CN110256676A - A kind of phenyl hydrogen-containing siloxane resin, high refractive index LED encapsulation silicon resin composition and preparation method thereof - Google Patents
A kind of phenyl hydrogen-containing siloxane resin, high refractive index LED encapsulation silicon resin composition and preparation method thereof Download PDFInfo
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- CN110256676A CN110256676A CN201910441456.4A CN201910441456A CN110256676A CN 110256676 A CN110256676 A CN 110256676A CN 201910441456 A CN201910441456 A CN 201910441456A CN 110256676 A CN110256676 A CN 110256676A
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- refractive index
- phenyl
- water
- tetramethyl
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- -1 phenyl hydrogen Chemical compound 0.000 title claims abstract description 130
- 229920005989 resin Polymers 0.000 title claims abstract description 129
- 239000011347 resin Substances 0.000 title claims abstract description 129
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 81
- 239000001257 hydrogen Substances 0.000 title claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 75
- 239000010703 silicon Substances 0.000 title claims abstract description 75
- 238000005538 encapsulation Methods 0.000 title claims abstract description 37
- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 177
- 238000010792 warming Methods 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 239000011259 mixed solution Substances 0.000 claims abstract description 58
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 48
- 230000007062 hydrolysis Effects 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920002050 silicone resin Polymers 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 82
- 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 53
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims description 50
- 239000012744 reinforcing agent Substances 0.000 claims description 48
- 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 46
- 238000002156 mixing Methods 0.000 claims description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 38
- 238000006482 condensation reaction Methods 0.000 claims description 26
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 26
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 25
- 229910000077 silane Inorganic materials 0.000 claims description 25
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 claims description 25
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 238000009833 condensation Methods 0.000 claims description 18
- 230000005494 condensation Effects 0.000 claims description 18
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 18
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 16
- 239000004305 biphenyl Substances 0.000 claims description 16
- 235000010290 biphenyl Nutrition 0.000 claims description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- 238000005292 vacuum distillation Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 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 claims description 9
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims 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 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- PHMNXPYGVPEQSJ-UHFFFAOYSA-N Dimethoxane Chemical compound CC1CC(OC(C)=O)OC(C)O1 PHMNXPYGVPEQSJ-UHFFFAOYSA-N 0.000 claims 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000002562 thickening agent Substances 0.000 claims 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 1
- 238000004383 yellowing Methods 0.000 abstract description 9
- 238000002834 transmittance Methods 0.000 abstract description 7
- 230000036961 partial effect Effects 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 177
- 239000000243 solution Substances 0.000 description 126
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 87
- 239000002904 solvent Substances 0.000 description 81
- 239000000047 product Substances 0.000 description 69
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 48
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 48
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 31
- 238000007711 solidification Methods 0.000 description 30
- 230000008023 solidification Effects 0.000 description 30
- 230000006837 decompression Effects 0.000 description 28
- 239000000463 material Substances 0.000 description 25
- 229960000583 acetic acid Drugs 0.000 description 24
- 239000012362 glacial acetic acid Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 150000001335 aliphatic alkanes Chemical class 0.000 description 17
- 239000003153 chemical reaction reagent Substances 0.000 description 17
- 125000000524 functional group Chemical group 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001228 spectrum Methods 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
- 238000004566 IR spectroscopy Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IXUAUYFVEXCZLW-UHFFFAOYSA-N CC(=C[SiH2]O[Si])C Chemical compound CC(=C[SiH2]O[Si])C IXUAUYFVEXCZLW-UHFFFAOYSA-N 0.000 description 1
- DMUUVRJNUPKXLL-UHFFFAOYSA-N CO[Si]OC.CC=C Chemical compound CO[Si]OC.CC=C DMUUVRJNUPKXLL-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JPADPHKEIXYMNG-UHFFFAOYSA-N ethenyl(silyloxy)silane Chemical compound [SiH3]O[SiH2]C=C JPADPHKEIXYMNG-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ILQHFISNNSQESO-UHFFFAOYSA-N naphthalene;hydrobromide Chemical compound Br.C1=CC=CC2=CC=CC=C21 ILQHFISNNSQESO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- XJWOWXZSFTXJEX-UHFFFAOYSA-N phenylsilicon Chemical compound [Si]C1=CC=CC=C1 XJWOWXZSFTXJEX-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Silicon Polymers (AREA)
- Led Device Packages (AREA)
Abstract
The present invention relates to a kind of phenyl hydrogen-containing siloxane resins, high refractive index LED encapsulation silicon resin composition and preparation method thereof.The phenyl hydrogen-containing siloxane resin is prepared via a method which to obtain: monomer, water and hydrolysis catalyst are mixed, organic solvent is added and obtains mixed solution, it is warming up to 30~60 DEG C of 1~5h of hydrolysis, point water is carried out again to react, washing is evaporated under reduced pressure up to the phenyl hydrogen-containing siloxane resin.The refractive index of phenyl hydrogen-containing siloxane resin provided by the invention is high, and flexibility and anti-yellowing property are excellent;When being used to prepare LED encapsulation silicone resin, there is high refractive index, excellent tensile strength, adhesion strength, light transmittance and yellowing resistance energy, partial properties have reached or higher than external similar imported product level, can satisfy the basic demand of LED encapsulation;The surface welded LED device of encapsulation has excellent air-tightness.
Description
Technical field
The invention belongs to technical field of electronic encapsulation, and in particular to a kind of phenyl hydrogen-containing siloxane resin, high refractive index LED
Encapsulate silicon resin composition and preparation method thereof.
Background technique
Light emitting diode (Light Emitting Diode, hereinafter referred to as LED) is that one kind can directly convert electric energy
For the semiconductor element of luminous energy.Compared to the lighting method of incandescent lamp or fluorescent lamp, there is low energy, service life length, environmental protection, color
Controllably, the advantages that small in size, is expected to the lighting source as a new generation and replaces conventional light source.Used in LED illumination device
Encapsulating material is mainly epoxy resin and organic siliconresin.Compared to epoxy resin, organosilicon has the advantages that numerous: such as excellent
Anti-ultraviolet ageing performance, weatherability, thermal stability, high transparency and high refractive index, insulating properties etc. are high-power LED encapsulation materials
The ideal chose of material.
As LED manufacture technology is constantly promoted, such as large power white light LED and the maturation of reflow soldering technology, greatly
The encapsulation technology of power LED has been increasingly becoming the key problem in technology of power-type LED development.Currently, the high property of power type LED encapsulation
Energy organic siliconresin relies on import substantially, and main core technology is monopolized by a small number of offshore companies such as DOW CORNING, SHIN-ETSU HANTOTAI, high
Cost limit the popularization of high power LED device.Therefore, demand of the industry to high refractive index transparent LED encapsulation silicon materials is got over
Come more urgent.Studies in China still falls within the starting stage at present, and there are also many blank, and the organosilicon encapsulating material of domestic production is still
It is only used for the mid and low-end products not high to performance requirement.High performance lED encapsulation silicone resin must have high refractive index, high light transmission
Rate, resistance to ultraviolet ability, heat-proof aging ability, the performances such as low stress, and wherein, improve the key point that refractive index is problem.
The refractive index of LED chip is usually all larger than 2.5, and the refractive index of encapsulating material is much smaller, the refractive index of the two
If differing too big, the light that LED chip issues can not may all take out because of total reflection, drop LED component optical efficiency
It is low.Therefore the refractive index for improving encapsulating material, reduces the difference with LED chip refractive index, can significantly improve LED takes light efficiency
Rate.In polysiloxanes, phenyl ring molar refraction with higher (Si-Ph Bond Refraction is 27.39, and in polymerizable organosilicon
In object, Si-CH3More only 1.75) only 7.57, Si-O key, therefore increases phenyl content, can promote polysiloxanes well
Refractive index.But the increase of phenyl content will will affect the brittleness of polysiloxanes, and material is made to be easier xanthochromia.
In consideration of it, developing a kind of has high refractive index and the impregnable organosilicon encapsulating material of remaining performance is with important
Research significance and application value.
Summary of the invention
It is an object of the invention to the defect for overcoming the refractive index of encapsulating material in the prior art low and deficiencies, provide one kind
Phenyl hydrogen-containing siloxane resin.Selection and dosage optimization of the present invention by specific monomer, the phenyl Silicon Containing Hydrogen oxygen being prepared
The content of phenyl greatly increases in alkane resin, improves refractive index;In addition the content of vinyl is also relatively reasonable, is conducive to solidify
Reaction;Simultaneously.The selection of tetramethyl-ring tetrasiloxane, so that introducing Si-H in the strand of phenyl hydrogen-containing siloxane resin simultaneously
Key and methylsiloxane segment can not only be effective as crosslinking agent use, but also flexibility greatly increases, finally obtained
The refractive index of phenyl hydrogen-containing siloxane resin is high, and flexibility and anti-yellowing property are excellent;When being used to prepare LED encapsulation silicone resin,
With high refractive index, excellent tensile strength, adhesion strength, light transmittance and yellowing resistance energy, partial properties have reached or are higher than state
The level of outer similar imported product, can satisfy the basic demand of LED encapsulation;The surface welded LED device of encapsulation has excellent
Air-tightness.
Another object of the present invention is to provide above-mentioned phenyl hydrogen-containing siloxane resins in preparing LED encapsulation silicone resin
Using.
Another object of the present invention is to provide a kind of high refractive index LED to encapsulate silicon resin composition.
Another object of the present invention is to provide the preparation methods of above-mentioned high refractive index LED encapsulation silicon resin composition.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of phenyl hydrogen-containing siloxane resin, the method for being prepared by the following procedure obtain: by monomer: phenyltrimethoxysila,e,
Dimethoxydiphenylsilane, tetramethyl-ring tetrasiloxane and tetramethyl disiloxane, water and the mixing of hydrolysis catalyst, add
Enter organic solvent and obtain mixed solution, be warming up to 30~60 DEG C of 1~5h of hydrolysis, then is warming up to 110~140 DEG C of points of water reactions 2
~11h, washing are evaporated under reduced pressure up to the phenyl hydrogen-containing siloxane resin;The phenyltrimethoxysila,e, diphenyl diformazan
The mass ratio of oxysilane, tetramethyl-ring tetrasiloxane and tetramethyl disiloxane be 15~25:45~55:10~20:1.5~
15。
Method provided by the invention is by selecting phenyltrimethoxysila,e, dimethoxydiphenylsilane, tetramethyl-ring
As monomer, the phenyl content of obtained phenyl hydrogen-containing siloxane resin is higher for tetrasiloxane and tetramethyl disiloxane, has
Higher refractive index;The selection of tetramethyl-ring tetrasiloxane simultaneously, so that in the strand of phenyl hydrogen-containing siloxane resin simultaneously
Si -- H bond and methylsiloxane segment are introduced, can not only be effective as crosslinking agent use, but also flexibility greatly increases.Most
The refractive index of the phenyl hydrogen-containing siloxane resin obtained eventually is high, and flexibility and anti-yellowing property are excellent.It is used to prepare LED encapsulation silicon
When resin, the LED that is prepared encapsulation silicone resin has a high refractive index, excellent tensile strength, adhesion strength, light transmittance and resistance to
Yellow performance, partial properties have reached or higher than external similar imported product level, can satisfy the basic demand of LED encapsulation;
The surface welded LED device of encapsulation has excellent air-tightness.
Preferably, the phenyltrimethoxysila,e, dimethoxydiphenylsilane, tetramethyl-ring tetrasiloxane and tetramethyl
The mass ratio of base disiloxane is 20:40:25:5.
Under the quality proportioning, phenyl hydrogen-containing siloxane resin has molecular weight appropriate, viscosity and silicone hydroxyl content, with
And more excellent refractive index and strand flexibility.
Preferably, the mass concentration of monomer is 25~75% in mixed solution.
It is further preferable that the mass concentration of monomer is 50% in mixed solution.
Preferably, the organic solvent is one or more of toluene, dimethylbenzene or benzene.
Preferably, the hydrolysis catalyst is concentrated hydrochloric acid, glacial acetic acid or AMBERLYST-15WET strong-acid type cation
One or more of exchanger resin.
Preferably, the molar ratio of the water and hydrolysis groups alkoxy is 1~1.4:1.
Preferably, the mass ratio of the phenyltrimethoxysila,e and hydrolysis catalyst is 15~25:1.2~5.8.
A kind of high refractive index LED encapsulation silicon resin composition, is grouped as by the group of following parts by weight:
The present invention is urged using phenylethylene based siloxane resins, phenyl hydrogen-containing siloxane resin as curing monomer in Karstedt
Solidify under the action of agent;And the preferably hyperbranched phenyl siloxane reinforcing agent of compatibility is selected, so that silicone resin solidfied material
Crosslinking points are more concentrated, can effective dispersive stress, or even formed " island structure ", play toughening and reinforcing effect;Selection has
The caking property and adhesive force of machine silicon tackifier raising silicone resin solidfied material and LED substrate, and obstruct the water in air etc., it obtains
LED encapsulation silicon resin composition phenyl content with higher and suitable contents of ethylene, refractive index is high, at the same have compared with
Good flexibility and yellowing resistance, partial properties have reached or higher than external similar imported product level, can satisfy LED envelope
The basic demand of dress;The surface welded LED device of encapsulation has excellent air-tightness.It is specific: tensile strength up to 1.4~
4.1MPa, adhesion strength are up to 0.3~1.2MPa, 450nm light transmittance close to 90%, shore hardness up to 60~85A, refractive index
Up to 1.56.
It should be understood that the high refractive index LED that Karstedt catalyst is unit quality (g) encapsulates silicon resin composition
10~20ppm of middle addition.
Preferably, the high refractive index LED encapsulation silicon resin composition is grouped as by the group of following parts by weight:
Preferably, the phenylethylene based siloxane resins are prepared via a method which to obtain:
S1: by monomer: dimethoxydiphenylsilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane
It is mixed with tetramethyl divinyl disiloxane, organic solvent is added and obtains mixed solution, hydrolyst is added;The diphenyl
Dimethoxysilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane and tetramethyl divinyl disiloxane
Mass ratio be 50~70:10~20:10~30:5~15;
S2: being added dropwise water at 30~60 DEG C and reaction be hydrolyzed, wash, vacuum distillation, and base catalyst adjusting pH is added and is
11~14, condensation reaction is carried out at 120~160 DEG C, is washed, and is evaporated under reduced pressure up to the phenylethylene based siloxane resins.
The present invention selects dimethoxydiphenylsilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane
The phenyl content of phenylethylene based siloxane resins can be improved as monomer with tetramethyl divinyl disiloxane, and obtain
Suitable contents of ethylene, and then improve refractive index and solidification effect;Simultaneously by selecting octamethylcy-clotetrasiloxane, in resin
Methylsiloxane segment is introduced in strand, flexibility greatly increases, the folding of finally obtained phenylethylene based siloxane resins
Rate height is penetrated, flexibility and anti-yellowing property are excellent.
Phenylethylene based siloxane resins are prepared in ad hoc approach and the refractive index of phenyl hydrogen-containing siloxane resin is close,
Further compensate for what routine techniques medium vinyl silicone resin and hydrogen-containing siloxane resin caused by refractive index difference
The problem of encapsulating material poor optical properties;In addition, the refractive index of the two is higher, by the mating reaction of the two, further mention
The high refractive index of LED encapsulation silicon resin composition, has more excellent comprehensive performance.
In addition, the preparation method simple process, easy post-processing will not generate corrosive substance.
Preferably, dimethoxydiphenylsilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane in S1
Mass ratio with tetramethyl divinyl disiloxane is 50:15:20:5.
Under the quality proportioning, phenylethylene based siloxane resins have more excellent refraction, flexibility and color inhibition
Performance.
Preferably, the mass fraction of monomer is 25~75% in S1 mixed solution.
It is further preferable that the mass fraction of monomer is 50% in S1 mixed solution.
Preferably, organic solvent is one or more of toluene, dimethylbenzene or benzene in S1.
Preferably, hydrolyst described in S1 is trifluoromethanesulfonic acid.
Make the pH of mixed solution less than 1 it is further preferable that trifluoromethanesulfonic acid is added in S1.
The dosage of water and basic catalyst can be controlled according to the requirement of existing hydrolysis and condensation reaction respectively in S2
System.
Preferably, S2 is 1~1.4:1 in the molar ratio of water and reactive group alkoxy.
Under normal circumstances, the dosage of water is the molar ratio of reactive functionality alkoxy when being 1:1, it can be achieved that preferable hydrolysis
Reaction.
The speed that water droplet adds can be adjusted according to the severe degree of hydrolysis, and 30~70s mono- drips under normal circumstances
Rate of addition is more appropriate, has been easy very much cyclic side products appearance fastly, influences the product transparency.
Preferably, base catalyst described in S2 be one of sodium hydroxide, potassium hydroxide or tetramethylammonium hydroxide or
It is a variety of.
Preferably, the hyperbranched phenyl siloxane reinforcing agent is prepared via a method which to obtain: by monomer: hexamethyl two
Siloxanes and tetramethyl divinyl disiloxane, water and acid catalyst mixing, are added organic solvent and obtain mixed solution, benzene is added dropwise
Base trimethoxy silane, then 0.5~4h of hydrolysis at 30~50 DEG C are warming up to 50~120 DEG C the reaction was continued 1~3h,
Washing is evaporated under reduced pressure up to the hyperbranched phenyl siloxane reinforcing agent;The hexamethyldisiloxane, tetramethyl divinyl
Disiloxane and the mass ratio of phenyltrimethoxysila,e are 5~15:10~20:15~25.
The present invention provides a kind of preparation methods of specific hyperbranched phenyl siloxane reinforcing agent.
The hyperbranched phenyl siloxane that the ad hoc approach is prepared, reaction process is simple, molecular weight can easily be accommodated, and
It is good with the compatibility of high refractive index encapsulation silicone resin, when being used for LED encapsulation silicon resin composition, it can further improve silicon tree
The toughness and intensity of rouge solidfied material.
Preferably, the structural formula of the hyperbranched phenyl siloxane reinforcing agent is as follows:
The present invention has included a kind of structural formula of hyperbranched phenyl siloxane reinforcing agent, and preceding method is prepared super
The structure of branching phenyl siloxane reinforcing agent is substantially similar, and difference is only that hyperbranched algebra is different, functional end-group
The position of vinyl and content difference.
Preferably, the hexamethyldisiloxane, tetramethyl divinyl disiloxane and phenyltrimethoxysila,e
Mass ratio is 12.5:12.5:25.
Preferably, the organic solvent is one or more of toluene, dimethylbenzene or benzene.
Preferably, the mass concentration of monomer is 25~75% in mixed solution.
It is further preferable that the mass concentration of monomer is 50% in mixed solution.
Preferably, the molar ratio of the water and hydrolysising group alkoxy is 0.4~0.75:1.
Preferably, the mass ratio of the hexamethyldisiloxane and acid catalyst is 5~15:2~6.
Preferably, the organic silicon rigidity-increasing stick is prepared via a method which to obtain: by monomer: phenyltrimethoxysila,e,
After dimethoxydiphenylsilane, methylvinyldimethoxysilane and tetramethyl divinyl disiloxane mixing, it is added
Organic solvent obtains mixed solution, and hydrolysis catalyst is added, reaction is hydrolyzed at 30~50 DEG C, washs, and adds after revolving
Enter silane coupling agent and condensation catalyst, is warming up to 80~140 DEG C of 1~7h of reaction;Washing filters up to the organosilicon
Tackifier;The phenyltrimethoxysila,e, diphenyl Dimethoxane base silane, methylvinyldimethoxysilane, tetramethyl
The mass ratio of base divinyl disiloxane and silane coupling agent is 15~25:25~35:10~20:2~15:10~20.
Preferably, the phenyltrimethoxysila,e, dimethoxydiphenylsilane, methyl ethylene dimethoxy silicon
The mass ratio of alkane, tetramethyl divinyl disiloxane and silane coupling agent is 20:30:15:5:15.
Preferably, the organic solvent is one or more of toluene, dimethylbenzene or benzene.
Preferably, the mass concentration of monomer is 25~75% in mixed solution.
It is further preferable that the mass concentration of monomer is 50% in mixed solution.
Preferably, the hydrolyst is trifluoromethanesulfonic acid.
It is further preferable that trifluoromethanesulfonic acid is added to pH less than 1.
Preferably, the silane coupling agent is one or more of KH-550, KH-560 or KH-570.
Preferably, the mass ratio of the phenyltrimethoxysila,e and silane coupling agent is 15~25:2~7.
Preferably, the condensation catalyst is one of potassium hydroxide, sodium hydroxide or tetramethylammonium hydroxide
Or it is several.
The preparation method of above-mentioned high refractive index LED encapsulation silicon resin composition, includes the following steps: phenyl vinyl silicon
Oxygen alkane and the mixing of phenyl hydrogen-containing siloxane, add hyperbranched phenyl siloxane, silicone resin tackifier and Karstedt catalyst,
Stirring, de-bubbled, gradually elevated cure encapsulates silicon resin composition up to the high refractive index LED.
Preferably, it is steeped using vacuum outgas.
Preferably, the solidification process is to be warming up to 100~150 DEG C of solidifications with the heating rate of 5~20 DEG C/min.
Specifically, 100 DEG C of solidification 1h are warming up to the heating rate of 10~20 DEG C/min, then proceed to be warming up to 130 DEG C
Solidify 2h, is continuously heating to 150 DEG C of solidification 3h.
Above-mentioned high refractive index LED encapsulation silicon resin composition as encapsulating material in LED encapsulation using also in this hair
In bright protection scope.
Compared with prior art, the invention has the following beneficial effects:
The present invention passes through selection and the dosage optimization of specific monomer, phenyl in the phenyl hydrogen-containing siloxane resin being prepared
Content greatly increase, improve refractive index;In addition the content of vinyl is also relatively reasonable, and it is moderate to be conducive to curing reaction acquisition
The degree of cross linking;Simultaneously by selecting octamethylcy-clotetrasiloxane, methylsiloxane segment, flexibility are introduced in molecular resin chain
It greatly increases, the refractive index of finally obtained phenylethylene based siloxane resins is high, and flexibility and anti-yellowing property are excellent;Over-expense
Change phenyl siloxane reinforcing agent and organic silicon rigidity-increasing stick can be further improved the mechanical strength and caking property of final material, is used for
When preparing LED encapsulation silicone resin, there is good heat resistance and anti-yellowing property, tensile strength is up to 1.4~4.1MPa, bonding
Intensity up to 0.3~1.2MPa, 450nm light transmittance close to 90%, shore hardness up to 60~85A, refractive index is up to 1.56, portion
Point performance, which has reached or is higher than, steps the portioned products such as figure, DOW CORNING, has many advantages, such as cheap, simple process, can satisfy
The basic demand of LED encapsulation, has industrial potentiality;The surface welded LED device of encapsulation has excellent air-tightness.
Detailed description of the invention
Fig. 1 is the infrared spectroscopy for the phenylethylene based siloxane resins that embodiment 1 provides;
Fig. 2 is the nucleus magnetic hydrogen spectrum for the phenylethylene based siloxane resins that embodiment 1 provides;
Fig. 3 is the infrared spectroscopy for the phenyl hydrogen-containing siloxane resin that embodiment 17 provides;
Fig. 4 is the nucleus magnetic hydrogen spectrum for the phenyl hydrogen-containing siloxane resin that embodiment 17 provides;
Fig. 5 is the infrared spectroscopy for the hyperbranched phenyl siloxane reinforcing agent that embodiment 33 provides;
Fig. 6 is the nucleus magnetic hydrogen spectrum for the hyperbranched phenyl siloxane reinforcing agent that embodiment 33 provides;
Fig. 7 is the infrared spectroscopy for the organic silicon rigidity-increasing stick that embodiment 45 provides;
Fig. 8 is the nucleus magnetic hydrogen spectrum for the organic silicon rigidity-increasing stick that embodiment 45 provides;
Fig. 9 is that the red ink test result of the surface welded LED packaging of embodiment 56 and comparative example 1, comparative example 2 is shone
Piece.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed
The condition suggested according to manufacturer;Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And replacement belongs to scope of the present invention.
Using the tensile property of universal testing machine test solidfied material, according to method as defined in national standard GB/T 16421-1996
Dumbbell shape tensile bars are poured, 5 Duplicate Samples is at least tested and is averaged.
Using the adhesive property of universal testing machine test solidfied material, referring to national standard GB/T13936-92 measurement silicone resin to aluminium
The tensile shear strength of piece is evaluated, and is at least tested 5 Duplicate Samples and is averaged.
The hardness of examination solidfied material is measured using shore A type hardness tester, is at least tested 5 Duplicate Samples and is averaged.
Using the light transmission of Japanese Shimadzu Corporation UV-3150 type ultraviolet-visible-near infrared spectrometer test solidfied material
Rate.In addition, carrying out light transmittance test, then the method according to ASTM E313 D1925 description to the solidfied material of different ageing times
Calculate yellowness index.
Liquid silicone is tested using the 2WE-T type digital display Abbe refractometer of Shanghai Li Guang precision instrument Co., Ltd and is consolidated
The refractive index of compound (with a thickness of 1mm), using naphthalene bromide as correcting medium.
The air-tightness that surface welded LED packaging is examined using red ink permeability test, if air-tightness is bad, after experiment
Device inside has red ink infiltration, and the observing to experiment front and back using optical microscopy.
Embodiment 1
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Infrared and nuclear magnetic spectrogram difference is as depicted in figs. 1 and 2, and molecular weight, appearance and refractive index data are as shown in table 1.
1260cm in Fig. 1-1Belong to Si-CH3Symmetric curvature vibration;1406cm-1The C=C scissors for belonging to Si-Vi are curved
Qu Zhendong;1429,1473,1457 and 1592cm-1Belong to the C=C stretching vibration of Si-Ph;2959cm-1Belong to CH3Stretch
Contracting vibration;3050 and 3070cm-1The C-H stretching vibration of phenyl ring is belonged to, preliminary proof is successfully prepared phenyl vinyl silicon oxygen
Alkane prepolymer, in 860cm-1And 3700-3600cm-1Between there is not the peak Si-OH, illustrate condensation reaction carry out it is more thorough
Bottom.
Chemical shift ownership is as follows in Fig. 2: 6.99~7.74ppm belongs to Si-Ph;0~0.27ppm belongs to Si-
CH3.Do not occur peak in 1.59ppm or so, illustrates the ratio for showing that preparation process can be such that condensation reaction carries out without containing Si-OH
Relatively completely.
Embodiment 2
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 0.5h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon
Oxygen alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 3
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 5h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 4
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 120 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 5
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 160 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 6
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% sodium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 7
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 2% tetramethylammonium hydroxide is added and adjusts pH, 150 DEG C
Lower progress condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl
Silicone resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 8
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.5% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 9
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water are depressurized at 55 DEG C with Rotary Evaporators, 1% potassium hydroxide is added and adjusts pH, is carried out at 150 DEG C
Condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenylethylene radical siloxane
Resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 10
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 60 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 11
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 6g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 12
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 8g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 13
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 10g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 14
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 50g dimethoxydiphenylsilane, 5g methylvinyldimethoxysilane, 20g octamethylcy-clotetrasiloxane,
5g tetramethyl divinyl disiloxane mixes postposition in a round bottom flask, and it is 50% that toluene, which is added, and is made into monomer mass ratio
Mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and rubs with reactive functionality etc.
Reaction is hydrolyzed by the pure water of ratio in you, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to during solution is in
Property.Abstraction solvent and water are depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, contracts at 150 DEG C
Reaction 2h is closed, separatory funnel is moved to and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtain phenylethylene radical siloxane tree
Rouge.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 15
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 30g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 16
The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.
By 60g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring
In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 10g tetramethyl divinyl disiloxane mixing postposition
50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group
Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution
It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into
Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen
Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.
Embodiment 17
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 11h.Solution is transferred in 500ml separatory funnel,
It is washed to solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.It is infrared
As shown in Figure 3 and Figure 4 with nuclear magnetic spectrogram difference, molecular weight, appearance and refractive index data are as shown in table 2.
Fig. 3 middle infrared absorption peak ownership is as follows: 1260cm-1Belong to Si-CH3Symmetric curvature vibration;1430 Hes
1593cm-1Belong to the C=C stretching vibration of Si-Ph;2166cm-1Belong to the stretching vibration of Si-H;2963cm-1It belongs to
CH3Stretching vibration;3072cm-1The C-H stretching vibration of phenyl ring is belonged to, preliminary proof is successfully prepared hydrogen-containing siloxane pre-polymerization
Object, in 860cm-1And 3700-3600cm-1Between there is not the peak Si-OH, illustrate condensation reaction carry out more thoroughly.
Chemical shift ownership is as follows in Fig. 4: 6.99~7.74ppm belongs to Si-Ph;5.17~6.13ppm belongs to Si-
H;0~0.22ppm belongs to Si-CH3。
Embodiment 18
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 120 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 19
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 110 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 20
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 140 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 21
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 19.5g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50
DEG C hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel,
It is washed to solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecule
Amount, appearance and refractive index data are as shown in table 2.
Embodiment 22
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 3.5g concentrated hydrochloric acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 23
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 2gAMBERLYST-15WET strongly acidic cation-exchange is set in a round bottom flask,
The toluene of the quality such as addition, is warming up to 50 DEG C of hydrolysis 4h, then be warming up to 130 DEG C, connects water segregator, and water is divided to react 4h.It will
Solution is transferred in 500ml separatory funnel, is washed to solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are
For phenyl hydrogen-containing siloxane resin.Molecular weight, appearance and refractive index data are as shown in table 2.
Embodiment 24
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 2h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 25
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 3h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 26
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 6h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 27
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 1.2g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 28
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 4.8g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 29
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane,
1.5g tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to
50 DEG C of hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred to 500ml separatory funnel
In, it is washed to solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Point
Son amount, appearance and refractive index data are as shown in table 2.
Embodiment 30
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 10g
Tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 31
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 5g tetramethyl-ring tetrasiloxane, 5g tetra-
Tetramethyldisiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C of water
Solution reaction 4h, then 140 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, is washed
It is presented to solution neutral.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.It is molecular weight, outer
It sees and refractive index data is as shown in table 2.
Embodiment 32
The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.
Weigh 30g phenyltrimethoxysila,e, 40g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g
Tetramethyl disiloxane, 13g H2O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C
Hydrolysis 4h, then 140 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water
It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight,
Appearance and refractive index data are as shown in table 2.
Embodiment 33
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H2O and 2% concentrated hydrochloric acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to
Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Infrared and core
Magnetic spectrum figure difference is as shown in Figure 5 and Figure 6, and molecular weight, appearance and refractive index data are as shown in table 3.
Fig. 5 middle infrared absorption peak ownership is as follows: 1253cm-1Belong to Si-CH3Symmetric curvature vibration;1430,1474 and
1594cm-1Belong to the C=C stretching vibration of Si-Ph;2958cm-1Belong to CH3Stretching vibration;3051 and 3073cm-1Return
Belong to the C-H stretching vibration of phenyl ring, preliminary proof is successfully prepared hyperbranched phenyl siloxane, in 860cm-1And 3700-
3600cm-1Between there is not the peak Si-OH, illustrate condensation reaction carry out more thoroughly.
Chemical shift ownership is as follows in Fig. 6: 6.70~8.00ppm belongs to Si-Ph;5.28~6.28ppm belongs to Si-
Vi;3.17~3.80ppm belongs to O-CH3;0~0.31ppm belongs to Si-CH3。
Embodiment 34
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H2O and 2% concentrated hydrochloric acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 50 DEG C the reaction was continued 2h, solution is transferred to
Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight,
Appearance and refractive index data are as shown in table 3.
Embodiment 35
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H2O and 2% concentrated hydrochloric acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 100 DEG C the reaction was continued 2h, solution is shifted
To separatory funnel, it is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecule
Amount, appearance and refractive index data are as shown in table 3.
Embodiment 36
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H2O and 2% glacial acetic acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to
Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight,
Appearance and refractive index data are as shown in table 3.
Embodiment 37
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H2O and 1% concentrated sulfuric acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to
Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight,
Appearance and refractive index data are as shown in table 3.
Embodiment 38
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H2O and 1% concentrated hydrochloric acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to
Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight,
Appearance and refractive index data are as shown in table 3.
Embodiment 39
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H2O and 5% concentrated hydrochloric acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to
Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight,
Appearance and refractive index data are as shown in table 3.
Embodiment 40
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 8g H2O and 2% glacial acetic acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to
Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight,
Appearance and refractive index data are as shown in table 3.
Embodiment 41
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 10g H2O and 2% glacial acetic acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 0.5h, solution is shifted
To separatory funnel, it is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecule
Amount, appearance and refractive index data are as shown in table 3.
Embodiment 42
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 3g hexamethyldisiloxane, 3g tetramethyl divinyl disiloxane, 6g H2O and 2% glacial acetic acid, mixing
In a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50% to postposition, and 20g phenyl is added dropwise
Trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to point
Liquid funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.It is molecular weight, outer
It sees and refractive index data is as shown in table 3.
Embodiment 43
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 30g hexamethyldisiloxane, 30g tetramethyl divinyl disiloxane, 6g H2O and 2% glacial acetic acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to
Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight,
Appearance and refractive index data are as shown in table 3.
Embodiment 44
The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.
Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H2O and 2% glacial acetic acid mix
Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 30g benzene is added dropwise
Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to
Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight,
Appearance and refractive index data are as shown in table 3.
Embodiment 45
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h.It will
Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing
Stick.Infrared and nuclear magnetic spectrogram difference is as shown in Figure 7 and Figure 8, and molecular weight, appearance and refractive index data are as shown in table 4.
Fig. 7 middle infrared absorption peak ownership is as follows: 909cm-1Belong to the vibration of epoxy group;1084cm-1Belong to C-O-
The stretching vibration of C;1408cm-1Belong to the C=C scissors bending vibration of Si-Vi;1430 and 1593cm-1Belong to the C of Si-Ph
=C stretching vibration;2941cm-1Belong to CH3Stretching vibration;3051cm-1The C-H stretching vibration of phenyl ring is belonged to, it is preliminary to demonstrate,prove
It is bright to be successfully prepared organic silicon rigidity-increasing stick, in 860cm-1And 3700-3600cm-1Between there is not the peak Si-OH, illustrate to be condensed
Reaction carries out more thorough.
Chemical shift ownership is as follows in Fig. 8: 6.99~7.74ppm belongs to Si-Ph;5.54~6.19ppm belongs to Si-
Vi;3.03~3.60ppm belongs to O-CH3;2.48ppm belonging to epoxy group;0~0.30ppm belongs to Si-CH3。
Embodiment 46
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 80 DEG C of reaction 5h.It will
Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing
Stick.Molecular weight, appearance and refractive index data are as shown in table 4.
Embodiment 47
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 140 DEG C of reaction 5h.It will
Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing
Stick.Molecular weight, appearance and refractive index data are as shown in table 4.
Embodiment 48
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 5g KH560 and 10gKH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 1h.It will
Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing
Stick.Molecular weight, appearance and refractive index data are as shown in table 4.
Embodiment 49
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 3h.It will
Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing
Stick.Molecular weight, appearance and refractive index data are as shown in table 4.
Embodiment 50
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 15g KH560 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h.Reaction solution is shifted
Into 500ml separatory funnel, it is washed to neutrality, 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing stick.Molecule
Amount, appearance and refractive index data are as shown in table 4.
Embodiment 51
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 15g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 3h.Reaction solution is shifted
Into 500ml separatory funnel, it is washed to neutrality, 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing stick.Molecule
Amount, appearance and refractive index data are as shown in table 4.
Embodiment 52
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 25g phenyltrimethoxysila,e, 35g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer for silane, 4.5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that mass ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h,
It hydrolyzes 1h again later, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings are except molten later
Agent and water, are added 5g KH560 and 10gKH570 silane coupling agent, and the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h.
Reaction solution is transferred in 500ml separatory funnel, neutrality is washed to, 150 DEG C of vacuum distillations remove solvent and water, obtain organosilicon
Tackifier.Molecular weight, appearance and refractive index data are as shown in table 4.
Embodiment 53
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 8g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h.It will
Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing
Stick.Molecular weight, appearance and refractive index data are as shown in table 4.
Embodiment 54
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 15g phenyltrimethoxysila,e, 25g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h.It will
Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing
Stick.Molecular weight, appearance and refractive index data are as shown in table 4.
Embodiment 55
The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.
Weigh 20g phenyltrimethoxysila,e, 35g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy
In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition
The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it
It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later
And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h.It will
Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing
Stick.Molecular weight, appearance and refractive index data are as shown in table 4.
Embodiment 56
The present embodiment provides high refractive index LED to encapsulate silicon resin composition, and preparation method is as follows.
By the 50g phenyl hydrogen-containing siloxane tree in the 50g phenylethylene based siloxane resins and embodiment 17 in embodiment 1
Rouge mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 33, the 1.5g organosilicon thickening in embodiment 45
The Karstedt catalyst of agent and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven
1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.It is sealed using surface-mount type
Dress technique is packaged component, and detects electronic part package after-poppet and silicone resin air-tightness using red ink experiment,
As illustrated in fig. 9.
Embodiment 57
The present embodiment provides high refractive index LED to encapsulate silicon resin composition, and preparation method is as follows.
By the 50g phenyl hydrogen-containing siloxane tree in the 50g phenylethylene based siloxane resins and embodiment 17 in embodiment 1
Rouge mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 10g in embodiment 33, the 1.5g organosilicon thickening in embodiment 45
The Karstedt catalyst of agent and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven
1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.
Embodiment 58
The present embodiment provides high refractive index LED to encapsulate silicon resin composition, and preparation method is as follows.
By the 40g phenyl hydrogen-containing siloxane tree in the 40g phenylethylene based siloxane resins and embodiment 17 in embodiment 1
Rouge mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 33, the 1.5g organosilicon thickening in embodiment 45
The Karstedt catalyst of agent and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven
1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.
Embodiment 59
The present embodiment provides high refractive index LED to encapsulate silicon resin composition, and preparation method is as follows.
By the 50g phenyl hydrogen-containing siloxane in the 50g phenylethylene based siloxane resins and embodiment 27 in embodiment 14
Resin mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 38, the 1.5g organic silicon rigidity-increasing in embodiment 51
The Karstedt catalyst of stick and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven
1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.
Embodiment 60
The present embodiment provides high refractive index LED to encapsulate silicon resin composition, and preparation method is as follows.
By the 50g phenyl hydrogen-containing siloxane in the 50g phenylethylene based siloxane resins and embodiment 31 in embodiment 11
Resin mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 36, the 1.5g organic silicon rigidity-increasing in embodiment 47
The Karstedt catalyst of stick and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven
1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.
Embodiment 61
The present embodiment provides high refractive index LED to encapsulate silicon resin composition, and preparation method is as follows.
By the 50g phenyl hydrogen-containing siloxane tree in the 50g phenylethylene based siloxane resins and embodiment 26 in embodiment 1
Rouge mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 44, the 1.5g organosilicon thickening in embodiment 52
The Karstedt catalyst of agent and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven
1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.
Comparative example 1
The present embodiment provides high refractive index LED to encapsulate silicon resin composition, and preparation method is as follows.
By the 50g phenylethylene based siloxane resins in embodiment 1, the 50g phenyl hydrogen-containing siloxane tree in embodiment 17
Rouge mixing, is added the Karstedt catalyst of 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 in baking oven
DEG C solidification 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h, acquisition transparent silicon resin cured product.Performance is as shown in table 5.Use table
Mounted packaging technology is packaged component, and using red ink experiment detection electronic part package after-poppet and silicone resin gas
Close property, as shown in figure 9b.
Comparative example 2
The present embodiment provides high refractive index LED to encapsulate silicon resin composition, and preparation method is as follows.
By the 50g phenyl hydrogen-containing siloxane tree in the 50g phenylethylene based siloxane resins and embodiment 17 in embodiment 1
Rouge mixing, adds the Karstedt catalyst of the 15g hyperbranched phenyl MT siloxanes and 10ppm in embodiment 33, and stirring is equal
Even, vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h in baking oven, obtains saturating
Bright silicone resin cured product.Performance is as shown in table 5.Component is packaged using surface-mount type packaging technology, and uses red ink
Water experiment detection electronic part package after-poppet and silicone resin air-tightness, as is shown in fig. 9 c.
The Nature comparison of the phenylethylene based siloxane resins prepared under 1 different condition of table
Such as table 1, the phenylethylene based siloxane resins being prepared under different condition in embodiment 1~16 all have higher
Refractive index, by change preparation condition, the molecular weight and mobility of adjustable phenylethylene based siloxane resins, specifically such as
Under: Examples 1 to 3 shows that when condensation reaction time is shorter, generation is mainly the lower oligomer of molecular weight, mobility
Preferably;With the extension of condensation reaction, the decline of product mobility is more inconvenient for subsequent cure operation.1,4,5 table of embodiment
Bright, influence of the temperature to polymer is complex, and increasing temperature can be improved ring-opening reaction rate, improves the molecule of polymer
Amount, but excessively high temperature can accelerate the progress of depolymerization back reaction, instead phenyl content is reduced, refractive index is caused to decline.It is real
It applies example 1,6,7 and shows that three kinds of resulting molecular weight of product of catalysts polymerization are very close, but obtained by NaOH catalytic polymerization
Product appearance be creamy white, (CH3)4NOH catalytic polymerization resulting product appearance is faint yellow in cream, and KOH makees obtained by catalytic polymerization
Product appearance in colorless and transparent, and molecular weight and refractive index reach requirement, therefore KOH is more preferably condensation reaction catalysis
Agent.When embodiment 1,8,9 shows that the amount of catalyst is excessive, rate of polymerization is too fast, and system is not easy to control, leads to the light transmission of product
Rate reduces.Embodiment 1,10 shows that hydrolysis temperature directly affects the hydrolysis rate of monomer and the appearance of final polymer, temperature mistake
Height results even in gel, it is difficult to obtain transparent uniform liquid.Embodiment 1,11,12,13,14 shows end-capping reagent tetramethyl two
The content of vinyl disiloxane can effectively control the molal weight of polymer, with the increase of end-capping reagent dosage, polymerization
Object molecular weight gradually reduces, if end-capping reagent is not added, the molecular weight of product is difficult to control, and is easy gelation;And add end-capping reagent can
So that product is with dimethylvinylsiloxy silicon substrate sealing end, with hydrogen-containing siloxane solidification process, hydrosilylation can extend
Strand improves the performance of cured product;Methylvinyldimethoxysilane content can also play the ethylene for adjusting product
The effect of base content.Embodiment 1,15,16 shows that dimethoxydiphenylsilane content can effectively adjust phenyl content and folding
Rate is penetrated, but content increase also results in mobility reduction.
The Nature comparison of the phenyl hydrogen containing siloxane resin prepared under 2 different condition of table
Such as table 2, the phenyl hydrogen containing siloxane resin being prepared under different condition in embodiment 17~32 all have compared with
High refractive index, by change preparation condition, the molecular weight and mobility of adjustable phenyl hydrogen containing siloxane resin, specifically
As follows: embodiment 17,21,24,25,26 shows that with the extension of reaction time, relative molecular weight first increases to be reduced afterwards, works as contracting
When the conjunction time is shorter, the unreacted silicone hydroxyl of remaining in system, so that condensation degree is inadequate, molecular weight is smaller;It is super when the time
After crossing 4h, polymer molecule depolymerization rate is greater than polycondensation rate, and the extension condensation time can make molecular weight become smaller, but can guarantee to gather
It is more regular to close object rearrangement.When embodiment 18,19,20,21 shows that condensation temp is lower, it is condensed not exclusively between silanol, product is in
Existing milky;And excessively high temperature can make polymer depolymerization rate increase, so that molecular weight of product reduces;Condensation temp 130
DEG C when prepolymer it is colorless and transparent and molecular weight is suitable, be more preferably condensation temp.Embodiment 20,21 shows water to product
Refractive index influences less, but can very big influence on the appearance of system;With increasing for amount of water, lead to the hydrolysis speed of each monomer
Rate is inconsistent, so that hydrolyzate is inhomogenous, and then is cyclized between the silanol that hydrolysis may be made to generate, milky is presented in product.It is real
It applies example 20,22,23 and shows that three kinds of different catalysts have certain catalytic effect, the molecular weight product of concentrated hydrochloric acid preparation is little, has
Color;For strong-acid cation-exchange resin since catalytic activity is slightly lower, molecular weight of product is not big enough, although having reacted filtering can remove
It goes, it is also possible to may be crushed and influence the transparency of product in whipping process;The prepolymer of glacial acetic acid preparation is colourless
Bright, molecular weight and refractive index are relatively met the requirements, and are more preferably catalyst.Embodiment 20,27,28 shows to use with catalyst
The increase of amount, molecular weight become larger until stabilization.Embodiment 20,29,30 shows the content of end-capping reagent tetramethyl disiloxane
The molal weight of polymer can be effectively controlled, with the increase of end-capping reagent dosage, polymer molecular weight is gradually reduced.Implement
Example 20,31,32 shows that adjusting raw material proportioning can change molecular weight of product and refractive index, general phenyltrimethoxysila,e phase
Raising to content can increase molecular weight and refractive index, but also be easy to cause solidfied material brittleness larger.
The Nature comparison of the hyperbranched phenyl siloxane reinforcing agent prepared under 3 different condition of table
Such as table 3, the hyperbranched phenyl siloxane reinforcing agent being prepared under different condition in embodiment 33~44 is all had
Higher refractive index, by change preparation condition, the molecular weight and mobility of adjustable hyperbranched phenyl siloxane reinforcing agent,
Specific as follows: when embodiment 33,34,35 shows that condensation temp is lower, collision probability is lower between silicone hydroxyl at this time, effective collision
It reduces, the extent of reaction reduces, and the polymer molecular weight of generation is smaller, and mobility is preferable;If condensation temp is excessively high, point of system
Son movement is fierce, and the effective collision between silicone hydroxyl is accelerated, and the progress of condensation reaction is promoted, and the molecular weight of product of generation is larger,
Molecular chain movement becomes difficult, so that polymer viscosity significantly becomes larger, becomes gel when serious.Embodiment 33,36,37 shows not
Same catalyst is affected to the hydrolytic condensation of siloxanes, and sulphuric acid catalysis activity is higher, and molecular weight of product is obviously greater than
Glacial acetic acid and concentrated hydrochloric acid catalysate, glacial acetic acid and concentrated hydrochloric acid product be more preferably under same catalyst concentration.Embodiment 33,38,39
Show the raising in scope of experiment with catalyst amount, the hydrolysis of siloxanes and condensation rate are continuously increased, the extent of reaction
It improves, the polymer molecular weight of generation also increases, and the viscosity of product at this time increases.Embodiment 36,40,41 shows different
Apparent difference can occur for the viscosity of amount of water, product, and when amount of water is more, product has a large amount of hydroxyl, due to molecule
Between hydrogen bond action the viscosity of product can be made to become larger;When amount of water is less, the polymer molecular weight after condensation is smaller, viscosity compared with
It is low, good fluidity, but the polymer molecular weight generated is too low, can decline to the reinforcing effect of material, therefore, in order to ensure that product has
Certain reinforcing effect and suitable molecular weight need to control the ratio of water and methoxy functional group.36,42,43 table of embodiment
Bright, the ratio of hexamethyldisiloxane and tetramethyl divinyl disiloxane end-capping reagent is affected to molecular weight of product, when
When end-capping reagent dosage is lower, molecular weight is larger, and mobility decline, the active group of molecule chain end such as vinyl can be reduced, instead
It answers site to reduce, when being added in matrix, effective reinforcement cannot be carried out to matrix;When end-capping reagent dosage is excessive, molecule
Measure lower, the viscosity of product is smaller at this time, but excessive end-capping reagent causes reaction site to increase, if at this time as reinforced filling,
Also the mechanical property such as degraded toughness that can make product is added in matrix, and material easily becomes fragile.When the variation of end-capping reagent ratio, also mean
The variation of phenyltrimethoxysila,e content, in conjunction with embodiment 44, as a result also turn out improve phenyltrimethoxysila,e contain
Amount, can increase the refractive index of product.
The Nature comparison of the organic silicon rigidity-increasing stick prepared under 4 different condition of table
Such as table 4, the organic silicon rigidity-increasing stick being prepared under different condition in embodiment 45~55 all has higher refraction
Rate, by changing preparation condition, the molecular weight and mobility of adjustable organic silicon rigidity-increasing stick be specific as follows: embodiment 45,46,
After 47 show that condensation temp influences less the refractive index of product, but condensation molecular weight first becomes larger with the raising of reaction temperature
Reduce.Embodiment 45,48,49 shows that the extension with the condensation time, condensation reach dynamic equilibrium, and product molecule amount is larger,
So that the mobility of product declines, viscosity becomes larger;And with the extension of condensation time, the siloxanes for being condensed generation is reset more
Sufficiently, the copolymer of generation is further rearranged into regular structure.Embodiment 45,50,51 shows KH560 depositing due to amino
It is light yellow product can be made to have, and individually the compounding in the smaller situation of KH570 KH560 content does not affect the face of product
Color, furthermore coupling agent influences molecular weight of product and refractive index little.Embodiment 45,52,53 shows with end-capping reagent dosage
Increase, the number-average molecular weight of product gradually decreases, and illustrates that end-capping reagent can carry out very big adjusting to the molecular weight of polymer;This
Outside, it can be seen that end-capping reagent dosage refractive index is affected, as end-capping reagent dosage increases, phenyl content relative reduction, folding
The rate of penetrating gradually decreases.Embodiment 45,54,55 shows can be by control phenyltrimethoxysila,e and diphenyl Dimethoxane
The additional amount of base silane adjusts refractive index, and phenyl content of monomer is higher, and refractive index is bigger;But refractive index is not more Gao Yue
It is good, when refractive index difference is larger, it will lead to and decline with the compatibility of other components, influence final LED encapsulation silicone resin solidfied material
Light transmittance.
5 silicone resin Solidified enzyme of table compares
Embodiment 56,57,58, comparative example 1 and comparative example 2 show hyperbranched phenyl siloxane reinforcing agent and organic silicon rigidity-increasing
The increase of stick ratio plays a significant role the mechanical strength and adhesion strength that improve product.Embodiment 56,59,60 shows
By reasonably select different condition under composition, can reach higher comprehensive performance, by with several commercialization silicone resin
Comparison, show using this method preparation silicone resin have more excellent refractive index, tensile strength and adhesion strength.
Fig. 9 is the surface welded LED wrapper of embodiment 56 (Fig. 9-a), comparative example 1 (Fig. 9-b) and comparative example 2 (Fig. 9-c)
The red ink test result photo of part.From figure it is found that embodiment 56 encapsulate substrate in red ink 80 DEG C boil two hours after,
Chip interior does not have red ink infiltration, and the caking property of the silicone material and substrate that illustrate preparation is preferable, can effectively obstruct
The intrusion of steam, oxygen and dust etc. has enough air-tightness.And it is not added with hyperbranched phenyl siloxane reinforcing agent and organic
There is a small amount of red ink infiltration at the product (comparative example 1) of silicon tackifier and product (comparative example 2) edge for being not added with tackifier.
Those of ordinary skill in the art will understand that embodiment here be to help reader understand it is of the invention
Principle, it should be understood that protection scope of the present invention is not limited to such specific embodiments and embodiments.This field it is common
Technical staff disclosed the technical disclosures can make the various various other tools for not departing from essence of the invention according to the present invention
Body variations and combinations, these variations and combinations are still within the scope of the present invention.
Claims (10)
1. a kind of phenyl hydrogen-containing siloxane resin, which is characterized in that be prepared via a method which to obtain: by monomer: phenyl front three
Oxysilane, dimethoxydiphenylsilane, tetramethyl-ring tetrasiloxane and tetramethyl disiloxane, water and hydrolysis catalysis
Agent mixing is added organic solvent and obtains mixed solution, is warming up to 30~60 DEG C of 1~5h of hydrolysis, then be warming up to 110~140 DEG C
Water is divided to react 2~11h, washing is evaporated under reduced pressure up to the phenyl hydrogen-containing siloxane resin;The phenyltrimethoxysila,e,
The mass ratio of dimethoxydiphenylsilane, tetramethyl-ring tetrasiloxane and tetramethyl disiloxane is 15~25:45~55:10
~20:1.5~15.
2. phenyl hydrogen-containing siloxane resin according to claim 1, which is characterized in that the phenyltrimethoxysila,e, two
The mass ratio of phenyidimethoxysilane, tetramethyl-ring tetrasiloxane and tetramethyl disiloxane is 20:40:25:5.
3. phenyl hydrogen-containing siloxane resin according to claim 1, which is characterized in that the mass concentration of monomer in mixed solution
It is 25~75%.
4. a kind of high refractive index LED encapsulates silicon resin composition, which is characterized in that be grouped as by the group of following parts by weight:
5. high refractive index LED encapsulates silicon resin composition according to claim 4, which is characterized in that by following parts by weight
Group be grouped as:
6. high refractive index LED encapsulates silicon resin composition according to claim 4, which is characterized in that the phenyl vinyl
Silicone resin is prepared via a method which to obtain:
S1: by monomer: dimethoxydiphenylsilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane and four
Divinyl disiloxane mixing is added organic solvent and obtains mixed solution, hydrolyst is added;The diphenyl diformazan
The matter of oxysilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane and tetramethyl divinyl disiloxane
Amount is than being 50~70:10~20:10~30:5~15;
S2: being added dropwise water at 30~60 DEG C and reaction be hydrolyzed, wash, vacuum distillation, be added base catalyst adjust pH for 11~
14, condensation reaction is carried out at 120~160 DEG C, is washed, and is evaporated under reduced pressure up to the phenylethylene based siloxane resins.
7. high refractive index LED encapsulates silicon resin composition according to claim 4, which is characterized in that the hyperbranched phenyl
Siloxanes reinforcing agent is prepared via a method which to obtain: by monomer: two silicon oxygen of hexamethyldisiloxane and tetramethyl divinyl
Alkane, water and acid catalyst mixing, are added organic solvent and obtain mixed solution, phenyltrimethoxysila,e is added dropwise, then 30~50
0.5~4h of hydrolysis at DEG C, is warming up to 50~120 DEG C the reaction was continued 1~3h, and washing is evaporated under reduced pressure up to described hyperbranched
Phenyl siloxane reinforcing agent;The hexamethyldisiloxane, tetramethyl divinyl disiloxane and phenyltrimethoxysila,e
Mass ratio be 5~15:10~20:15~25.
8. high refractive index LED encapsulates silicon resin composition according to claim 7, which is characterized in that the hyperbranched phenyl
The structural formula of siloxanes reinforcing agent is as follows:
9. high refractive index LED encapsulates silicon resin composition according to claim 4, which is characterized in that the organosilicon thickening
Agent is prepared via a method which to obtain: by monomer: phenyltrimethoxysila,e, dimethoxydiphenylsilane, methyl ethylene
After dimethoxysilane and tetramethyl divinyl disiloxane mixing, organic solvent is added and obtains mixed solution, hydrolysis is added and urges
Reaction washing is hydrolyzed at 30~50 DEG C, silane coupling agent and condensation catalyst is added after revolving, is warming up to for agent
80~140 DEG C of 1~7h of reaction;Washing filters up to the organic silicon rigidity-increasing stick;The phenyltrimethoxysila,e, diphenyl
The matter of Dimethoxane base silane, methylvinyldimethoxysilane, tetramethyl divinyl disiloxane and silane coupling agent
Amount is than being 15~25:25~35:10~20:2~15:10~20.
10. the preparation method of any high refractive index LED encapsulation silicon resin composition of claim 4~9, which is characterized in that
Include the following steps: to mix phenylethylene radical siloxane and phenyl hydrogen-containing siloxane, adds hyperbranched phenyl siloxane, silicon
Tackifier resin and Karstedt catalyst, stirring, de-bubbled solidify up to high refractive index LED encapsulation silicone resin combination
Object.
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