MXPA96003777A - Catalysts of microparticles for reactions of hidrosililation and compositions of siliconatermendurecibles that contain the catalyst - Google Patents
Catalysts of microparticles for reactions of hidrosililation and compositions of siliconatermendurecibles that contain the catalystInfo
- Publication number
- MXPA96003777A MXPA96003777A MXPA/A/1996/003777A MX9603777A MXPA96003777A MX PA96003777 A MXPA96003777 A MX PA96003777A MX 9603777 A MX9603777 A MX 9603777A MX PA96003777 A MXPA96003777 A MX PA96003777A
- Authority
- MX
- Mexico
- Prior art keywords
- catalyst
- weight
- microparticle
- catalysts
- component
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000011859 microparticle Substances 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 title description 3
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000009477 glass transition Effects 0.000 claims abstract description 17
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 7
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 6
- 125000005375 organosiloxane group Chemical group 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 37
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 39
- -1 polysiloxane Polymers 0.000 description 28
- 239000000243 solution Substances 0.000 description 22
- 229910052697 platinum Inorganic materials 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007921 spray Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- MQSZOZMNAJHVML-UHFFFAOYSA-N 3-phenylbut-1-yn-1-ol Chemical compound OC#CC(C)C1=CC=CC=C1 MQSZOZMNAJHVML-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CGMFKBXPQJJHBR-UHFFFAOYSA-N [SiH3]O[SiH](C=C)C=C Chemical compound [SiH3]O[SiH](C=C)C=C CGMFKBXPQJJHBR-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000003158 alcohol group Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical group C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- QRLBICHXRCOJDU-UHFFFAOYSA-N methyl(phenyl)silane Chemical group C[SiH2]C1=CC=CC=C1 QRLBICHXRCOJDU-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Chemical class CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a microparticle catalyst for use in hydrosilylation reactions. The catalyst consists of microparticles with an average particle diameter of 0.1 to 20æm, consisting of a metal catalyst for hydrosilylation reactions, a disiloxane having the general formula (R 1 R 2ArSi) 2O, wherein R 1 is an alkenyl group, R 2 is a monovalent hydrocarbon group and Ar is an aryl group and a resin having a glass transition temperature of 40 to 200øC. Also described is a thermosetting silicone composition in combination with the microparticle catalyst.
Description
MICROPARTICLE CATALYSTS FOR HYDROSILILATION REACTIONS AND THERMO-DENSITIZED SILICONE COMPOSITIONS
WHAT CONTAINS THE CATALYST
DESCRIPTION OF THE INVENTION
This invention relates to a microparticulate catalyst for hydrosilylation reactions and thermosetting silicone compositions containing the catalyst. The microparticulate catalysts have catalytic activity and provide thermosetting silicone compositions of superior storage stability, which can be maintained in an unhardened state for extended periods. Generally, thermoplastic resin catalysts containing metal catalysts, hydrosilylation reactions and thermosetting silicone compositions containing such catalysts are known. For example, catalysts having softening points or melting points in the order of 40 to 200 ° C have been proposed in JP-A 49-134786, 58-37053, 2-4833 and 2-9448. Catalysts have also been proposed in microparticles formed of metal catalysts and organic resins in JP-A 5837053, 64-45468, 64-47442, 64-51140, 3-68659 and 7-41678. However, the metal catalysts REF: 23051 of these microparticulate catalysts are easily decomposed by heating operations during manufacture, with decreased catalytic activity. Even when the decomposition is very light and sufficient catalytic activity is obtained, the discoloration due to decomposition products can not be avoided. Furthermore, when these microparticulate catalysts are used as a curing catalyst in an organosiloxane composition, there is a problem that the hardening of the composition proceeds during storage and that an unhardened state is not maintained for a prolonged period. As a result of intensive studies, this invention was led to discover that the above problems are solved when a metal catalyst for the hydrosilylation reactions and the specified disiloxanes are present together in the claimed microparticle catalysts for the hydrosilylation reactions. The aim of this invention is to provide a microparticle catalyst for the hydrosilylation reactions of higher catalytic activity and to provide a thermosetting silicone composition of superior storage stability, which is stored in an unhardened state for extended periods. This invention is a microparticle catalyst, having an average particle diameter of 0.1 to 20 μm for hydrosilylation reactions, comprising: (i) a metal catalyst for hydrosilylation reactions having from 0.01 to 5% by weight of atoms of metal; (ii) from 0.1 to 5% by weight of a disiloxane having the general formula (R1R2ArSi) 20, wherein R1 is an alkenyl group, R2 is a monovalent hydrocarbon group and Ar is an aryl group; and (iii) a resin having a glass transition temperature of 40 to 200 ° C. This invention also relates to a thermosetting silicone composition comprising: (A) 100 parts by weight of the organopolysiloxane containing an average of at least two alkenyl groups bonded by silicon per molecule; (B) an organohydrogenpolysiloxane, containing an average of at least two hydrogen atoms bonded by silicon per molecule, in an amount sufficient to provide an amount such that the ratio of the number of moles of hydrogen atoms attached to the silicon in this component and the number of moles of alkenyl groups attached to the silicon in component (A) is in the range of 0.5 / 1 to 10/1; and (C) from 0.005 to 100 parts by weight of a microparticle catalyst for the hydrosilylation reactions, comprising (i) a metal catalyst for hydrosilylation reactions having from 0.01 to 5% by weight of metal atoms; (ii) from 0.01 to 5% by weight of a disiloxane having the general formula (R1R2ArSi) 20, wherein R1 is an alkenyl group, R2 is a monovalent hydrocarbon group and Ar is an aryl group; and (iii) a resin having a glass transition temperature of 40 to 200 °; wherein the microparticulate catalyst has an average particle diameter of 0.1 to 20 μm. The metal catalyst of this invention is a metal catalyst that has catalytic activity for the hydrosilylation reactions. Examples include, but are not limited to, platinum catalysts, such as chloroplatinic acid, or chloroplatinic acid modified with alcohol; platinum and olefin complexes; complexes of platinum or chloroplatinic acid and diketones; complexes of platinum or chloroplatinic acid and divinyldisiloxane; platinum transported in alumina, silica and carbon black; palladium catalysts such as tetrakis (triphenyl-phosphine) palladium; and metal catalysts such as rhodium, nickel and cobalt. Of these, platinum catalysts are preferred and the platinum and divinyldisiloxane complexes are particularly preferred from the point of view of catalytic activity. These catalysts can be used individually or as a mixture of two or more. A catalyst that has dissolved in a liquid can also be used. When a complex of platinum and divinyldisiloxane is used, it can be dissolved in an alcohol, a hydrocarbon solvent or a liquid polysiloxane at normal temperature. The amount of the metal catalyst in the microparticle of this invention is from 0.01 to 5% by weight and preferably from 0.05 to 2% by weight as metal atoms. When the content is less than 0.01% by weight, the amount of the composition of this invention is excessive and the inherent properties of the composition are lost.
When it exceeds 5% by weight, it is difficult to maintain the metallic catalyst in the microparticle of this invention. The microparticle catalysts of the present invention are characterized by the presence of a disiloxane having the general formula (R1R2ArSi) 20, The disiloxane acts to stabilize the metal catalyst of our microparticle particle catalyst. When added to a composition that is cured by means of a hydrosilylation reaction, the composition can be maintained in an uncured state for a prolonged period. In the above formula, R1 is an alkenyl group, preferably a vinyl group or an allyl group. Of these, vinyl groups are particularly preferred. R2 is a monovalent hydrocarbon group. R 2 is exemplified, but not limited to, alkyl groups such as a methyl group or an ethyl group; alkenyl groups, such as a vinyl group or an allyl group; and aryl groups, such a phenyl group or a naphthyl group. Ar of the formula is an aryl group and preferably a phenyl group a naphthyl group. Of these, phenyl groups are preferable. Examples of disiloxanes which are used in the present invention include, but are not limited to, syn-divinyl dimethyldiphenyldisiloxane, syn-divinyltetraphenyldisiloxane and syn-tetravinyldiphenyldisiloxane. The amount of disiloxane present in the microparticle catalysts of the present invention is from 0.1 to 5% by weight. When the amount of disiloxane is less than 0.1% by weight, the effect of the disiloxane can not be manifested. When the amount of the disiloxane present in the microparticulate catalyst exceeds 5% by weight, the compositions containing the microparticulate catalyst tend to harden during storage. The resin that is used in the microparticulate catalyst must not be a substance that poisons the metal catalyst for hydrosilylation reactions. Examples of usable resins include, but are not limited to, silicone resins, polysilane resins, polycarbonate resins, acrylic resins such as polymethyl acrylate and copolymers of methyl methacrylate and butyl methacrylate, polyester resins, polyethylene, polystyrene, chloride of polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride and polyvinylidene chloride copolymers, polyamides, cellulose esters such as cellulose acetate and cellulose acetate butyrate. Suitable silicone resins include, for example, the resins formed of monophenylsiloxane units, diphenylsiloxane units and dimethylsiloxane units; resins formed of monophenylsiloxane units and dimethylsiloxane units; and the resins formed of monophenylsiloxane units and methylvinylsiloxane units. The polysilane resins may include, for example, the resins formed of methylphenylsilane units and dimethylsilane units. It is necessary that the transition point of glass of these resins, are in the range of 40 to 200 ° C. When the glass transition point of the resin is less than 40 ° C, the manufacture of the microparticulate catalysts of this invention is difficult and compositions containing this microparticulate catalyst can not be stored for extended periods in a state without toughen. When the glass transition point exceeds 200 ° C, the cure rate of the composition containing the microparticle catalyst is not sufficient. The resins mentioned in the above are all known as thermoplastic resins. Resins that are generally classified as thermosetting resins can also be used. The heat setting resins that are useful in the present invention should also have glass transition points within the range of 40 to 200 ° C. The glass transition point is determined using a DSC (differential scanning calorimeter). The microparticle catalyst of the present invention, has an average particle diameter of 0.1 to 20 μm. When the average particle diameter is less than 0.1 μm, the storage stability of the compositions containing the microparticulate catalyst is not sufficient. When the diameter of the average particle exceeds 20 μm, the curing of the compositions containing the microparticulate catalyst is not uniform. There are no particular limitations on the form of the catalyst in microparticles. However, a spherical shape is advantageous to obtain good reproducibility of the inhibition of the catalytic activity and manifestation of the catalytic activity.
The methods of making the particulate catalyst of this invention include, for example, a method in which the metal catalyst, the disiloxane and the resin are dissolved in a solvent such as toluene, after which a resin containing the metal catalyst and the disiloxane is manufactured by drying on evaporation of the solvent (see JP-A 58-37053); a method in which the metal catalyst, the disiloxane and the resin are dissolved in a solvent having a low boiling point, such as methylene chloride, chloroform, tetrahydrofuran or diethyl ether, then the solution of the product is added in droplets to a aqueous solution of a surfactant, to form an emulsion of oil and water type, therefore the solid microparticles are obtained by gradually removing the solvent (see JP-A 2-4833); and a method in which the metal catalyst, the disiloxane and the resin are dissolved in a solvent such as toluene or dicyclomethane, the solution is sprayed immediately in a stream of hot air, with the solvent being volatilized and with the resin containing the metal catalyst and the disiloxane in the spray state which is solidified (see JP-A 4-29748). The microparticle catalyst of this invention, obtained in this form, can be used in this unaltered form, or the metal catalyst which is present on the surface of the particles, can be removed by washing using a solvent such as methyl alcohol, ethyl alcohol, hexamethyldisiloxane and octamethylcyclotetrasiloxane, which removes the metal catalysts without dissolving the resin. The component (A), which is an organopolysiloxane, is the component which forms the main agent of the silicone composition of this invention, has an average of at least two alkenyl groups bonded by silicon per molecule. Examples of the alkenyl groups include vinyl, allyl and hexenyl. Examples of organic groups that are bonded with the silicon atom, in addition to the alkenyl group in this organopolysiloxane include alkyl, such as methyl, ethyl, propyl, butyl, hexyl and octyl; aryl, such as phenyl; and monovalent hydrocarbon groups as exemplified by substituted hydrocarbons such as the 3,3,3-trifluoropropyl groups. The number of organic groups that are bonded to the silicon atom, must average from 1.0 to 2.3. This organopolysiloxane is generally a straight chain, but it can also have some branched chains. The viscosity of this organopolysiloxane at 25 ° C is in the range of 10 to 1,000,000 mm2 / s (centipoise). Examples of organopolysiloxanes, which constitute this component, include dimethylpolysiloxane blocked at both terminals by dimethylvinylsiloxane groups, dimethylsiloxane-methylvinylsiloxane copolymers blocked at both terminals by trimethylsiloxane groups, dimethylsiloxane-methylhexenylsiloxane copolymers blocked at both terminals by dimethylhexenylsiloxane groups and methyltrifluoropropylpolysiloxanes blocked at both terminals by dimethylvinylsiloxane groups. Individual polymers, copolymers or mixtures of two or more polymers can be used. Component (B), an organohydrogenpolysiloxane, is the crosslinking agent for component (A). Component (B) has an average of at least two hydrogen atoms bonded by silicon per molecule. The organic groups which are bonded with the silicon atoms in this component, in addition to the hydrogen atoms include alkyl groups, such as methyl, ethyl, propyl, butyl, hexyl and octyl; aryl groups, such as phenyl; and monovalent hydrocarbon groups, as exemplified by substituted hydrocarbons such as the 3,3,3-trifluoropropyl groups. The molecular structure of this organohydrogenpolysiloxane can be straight chain, network or three dimensional. Individual polymers, copolymers or mixtures of two or more polymers can be used. The viscosity of this organohydrogenpolysiloxane at 25 ° C is in the range of 0.5 to 50, 000 mm2 (s) (centipoise) and preferably in the range of 1 to 10,000 mm2 / s (centipoise) The amount of this component forming the compound is an amount such that the ratio of the moles of hydrogen atoms attached to silicon in this component, the number of moles of alkenyl groups attached to the silicon in component (A) is in the range of 0.5 / 1 to 10/1. The organohydrogenpolysiloxane can be a copolymer of dimethylsiloxane-methylhydrogensiloxane blocked in both terminals by trimethylsiloxane groups, a di-ethylsiloxane-methylhydrogensiloxane copolymer blocked at both terminals, by dimethyhydrogenosiloxane groups or a methylhydrocyclosiloxane having three or more silicon atoms Component (C) is a microparticulate catalyst for the hydrosilylation reactions described herein. The component (C) is the catalyst for effecting the crosslinking of the component (A), the alkenyl groups bound with silicon atoms. or and component (B), the hydrogen atoms bonded with the silicon atoms, by means of a hydrosilylation reaction. The microparticle catalyst of this invention has an average particle diameter of 0.1 to 20 μm and contains the metal catalyst mentioned above in an amount of 0.01 to 5% by weight as metal atoms with 0.1 to 5% by weight of the metal catalyst. disiloxane mentioned in the above. The amount of this component that is formed as a compound is in the range of 0.005 to 100 parts of the component (C) per 100 parts by weight of the component (A) and preferably, in the range of 0.1 to 100 ppm, calculated as atoms of metal, in the composition of organosiloxane. The composition of this invention is formed of the components (A) to (C) mentioned in the above. In addition, various additives may be forming a compound as long as the objects of the invention are not impaired. The additives which may be forming a compound in the compositions of the present invention include, but are not limited to, powdered silicas, such as silica foam and wet silica, silica powder that has been subjected to surface hydrophobic treatment.; crepe hardening inhibitors; polymers other than silicone; organic solvents; iron oxide; heat resistant agents, such as rare earth compounds; flame retardants, such as manganese carbonate and titanium oxide in aerosol; phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylenediamine and benzotriazole; sulfur-containing compounds; acetylene compounds; compounds containing two or more alkenyl groups; hydroperoxy compounds; compounds that inhibit the hydrosilylation reaction such as maleic acid derivatives; diatomaceous earth; calcium carbonate; glass fibers; and carbon black.
The composition of this invention is easily obtained by mixing the components mentioned in the above (A) to (C) uniformly. For example, component (C) can be added to a small amount of component (A) and dispersed uniformly, after blocking this mixture can be added to a mixture of component (A) and component (B). It is advantageous that the temperature does not exceed the glass transition temperature of the resin, which constitutes component (C) by more than 50 ° C. The microparticulate catalyst for the hydrosilylation reaction is of high catalytic activity and the discoloration due to the products of decomposition is not observed. Because of this, the claimed microparticle catalyst of the invention is suitable for use as a catalyst for elastomers and resin compositions, in which an organopolysiloxane is used as the base polymer. In addition, the thermosetting silicone composition of this invention, which contains the microparticulate catalyst, has the characteristics of remaining in an unhardened state at room temperature for prolonged periods and after storage, curing quickly with heat. Accordingly, the silicone composition of this invention is extremely useful as a single thermosetting silicone composition, in solution.
Next, a detailed description of this invention is demonstrated by means of the examples. In the examples, Ph denotes a phenyl group, Me indicates a methyl group, Vi indicates a vinyl group and g is in grams. The viscosity is the value determined at 25 ° and cp is centipoise.
COMPARATIVE EXAMPLE 1
6 g of the aqueous chloroplatinic acid solution (content of platinum metal of 33% by weight) and 16 g of 1,3-divinyl tetrametidyl disiloxane are dissolved in 35 g of isopropyl alcohol. 10 g of sodium bicarbonate are added to this solution and a reaction is carried out in a suspended state for 30 minutes at 70 to 80 ° C as the solution is stirred. After cooling the solid component is removed by filtration and a solution of isopropyl alcohol at 4.2% by weight of the platinum vinyl siloxane component containing the platinum metal is prepared.
EXAMPLE 1
819 g of the thermoplastic silicone resin, which has a glass transition point of 66.5 ° C as indicated by the average unit formula (PhSiO3 2) 0 78 (Me2SiO) 0 22 and which has a glass transition point of 66.5 ° C, 72 g of the thermoplastic silicone resin, which has a glass transition point of 65.2 ° C as indicated by the average unit formula (PhSi03 // 2) 0 _7Q (MeViSiO) 0 _22 y; having a glass transition point of 65.2 ° C and 9.0 g of syn-dimethyldiphenyldivinylsiloxane are introduced into a mixed solvent of 500 g of toluene and 4,600 g of dichloromethane in a vessel equipped with a stirrer and stirred to a uniform state. Then, 88.8 g of the isopropyl alcohol solution of the platinum vinylsiloxane complex obtained in Comparative Example 1 are introduced into this mixture and a uniform solution is obtained by mixing. This solution is sprayed continuously in a spray dryer tank
(manufactured by Ashizawa Nitro Atomizers Ltd., in which nitrogen gas was present as the flow of hot gas using a dual fluid nozzle.) The hot flow temperature of the nitrogen gas was 95 ° C at the inlet of the spray dryer. and it was 45 ° C at the spray dryer outlet with the flow velocity of the hot gas at 1.3 m3 / minute.The operation is carried out for 1 hour under the conditions mentioned in the above, and 415 g of the catalyst in microparticles, white for the hydrosilylation reaction that was produced, are collected by means of a retrofilter.The average particle diameter of the microparticle catalyst obtained was 1.5 μm and the platinum content was 0.40% by weight as metal atoms.
COMPARATIVE EXAMPLE 2
408 g of the microparticle catalyst for the hydrosilylation reaction was manufactured in the same manner as in Example 1, except that syn-dimethyldiphenyldivinylsiloxane was not added and the amount of the thermoplastic silicone resin, forming a compound was changed to 828 g. The obtained microparticle catalyst was white-gray; its average particle diameter was 1.6 μm; and its platinum content was 0.40% by weight.
EXAMPLE 2
g of fuming silica, the surface of which was subjected to the hydrophobic treatment with hexamethyldisilazane, with a specific surface area of 150 m / g, is added to and mixed thoroughly with a mixture of 100 g of dimethylpolysiloxane terminated in dimethylvinylsiloxane from a viscosity of 12,000 mm2 / s (cp) and 100 g of dimethypolysiloxane terminated in dimethylvinylsiloxane of a viscosity of 1,500 mm / s (cp), after which 2.8 g of a diorganosiloxane as indicated by the average molecular formula Me3SiO (Me2SiO) 3 (MeHSiO) 5SiMe3 and 0.04 g of phenylbutynol are added and then mixed to a uniform state. Next, the microparticle catalyst of Example 1 is added to this mixture in an amount such that the platinum metal content of the mixture was 5 ppm, after which the materials are completely mixed, with a thermosetting silicone composition which is prepared. The thermosetting characteristics of the obtained thermosetting silicone composition are determined at 130 ° C and 150 ° C with a Curastometer ™ Model 5 (manufactured by Orientech Company). The thermosetting characteristics are determined by taking the time until the torque is reached to a maximum of 10% as the hardening initiation time (T ^ Q) and the time until the torque reaches a maximum of 90% when the hardening time ends (Tgo). The product of the thermosetting silicone composition is introduced into a sealed container and aged at 50 ° C. The number of days required for hardening was determined and the discovery was reported as stability during storage. The results are shown in Table 1. Based on these results, it was found that the rate of curing during heating increased and that the non-hardening state at room temperature could be maintained for prolonged periods by adding syn-dimethyldiphenyl-divinyldisiloxane.
COMPARATIVE EXAMPLE 3
The thermosetting silicone composition of Example 2 was prepared in the same manner except that the microparticle catalyst for the hydrosilylation reactions obtained in Comparative Example 2 is added in place of the microparticle catalyst of Example 1. The thermosetting and storage stability properties of the obtained thermosetting silicone composition are determined as in Example 2. The results are also shown in Table 1.
Table 1 Example 2 Comparative Example 3
Thermosetting characteristics 130 ° C T10 (seconds) 72.6 78.0 T90 (seconds) 84.6 91.2 150 ° C T1Q (seconds) 23.4 23.4 T90 (seconds) 29.4 30.0 Stability during storage (days) 41 29 EXAMPLE 3
500 g of the polycarbonate resin having a glass transition point of about 140 ° C (Inpilon H-3000 manufactured by Mitsubishi Gas Chemical Company, Ltd. of Tokyo Japan) are dissolved in 8.5 kg of dichloromethane and 5.0 g are added. of syn-dimethylphenyldivinyl-disiloxane and 1.0 kg of toluene and mixed. Next, 23.8 g of the isopropyl alcohol solution of the platinum vinyl siloxane complex obtained in Comparative Example 1 are introduced and mixed with this solution, until a uniform solution is obtained. This solution is sprayed continuously in the spray dryer tank of Example 1. The temperature of the hot flow of nitrogen gas was 100 ° C at the inlet of the spray dryer and was 70 ° C at the spray dryer outlet with the hot gas flow rate at 1.3 m3 / minute. The operation is carried out for 5 hours under the conditions mentioned in the above and 380 g of the catalyst in microparticles, white for the hydrosilylation reaction that was produced, are collected by means of a retrofilter. The average particle diameter of the microparticle catalyst obtained was 1.47 μm and the platinum content was 0.2% by weight.
COMPARATIVE EXAMPLE 4
408 g of the microparticle catalyst for the hydrosilylation reaction was manufactured in the same manner, except that syn-dimethyldiphenyldivinyldisiloxane was not added in Example 3. The obtained microparticle catalyst was gray, its average particle diameter was 1.44 μm; and its platinum content was 0.2% by weight.
EXAMPLE 4
g of fuming silica, with a specific surface area of 150 m / g, the surface of which had been subjected to the hydrophobic treatment with hexamethyldisilazane, is added to and mixed thoroughly with a mixture of 100 g of dimethylpolysiloxane terminated in dimethylvinylsiloxane from a viscosity of 12,000 mm2 / s (cp) and 100 g of dimethypolysiloxane terminated in dimethylvinylsiloxane of a viscosity of 1,500 mm2 / s (cp), after which 2.8 g of a diorganosiloxane as indicated by the average molecular formula Me3SiO (Me2SiO) 3 (MeHSiO) 5SiMe3 and 0.04 g of phenylbutynol are added and then mixed to a uniform state. Next, the microparticle catalyst of Example 3 is added to this mixture in an amount such that the platinum metal content of the mixture was 2.5 ppm, after which the materials are thoroughly mixed, with a thermosetting silicone composition which is prepared. The thermosetting characteristics of the thermosetting silicone composition obtained are determined at 150 ° C and 170 ° C with a Curastometer ™ model 5 similar to that used in Example 2. The thermosetting characteristics are determined (T10) and (g0) as in Example 2. The product of the thermosetting silicone composition is introduced into a sealed container and aged at 50 ° C. The number of days for hardening was determined and the discovery was taken as stability during storage. The results are shown in Table 2. Based on these results, it was found that the curing rate during heating increased and that the non-hardening state at room temperature could be maintained for prolonged periods by adding syn-dimethyldiphenyl-divinyldisiloxane.
COMPARATIVE EXAMPLE 5
The thermosetting silicone composition of Example 4 was prepared in the same manner except that the microparticle catalyst for the hydrosilylation reactions obtained in Comparative Example 4 is added in place of the microparticle catalyst of Example 3. The thermosetting properties and The storage stability of the thermosetting silicone composition obtained is determined as in Example 4. The results are shown in Table 2.
Table 2
Example 4 Comparative Example 5
Heat curing characteristics 150 ° C T1Q (seconds) 130.8 167.4 T90 (seconds) 162.0 205.2 170 ° C T10 (seconds) 26.4 30.6 T9Q (seconds) 39.6 48.6 Stability during storage (days) 247 217
EXAMPLE 5
500 g of a copolymer of methyl methacrylate and butyl methacrylate having a glass transition point of about 80 ° C (ELVACITE ™ 2013, a registered trademark of EI Du Pont De Nemours &Co. of Wilmington, DE) is They dissolve in 8.5 kg of dichloromethane and 5.0 g of syn-dimethylphenyldivinyldisiloxane. Then 1.0 kg of toluene and mixed. Then, 44.4 g of the isopropyl alcohol solution of the platinum vinyl siloxane complex obtained in Comparative Example 1 are introduced and mixed with this solution, until a uniform solution is obtained. This solution is sprayed continuously in the spray dryer tank of Example 1. The temperature of the hot flow of nitrogen gas was 95 ° C at the inlet of the spray dryer and was 50 ° C at the spray dryer outlet with the hot gas flow rate at 1.3 m3 / minute. The operation is carried out for 5 hours under the conditions mentioned in the above and 365 g of the catalyst in microparticles, white for the hydrosilylation reaction that was produced, are collected by means of a retrofilter. The average particle diameter of the obtained microparticle catalyst was 1.78 μm and the platinum content was 0.4% by weight.
EXAMPLE 6
g of fuming silica, with a specific surface area of 150 m / g, the surface of which had been subjected to the hydrophobic treatment with hexamethyldisilazane, is added to and mixed thoroughly with a mixture of 100 g of dimethylpolysiloxane terminated in dimethylvinylsiloxane from a viscosity of 12,000 mm: 's (cp) and 100 g of dimethypolysiloxane terminated in dimethylvinylsiloxane of a viscosity of 1,500 mm2 / s (cp), after which 2.8 g of a diorganosiloxane as indicated by the average molecular formula Me3SiO (Me2SiO ) 3 (MeHSiO) 5SiMe3 and 0.04 g of phenylbutynol are added and then mixed to a uniform state. Next, the microparticle catalyst of Example 5 is added to this mixture in an amount such that the platinum metal content of the mixture was 5 ppm, after which the materials are completely mixed, with a thermosetting silicone composition which is prepared. The thermosetting characteristics of the obtained thermosetting silicone composition are determined at 130 ° C and 150 ° C with a Curastometer ™ Model 5 as used in Example 2. The thermosetting characteristics are determined (T10) and (T9Q) as in Example 2. At 130 ° C, the T10 value of the obtained silicone composition was 85.6 seconds and the T90 value was 98.2 seconds. At 150 ° C the value of T10 was 32.6 seconds and the value of T9Q was 46.2 seconds. When this thermosetting silicone composition was aged at 50 ° C, an unhardened state is maintained for 87 days.
EXAMPLE 7
500 g of resin with a glass transition point of about 140 ° C (IUPILON ™ H-3000, a registered trademark of Mitsubishi Gas Chemicals Company, LTD) are dissolved in 8.5 kg of dichloromethane and 5.0 g of syn-dimethylphenyldivinyldisiloxane. Then, 1.0 kg of toluene are added and mixed. Next, 23.8 g of the isopropyl alcohol solution of the platinum vinyl siloxane complex obtained in Comparative Example 1 are introduced and mixed with this solution, until a uniform solution is obtained. This solution is sprayed continuously in the spray dryer tank of Example 1. The temperature of the hot flow of nitrogen gas was 100 ° C at the inlet of the spray dryer and was 70 ° C at the spray dryer outlet with the hot gas flow rate at 1.3 m3 / minute. The operation is carried out for 5 hours under the conditions mentioned in the foregoing and 385 g of the catalyst in microparticles, white for the hydrosilylation reaction that was produced, are collected by means of a retrofilter. The average particle diameter of the obtained microparticle catalyst was 1.52 μm and the platinum content was 0.2% by weight.
EXAMPLE 8
g of fuming silica, with a specific surface area of 150 m2 / g, the surface of which had been subjected to the hydrophobic treatment with hexamethyldisilazane, is added to and mixed thoroughly with a mixture of 100 g of dimethylpolysiloxane terminated in dimethylvinylsiloxane from a viscosity of 12,000 mm2 / s (cp) and 100 g of dimethypolysiloxane terminated in dimethylvinylsiloxane of a viscosity of 1,500 mm2 / s (cp), after which 2.8 g of a diorganosiloxane as indicated by the average molecular formula Me3SiO (Me2SiO) 3 (MeHSiO) 5SiMe3 and 0.04 g of phenylbutynol are added and then mixed to a uniform state. Next, the microparticle catalyst of Example 7 is added to this mixture in an amount such that the platinum metal content of the mixture was 2.5 ppm, after which the materials are completely mixed, with a thermosetting silicone composition which is prepared. The thermosetting characteristics of the obtained thermosetting silicone composition are determined at 150 ° C and 170 ° C with a Curastometer ™ model 5 as in Example 2. The thermoset characteristics of (T10) and (Tgo) are determined in a similar way in Example 2. At 150 ° C, the T1Q value of the obtained silicone composition was 122.1 seconds and the T9Q value was 157.1 seconds. At 170 ° C the T1Q value was 26.0 seconds and the Tgo value was 38.1 seconds. When this thermosetting silicone composition was aged at 50 ° C, an unhardened state is maintained for 268 days. In this way, the microparticulate catalyst for the hydrosilylation reactions of this invention is formed of a metal catalyst for specified hydrosilylation reactions, disiloxanes and a resin having a glass transition point of 40 to 200 ° C and has a high catalytic activity. In addition, the thermosetting silicone composition containing this microparticulate catalyst in this invention has superior storage stability and an unhardened state that can be maintained for a prolonged period. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers. Having described the invention as above, property is claimed as contained in the following:
Claims (2)
1. A catalyst in microparticles, characterized in that it comprises: (i) a metal catalyst comprising 0.01 to 5% by weight of metal atoms; (ii) from 0.01 to 5% by weight of a disiloxane having the general formula (R1R2ArSi) 20, wherein R1 is an alkenyl group, R2 is a monovalent hydrocarbon group and Ar is an aryl group; and (iii) a resin having a glass transition temperature of 40 to 200 °; wherein the microparticulate catalyst has an average particle diameter of 0.1 to 20 μm.
2. An organosiloxane composition characterized in that it comprises: (A) 100 parts by weight of an organopolysiloxane having an average of at least two alkenyl groups bonded to silicon per molecule; (B) an organohydrogenpolysiloxane, having an average of at least two hydrogen atoms attached to the silicon per molecule, in an amount sufficient to provide a ratio of the number of moles of hydrogen atoms attached to the silicon, bound in the component (B) ) to the number of moles of alkenyl groups attached to the silicon in component (A) which is in the range of 0.5 / 1 to 10/1; and (C) from 0.005 to 100 parts by weight of the microparticle catalyst according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07-246619 | 1995-08-31 | ||
| JP24661995A JP3763484B2 (en) | 1995-08-31 | 1995-08-31 | Fine particle catalyst for hydrosilylation reaction and heat curable silicone composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA96003777A true MXPA96003777A (en) | 1997-06-01 |
| MX9603777A MX9603777A (en) | 1997-06-28 |
Family
ID=17151105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9603777A MX9603777A (en) | 1995-08-31 | 1996-08-30 | Micro-particles catalysts for hydrosilylation reactions and thermosetting silicone compositions containing the catalyst. |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5789334A (en) |
| EP (1) | EP0761761B1 (en) |
| JP (1) | JP3763484B2 (en) |
| KR (1) | KR100432257B1 (en) |
| DE (1) | DE69619042T2 (en) |
| MX (1) | MX9603777A (en) |
| MY (1) | MY115842A (en) |
| TW (1) | TW426543B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19741201A1 (en) * | 1997-09-18 | 1999-03-25 | Wacker Chemie Gmbh | Organoaluminium compounds immobilised on organopolysiloxane microcrogel particles used as cocatalysts |
| US6030919A (en) * | 1998-08-13 | 2000-02-29 | General Electric Company | Platinum hydrosilylation catalyst and method for making |
| JP2002265786A (en) * | 2001-03-09 | 2002-09-18 | Dow Corning Toray Silicone Co Ltd | Curable organopolysiloxane composition and method for manufacturing semiconductor device |
| US7750106B2 (en) * | 2005-12-21 | 2010-07-06 | Avon Products, Inc. | Cosmetic compositions having in-situ hydrosilylation cross-linking |
| JP2009529409A (en) * | 2006-03-10 | 2009-08-20 | ピーピージー インダストリーズ オハイオ インコーポレーテツド | Heterogeneous hydrosilylation catalyst, polymer formed by the catalyst, and related coating compositions |
| CN101172245B (en) * | 2006-11-02 | 2010-10-27 | 中国石油化工股份有限公司 | Methylbenzene shape-selective disproportionation reaction catalyzer |
| US8133478B2 (en) | 2007-05-09 | 2012-03-13 | Avon Products Inc. | Cosmetic nanocomposites based on in-situ cross-linked POSS materials |
| US8263055B2 (en) * | 2007-08-01 | 2012-09-11 | Avon Products, Inc. | Long lasting and waterproof lash extension composition |
| SG190061A1 (en) | 2010-12-01 | 2013-06-28 | Novartis Ag | Lens molds having atmospheric plasma coatings thereon |
| JP2014506263A (en) * | 2010-12-08 | 2014-03-13 | ダウ コーニング コーポレーション | Siloxane composition suitable for making an encapsulant |
| US20140008697A1 (en) * | 2010-12-08 | 2014-01-09 | Brian R. Harkness | Siloxane Compositions Including Titanium Dioxide Nanoparticles Suitable For Forming Encapsulants |
| US9139699B2 (en) | 2012-10-04 | 2015-09-22 | Dow Corning Corporation | Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts |
| EP2785513B1 (en) | 2011-11-29 | 2016-12-21 | Novartis AG | Method of treating a lens forming surface of at least one mold half for molding ophthalmic lenses |
| JP6133592B2 (en) * | 2012-12-22 | 2017-05-24 | 東レ・ダウコーニング株式会社 | Low platinum content hydrosilylation reaction crosslinkable silicone rubber powder, cosmetic and method for producing silicone rubber powder |
| WO2016052521A2 (en) * | 2014-09-29 | 2016-04-07 | 住友理工株式会社 | Silicone rubber composition, silicone rubber crosslinked body, integrally molded body, and manufacturing method for integrally molded body |
| JP6714613B2 (en) | 2015-11-30 | 2020-06-24 | 住友理工株式会社 | Elastic roll for electrophotographic apparatus and manufacturing method thereof |
| JP6656045B2 (en) * | 2016-03-29 | 2020-03-04 | 信越化学工業株式会社 | Resin composition containing supported platinum catalyst, thermosetting organopolysiloxane composition using the same, and method of curing the same |
| JP6585535B2 (en) | 2016-03-29 | 2019-10-02 | 住友理工株式会社 | Silicone rubber composition and crosslinked silicone rubber |
| CN110088207B (en) * | 2016-11-11 | 2022-10-14 | 陶氏东丽株式会社 | Curable silicone composition and optical semiconductor device using the same |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5341707B2 (en) * | 1973-04-26 | 1978-11-06 | ||
| DE3131734A1 (en) * | 1981-08-11 | 1983-02-24 | Bayer Ag, 5090 Leverkusen | HEAT-CURABLE ORGANOPOLYSILOXANE MIXTURES |
| US4421903A (en) * | 1982-02-26 | 1983-12-20 | General Electric Company | Platinum complex catalysts |
| US4847228A (en) * | 1987-06-02 | 1989-07-11 | Toray Silicone Co., Ltd. | Platinum-alkenylsiloxane complex catalyst composition |
| US4874667A (en) * | 1987-07-20 | 1989-10-17 | Dow Corning Corporation | Microencapsulated platinum-group metals and compounds thereof |
| US4784879A (en) * | 1987-07-20 | 1988-11-15 | Dow Corning Corporation | Method for preparing a microencapsulated compound of a platinum group metal |
| US4766176A (en) * | 1987-07-20 | 1988-08-23 | Dow Corning Corporation | Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts |
| US4791186A (en) * | 1988-01-04 | 1988-12-13 | Dow Corning Corporation | Method for preparing storage stable, one part curable polyorganosiloxane compositions |
| JP2665941B2 (en) * | 1988-06-29 | 1997-10-22 | 東レ・ダウコーニング・シリコーン株式会社 | Granules containing platinum-based catalyst for hydrosilylation reaction |
| JPH0214244A (en) * | 1988-06-30 | 1990-01-18 | Toray Dow Corning Silicone Co Ltd | Thermosetting organopolysiloxane composition |
| JP2808001B2 (en) * | 1988-11-25 | 1998-10-08 | 東レ・ダウコーニング・シリコーン株式会社 | Organopolysiloxane composition for forming release cured film |
| US5015691A (en) * | 1989-05-22 | 1991-05-14 | General Electric Company | One part heat curable organopolysiloxane compositions |
| JP2608484B2 (en) * | 1990-05-24 | 1997-05-07 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing catalyst-containing thermoplastic resin fine particles for hydrosilylation reaction |
| US5270422A (en) * | 1992-07-02 | 1993-12-14 | Dow Corning Corporation | Curing catalyst compositions and method for preparing same |
| JP3073884B2 (en) * | 1993-05-10 | 2000-08-07 | 信越化学工業株式会社 | Heat-curable silicone elastomer composition |
| US5494750A (en) * | 1993-05-10 | 1996-02-27 | Shin-Etsu Chemical Co., Ltd. | Heat-curable silicone elastomer composition |
| JP3464506B2 (en) * | 1993-07-29 | 2003-11-10 | 東レ・ダウコーニング・シリコーン株式会社 | Catalyst for hydrosilylation reaction |
-
1995
- 1995-08-31 JP JP24661995A patent/JP3763484B2/en not_active Expired - Lifetime
-
1996
- 1996-08-28 TW TW085110471A patent/TW426543B/en not_active IP Right Cessation
- 1996-08-30 MY MYPI96003610A patent/MY115842A/en unknown
- 1996-08-30 EP EP96306301A patent/EP0761761B1/en not_active Expired - Lifetime
- 1996-08-30 MX MX9603777A patent/MX9603777A/en not_active IP Right Cessation
- 1996-08-30 KR KR1019960036646A patent/KR100432257B1/en not_active Expired - Lifetime
- 1996-08-30 DE DE69619042T patent/DE69619042T2/en not_active Expired - Lifetime
- 1996-08-30 US US08/706,031 patent/US5789334A/en not_active Expired - Lifetime
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0761761B1 (en) | Microparticle catalysts for hydrosilylation reactions and thermosetting silicone compositions containing said catalyst | |
| MXPA96003777A (en) | Catalysts of microparticles for reactions of hidrosililation and compositions of siliconatermendurecibles that contain the catalyst | |
| US5135960A (en) | Sponge-forming organosiloxane composition | |
| CA1306572C (en) | Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts | |
| US5015691A (en) | One part heat curable organopolysiloxane compositions | |
| US5232959A (en) | Organohydrogenpolysiloxanes and curable organosiloxane compositions containing same | |
| US6020409A (en) | Routes to dielectric gel for protection of electronic modules | |
| US5204384A (en) | One-part curable organosiloxane composition | |
| US5015716A (en) | Particulate material comprising a platinum-containing hydrosilylaton catalyst and a diorganopolysilane | |
| EP0352493A1 (en) | Thermosetting organosiloxane composition | |
| JPS5837053A (en) | Thermosetting organopolysiloxane mixture | |
| US5877237A (en) | Thermosetting silicone composition | |
| CA2037653A1 (en) | Storage stable one-part organosiloxane compositions | |
| JP3119481B2 (en) | One-part heat-curable organopolysiloxane composition | |
| JP4646363B2 (en) | Silicone rubber composition | |
| JPH0826225B2 (en) | Heat-curable silicone elastomer composition | |
| JPH0441562A (en) | Thermally curable organopolysiloxane composition | |
| JPH03160054A (en) | Thermally curable organopolysiloxane composition | |
| JP3088011B2 (en) | Heat-curable organopolysiloxane composition | |
| EP0651008B1 (en) | Heat-curing organopolysiloxane composition | |
| JP2854763B2 (en) | Heat-curable organopolysiloxane composition | |
| EP0440168A2 (en) | One-part curable organosiloxane composition | |
| JP2526188B2 (en) | Thermosetting organopolysiloxane composition | |
| JP3566361B2 (en) | Method for producing metal catalyst-containing resin fine particles for hydrosilylation reaction and heat-curable silicone composition containing resin fine particles obtained by this method | |
| KR0133520B1 (en) | Thermosetting organosiloxane composition |