CN109384931B - Preparation method and application of photosensitive silicone resin containing polyurethane bridged polysilsesquioxane - Google Patents
Preparation method and application of photosensitive silicone resin containing polyurethane bridged polysilsesquioxane Download PDFInfo
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- CN109384931B CN109384931B CN201810968070.4A CN201810968070A CN109384931B CN 109384931 B CN109384931 B CN 109384931B CN 201810968070 A CN201810968070 A CN 201810968070A CN 109384931 B CN109384931 B CN 109384931B
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- China
- Prior art keywords
- polyurethane
- silane
- silicone resin
- bridged polysilsesquioxane
- photosensitive silicone
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000734 polysilsesquioxane polymer Polymers 0.000 title claims abstract description 66
- 239000004814 polyurethane Substances 0.000 title claims abstract description 56
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 55
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 19
- 238000003848 UV Light-Curing Methods 0.000 claims abstract description 14
- -1 alkoxy silane Chemical compound 0.000 claims description 36
- 229910000077 silane Inorganic materials 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 claims description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 244000028419 Styrax benzoin Species 0.000 claims description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229960002130 benzoin Drugs 0.000 claims description 5
- 235000019382 gum benzoic Nutrition 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 4
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 claims description 3
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 claims description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 3
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 claims description 3
- RAWPGIYPSZIIIU-UHFFFAOYSA-N [benzoyl(phenyl)phosphoryl]-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 RAWPGIYPSZIIIU-UHFFFAOYSA-N 0.000 claims description 3
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 3
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 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 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 3
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 abstract 1
- 239000007822 coupling agent Substances 0.000 description 15
- 239000005022 packaging material Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 241000269333 Caudata Species 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
-
- 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
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- 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
Landscapes
- 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)
- Polyurethanes Or Polyureas (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to the field of organic polymer materials, and aims to solve the problems of the existing UV-cured organic silicon materials. And then respectively preparing the UV-cured silicone resin containing the polyurethane-bridged polysilsesquioxane by using the obtained polyurethane-bridged hydroxyl-terminated polysilsesquioxane as a raw material through a cohydrolysis condensation reaction. In the photosensitive silicone resin material, the polyurethane bridging chain segment is obtained by taking PTMG as a raw material to react, and a cured product obtained by UV curing of the photosensitive silicone resin has the hardness of 60-80 Shore A, and has good flexibility and air tightness and good bonding with an LED bracket.
Description
Technical Field
The invention relates to the field of organic polymer materials, in particular to UV curing molding LED packaging silicon resin containing polyurethane bridging polysilsesquioxane chain segments and a preparation method thereof.
Background
Generally, after the packaging material is dispensed, the LED packaging is realized by heating, curing and molding, and the production cycle is long and the energy consumption is high. Ultraviolet (UV) curing LED packaging materials are available, and the packaging materials can be completely cured after being dispensed and irradiated by UV for several minutes or even tens of seconds, so that the LED lighting device is packaged, the energy consumption is greatly reduced, and the production efficiency is improved. However, the heat resistance and mechanical properties of the existing UV-curable silicone materials need to be improved.
In addition, the properties possessed by molded silicone make it useful for designing and injection molding complex shapes, thicker and larger parts, and even recesses, which are difficult to achieve with other optical materials currently on the market. Specific uses of molded silicones include secondary optics (light diffusing, concentrating, and distributing optics), light pipes, and light pipes for LED lamps and LED light sources. The comprehensive characteristics of high temperature resistance, ultraviolet resistance and no yellowing can improve the luminous flux maintenance rate of the material, so that the material becomes an ideal choice for indoor and outdoor illumination purposes, and the risk of degradation and aging of plastic materials does not exist. At present, the molded silicone resins used by LED packaging enterprises in China are Dow Corning MS-1002 and Dow Corning MS-1003 molded silicone resins, and are monopolized by foreign and foreign international companies.
Bridged polysilsesquioxanes are one type of polysilsesquioxanes that have a specific organic-inorganic hybrid three-dimensional network structure that corresponds to a network structure in which organic groups are uniformly distributed as a component in the silica inorganic component, and can also be viewed as a three-dimensional network structure formed by "bridging (crosslinking)" the silica inorganic component by organic groups. In the bridged polysilsesquioxane molecule, the final aim of bridging through covalent bonds is to better mix the organic-inorganic components at the molecular level, so that the amorphous polymer can have the properties of two different components, namely organic and inorganic, and the synergistic effect of the two components is fully exerted. In addition, the bulk properties of the material can be altered by changing the organic components. Since the organic component has a complicated variability, materials having different properties can be obtained by adjusting its rigidity, length, hydrophilicity, and the like. [ development of Guanshiyou, Yan salamander, Liu honeycomb and bridged polysilsesquioxane, macromolecule Notification, 2014,12,60-67]
Polyurethane (PU) molecules contain a characteristic group-NH-CO-, has the characteristics of strong wear resistance, organic solvent and chemical resistance, excellent adhesive force and the like, and is widely used in the fields of petroleum, automobiles, textiles, printing, medical treatment, sports, buildings and the like. Many researchers desire to combine the advantages of silicones (polysiloxanes) and polyurethanes to obtain materials with superior properties. However, because the solubility parameters of polysiloxane and polyurethane are very different, the results of simple blending, in-situ polymerization and formation of interpenetrating network polymers are not satisfactory. The best method for modifying polyurethane with silicone is copolymerization modification. A small amount of polyurethane is introduced into organic silicon, so that the mechanical strength, corrosion resistance, adhesive force and other properties of the organic silicon can be effectively improved, and the organic silicon is a novel polymer material with a great development prospect. (Fengbei, Ningye, Wangbuan, Tangshiying, Muslim, preparation method and application prospect of polyurethane modified organic silicon, Guangzhou chemical industry 2010, 38 (8): 6-7) because the LED packaging material needs good performances such as aging resistance, corrosion resistance and moisture resistance, the PU modified LED packaging material should be free of PEG chain segments with too good hydrophilic performance in molecules as far as possible. Polytetramethylene ether glycol (polytetrahydrofuran (PTMG)) with two ends of hydroxyl is used as an important chemical raw material and is mainly used for preparing spandex, elastomers, adhesives, coatings, sealants and other fields, and polyurethane products prepared from the polytetramethylene ether glycol are wear-resistant, chemical corrosion-resistant, and have good flexibility and rebound resilience.
Disclosure of Invention
In order to solve the problems of the existing UV curing organic silicon material, the invention provides a preparation method of photosensitive silicone resin containing polyurethane bridging polysilsesquioxane and application of the photosensitive silicone resin in UV curing molding LED packaging.
The invention is realized by the following technical scheme: the preparation method of the photosensitive silicone resin containing the polyurethane bridged polysilsesquioxane comprises the following steps:
(1) PTMG reacts with trifunctional alkoxy silane with isocyanate group in solvent A to prepare silane coupling agent solution with trifunctional alkoxy at two ends and polyurethane chain segment in the middle;
preferably, the PTMG is subjected to dehydration under reduced pressure at 105 ℃ for 2-4h, and the PTMG is a commercial product selected from one or more of PTMG with a molecular weight of 250 (abbreviated as PTMG-250, and abbreviated as similar hereinafter), PTMG-650, PTMG-1000, PTMG-1400, PTMG-1800 and PTMG-2000. By introducing the polyurethane-bridged hydroxyl-terminated polysilsesquioxane prepared by taking PTMG as a raw material into a molecular chain of the UV-cured silicone resin, the flexibility of the UV-cured silicone resin is improved, and the bonding performance of the UV-cured silicone resin and the PPA (PPA) of the LED bracket is improved.
Preferably, the trifunctional alkoxy silane with the isocyanate group is one or two selected from 3-isocyanate propyl trimethoxy silane and 3-isocyanate propyl triethoxy silane; the molar ratio of isocyanate to PTMG was 2:1, otherwise resulting in incomplete reaction of the functional groups, either an excess of hydroxyl groups or an excess of isocyanate groups, so that the product is not pure.
The solvent A is selected from one or more of acetone, dichloromethane, dichloroethane, petroleum ether and tetrahydrofuran, the using amount of the solvent A is the amount for dissolving the solute, and preferably, the using amount of the solvent A is 0.5-3 times, more preferably 0.5-2 times of the total mass of the reaction raw materials.
Preferably, the reaction steps are: dripping trifunctional alkoxy silane with isocyanate groups into PTMG and a solvent A at the temperature of 20-60 ℃, reacting for 2-8 h, and preferably: and (3) dropwise adding trifunctional alkoxy silane with isocyanate groups into the PTMG and the solvent A at the temperature of 30-50 ℃, and reacting for 2-4 h.
(2) Dropwise adding a mixture of dioxane, water and a catalyst A into the coupling agent solution with polyurethane chain segments at two ends obtained in the step (1), carrying out slow hydrolysis-condensation reaction after dropwise adding, filtering to remove the catalyst, and evaporating the solvent under reduced pressure to prepare hydroxyl-terminated polyurethane-bridged polysilsesquioxane;
the catalyst A is selected from one or more of sodium carbonate, potassium hydroxide and sodium hydroxide, and the dosage of the catalyst A is 0.5-5% of the mass of the coupling agent with polyurethane chain segments at two ends.
The using amount of water is 2:1 according to the mole number of the water and the mole number of the obtained coupling agent with the polyurethane chain segments at two ends, and the polysilsesquioxane with a regular structure cannot be obtained when the water is not enough and the water is too much.
The usage amount of the dioxane is 10-100 times of the mass of water.
Preferably, after the mixture is dripped for 1-2 h, the reaction time of slow hydrolysis-condensation is 24-72 h at the temperature of 0-30 ℃.
(3) And (3) carrying out hydrolysis-condensation reaction on the hydroxyl-terminated polyurethane-bridged polysilsesquioxane obtained in the step (2) and siloxane containing acryloxy, difunctional alkoxy silane and trifunctional alkoxy silane in a solvent B under the catalysis of a catalyst B, and treating to obtain the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane.
Hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane, acryloxy-containing siloxane, difunctional alkoxy silane and trifunctional alkoxy silane;
the usage amount of the hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane is 5-30% of the total mass of the silane;
the siloxane containing the acryloxy is selected from one or more of methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, methacryloxypropylmethyldimethoxysilane and methacryloxypropylmethyldiethoxysilane, and the using amount of the siloxane is 2-25% of the total mass of the silane;
the difunctional alkoxysilane is selected from one or more of dimethyl dimethoxysilane, dimethyl diethoxysilane, methylphenyl dimethoxysilane, methylphenyl diethoxysilane, diphenyl dimethoxysilane and diphenyl diethoxysilane, and the using amount of the difunctional alkoxysilane is 10-30% of the mass of the silane;
the trifunctional alkoxy silane is selected from one or more of methyltrimethoxy silane, methyltriethoxy silane, phenyl trimethoxy silane and phenyl triethoxy silane, and the using amount is the balance of the mass of the silane;
the catalyst B is selected from one or more of sulfuric acid, hydrochloric acid, phosphoric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and acetic acid, and the usage amount of the catalyst B is 0.5-10% of the total mass of silane; preferably, the catalyst B is one or more selected from sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid, and the usage amount of the catalyst B is 1-3 wt% of the total mass of silane.
The solvent B is one selected from toluene, xylene, petroleum ether, ethyl acetate and butyl acetate, and the amount of the solvent B is the amount for dissolving the solute. Preferably, the solvent B is one selected from toluene, ethyl acetate and butyl acetate.
Preferably, the hydrolysis-condensation reaction temperature is 30-78 ℃, the reaction time is 0.5-12 h,
preferably, the solvent and low-boiling-point substances are removed at 120 mmHg/120-180 ℃ in the treatment process, and the photosensitive silicone resin containing the polyurethane bridged polysilsesquioxane and having the viscosity of 3000-40000 cp is obtained.
The invention prepares the polyurethane-bridged hydroxyl-terminated polysilsesquioxane by the hydrolysis reaction of PTMG and trifunctional alkoxy silane with isocyanate group under the action of a catalyst. And then respectively preparing the UV-cured silicone resin containing the polyurethane-bridged polysilsesquioxane by using the obtained polyurethane-bridged hydroxyl-terminated polysilsesquioxane as a raw material through a cohydrolysis condensation reaction.
The application of the photosensitive silicone resin containing the polyurethane bridged polysilsesquioxane obtained by the preparation method of the photosensitive silicone resin containing the polyurethane bridged polysilsesquioxane in UV curing molding LED packaging comprises the steps of mixing the photosensitive silicone resin containing the polyurethane bridged polysilsesquioxane with a photoinitiator, defoaming the mixture in vacuum for 15-30 min, injecting the mixture into an LED bowl cup through a molding extruder, and curing the mixture for 0.5-30 min through UV, wherein the preferable curing time is 1-10 min.
The LED packaging material has the light transmittance of more than 95 percent and has no penetration after 1.5 h of a red ink test.
Preferably, the UV power is 0.1-3 KW, and more preferably, the UV power is 0.5-3 KW.
The photoinitiator is selected from benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenylethanone, alpha-dimethoxy-alpha-phenylacetophenone, alpha-diethoxyacetophenone, alpha-hydroxyalkyl phenone, alpha-aminoalkyl phenone, aroylphosphine oxide, dibenzoylphenylphosphine oxide, benzophenone, 2, 4-dihydroxy benzophenone, Michler's ketone; one or more of thiopropoxy thioxanthone and isopropyl thioxanthone is used in an amount which is 1-15% of the mass of the photosensitive silicone resin containing the polyurethane bridged polysilsesquioxane, and the preferable amount is 5-10%.
Compared with the prior art, the invention has the beneficial effects that: the hardness of the LED packaging material is 60-80 Shore A, the LED packaging material has good flexibility and air tightness, is well bonded with an LED support, and can be used for packaging molded UV curing LEDs and other electronic components.
Detailed Description
The present invention is further illustrated by the following examples, in which the starting materials are either commercially available or prepared by conventional methods.
The examples are not intended to limit the scope of the invention.
Example 1
(1) To a clean three-necked flask containing PTMG-250 (25 g, 0.1 mol) dehydrated under reduced pressure at 105 ℃ for 2 hours and 66g of acetone was added dropwise 3-isocyanatopropyltrimethoxysilane (41.056 g, 0.2 mol) at 30 ℃ for about 0.5 hour, and after completion of the addition, reacted at 30 ℃ for 4 hours to prepare 132.056g of an acetone solution of a coupling agent having a polyurethane segment.
(2) And (2) dropwise adding a mixed solution of 108g of dioxane, 10.8g of distilled water and 0.66 g of potassium carbonate into the coupling agent with the polyurethane chain segment obtained in the step (1) at 20 ℃, sealing after dropping for 2h, stirring at 20 ℃, carrying out hydrolysis-condensation reaction for 24 h, filtering to remove the potassium carbonate, and carrying out reduced pressure evaporation to obtain 52.256g of hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane.
(3) Adding 52.256g of hydroxyl-terminated polyurethane-bridged polysilsesquioxane obtained in the step (2) and 27.93g of methacryloxypropyltrimethoxysilane, 93.05 g of dimethyldimethoxysilane, 136.2 g of methyltrimethoxysilane and 300g of toluene into a 2L dry clean three-necked bottle, dropwise adding a mixed solution of 300g of deionized water and 6g of 98% concentrated sulfuric acid into the mixture under stirring at 60 ℃, carrying out cohydrolysis-condensation reaction for 6 hours at 60 ℃ after dropwise addition is finished for about 60 minutes, standing for layering, washing an oil phase to be neutral by using the deionized water, and removing the toluene and low molecules under reduced pressure at 120mmHg/160 ℃ to obtain 186g of photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane with the viscosity of 15000 cp.
Application example 1
186g of the obtained silicone resin LED packaging material is mixed with 9.3g of alpha, alpha-diethoxyacetophenone and 9.3g of thiopropoxy thioxanthone, and the mixture is subjected to vacuum defoamation for 30min, then is subjected to injection molding by a molding extruder into an LED bowl and then is subjected to UV curing for 10 min for molding. The hardness of the cured product was 80 Shore A, and the light transmittance was 98.5%.
Example 2
(1) To a clean three-necked flask containing PTMG-2000 (200 g, 0.1 mol) dehydrated under reduced pressure at 105 ℃ for 2 hours and 125 g of tetrahydrofuran was added dropwise 3-isocyanatopropyltriethoxysilane (49.4 g, 0.2 mol) at 60 ℃ for about 0.5 hour, reacted at 60 ℃ for 2 hours after completion of the dropwise addition, and then the tetrahydrofuran was distilled off under reduced pressure to prepare 374.4 g of a tetrahydrofuran solution of a coupling agent having a polyurethane segment.
(2) And (2) dropwise adding a mixed solution of 1080g of dioxane, 10.8g of distilled water and 5.457g of sodium carbonate into the coupling agent with the polyurethane chain segment obtained in the step (1) at 0 ℃, sealing after dropping for 2 hours, stirring at 0 ℃ for hydrolysis-condensation reaction for 72 hours, filtering to remove the sodium carbonate, and evaporating under reduced pressure to obtain 235.6 g of hydroxyl-terminated polyurethane-bridged polysilsesquioxane.
(3) Adding 220.9g of hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane obtained in the step (2) and 29.23 g of methacryloxypropyltriethoxysilane, 26.04g of methacryloxypropylmethyldiethoxysilane, 192.32 g of dimethyldimethoxysilane, 178.3 g of methyltriethoxysilane, 99.15g of phenyltrimethoxysilane and 900g of xylene into a 2L dry clean three-necked bottle, dropwise adding a mixed solution of 500g of deionized water and 30.3g of 36.5% concentrated hydrochloric acid at the temperature of 60 ℃ under stirring, carrying out cohydrolysis-condensation reaction at the temperature of 70 ℃ for 8 hours after dropping for about 80 minutes, standing for layering, washing an oil phase to be neutral by using the deionized water, and removing the xylene and low molecules under reduced pressure at the temperature of 120mmHg/180 ℃ to obtain 454.1g of photosensitive silicone resin containing the bridged polyurethane-containing polysilsesquioxane with the viscosity of 40000 cp.
Application example 2
454.1g of the obtained silicone resin LED packaging material is mixed with 36.3 g of benzoin isopropyl ether, and the mixture is subjected to vacuum defoamation for 30min, then is subjected to injection molding into an LED bowl through a molding extruder, and then is subjected to UV curing for 10 min for molding. The hardness of the cured product was 60 Shore A, and the light transmittance was 95.0%.
Example 3
(1) To a clean three-necked flask containing PTMG-1000 (50 g, 0.05 mol), PTMG-1800 (90 g, 0.05 mol), 355 g methylene chloride and 200g petroleum ether dehydrated under reduced pressure at 105 ℃ for 2 hours, 3-isocyanatopropyltrimethoxysilane (20.528 g, 0.1 mol) and 3-isocyanatopropyltriethoxysilane (24.7 g, 0.1 mol) were added dropwise at 40 ℃ for about 0.5 hour, and after completion of the dropwise addition, the mixture was reacted at 40 ℃ for 6 hours to obtain 740.2 g of a solution of a coupling agent having a polyurethane segment.
(2) And (2) dropwise adding a mixed solution of 100g of dioxane, 432g of distilled water and 5.457g of potassium hydroxide into the coupling agent with the polyurethane chain segment obtained in the step (1) at 20 ℃, sealing after 1.5 h of dropwise adding, stirring at 20 ℃ for hydrolysis-condensation reaction for 48h, filtering to remove potassium hydroxide, and evaporating under reduced pressure to obtain 171.4 g of hydroxyl-terminated polyurethane-bridged polysilsesquioxane.
(3) Adding 174.0g of hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane obtained in the step (2) and 17.059 g of methacryloxypropyltriethoxysilane, 84g of methylphenyldiethoxysilane, 192.32 g of dimethyldimethoxysilane, 178.3 g of methyltriethoxysilane, 173.2 g of phenyltrimethoxysilane and 400g of ethyl acetate into a 2L dry clean three-necked bottle, dropwise adding a mixed solution of 500g of deionized water and 4.19g of trifluoromethanesulfonic acid at the temperature of 60 ℃ under stirring, carrying out cohydrolysis-condensation reaction at the temperature of 60 ℃ for 8 hours after dropping for about 80 minutes, standing for layering, washing an oil phase to be neutral by using the deionized water, and removing the ethyl acetate and low molecules under reduced pressure at the temperature of 120mmHg/120 ℃ to obtain 285.2 g of photosensitive silicon resin containing the polyurethane-containing bridged polysilsesquioxane with the viscosity of 28000 cp.
Application example 3
285.2 g of the obtained silicon resin LED packaging material is mixed with 8.55 g of aroylphosphine oxide and 5.70g of bis-benzoylphenylphosphine oxide, and after vacuum deaeration for 30min, the mixture is injected into an LED bowl through a molding extruder, and then UV curing is carried out for 30min for molding. The hardness of the cured product was 68 Shore A, and the light transmittance was 97.0%.
Example 4
(1) To a clean three-necked flask containing PTMG-650 (32.5 g, 0.05 mol), PTMG-1400 (70 g, 0.05 mol) and 100g of dichloroethane dehydrated under reduced pressure at 105 ℃ for 2 hours, 3-isocyanatopropyltriethoxysilane (49.4 g, 0.2 mol) was added dropwise at 20 ℃ for about 0.5 hour, and after completion of the addition, the reaction was carried out at 20 ℃ for 8 hours to prepare 251.9g of an dichloroethane solution of a coupling agent having a polyurethane segment.
(2) And (2) dropwise adding a mixed solution of 540 g of dioxane, 10.8g of distilled water and 5.457g of sodium hydroxide into the coupling agent with the polyurethane chain segment obtained in the step (1) at 10 ℃, sealing after dripping for 2h, stirring at 20 ℃ for hydrolysis-condensation reaction for 48h, filtering to remove the sodium hydroxide, and evaporating under reduced pressure to obtain 138.1g of hydroxyl-terminated polyurethane-bridged polysilsesquioxane.
(3) 138.1g of the hydroxyl-terminated polyurethane-bridged polysilsesquioxane obtained in (2) were charged in a 2L dry clean three-necked flask with 49.68 g of methacryloxypropyltrimethoxysilane, 104.16 g of methacryloxypropylmethyldiethoxysilane, 65 g of dimethyldiethoxysilane, 50g of diphenyldiethoxysilane, 210 g of methyltriethoxysilane, 89g of phenyltriethoxysilane and 500g of butyl acetate, dropping 500g deionized water and 70.6g acetic acid mixed solution under stirring at 50 deg.C, after dropping for about 80min, carrying out cohydrolysis-condensation reaction for 6h at 50 ℃, standing for layering, washing an oil phase to be neutral by deionized water, butyl acetate and low molecular weight were removed under reduced pressure at 120mmHg/160 ℃ to obtain 526.7g of a polyurethane-bridged polysilsesquioxane-containing photosensitive silicone resin having a viscosity of 3000 cp.
Application example 4
526.7g of the obtained silicone LED encapsulating material was mixed with 10.52 g of benzoin butyl ether, 5.267g of alpha-aminoalkylbenzophenone, 5.267g of 2, 4-dihydroxybenzophenone and 10.52 g of isopropyl thioxanthone, subjected to vacuum defoamation for 30min, subjected to injection molding by a molding extruder into an LED bowl, and subjected to UV curing for 25 min to form the silicone LED encapsulating material. The hardness of the cured product was 76 Shore A, and the light transmittance was 98.0%.
Example 5
(1) To a clean three-necked flask containing PTMG-650 (32.5 g, 0.05 mol), PTMG-2000 (100 g, 0.05 mol) and 265 g of tetrahydrofuran dehydrated under reduced pressure at 105 ℃ for 2 hours, 3-isocyanatopropyltriethoxysilane (49.4 g, 0.2 mol) was added dropwise at 30 ℃ for about 0.5 hour, and after completion of the addition, the reaction was carried out at 40 ℃ for 8 hours to prepare 446.9 g of a tetrahydrofuran solution of a coupling agent having a polyurethane segment.
(2) Dropwise adding a mixed solution of 648 g of dioxane, 10.8g of distilled water and 14.552 g of potassium carbonate into the coupling agent with the polyurethane chain segment obtained in the step (1) at 10 ℃, sealing after 2.0h of dropwise addition, stirring at 30 ℃ for hydrolysis-condensation reaction for 48h, filtering to remove potassium carbonate, and evaporating under reduced pressure to obtain 168.1g of hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane.
(3) Adding 33.62 g of hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane obtained in the step (2) and 58.0 g of methacryloxypropyltriethoxysilane, 104.16 g of methacryloxypropylmethyldiethoxysilane, 64.11 g of dimethyldimethoxysilane, 258.3 g of methyltriethoxysilane, 160.15g of phenyltrimethoxysilane and 900g of petroleum ether into a 2L dry clean three-necked bottle, dropwise adding a mixed solution of 500g of deionized water and 40g of p-toluenesulfonic acid under stirring at 60 ℃, carrying out cohydrolysis-condensation reaction for 2 hours at 60 ℃ after completing dropwise addition for about 80 minutes, standing for layering, washing an oil phase to be neutral by using deionized water, and removing the petroleum ether and low molecules under reduced pressure at 120mmHg/180 ℃ to obtain 421.7g of photosensitive silicone resin containing polyurethane-containing bridged polysilsesquioxane with the viscosity of 16000 cp.
Application example 5
421.7g of the obtained silicon resin LED packaging material is mixed with 4.217 g of benzoin dimethyl ether, 4.217 g of diphenylethanone and 8.434g of alpha, alpha-diethoxyacetophenone, and after vacuum defoaming is carried out for 30min, the mixture is injected into an LED bowl cup through a molding extruder, and then UV curing is carried out for 30min for molding. The hardness of the cured product was 74 Shore A, and the light transmittance was 98.0%.
Example 6
(1) To a clean three-necked flask containing PTMG-650 (32.5 g, 0.05 mol), PTMG-2000 (100 g, 0.05 mol) and 265 g of acetone dehydrated under reduced pressure at 105 ℃ for 2 hours, 3-isocyanatopropyltrimethoxysilane (41.056 g, 0.2 mol) was added dropwise at 30 ℃ for about 0.5 hour, and after completion of the addition, the mixture was reacted at 30 ℃ for 4 hours to prepare 438.556 g of an acetone solution of a coupling agent having a polyurethane segment.
(2) And (2) dropwise adding a mixed solution of 108g of dioxane, 10.8g of distilled water and 2.19g of potassium carbonate into the coupling agent with the polyurethane chain segment obtained in the step (1) at 30 ℃, sealing after 1 h of dropwise adding, stirring at 30 ℃ for hydrolysis-condensation reaction for 72h, filtering to remove the potassium carbonate, and evaporating under reduced pressure to obtain 168.1g of hydroxyl-terminated polyurethane-bridged polysilsesquioxane.
(3) Adding 168.1g of hydroxyl-terminated polyurethane-bridged polysilsesquioxane obtained in the step (2) and 14.502 g of methacryloxypropyltriethoxysilane, 26.04g of methacryloxypropylmethyldiethoxysilane, 192.32 g of dimethyldimethoxysilane, 178.3 g of methyltriethoxysilane, 99.15g of phenyltrimethoxysilane and 400g of toluene into a 2L dry clean three-necked bottle, dropwise adding a mixed solution of 500g of deionized water and 8.92 g of 36.5% concentrated hydrochloric acid at the temperature of 60 ℃ under stirring, carrying out cohydrolysis-condensation reaction at the temperature of 65 ℃ for 8h after completing dropping for about 80min, standing for layering, washing an oil phase to be neutral by using the deionized water, and removing the toluene and low molecules under reduced pressure at the temperature of 120mmHg/140 ℃ to obtain 454.1g of photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane with the viscosity of 8000 cp.
Application example 6
454.1g of the obtained silicone resin LED packaging material is mixed with 45.4 g of alpha, alpha-dimethoxy-alpha-phenylacetophenone, and after vacuum defoaming for 30min, the mixture is injected into an LED bowl cup through a molding extruder, and then the LED bowl cup is formed through UV curing for 30 min. The hardness of the cured product was 68 Shore A, and the light transmittance was 98.0%.
Claims (10)
1. A preparation method of photosensitive silicone resin containing polyurethane bridged polysilsesquioxane is characterized by comprising the following steps:
(1) polytetramethylene ether glycol (PTMG) reacts with trifunctional alkoxy silane with isocyanate groups in a solvent A to prepare a silane coupling agent solution with trifunctional alkoxy groups at two ends and a polyurethane chain segment in the middle;
(2) dropwise adding a mixture of dioxane, water and a catalyst A into the silane coupling agent solution with trifunctional alkoxy at two ends and a polyurethane chain segment in the middle obtained in the step (1), carrying out hydrolysis-condensation reaction after dropwise adding, filtering to remove the catalyst, and evaporating the solvent under reduced pressure to prepare hydroxyl-terminated polyurethane-bridged polysilsesquioxane;
(3) hydrolyzing and condensing the hydroxyl-terminated polyurethane-bridged polysilsesquioxane obtained in the step (2) and acryloxy-containing silane, difunctional alkoxy silane and trifunctional alkoxy silane in a solvent B under the catalysis of a catalyst B, and treating to obtain the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane;
the acryloxy-containing silane is selected from one or more of methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane and methacryloxypropylmethyldiethoxysilane,
the difunctional alkoxysilane is one or more selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane,
the trifunctional alkoxy silane is selected from one or more of methyltrimethoxy silane, methyltriethoxy silane, phenyl trimethoxy silane and phenyl triethoxy silane.
2. The method for preparing the photosensitive silicone resin containing polyurethane-bridged polysilsesquioxane according to claim 1, wherein the trifunctional alkoxysilane having an isocyanate group in step (1) is one or two selected from the group consisting of 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane; the molar ratio of isocyanate to PTMG was 2: 1.
3. the method for preparing the photosensitive silicone resin containing polyurethane-bridged polysilsesquioxane as recited in claim 1, wherein the solvent A in step (1) is one or more selected from the group consisting of acetone, dichloromethane, dichloroethane, petroleum ether, and tetrahydrofuran.
4. The method for preparing the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane as recited in claim 1, wherein the reaction step of step (1) is: and (3) dropwise adding trifunctional alkoxy silane with isocyanate groups into the PTMG and the solvent A at the temperature of 20-60 ℃, and reacting for 2-8 h.
5. The method for preparing the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane according to claim 1, wherein the catalyst A in the step (2) is one or more selected from sodium carbonate, potassium hydroxide and sodium hydroxide, and the amount of the catalyst A is 0.5-5% of the mass of the silane coupling agent with the trifunctional alkoxy groups at two ends and the polyurethane chain segment in the middle; the using amount of the water is 2:1 according to the mole number of the water and the mole number of the silane coupling agent with trifunctional alkoxy groups at two ends and a polyurethane chain segment in the middle, and the using amount of the dioxane is 10-100 times of the mass of the water.
6. The method of claim 1, wherein the polyurethane-bridged polysilsesquioxane-containing photosensitive silicone resin,
the usage amount of the hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane is 5-30% of the total mass of the hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane, acryloxy-containing silane, difunctional alkoxy silane and trifunctional alkoxy silane;
the usage amount of the silane containing the acryloxy is 2-25% of the total mass of the hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane, the silane containing the acryloxy, the difunctional alkoxysilane and the trifunctional alkoxysilane;
the using amount of the difunctional alkoxy silane is 10-30% of the total mass of the hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane, the acryloxy-containing silane, the difunctional alkoxy silane and the trifunctional alkoxy silane;
the catalyst B is selected from one or more of sulfuric acid, hydrochloric acid, phosphoric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and acetic acid, and the usage amount of the catalyst B is 0.5-10% of the total mass of hydroxyl-terminated polyurethane-containing bridged polysilsesquioxane, acryloxy-containing silane, difunctional alkoxy silane and trifunctional alkoxy silane;
the solvent B is one selected from toluene, xylene, petroleum ether, ethyl acetate and butyl acetate.
7. The method for preparing the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane as recited in claim 1, wherein the hydrolysis-condensation reaction temperature in the step (3) is 30-78 ℃ and the reaction time is 0.5-12 h.
8. The preparation method of the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane as claimed in claim 1, wherein the treatment process in the step (3) comprises the steps of washing the oil phase in the reaction system with water to be neutral, and removing the solvent and low-boiling-point substances at 120 mmHg/120-180 ℃ to obtain the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane and having the viscosity of 3000-40000 cp.
9. The application of the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane obtained by the preparation method of the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane in the UV curing molding LED package according to claim 1 is characterized in that the photosensitive silicone resin containing the polyurethane-bridged polysilsesquioxane and a photoinitiator are mixed, subjected to vacuum defoaming for 15-30 min, injected into an LED bowl through a molding extruder, and subjected to UV curing for 0.5-30 min for molding.
10. Use of a photosensitive silicone resin comprising a polyurethane-bridged polysilsesquioxane according to claim 9, characterised in that said photoinitiator is selected from the group consisting of benzoin, benzoin bis-methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenylethanone, α -dimethoxy- α -phenylacetophenone, α -diethoxyacetophenone, α -hydroxyalkylphenone, α -aminoalkylbenzophenone, aroylphosphine oxide, bis-benzoylphenylphosphine oxide, benzophenone, 2, 4-dihydroxybenzophenone, Michler's ketone; one or more of thiopropoxy thioxanthone and isopropyl thioxanthone, wherein the using amount of the thiopropoxy thioxanthone and the isopropyl thioxanthone is 1-15% of the mass of the photosensitive silicone resin containing the polyurethane bridged polysilsesquioxane.
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