addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm −1 by infrared absorption (FT-IR) of SiH group and the peak at 4.6 ppm by 1 H NMR almost disappeared (reaction rate of SiH> 99%). In addition, gelation of the reaction system was not confirmed. As a result of 1 H NMR analysis, the 5.5 ppm peak derived from the methacrylic double bond of allyl methacrylate was slightly reduced, and the 5.2 ppm peak derived from the allyl double bond of allyl methacrylate was also reduced. (Reaction rate of methacryl group of allyl methacrylate: 7.8%).
その後、揮発成分を留去して、上記一般式（１）で表され、Ｒ１がメチル基、Ｒ２がメタアクリロキシ基、Ｘが−（ＣＨ２）３−であり、ａ、ｂ及びｃが、それぞれ、３〜４、０〜１及び０であり、ｂ／（ａ＋ｂ）の平均値が０．２２である付加反応生成物のオルガノポリシロキサン７５ｇを得た。 Thereafter, the volatile component is distilled off, represented by the general formula (1), wherein R 1 is a methyl group, R 2 is a methacryloxy group, X is — (CH 2 ) 3 —, and a, b and c are The addition reaction product organopolysiloxane 75g was 3-4, 0-1 and 0, respectively, and the average value of b / (a + b) was 0.22.
［実施例４］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）及び、ベンゾイルアセトン１１７ｇ（０．７モル、［ベンゾイルアセトン］／［ＳｉＨ］のモル比＝１．７５）、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して４．０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。フラスコ内容物の分析を行ったところ、ＳｉＨ基の赤外吸光（ＦＴ−ＩＲ）による２１３０ｃｍ−１の特性吸収及び１Ｈ ＮＭＲによる４．６ｐｐｍのピークは減少していた（ＳｉＨの反応率：９３％）。また、反応系のゲル化も確認されなかった。１Ｈ ＮＭＲによる解析の結果、アリルメタクリレートのメタクリル基の二重結合に由来する５．５ｐｐｍのピークは減少せず、アリルメタクリレートのアリル基の二重結合に由来する５．２ｐｐｍのピークのみが減少していた（アリルメタクリレートのメタクリル基の反応率＜２％）。
[Example 4]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol), 117 g of benzoylacetone (0.7 mol, [benzoylacetone] / [SiH] molar ratio = 1.75), 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor), and a nitrogen gas atmosphere Warm to 40 ° C. with stirring under. Thereafter, platinum 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex is added in an amount such that the platinum metal is 4.0 ppm based on the weight of the organopolysiloxane which is an addition reaction product. Added. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm −1 by infrared absorption (FT-IR) of SiH group and the peak at 4.6 ppm by 1 H NMR were reduced (SiH reaction rate: 93 %). In addition, gelation of the reaction system was not confirmed. As a result of analysis by 1 H NMR, the 5.5 ppm peak derived from the methacrylic double bond of allyl methacrylate did not decrease, but only the 5.2 ppm peak derived from the allyl double bond of allyl methacrylate decreased. (Reaction rate of methacryl group of allyl methacrylate <2%).
その後、揮発成分を留去して、上記一般式（１）で表され、Ｒ１がメチル基、Ｒ２がメタアクリロキシ基、Ｘが−（ＣＨ２）３−であり、ａ、ｂ及びｃが、それぞれ、３〜４、０〜１及び０であり、ｂ／（ａ＋ｂ）の平均値が０．１８である付加反応生成物のオルガノポリシロキサン６５ｇを得た。 Thereafter, the volatile component is distilled off, represented by the general formula (1), wherein R 1 is a methyl group, R 2 is a methacryloxy group, X is — (CH 2 ) 3 —, and a, b and c are The addition reaction product organopolysiloxane (65 g) was 3 to 4, 0 to 1 and 0, and the average value of b / (a + b) was 0.18.
［実施例５］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）及び、アセチルアセトン５２ｇ（０．５モル、［アセチルアセトン］／［ＳｉＨ］のモル比＝１．２５）、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、白金のアセチルアセトン錯体を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して２０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。フラスコ内容物の分析を行ったところ、ＳｉＨ基の赤外吸光（ＦＴ−ＩＲ）による２１３０ｃｍ−１の特性吸収及び１Ｈ ＮＭＲによる４．６ｐｐｍのピークは減少していた（ＳｉＨの反応率：９０％）。また、反応系のゲル化も確認されなかった。１Ｈ ＮＭＲによる解析の結果、アリルメタクリレートのメタクリル基の二重結合に由来する５．５ｐｐｍのピークは減少せず、アリルメタクリレートのアリル基の二重結合に由来する５．２ｐｐｍのピークのみが減少していた（アリルメタクリレートのメタクリル基の反応率＜２％）。
[Example 5]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol) and 52 g of acetylacetone (0.5 mol, [acetylacetone] / [SiH] molar ratio = 1.25) and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were added under nitrogen gas atmosphere. Warm to 40 ° C. with stirring. Then, the platinum acetylacetone complex was added in an amount such that the platinum metal was 20 ppm based on the weight of the organopolysiloxane as an addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm −1 by infrared absorption (FT-IR) of SiH group and the peak at 4.6 ppm by 1 H NMR were decreased (reaction rate of SiH: 90 %). In addition, gelation of the reaction system was not confirmed. As a result of analysis by 1 H NMR, the 5.5 ppm peak derived from the methacrylic double bond of allyl methacrylate did not decrease, but only the 5.2 ppm peak derived from the allyl double bond of allyl methacrylate decreased. (Reaction rate of methacryl group of allyl methacrylate <2%).
その後、揮発成分を留去して、上記一般式（１）で表され、Ｒ１がメチル基、Ｒ２がメタアクリロキシ基、Ｘが−（ＣＨ２）３−であり、ａ、ｂ及びｃが、それぞれ、３〜４、０〜１及び０であり、ｂ／（ａ＋ｂ）の平均値が０．０８である付加反応生成物のオルガノポリシロキサン６０ｇを得た。 Thereafter, the volatile component is distilled off, represented by the general formula (1), wherein R 1 is a methyl group, R 2 is a methacryloxy group, X is — (CH 2 ) 3 —, and a, b and c are The addition reaction product organopolysiloxane 60g was 3-4, 0-1 and 0, respectively, and the average value of b / (a + b) was 0.08.
［比較例１］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）及び、アセチルアセトン３３ｇ（０．３モル、［アセチルアセトン］／［ＳｉＨ］のモル比＝０．７５）、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して４．０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。反応系のゲル化が確認され、分析が困難になった。
[Comparative Example 1]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol), 33 g of acetylacetone (0.3 mol, [acetylacetone] / [SiH] molar ratio = 0.75), and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) are added under a nitrogen gas atmosphere. Warm to 40 ° C. with stirring. Thereafter, platinum 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex is added in an amount such that the platinum metal is 4.0 ppm based on the weight of the organopolysiloxane which is an addition reaction product. Added. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. The gelation of the reaction system was confirmed, making analysis difficult.
［比較例２］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）及び、アセチルアセトン５２５ｇ（５．２モル、［アセチルアセトン］／［ＳｉＨ］のモル比＝１２．６）、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して４．０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。フラスコ内容物の分析を行ったところ、ＳｉＨ基の赤外吸光（ＦＴ−ＩＲ）による２１３０ｃｍ−１の特性吸収及び１Ｈ ＮＭＲによる４．６ｐｐｍのピークは若干減少したが、反応の進行は非常に遅かった（ＳｉＨの反応率：３２％）。反応系のゲル化は確認されなかった。１Ｈ ＮＭＲによる解析の結果、アリルメタクリレートのメタクリル基の二重結合に由来する５．５ｐｐｍのピークは減少せず、アリルメタクリレートのアリル基の二重結合に由来する５．２ｐｐｍのピークは若干減少した（アリルメタクリレートのメタクリル基の反応率＜２％）。
[Comparative Example 2]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol), 525 g of acetylacetone (5.2 mol, [acetylacetone] / [SiH] molar ratio = 12.6), and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were added under a nitrogen gas atmosphere. Warm to 40 ° C. with stirring. Thereafter, platinum 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex is added in an amount such that the platinum metal is 4.0 ppm based on the weight of the organopolysiloxane which is an addition reaction product. Added. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm −1 by infrared absorption (FT-IR) of SiH group and the peak at 4.6 ppm by 1 H NMR were slightly reduced, but the progress of the reaction was very high. It was slow (SiH reaction rate: 32%). Gelation of the reaction system was not confirmed. As a result of analysis by 1 H NMR, the 5.5 ppm peak derived from the methacrylic double bond of allyl methacrylate did not decrease, and the 5.2 ppm peak derived from the allylic double bond of allyl methacrylate decreased slightly. (Reaction rate of methacryl group of allyl methacrylate <2%).
［比較例３］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）、アセチルアセトンの代わりにトルエン５２ｇ、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して４．０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。反応系のゲル化が確認され、分析が困難になった。
[Comparative Example 3]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol), 52 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were added instead of acetylacetone, and the mixture was heated to 40 ° C. with stirring in a nitrogen gas atmosphere. Thereafter, platinum 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex is added in an amount such that the platinum metal is 4.0 ppm based on the weight of the organopolysiloxane which is an addition reaction product. Added. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. The gelation of the reaction system was confirmed, making analysis difficult.
［比較例４］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）、アセチルアセトンの代わりにメチルエチルケトン５２ｇ、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して４．０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。反応系のゲル化が確認され、分析が困難になった。
[Comparative Example 4]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol), 52 g of methyl ethyl ketone and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were added in place of acetylacetone, and the mixture was heated to 40 ° C. with stirring in a nitrogen gas atmosphere. Thereafter, platinum 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex is added in an amount such that the platinum metal is 4.0 ppm based on the weight of the organopolysiloxane which is an addition reaction product. Added. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. The gelation of the reaction system was confirmed, making analysis difficult.
［比較例５］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）、アセチルアセトンの代わりにトルエン５２ｇ、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、白金のアセチルアセトン錯体を、白金金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して２０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。反応系のゲル化が確認され、分析が困難になった。
[Comparative Example 5]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol), 52 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were added instead of acetylacetone, and the mixture was heated to 40 ° C. with stirring in a nitrogen gas atmosphere. Then, the platinum acetylacetone complex was added in an amount such that the platinum metal was 20 ppm based on the weight of the organopolysiloxane as an addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. The gelation of the reaction system was confirmed, making analysis difficult.
［比較例６］
撹拌装置、温度計、還流冷却器を取り付けた０．５Ｌの３つ口フラスコに、１，３，５，７−テトラメチルシクロテトラシロキサン２５ｇ（ＳｉＨ：０．４モル）、アリルメタクリレート１３０ｇ（１．０モル）及び、アセチルアセトン５２ｇ（０．５モル、［アセチルアセトン］／［ＳｉＨ］のモル比＝１．２５）、ハイドロキノンモノメチルエーテル０．０５ｇ（重合禁止剤）を添加し、窒素ガス雰囲気下で攪拌しながら４０℃に加温した。その後、クロロトリス（トリフェニルホスフィン）ロジウム（Ｉ）を、ロジウム金属が、付加反応生成物であるオルガノポリシロキサンの重量に対して１０ｐｐｍとなる量を添加した。ヒドロシリル化反応の開始を確認した後、この反応系を保温、水冷又は空冷によって３５〜４５℃に保ちながら、７２時間攪拌した。フラスコ内容物の分析を行ったところ、ＳｉＨ基の赤外吸光（ＦＴ−ＩＲ）による２１３０ｃｍ−１の特性吸収及び１Ｈ ＮＭＲによる４．６ｐｐｍのピークは若干減少したが、反応はほとんど進まなかった（ＳｉＨの反応率：３％）。反応系のゲル化は確認されなかった。１Ｈ ＮＭＲによる解析の結果、アリルメタクリレートのメタクリル基の二重結合に由来する５．５ｐｐｍのピークは減少せず、アリルメタクリレートのアリル基の二重結合に由来する５．２ｐｐｍのピークは若干減少したが、反応はほとんど進まなかった（アリルメタクリレートのメタクリル基の反応率＜２％）。
[Comparative Example 6]
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) and 130 g of allyl methacrylate (1 0.0 mol) and 52 g of acetylacetone (0.5 mol, [acetylacetone] / [SiH] molar ratio = 1.25) and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were added under nitrogen gas atmosphere. Warm to 40 ° C. with stirring. Thereafter, chlorotris (triphenylphosphine) rhodium (I) was added in such an amount that the rhodium metal was 10 ppm relative to the weight of the organopolysiloxane as an addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 35 to 45 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm −1 by infrared absorption (FT-IR) of SiH group and the peak at 4.6 ppm by 1 H NMR were slightly reduced, but the reaction hardly proceeded. (SiH reaction rate: 3%). Gelation of the reaction system was not confirmed. As a result of analysis by 1 H NMR, the 5.5 ppm peak derived from the methacrylic double bond of allyl methacrylate did not decrease, and the 5.2 ppm peak derived from the allylic double bond of allyl methacrylate decreased slightly. However, the reaction hardly proceeded (reaction rate of methacryl group of allyl methacrylate <2%).
実施例及び比較例の結果を表１及び２に示す。また、表中における略号で表わした成分を表３に示す。 The results of Examples and Comparative Examples are shown in Tables 1 and 2. In addition, Table 3 shows components represented by abbreviations in the table.
本発明によれば、一つの反応容器内においてワンポットで簡便に（メタ）アクリロキシ基含有オルガノポリシロキサンを、ゲル化などの副反応を伴うことなく工業的に容易に製造することができる。そのため、分子設計どおりの（メタ）アクリロキシ基含有オルガノポリシロキサンを効率よく製造できる。 According to the present invention, a (meth) acryloxy group-containing organopolysiloxane can be easily and industrially easily produced without side reactions such as gelation in one reaction vessel in one pot. Therefore, the (meth) acryloxy group-containing organopolysiloxane according to the molecular design can be efficiently produced.
Claims (4)
（式中Ｒ1は置換若しくは非置換の炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基又はアラルキル基を示し、Ｒ２はアクリロキシ基又はメタアクリロキシ基を示し、Ｘは炭素数１〜１０の二価の炭化水素基を示し、ａは１以上の整数、ｂ及びｃはそれぞれ独立に０以上の整数を示し、ｂ／（ａ＋ｂ）の平均値は０．０５〜０．２５であり、ａ＋ｂ＋ｃは３〜２０の整数であり、同一分子中の複数のＲ１及びＲ２はそれぞれ同一でも異なっていてもよい。）で表されるオルガノポリシロキサン。 The following general formula (1):
(Wherein R 1 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group or an aralkyl group; R 2 represents an acryloxy group or a methacryloxy group; Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, a is an integer of 1 or more, b and c each independently represents an integer of 0 or more, and the average value of b / (a + b) is 0.05 to And a + b + c is an integer of 3 to 20, and a plurality of R 1 and R 2 in the same molecule may be the same or different.)
（式中Ｒ1は置換若しくは非置換の炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、アリール基又はアラルキル基を示し、ｄは１以上の整数を示し、ｅは０以上の整数を示し、ｄ＋ｅは３〜２０の整数である。）で表されるハイドロジェンポリシロキサン（Ａ）と、アルケニル基を有する（メタ）アクリレート化合物（Ｂ）との付加反応を、ヒドロシリル化反応触媒（Ｃ）の存在下で行う工程を備え、
前記付加反応が、ハイドロジェンポリシロキサン（Ａ）のＳｉＨ基に対するモル比が１．２〜１０．０の量のβ−ジケトン化合物（Ｄ）の存在下において行われ、
前記ヒドロシリル化反応触媒（Ｃ）が白金又は白金錯体である、請求項１に記載のオルガノポリシロキサンの製造方法。 The following general formula (2):
(Wherein R 1 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group or an aralkyl group, d represents an integer of 1 or more, and e represents 0 The above-mentioned integer is represented, and d + e is an integer of 3 to 20.) The hydrosilylation reaction of the hydrogen polysiloxane (A) represented by (A) and the (meth) acrylate compound (B) having an alkenyl group is performed. A step of performing in the presence of the reaction catalyst (C),
The addition reaction is performed in the presence of β-diketone compound (D) in an amount of 1.2 to 10.0 molar ratio of hydrogen polysiloxane (A) to SiH groups,
The method for producing an organopolysiloxane according to claim 1, wherein the hydrosilylation reaction catalyst (C) is platinum or a platinum complex.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012211235A (en) * | 2011-03-31 | 2012-11-01 | Asahi Kasei Chemicals Corp | Organopolysiloxane and thermosetting resin composition using the same, sealant for optical semiconductor, die-bonding material for optical semiconductor |
| WO2022066342A1 (en) * | 2020-09-24 | 2022-03-31 | Dow Silicones Corporation | Methods for the preparation and use of silyl ester compounds |
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| JPH05301881A (en) * | 1992-04-23 | 1993-11-16 | Toray Dow Corning Silicone Co Ltd | Production of acryloxy or methacryloxy group-containing organosilicon compound and its production |
| JP2009535464A (en) * | 2006-05-03 | 2009-10-01 | ビジョン シーアールシー リミティド | Biological polysiloxane |
| JP2010503175A (en) * | 2006-09-07 | 2010-01-28 | エルジー・ケム・リミテッド | Gel polymer electrolyte and electrochemical device provided with the same |
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| JPS5024947B1 (en) * | 1969-04-02 | 1975-08-20 | ||
| JPH02163166A (en) * | 1988-12-15 | 1990-06-22 | Toray Dow Corning Silicone Co Ltd | Production of organopolysiloxane-based polymer and radiation curing composition |
| JPH05301881A (en) * | 1992-04-23 | 1993-11-16 | Toray Dow Corning Silicone Co Ltd | Production of acryloxy or methacryloxy group-containing organosilicon compound and its production |
| JP2009535464A (en) * | 2006-05-03 | 2009-10-01 | ビジョン シーアールシー リミティド | Biological polysiloxane |
| JP2010503175A (en) * | 2006-09-07 | 2010-01-28 | エルジー・ケム・リミテッド | Gel polymer electrolyte and electrochemical device provided with the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012211235A (en) * | 2011-03-31 | 2012-11-01 | Asahi Kasei Chemicals Corp | Organopolysiloxane and thermosetting resin composition using the same, sealant for optical semiconductor, die-bonding material for optical semiconductor |
| WO2022066342A1 (en) * | 2020-09-24 | 2022-03-31 | Dow Silicones Corporation | Methods for the preparation and use of silyl ester compounds |
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