CN109705352A - A kind of vinyl polysiloxane and its preparation method and application - Google Patents
A kind of vinyl polysiloxane and its preparation method and application Download PDFInfo
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- CN109705352A CN109705352A CN201910020256.1A CN201910020256A CN109705352A CN 109705352 A CN109705352 A CN 109705352A CN 201910020256 A CN201910020256 A CN 201910020256A CN 109705352 A CN109705352 A CN 109705352A
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- Prior art keywords
- oxygen
- phenyl
- epoxy
- propyl
- vinyl
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- -1 polysiloxane Polymers 0.000 title claims abstract description 122
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 89
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 88
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000004593 Epoxy Substances 0.000 claims abstract description 63
- 239000001301 oxygen Substances 0.000 claims abstract description 62
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 62
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 60
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 42
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 35
- 238000004806 packaging method and process Methods 0.000 claims abstract description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 28
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 28
- IWQPVKKGSBGBBS-UHFFFAOYSA-N [O]CC1CO1 Chemical compound [O]CC1CO1 IWQPVKKGSBGBBS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000011541 reaction mixture Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims description 10
- LMVLVUPTDRWATB-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-ol Chemical compound CO[Si](C)(OC)CCCO LMVLVUPTDRWATB-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 9
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 6
- 229910020487 SiO3/2 Inorganic materials 0.000 claims description 5
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 5
- YYUPXWUUUZXFHG-UHFFFAOYSA-N ethoxy-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)OCC YYUPXWUUUZXFHG-UHFFFAOYSA-N 0.000 claims description 5
- ZMWJQGOYIBHQJG-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-ol Chemical compound CCO[Si](C)(OCC)CCCO ZMWJQGOYIBHQJG-UHFFFAOYSA-N 0.000 claims description 4
- 229910020388 SiO1/2 Inorganic materials 0.000 claims description 4
- 229910020447 SiO2/2 Inorganic materials 0.000 claims description 4
- RBIILJCATVGHHI-UHFFFAOYSA-N [diethoxy(phenyl)silyl]methanamine Chemical compound NC[Si](OCC)(OCC)C1=CC=CC=C1 RBIILJCATVGHHI-UHFFFAOYSA-N 0.000 claims description 4
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- SEAZOECJMOZWTD-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethyl)silane Chemical compound CO[Si](OC)(OC)CC1CO1 SEAZOECJMOZWTD-UHFFFAOYSA-N 0.000 claims description 4
- REUVNZSRBMGWAF-UHFFFAOYSA-N (3,5-dimethylphenyl)-dimethoxysilane Chemical compound CO[SiH](OC)c1cc(C)cc(C)c1 REUVNZSRBMGWAF-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 2
- 239000004305 biphenyl Substances 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 16
- 239000000758 substrate Substances 0.000 abstract description 16
- 239000000853 adhesive Substances 0.000 abstract description 7
- 229920001971 elastomer Polymers 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 238000010792 warming Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 238000005292 vacuum distillation Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- JPADPHKEIXYMNG-UHFFFAOYSA-N ethenyl(silyloxy)silane Chemical compound [SiH3]O[SiH2]C=C JPADPHKEIXYMNG-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 229920002050 silicone resin Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- YAXILWBZMNNJPU-UHFFFAOYSA-N (3,5-dimethylphenyl)-diethoxysilane Chemical compound CCO[SiH](OCC)c1cc(C)cc(C)c1 YAXILWBZMNNJPU-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 3
- ASGKDLGXPOIMTM-UHFFFAOYSA-N diethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OCC)OCC)CCC2OC21 ASGKDLGXPOIMTM-UHFFFAOYSA-N 0.000 description 3
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- JGFBAEWZVAYFPH-UHFFFAOYSA-N CCCCCC[Si](OCC)(OCC)OCC.[O] Chemical compound CCCCCC[Si](OCC)(OCC)OCC.[O] JGFBAEWZVAYFPH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- XOKARSVKDDSKPA-UHFFFAOYSA-N [O].C1(=CC=CC=C1)[Si] Chemical compound [O].C1(=CC=CC=C1)[Si] XOKARSVKDDSKPA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- ARLJCLKHRZGWGL-UHFFFAOYSA-N ethenylsilicon Chemical compound [Si]C=C ARLJCLKHRZGWGL-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The present invention provides a kind of vinyl polysiloxane and its preparation method and application, the vinyl polysiloxane has general formula shown in formula (I)；Wherein, 1,0 < d < 1 of a+b+c+d=1,0 < a < 1,0≤b < 1,0≤c <；R1Selected from one of phenyl, methyl, 3- (the third oxygen of 2,3- epoxy) propyl, 8- (glycidyl oxygen) n-octyl, epoxybutyl, glycidyl, epoxyhexyl and 2- (3,4- epoxycyclohexyl) ethyl or a variety of；R2Selected from one of phenyl, methyl, 3- (the third oxygen of 2,3- epoxy) propyl and 2- (3,4- epoxycyclohexyl) ethyl or a variety of；R3Selected from phenyl and/or 3- (the third oxygen of 2,3- epoxy) propyl；Me is methyl, and Vi is vinyl.Compared with prior art, vinyl polysiloxane refractive index with higher provided by the invention and included Efficient Adhesive Promotion, when preparing LED high refractive index packaging silicon rubber, without add tackifying assistant can reach with the good adhesive effect of substrate, be suitble to LED high roll over packaging silicon rubber in apply.
Description
Technical field
The present invention relates to silicone resin technical fields, are to be related to a kind of vinyl polysiloxane and its preparation side more specifically
Method and application.
Background technique
Light emitting diode (LED) is referred to as forth generation lighting source, since it is long, small in size with the service life, low energy consumption, opens
The advantages such as dynamic fast, luminous efficiency height, be widely used to liquid crystal display, illumination, traffic lights, detector, electronic equipment, etc.
Field.
Organosilicon material has many advantages, such as excellent heat-resisting and ultraviolet light and aging performance, and high transparency, low internal stress are recognized
To be ideal LED encapsulation material, just gradually substituted epoxy resinae encapsulating material, wherein the high refractive index silica gel containing phenyl
(refractive index > 1.5) has higher smooth extraction efficiency, more preferably high-low temperature resistant, resistance to vulcanization, the resistance to performances such as ultraviolet.But by
It is unsatisfactory in pure organic silica gel itself and the adhesive effect of LED support substrate, how to improve the viscous of LED packaging silicon rubber and substrate
Effect is connect, is always that silica gel producer and research institution research and develop improved direction, lamp bead can be improved in the raising with substrate bonding power
Impact, it is resistance to infiltration, it is resistance to vulcanization etc. performance indexess.
In recent years, the patent of invention for improving LED packaging silicon rubber bonding force gradually increases.It wherein, is greatly logical
The cementability for adding related tackifying assistant to improve silica gel is crossed, this method exists and base rubber poor compatibility, Yi Yinqi catalyst poisoning
The problems such as.As the Chinese patent of Publication No. CN103805128A disclose a kind of high refractive index LED packaging plastic bonding agent and
Its synthetic method, this method is using organotin catalyzed terminal hydroxy group methyl vinyl phenyl silicone oil and KH560 dealcoholization condensation reaction system
Standby tackifier；But the tackifier be used for LED packaging silicon rubber when, organotin therein may make to lead to Pt catalyst poisoning,
Influence solidification.For another example the Chinese patent of Publication No. CN106008983A discloses a kind of silicon boron tackifier, Publication No.
The Chinese patent of CN106397771A discloses a kind of containing acrylate-based, epoxy group organic silicon rigidity-increasing stick；But such increasing
The index of refraction of stick is lower, using muddy the case where whitening is easy to appear in high refractive index silica gel, to will affect product
Transparency.In addition, being to improve the bonding force of silica gel by increasing the bonding group in base rubber molecule, but prepare there are also one kind
Process is relative complex, and technology stability is not good enough, is easy to get the product of applied defect.Such as Publication No. CN108384010A
Chinese patent discloses a kind of epoxidation modification methyl phenyl silicone resin and preparation method thereof, and this method uses 3- glycidol ether
Oxygroup hydroxypropyl methyl dimethoxysilane and aminomethyl phenyl dimethoxysilane are raw material, pass through hydrolysis-condensation reaction synthesizing epoxy
Change modifying methylphenyl silicone resin；But the preparation of this method is the molecule of D structure, structure is relatively simple, has in practical applications
Certain limitation.For another example the Chinese patent of Publication No. CN104877138A discloses a kind of silicone resin with adhesive property
And preparation method thereof, this method uses trialkoxy silane, dialkoxy silicane, epoxy group hydrocarbyl si lanes, acryloxy silicon
Alkane, boron-containing compound and end-capping reagent are reacted under the action of acid as catalyst under water and organic solvent environment, by drift
It washes, dry, obtained colorless and transparent organic siliconresin；But a variety of alkoxy silanes hydrolyze together in this method, due to various
Alkoxy silane hydrolysis rate is different, is easy to get the wide product of mixed and disorderly molecular structure and molecular weight distribution, and urge in acid
Effective dehydrating condensation process is not carried out after changing hydrolysis, is easy that there are a certain amount of silicone hydroxyls in resulting silicone resin, especially
In the biggish phenyl polysiloxane of preparation steric hindrance, the silicone hydroxyl contained in silicone resin will affect the properties of packaging silicon rubber.
In conclusion developing, a kind of preparation process is simple, stablizes, good compatibility and silicon tree with Efficient Adhesive Promotion itself
Rouge, can not only save the process and risk of addition tackifying assistant, but also packaging silicon rubber can be improved to the cementability of substrate, become this
Field technical staff technical problem urgently to be resolved.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of vinyl polysiloxane and its preparation method and application, this hair
The vinyl polysiloxane of bright offer refractive index with higher and included Efficient Adhesive Promotion are suitble to roll in packaging silicon rubber in LED high and answer
With.
The present invention provides a kind of vinyl polysiloxanes, have general formula shown in formula (I):
(R1SiO3/2)a(R2 2SiO2/2)b(Me2R3SiO1/2)c(Me2ViSiO1/2)dFormula (I)；
Wherein, 1,0 < d < 1 of a+b+c+d=1,0 < a < 1,0≤b < 1,0≤c <；R1Selected from phenyl, methyl, 3- (2,
The third oxygen of 3- epoxy) propyl, 8- (glycidyl oxygen) n-octyl, epoxybutyl, glycidyl, epoxyhexyl and 2- (3,4- epoxy
Cyclohexyl) one of ethyl or a variety of；R2Selected from phenyl, methyl, 3- (the third oxygen of 2,3- epoxy) propyl and 2- (3,4- epoxide ring
Hexyl) one of ethyl or a variety of；R3Selected from phenyl and/or 3- (the third oxygen of 2,3- epoxy) propyl；Me is methyl, and Vi is ethylene
Base.
Preferably, the R1In include phenyl, the content of the phenyl is more than or equal to 90mol%.
The present invention also provides a kind of preparation methods of vinyl polysiloxane described in above-mentioned technical proposal, including following step
It is rapid:
A) water, acidic catalyst and tetramethyl divinyl disiloxane are mixed, adds phenyl siloxane and containing ring
The mixture of the siloxanes of oxygroup carries out first set reaction, obtains reaction mixture；
B) aromatic hydrocarbon will be added in obtained reaction mixture in step a) and basic catalyst carries out the second secondary response, instead
Successively neutralized product, rinsing, vacuum distillation are answered, vinyl polysiloxane is obtained；The aromatic hydrocarbon is toluene or dimethylbenzene.
Preferably, acidic catalyst described in step a) be selected from one of hydrochloric acid, sulfuric acid, acetic acid and trifluoromethanesulfonic acid or
It is a variety of.
Preferably, phenyl siloxane described in step a) be selected from phenyltrimethoxysila,e, dimethoxydiphenylsilane,
Aminomethyl phenyl dimethoxysilane, phenyl triethoxysilane, diphenyl diethoxy silane, aminomethyl phenyl diethoxy silicon
One of alkane, 3,5-dimethylphenyl dimethoxysilane and 3,5-dimethylphenyl diethoxy silane are a variety of.
Preferably, the siloxanes described in step a) containing epoxy group is selected from 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicon
Alkane, 3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl dimethoxysilane, 3-
(the third oxygen of 2,3- epoxy) hydroxypropyl methyl diethoxy silane, 3- (the third oxygen of 2,3- epoxy) propyl-dimethyl Ethoxysilane, [8-
(glycidyl oxygen)-n-octyl] trimethoxy silane, glycidyl trimethoxy silane, epoxybutyl trimethoxy silane, ring
Oxygen hexyl triethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) second
One of ethyl triethoxy silicane alkane and 2- (3,4- epoxycyclohexyl) ethyl-methyl diethoxy silane are a variety of.
Preferably, the temperature of first set reaction described in step a) is 30 DEG C~80 DEG C, and the time is 2h~6h.
Preferably, basic catalyst described in step b) is selected from KOH, NaOH, LiOH and Ba (OH)2One of or it is more
Kind.
Preferably, the temperature of the second secondary response described in step b) is 90 DEG C~120 DEG C, and the time is 2h~6h.
The present invention also provides described in vinyl polysiloxane described in a kind of above-mentioned technical proposal or above-mentioned technical proposal
Application of the vinyl polysiloxane that preparation method is prepared in LED high folding packaging silicon rubber.
The present invention provides a kind of vinyl polysiloxane and its preparation method and application, the vinyl polysiloxane has formula
(I) general formula shown in；Wherein, 1,0 < d < 1 of a+b+c+d=1,0 < a < 1,0≤b < 1,0≤c <；R1Selected from phenyl, methyl,
3- (the third oxygen of 2,3- epoxy) propyl, 8- (glycidyl oxygen) n-octyl, epoxybutyl, glycidyl, epoxyhexyl and 2- (3,4-
Epoxycyclohexyl) one of ethyl or a variety of；R2Selected from phenyl, methyl, 3- (the third oxygen of 2,3- epoxy) propyl and 2- (3,4- ring
Oxygen cyclohexyl) one of ethyl or a variety of；R3Selected from phenyl and/or 3- (the third oxygen of 2,3- epoxy) propyl；Me is methyl, and Vi is
Vinyl.Compared with prior art, the bases such as phenyl, vinyl and epoxy group are included in vinyl polysiloxane provided by the invention
Group, by controlling above-mentioned not isoplastic ratio, making vinyl polysiloxane refractive index with higher and carrying Efficient Adhesive Promotion,
When preparing LED high refractive index packaging silicon rubber, without add tackifying assistant can reach with the good adhesive effect of substrate, be suitble to
It is applied in LED high folding packaging silicon rubber.The experimental results showed that the refractive index of vinyl polysiloxane provided by the invention is 1.548
More than, and there is excellent adhesive effect as the LED high folding packaging silicon rubber of primary raw material preparation.
In addition, preparation method simple process provided by the invention, stabilization, reproducible, raw material is easy to get, and is easy to amplify, and fits
Preferably it is mass produced.
Detailed description of the invention
Fig. 1 is the characterization map for the vinyl polysiloxane that the embodiment of the present invention 1 provides.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of vinyl polysiloxanes, have general formula shown in formula (I):
(R1SiO3/2)a(R2 2SiO2/2)b(Me2R3SiO1/2)c(Me2ViSiO1/2)dFormula (I)；
Wherein, 1,0 < d < 1 of a+b+c+d=1,0 < a < 1,0≤b < 1,0≤c <；R1Selected from phenyl, methyl, 3- (2,
The third oxygen of 3- epoxy) propyl, 8- (glycidyl oxygen) n-octyl, epoxybutyl, glycidyl, epoxyhexyl and 2- (3,4- epoxy
Cyclohexyl) one of ethyl or a variety of；R2Selected from phenyl, methyl, 3- (the third oxygen of 2,3- epoxy) propyl and 2- (3,4- epoxide ring
Hexyl) one of ethyl or a variety of；R3Selected from phenyl and/or 3- (the third oxygen of 2,3- epoxy) propyl；Me is methyl, and Vi is ethylene
Base.
In the present invention, R1Selected from phenyl, methyl, 3- (the third oxygen of 2,3- epoxy) propyl, 8- (glycidyl oxygen) n-octyl,
One of epoxybutyl, glycidyl, epoxyhexyl and 2- (3,4- epoxycyclohexyl) ethyl are a variety of, preferably phenyl,
One of 3- (the third oxygen of 2,3- epoxy) propyl and 2- (3,4- epoxycyclohexyl) ethyl are a variety of.In the present invention, the R1
In preferably include phenyl, the content of the phenyl is preferably greater than or equal to 90mol%.
In the present invention, R2Selected from phenyl, methyl, 3- (the third oxygen of 2,3- epoxy) propyl and 2- (3,4- epoxycyclohexyl) second
One of base is a variety of, preferably one of phenyl, methyl and 3- (2,3- the third oxygen of epoxy) propyl or a variety of.
In the present invention, R3Selected from phenyl and/or 3- (2,3- the third oxygen of epoxy) propyl, preferably 3- (2,3- the third oxygen of epoxy)
Propyl.
It is above-mentioned by controlling comprising groups such as phenyl, vinyl and epoxy groups in vinyl polysiloxane provided by the invention
Not isoplastic ratio makes vinyl polysiloxane refractive index with higher and included Efficient Adhesive Promotion, in preparation LED high refraction
When rate packaging silicon rubber, it can reach and the good adhesive effect of substrate without adding tackifying assistant.
The present invention also provides a kind of preparation methods of vinyl polysiloxane described in above-mentioned technical proposal, including following step
It is rapid:
A) water, acidic catalyst and tetramethyl divinyl disiloxane are mixed, adds phenyl siloxane and containing ring
The mixture of the siloxanes of oxygroup carries out first set reaction, obtains reaction mixture；
B) aromatic hydrocarbon will be added in obtained reaction mixture in step a) and basic catalyst carries out the second secondary response, instead
Successively neutralized product, rinsing, vacuum distillation are answered, vinyl polysiloxane is obtained；The aromatic hydrocarbon is toluene or dimethylbenzene.
The present invention first mixes water, acidic catalyst and tetramethyl divinyl disiloxane, adds phenyl silicon oxygen
The mixture of alkane and the siloxanes containing epoxy group carries out first set reaction, obtains reaction mixture.The present invention is not special to water
Limitation, using deionized water well known to those skilled in the art.
In the present invention, the acidic catalyst be preferably selected from one of hydrochloric acid, sulfuric acid, acetic acid and trifluoromethanesulfonic acid or
It is a variety of, more preferably hydrochloric acid or trifluoromethanesulfonic acid.The present invention is not particularly limited the source of the acidic catalyst, using this
The commercial goods of above-mentioned hydrochloric acid, sulfuric acid, acetic acid and trifluoromethanesulfonic acid known to the technical staff of field.
In the present invention, the tetramethyl divinyl disiloxane is raw material well known to those skilled in the art, this hair
It is bright that it is not specifically limited to this.
In the present invention, the mass ratio of the water, acidic catalyst and tetramethyl divinyl disiloxane is preferably (50
~100): (0.1~10): (10~50), more preferably (66.8~73.3): (0.34~5.1): (27.5~31.7).
The present invention is not particularly limited the mixed mode, using mechanical stirring well known to those skilled in the art or
The technical solution manually stirred, it is therefore an objective to be uniformly mixed each reaction raw materials.In the present invention, the mixed time is excellent
It is selected as 10min~20min, more preferably 15min.
In the present invention, the phenyl siloxane be preferably selected from phenyltrimethoxysila,e, dimethoxydiphenylsilane,
Aminomethyl phenyl dimethoxysilane, phenyl triethoxysilane, diphenyl diethoxy silane, aminomethyl phenyl diethoxy silicon
One of alkane, 3,5-dimethylphenyl dimethoxysilane and 3,5-dimethylphenyl diethoxy silane are a variety of, more preferably phenyl
Trimethoxy silane and/or dimethoxydiphenylsilane.The present invention is not particularly limited the source of the phenyl siloxane,
Using above-mentioned phenyltrimethoxysila,e well known to those skilled in the art, dimethoxydiphenylsilane, aminomethyl phenyl diformazan
Oxysilane, phenyl triethoxysilane, diphenyl diethoxy silane, aminomethyl phenyl diethoxy silane, 3,5-dimethylphenyl
The commercial goods of dimethoxysilane and 3,5-dimethylphenyl diethoxy silane.In the present invention, the phenyl siloxane
Dosage be preferably 1 times~14 times, more preferably 6 times~9 times of above-mentioned tetramethyl divinyl disiloxane quality.
In the present invention, the siloxanes containing epoxy group is preferably selected from 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicon
Alkane, 3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl dimethoxysilane, 3-
(the third oxygen of 2,3- epoxy) hydroxypropyl methyl diethoxy silane, 3- (the third oxygen of 2,3- epoxy) propyl-dimethyl Ethoxysilane, [8-
(glycidyl oxygen)-n-octyl] trimethoxy silane, glycidyl trimethoxy silane, epoxybutyl trimethoxy silane, ring
Oxygen hexyl triethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) second
One of ethyl triethoxy silicane alkane and 2- (3,4- epoxycyclohexyl) ethyl-methyl diethoxy silane are a variety of, more preferably
3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl dimethoxysilane, 3- (2,3-
The third oxygen of epoxy) propyl-dimethyl Ethoxysilane or 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane.The present invention is to institute
The source for stating the siloxanes containing epoxy group is not particularly limited, using above-mentioned 3- (2,3- epoxies well known to those skilled in the art
Third oxygen) propyl trimethoxy silicane, 3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane, 3- (the third oxygen of 2,3- epoxy) propyl first
Base dimethoxysilane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl diethoxy silane, 3- (the third oxygen of 2,3- epoxy) dimethylamine
Base oxethyl silane, [8- (glycidyl oxygen)-n-octyl] trimethoxy silane, glycidyl trimethoxy silane, epoxy fourth
Base trimethoxy silane, epoxyhexyl triethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 2- (3,
4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane and 2- (3,4- epoxycyclohexyl) ethyl-methyl diethoxy silane it is commercially available
Commodity.In the present invention, the mass ratio of the siloxanes and phenyl siloxane containing epoxy group is preferably (150~300):
(5~40), more preferably (219~234.8): (10~32.22).
In the present invention, the mode of the mixture that phenyl siloxane and the siloxanes containing epoxy group is added preferably is used
Constant pressure funnel is added dropwise.
In the present invention, the temperature of the first set reaction is preferably 30 DEG C~80 DEG C, more preferably 65 DEG C~75 DEG C；Institute
The time for stating first set reaction is preferably 2h~6h.
After obtaining the reaction mixture, aromatic hydrocarbon and basic catalyst is added in the present invention in obtained reaction mixture
The second secondary response is carried out, reaction product is successively neutralized, rinsing, is evaporated under reduced pressure, and obtains vinyl polysiloxane.In the present invention,
The aromatic hydrocarbon is toluene or dimethylbenzene, preferably toluene.The present invention is not particularly limited the source of the aromatic hydrocarbon, uses
The commercial goods of toluene and dimethylbenzene well known to those skilled in the art.In the present invention, the dosage of the aromatic hydrocarbon is excellent
It is selected as 5 times~15 times of above-mentioned tetramethyl divinyl disiloxane quality, more preferably 9 times~11 times.
In the present invention, the basic catalyst is preferably selected from KOH, NaOH, LiOH and Ba (OH)2One of or it is more
Kind, more preferably KOH.The present invention is not particularly limited the source of the basic catalyst, ripe using those skilled in the art
The commercial goods for the above-mentioned metal hydroxides known.In the present invention, the mass ratio of the basic catalyst and aromatic hydrocarbon
Preferably (1~5): (200~400), more preferably (1.51~4.01): (292.4~317.4).
In the present invention, the temperature of second secondary response is preferably 90 DEG C~120 DEG C, more preferably 110 DEG C；Described
The time of secondary response is preferably 2h~6h, more preferably 3h.
In the present invention, acid used in the neutralization is preferably hydrochloric acid, sulfuric acid, formic acid, acetic acid, benzoic acid, ethanedioic acid, third
One of diacid and terephthalic acid (TPA) are a variety of, more preferably hydrochloric acid.
Reaction product is washed to neutrality through the rinse cycle by the present invention, and using vacuum distillation removing low molecule, originally
It is not specifically limited to this for invention.
Preparation method simple process provided by the invention, stabilization, reproducible, raw material is easy to get, and is easy to amplify, and is suitable for big rule
Mould production.
The present invention also provides described in vinyl polysiloxane described in a kind of above-mentioned technical proposal or above-mentioned technical proposal
Application of the vinyl polysiloxane that preparation method is prepared in LED high folding packaging silicon rubber.Vinyl silicon provided by the invention
Resin can be used as the existing LED high raw material components for rolling over base rubber in packaging silicon rubber, in preparation LED high refractive index packaging silicon rubber
When, it can reach and the good adhesive effect of substrate without adding tackifying assistant.
The present invention provides a kind of vinyl polysiloxane and its preparation method and application, the vinyl polysiloxane has formula
(I) general formula shown in；Wherein, 1,0 < d < 1 of a+b+c+d=1,0 < a < 1,0≤b < 1,0≤c <；R1Selected from phenyl, methyl,
3- (the third oxygen of 2,3- epoxy) propyl, 8- (glycidyl oxygen) n-octyl, epoxybutyl, glycidyl, epoxyhexyl and 2- (3,4-
Epoxycyclohexyl) one of ethyl or a variety of；R2Selected from phenyl, methyl, 3- (the third oxygen of 2,3- epoxy) propyl and 2- (3,4- ring
Oxygen cyclohexyl) one of ethyl or a variety of；R3Selected from phenyl and/or 3- (the third oxygen of 2,3- epoxy) propyl；Me is methyl, and Vi is
Vinyl.Compared with prior art, the bases such as phenyl, vinyl and epoxy group are included in vinyl polysiloxane provided by the invention
Group, by controlling above-mentioned not isoplastic ratio, making vinyl polysiloxane refractive index with higher and carrying Efficient Adhesive Promotion,
When preparing LED high refractive index packaging silicon rubber, without add tackifying assistant can reach with the good adhesive effect of substrate, be suitble to
It is applied in LED high folding packaging silicon rubber.The experimental results showed that the refractive index of vinyl polysiloxane provided by the invention is 1.548
More than, and there is excellent adhesive effect as the LED high folding packaging silicon rubber of primary raw material preparation.
In addition, preparation method simple process provided by the invention, stabilization, reproducible, raw material is easy to get, and is easy to amplify, and fits
Preferably it is mass produced.
In order to further illustrate the present invention, it is described in detail below by following embodiment.Following embodiment of the present invention
Raw material used is commercial goods.
Embodiment 1
(1) 71.8g deionized water, 0.49g trifluoromethanesulfonic acid, 27.5g tetramethyl two are added into 1000mL three-necked flask
After stirring 15min, 233.7g phenyltrimethoxysila,e and 10.5g 3- is added dropwise with constant pressure funnel in vinyl disiloxane
The mixed liquor of (2,3- the third oxygen of epoxy) propyl trimethoxy silicane is warming up to 65 DEG C after being added dropwise to complete, react 2h, and it is mixed to obtain reaction
Close object.
(2) 299.4g toluene and 1.63gKOH are added in the reaction mixture obtained under stiring to step (1), is warming up to
110 DEG C of reaction 3h are added 3.48g concentrated hydrochloric acid (36.5wt%) and neutralize, are washed to neutrality after cooling, take oily mutually vacuum distillation removing
Low molecule obtains colorless and transparent vinyl polysiloxane 184.6g.
The expression formula for the vinyl polysiloxane that the embodiment of the present invention 1 provides are as follows:
(PhSiO3/2)0.866(R1SiO3/2)0.032(Me2ViSiO1/2)0.102Formula (I-1)；
Wherein, R1For 3- (2,3- the third oxygen of epoxy) propyl, Ph is phenyl, and Me is methyl, and Vi is vinyl；The vinyl silicon
The characterization spectrogram of resin is shown in Figure 1.
Through detecting, the refractive index for the vinyl polysiloxane that the embodiment of the present invention 1 provides is 1.5532, and contents of ethylene is
4.03wt%.
Embodiment 2
(1) 69.5g deionized water, 0.47g trifluoromethanesulfonic acid, 30.3g tetramethyl two are added into 1000mL three-necked flask
After stirring 15min, 225.5g phenyltrimethoxysila,e and 10.7g 3- is added dropwise with constant pressure funnel in vinyl disiloxane
The mixed liquor of (2,3- the third oxygen of epoxy) hydroxypropyl methyl dimethoxysilane is warming up to 70 DEG C after being added dropwise to complete, react 2h, obtains anti-
Answer mixture.
(2) 293.7g toluene and 1.57gKOH are added in the reaction mixture obtained under stiring to step (1), is warming up to
110 DEG C of reaction 3h are added 3.37g concentrated hydrochloric acid (36.5wt%) and neutralize, are washed to neutrality after cooling, take oily mutually vacuum distillation removing
Low molecule obtains colorless and transparent vinyl polysiloxane 183.2g.
The expression formula for the vinyl polysiloxane that the embodiment of the present invention 2 provides are as follows:
(PhSiO3/2)0.850(R2MeSiO2/2)0.036(Me2ViSiO1/2)0.114Formula (I-2)；
Wherein, R2For 3- (2,3- the third oxygen of epoxy) propyl, Ph is phenyl, and Me is methyl, and Vi is vinyl.
Through detecting, the refractive index for the vinyl polysiloxane that the embodiment of the present invention 2 provides is 1.5523, and contents of ethylene is
4.48wt%.
Embodiment 3
(1) 71.5g deionized water, 0.49g trifluoromethanesulfonic acid, 30.3g tetramethyl two are added into 1000mL three-necked flask
After stirring 15min, 225.5g phenyltrimethoxysila,e and 21.5g 3- is added dropwise with constant pressure funnel in vinyl disiloxane
The mixed liquor of (2,3- the third oxygen of epoxy) hydroxypropyl methyl dimethoxysilane is warming up to 70 DEG C after being added dropwise to complete, react 2h, obtains anti-
Answer mixture.
(2) 306.2g toluene and 1.65gKOH are added in the reaction mixture obtained under stiring to step (1), is warming up to
110 DEG C of reaction 3h are added 3.50g concentrated hydrochloric acid (36.5wt%) and neutralize, are washed to neutrality after cooling, take oily mutually vacuum distillation removing
Low molecule obtains the vinyl polysiloxane 190.4g of pale yellow transparent.
The expression formula for the vinyl polysiloxane that the embodiment of the present invention 3 provides are as follows:
(PhSiO3/2)0.821(R2MeSiO2/2)0.070(Me2ViSiO1/2)0.109Formula (I-3)；
Wherein, R2For 3- (2,3- the third oxygen of epoxy) propyl, Ph is phenyl, and Me is methyl, and Vi is vinyl.
Through detecting, the refractive index for the vinyl polysiloxane that the embodiment of the present invention 3 provides is 1.5507, and contents of ethylene is
4.25wt%.
Embodiment 4
(1) 73.3g deionized water, 0.51g trifluoromethanesulfonic acid, 30.3g tetramethyl two are added into 1000mL three-necked flask
After stirring 15min, 225.5g phenyltrimethoxysila,e and 32.22g is added dropwise with constant pressure funnel in vinyl disiloxane
The mixed liquor of 3- (2,3- the third oxygen of epoxy) hydroxypropyl methyl dimethoxysilane is warming up to 75 DEG C after being added dropwise to complete, react 2h, obtain
Reaction mixture.
(2) 317.4g toluene and 1.66gKOH are added in the reaction mixture obtained under stiring to step (1), is warming up to
110 DEG C of reaction 3h are added 3.56g concentrated hydrochloric acid (36.5wt%) and neutralize, are washed to neutrality after cooling, take oily mutually vacuum distillation removing
Low molecule obtains the vinyl polysiloxane 199.6g of light yellow clear.
The expression formula for the vinyl polysiloxane that the embodiment of the present invention 4 provides are as follows:
(PhSiO3/2)0.793(R2MeSiO2/2)0.102(Me2ViSiO1/2)0.105Formula (I-4)；
Wherein, R2For 3- (2,3- the third oxygen of epoxy) propyl, Ph is phenyl, and Me is methyl, and Vi is vinyl.
Through detecting, the refractive index for the vinyl polysiloxane that the embodiment of the present invention 4 provides is 1.5487, and contents of ethylene is
4.06wt%.
Embodiment 5
(1) 67.4g deionized water, 5.1g concentrated hydrochloric acid (36.5wt%), 31.7g tetramethyl are added into 1000mL three-necked flask
Base divinyl disiloxane, stir 15min after, with constant pressure funnel be added dropwise 219.0g phenyltrimethoxysila,e and
The mixed liquor of 10.0g 3- (2,3- the third oxygen of epoxy) propyl-dimethyl Ethoxysilane is warming up to 75 DEG C, reaction after being added dropwise to complete
2h obtains reaction mixture.
(2) 292.4g toluene and 4.01gKOH are added in the reaction mixture obtained under stiring to step (1), is warming up to
110 DEG C of reaction 3h are added 2.45g concentrated hydrochloric acid (36.5wt%) and neutralize, are washed to neutrality after cooling, take oily mutually vacuum distillation removing
Low molecule obtains colorless and transparent vinyl polysiloxane 180.2g.
The expression formula for the vinyl polysiloxane that the embodiment of the present invention 5 provides are as follows:
(PhSiO3/2)0.843(R3Me2SiO1/2)0.035(Me2ViSiO1/2)0.122Formula (I-5)；
Wherein, R3For 3- (2,3- the third oxygen of epoxy) propyl, Ph is phenyl, and Me is methyl, and Vi is vinyl.
Through detecting, the refractive index for the vinyl polysiloxane that the embodiment of the present invention 5 provides is 1.5518, and contents of ethylene is
4.76wt%.
Embodiment 6
(1) 71.8g deionized water, 0.49g trifluoromethanesulfonic acid, 27.5g tetramethyl two are added into 1000mL three-necked flask
After stirring 15min, 233.7g phenyltrimethoxysila,e and 10.9g 2- is added dropwise with constant pressure funnel in vinyl disiloxane
The mixed liquor of (3,4- epoxycyclohexyl) ethyl trimethoxy silane is warming up to 75 DEG C after being added dropwise to complete, react 2h, reacted
Mixture.
(2) 300.4g toluene and 1.63gKOH are added in the reaction mixture obtained under stiring to step (1), is warming up to
110 DEG C of reaction 3h are added 3.48g concentrated hydrochloric acid (36.5wt%) and neutralize, are washed to neutrality after cooling, take oily mutually vacuum distillation removing
Low molecule obtains colorless and transparent vinyl polysiloxane 182.5g.
The expression formula for the vinyl polysiloxane that the embodiment of the present invention 6 provides are as follows:
(PhSiO3/2)0.867(R1SiO3/2)0.033(Me2ViSiO1/2)0.100Formula (I-6)；
Wherein, R1For 2- (3,4- epoxycyclohexyl) ethyl, Ph is phenyl, and Me is methyl, and Vi is vinyl.
Through detecting, the refractive index for the vinyl polysiloxane that the embodiment of the present invention 6 provides is 1.5529, and contents of ethylene is
3.95wt%.
Embodiment 7
(1) 66.8g deionized water, 0.34g trifluoromethanesulfonic acid, 28.6g tetramethyl two are added into 1000mL three-necked flask
After stirring 15min, 197.4g phenyltrimethoxysila,e, 37.4g hexichol is added dropwise with constant pressure funnel in vinyl disiloxane
The mixed liquor of base dimethoxysilane and 15.5g 3- (2,3- the third oxygen of epoxy) hydroxypropyl methyl dimethoxysilane, after being added dropwise to complete
65 DEG C are warming up to, 2h is reacted, obtains reaction mixture.
(2) 300.6g toluene and 1.51gKOH are added in the reaction mixture obtained under stiring to step (1), is warming up to
110 DEG C of reaction 3h are added 3.24g concentrated hydrochloric acid (36.5wt%) and neutralize, are washed to neutrality after cooling, take oily mutually vacuum distillation removing
Low molecule obtains colorless and transparent vinyl polysiloxane 191.7g.
The expression formula for the vinyl polysiloxane that the embodiment of the present invention 7 provides are as follows:
(PhSiO3/2)0.748(Ph2SiO2/2)0.115(R2MeSiO2/2)0.031(Me2ViSiO1/2)0.106Formula (I-7)；
Wherein, R2For 3- (2,3- the third oxygen of epoxy) propyl, Ph is phenyl, and Me is methyl, and Vi is vinyl.
Through detecting, the refractive index for the vinyl polysiloxane that the embodiment of the present invention 7 provides is 1.5578, and contents of ethylene is
3.97wt%.
Embodiment 8
(1) vinyl polysiloxane for providing embodiment 1 and phenyl hydrogen-containing silicon oil (0.42wt%) are by vinyl material
The ratio of amount/si-h bond substance amount=0.75/1 prepares base rubber；50g base rubber and 0.12g inhibitor, 0.25g high is taken to reflect again
Rate platinum catalyst is uniformly mixed, and the deaeration 30min in the case where vacuum degree is 0.1MPa obtains LED high folding packaging silicon rubber.
(2) respectively using PPA, aluminium flake and steel disc as substrate, by the condition of cure and GB/T of 100 DEG C/1h+150 DEG C/3h
Sample to be tested is prepared in 7124-2008.
Embodiment 9
(1) vinyl polysiloxane for providing embodiment 2 and phenyl hydrogen-containing silicon oil (0.42wt%) are by vinyl material
The ratio of amount/si-h bond substance amount=0.75/1 prepares base rubber；50g base rubber and 0.12g inhibitor, 0.25g high is taken to reflect again
Rate platinum catalyst is uniformly mixed, and the deaeration 30min in the case where vacuum degree is 0.1MPa obtains LED high folding packaging silicon rubber.
(2) respectively using PPA, aluminium flake and steel disc as substrate, by the condition of cure and GB/T of 100 DEG C/1h+150 DEG C/3h
Sample to be tested is prepared in 7124-2008.
Embodiment 10
(1) vinyl polysiloxane for providing embodiment 3 and phenyl hydrogen-containing silicon oil (0.42wt%) are by vinyl material
The ratio of amount/si-h bond substance amount=0.75/1 prepares base rubber；50g base rubber and 0.12g inhibitor, 0.25g high is taken to reflect again
Rate platinum catalyst is uniformly mixed, and the deaeration 30min in the case where vacuum degree is 0.1MPa obtains LED high folding packaging silicon rubber.
(2) respectively using PPA, aluminium flake and steel disc as substrate, by the condition of cure and GB/T of 100 DEG C/1h+150 DEG C/3h
Sample to be tested is prepared in 7124-2008.
Embodiment 11
(1) vinyl polysiloxane for providing embodiment 4 and phenyl hydrogen-containing silicon oil (0.42wt%) are by vinyl material
The ratio of amount/si-h bond substance amount=0.75/1 prepares base rubber；50g base rubber and 0.12g inhibitor, 0.25g high is taken to reflect again
Rate platinum catalyst is uniformly mixed, and the deaeration 30min in the case where vacuum degree is 0.1MPa obtains LED high folding packaging silicon rubber.
(2) respectively using PPA, aluminium flake and steel disc as substrate, by the condition of cure and GB/T of 100 DEG C/1h+150 DEG C/3h
Sample to be tested is prepared in 7124-2008.
Embodiment 12
(1) vinyl polysiloxane for providing embodiment 5 and phenyl hydrogen-containing silicon oil (0.42wt%) are by vinyl material
The ratio of amount/si-h bond substance amount=0.75/1 prepares base rubber；50g base rubber and 0.12g inhibitor, 0.25g high is taken to reflect again
Rate platinum catalyst is uniformly mixed, and the deaeration 30min in the case where vacuum degree is 0.1MPa obtains LED high folding packaging silicon rubber.
(2) respectively using PPA, aluminium flake and steel disc as substrate, by the condition of cure and GB/T of 100 DEG C/1h+150 DEG C/3h
Sample to be tested is prepared in 7124-2008.
Embodiment 13
(1) vinyl polysiloxane for providing embodiment 6 and phenyl hydrogen-containing silicon oil (0.42wt%) are by vinyl material
The ratio of amount/si-h bond substance amount=0.75/1 prepares base rubber；50g base rubber and 0.12g inhibitor, 0.25g high is taken to reflect again
Rate platinum catalyst is uniformly mixed, and the deaeration 30min in the case where vacuum degree is 0.1MPa obtains LED high folding packaging silicon rubber.
(2) respectively using PPA, aluminium flake and steel disc as substrate, by the condition of cure and GB/T of 100 DEG C/1h+150 DEG C/3h
Sample to be tested is prepared in 7124-2008.
Embodiment 14
(1) vinyl polysiloxane for providing embodiment 7 and phenyl hydrogen-containing silicon oil (0.42wt%) are by vinyl material
The ratio of amount/si-h bond substance amount=0.75/1 prepares base rubber；50g base rubber and 0.12g inhibitor, 0.25g high is taken to reflect again
Rate platinum catalyst is uniformly mixed, and the deaeration 30min in the case where vacuum degree is 0.1MPa obtains LED high folding packaging silicon rubber.
(2) respectively using PPA, aluminium flake and steel disc as substrate, by the condition of cure and GB/T of 100 DEG C/1h+150 DEG C/3h
Sample to be tested is prepared in 7124-2008.
The sample to be tested progressive that embodiment 8~14 is provided respectively according to GB/T 7124-2008 using tensilon
It can test, as a result ginseng is shown in Table 1.
The performance data for the sample to be tested that 1 embodiment 8~14 of table provides
As shown in Table 1, the embodiment of the present invention 1~7 provide vinyl polysiloxane good compatibility and itself have it is good
Efficient Adhesive Promotion, the colorless and transparent vinyl polysiloxane that especially wherein embodiment 1,2,5,6,7 provides are suitble to roll in LED high
It is applied in packaging silicon rubber.
The above description of the disclosed embodiments, enables those skilled in the art to implement or use the present invention.It is right
A variety of modifications of these embodiments will be readily apparent to those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed herein
Widest scope.
Claims (10)
1. a kind of vinyl polysiloxane has general formula shown in formula (I):
(R1SiO3/2)a(R2 2SiO2/2)b(Me2R3SiO1/2)c(Me2ViSiO1/2)dFormula (I)；
Wherein, 1,0 < d < 1 of a+b+c+d=1,0 < a < 1,0≤b < 1,0≤c <；R1Selected from phenyl, methyl, 3- (2,3- ring
The third oxygen of oxygen) propyl, 8- (glycidyl oxygen) n-octyl, epoxybutyl, glycidyl, epoxyhexyl and 2- (3,4- epoxy hexamethylene
Base) one of ethyl or a variety of；R2Selected from phenyl, methyl, 3- (the third oxygen of 2,3- epoxy) propyl and 2- (3,4- epoxy hexamethylene
Base) one of ethyl or a variety of；R3Selected from phenyl and/or 3- (the third oxygen of 2,3- epoxy) propyl；Me is methyl, and Vi is ethylene
Base.
2. vinyl polysiloxane according to claim 1, which is characterized in that the R1In include phenyl, the phenyl contains
Amount is more than or equal to 90mol%.
3. a kind of preparation method of the described in any item vinyl polysiloxanes of claim 1~2, comprising the following steps:
A) water, acidic catalyst and tetramethyl divinyl disiloxane are mixed, adds phenyl siloxane and containing epoxy group
Siloxanes mixture carry out first set reaction, obtain reaction mixture；
B) aromatic hydrocarbon will be added in obtained reaction mixture in step a) and basic catalyst carries out the second secondary response, reaction produces
Object is successively neutralized, rinsing, is evaporated under reduced pressure, and obtains vinyl polysiloxane；The aromatic hydrocarbon is toluene or dimethylbenzene.
4. preparation method according to claim 3, which is characterized in that acidic catalyst described in step a) be selected from hydrochloric acid,
One of sulfuric acid, acetic acid and trifluoromethanesulfonic acid are a variety of.
5. preparation method according to claim 3, which is characterized in that phenyl siloxane described in step a) is selected from phenyl three
Methoxy silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, phenyl triethoxysilane, diphenyl two
Ethoxysilane, aminomethyl phenyl diethoxy silane, 3,5-dimethylphenyl dimethoxysilane and 3,5-dimethylphenyl diethoxy silicon
One of alkane is a variety of.
6. preparation method according to claim 3, which is characterized in that the siloxanes described in step a) containing epoxy group is selected from
3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane, 3- (2,3- epoxy
Third oxygen) hydroxypropyl methyl dimethoxysilane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl diethoxy silane, 3- (2,3- epoxy third
Oxygen) propyl-dimethyl Ethoxysilane, [8- (glycidyl oxygen)-n-octyl] trimethoxy silane, glycidyl trimethoxy
Silane, epoxybutyl trimethoxy silane, epoxyhexyl triethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy
Silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane and 2- (3,4- epoxycyclohexyl) ethyl-methyl diethoxy
One of silane is a variety of.
7. preparation method according to claim 3, which is characterized in that the temperature of first set reaction described in step a) is 30
DEG C~80 DEG C, the time is 2h~6h.
8. preparation method according to claim 3, which is characterized in that basic catalyst described in step b) be selected from KOH,
NaOH, LiOH and Ba (OH)2One of or it is a variety of.
9. preparation method according to claim 3, which is characterized in that the temperature of the second secondary response described in step b) is 90
DEG C~120 DEG C, the time is 2h~6h.
10. a kind of described in any item vinyl polysiloxanes of claim 1~2 or the described in any item preparations of claim 3~9
Application of the vinyl polysiloxane that method is prepared in LED high folding packaging silicon rubber.
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