CN103772426B - Organic silicon resin with high refractive index, preparation method and application thereof - Google Patents
Organic silicon resin with high refractive index, preparation method and application thereof Download PDFInfo
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- CN103772426B CN103772426B CN201410027779.6A CN201410027779A CN103772426B CN 103772426 B CN103772426 B CN 103772426B CN 201410027779 A CN201410027779 A CN 201410027779A CN 103772426 B CN103772426 B CN 103772426B
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- 229920005989 resin Polymers 0.000 title abstract description 19
- 239000011347 resin Substances 0.000 title abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 15
- 229910052710 silicon Inorganic materials 0.000 title abstract description 15
- 239000010703 silicon Substances 0.000 title abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 13
- -1 sulfydryl Chemical group 0.000 claims description 62
- 229920002050 silicone resin Polymers 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 35
- 229920001296 polysiloxane Polymers 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 20
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 229920002545 silicone oil Polymers 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 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 17
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 15
- 230000003301 hydrolyzing effect Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 125000003368 amide group Chemical group 0.000 claims description 6
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims 1
- 150000001343 alkyl silanes Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 6
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical group C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000012676 equilibrium polymerization Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VIJXFDYNPXVYJQ-UHFFFAOYSA-N triethoxy-(4-methoxyphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=C(OC)C=C1 VIJXFDYNPXVYJQ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention relates to organic silicon resin with high refractive index, a preparation method and an application thereof. Particularly, in the manufacturing process of the organic silicon resin, the organic silicon resin with high refractive index can be obtained by adding monomers shown in a formula I into a reaction system; in the formula, R1 and R2 are defined as the description in the specification. The organic silicon resin prepared by the invention is high in refractive index and can be used as an organic silicon adhesive in the field of LED (Light Emitting Diode) package.
Description
Technical Field
The invention belongs to the field of high-performance polymer manufacturing, and particularly relates to a two-component high-refractive-index organic silicon resin material containing alkoxy phenyl, and a preparation method and application thereof.
Background
The Light Emitting Diode (LED) is a light emitting element which can directly convert electric energy into light energy, is used as a novel high-efficiency solid light source, and has the remarkable advantages of long service life, energy conservation, environmental protection and the like. In recent years, with the rapid development of LED technology, the luminous efficiency is gradually improved, the application market of LEDs is wider, especially under the background of the increasing concern of global energy shortage, the prospects of LEDs in the lighting market are more spotlighted, and the LEDs will be one of the most promising high-tech fields for replacing the traditional light sources such as incandescent lamps, tungsten lamps and fluorescent lamps in the future.
The performance of LED encapsulation materials will also have a significant impact on the luminous efficiency, brightness, and lifetime of LED devices during their manufacture. The light output power of the lighting device can be obviously improved and the service life of the lighting device can be obviously prolonged by using the packaging material with ultraviolet resistance, thermal aging resistance, high refractive index and low stress. The epoxy resin is the most used packaging material, and has the advantages of excellent electrical insulation property, dielectric property, transparency, good cohesiveness, no generation of small molecular substances during curing, low shrinkage, good storage stability, flexible formula, simple and convenient operation and the like. However, it has high crosslinking density after curing, large internal stress, large brittleness and poor impact resistance, and the use temperature is generally not more than 150 ℃, so the application of the material is limited to a certain extent. Practical application shows that when the traditional epoxy resin, PC and PMMA are used as lens materials, the problem of incompatibility with an inner packaging material interface can be caused besides obvious insufficient aging resistance, so that the luminous efficiency of an LED device is sharply reduced after high-low temperature cycle experiments. Researches show that the transparency of the epoxy resin is reduced at about 150 ℃, the light output of the LED is weakened, the resin can be seriously degraded within the range of 135-145 ℃, and the LED has important influence on the service life of the LED. Under the condition of large current, the packaging material can even be carbonized, and a conductive channel is formed on the surface of the device, so that the device fails.
The silicone material has excellent heat resistance, weather resistance, moisture resistance, cold and thermal shock resistance and other performances, and related patent reports at home and abroad use the silicone material as an LED packaging material, such as chinese patent documents CN101544881A and CN101935455A, US patent documents US6815520B2, US7294682B2, US2004/0116640a1 and US2009/0221783a 1. The silicone materials for LED encapsulation reported in the prior patent are mainly classified into two types, one is methyl silicone resin, which has good adhesion, but the defects of general temperature resistance and low refractive index (about 1.43) generally exist, and belong to the lower class of silicone materials for LED encapsulation, and the other is methyl phenyl silicone resin, which has high refractive index (about 1.50) and excellent temperature resistance, but as the content of phenyl is increased, the rigidity of the material is correspondingly increased, thereby reducing the adhesion.
In summary, there is still no LED-encapsulating silicone material with high refractive index, excellent temperature resistance, and good adhesion in the art.
Disclosure of Invention
The invention aims to provide an LED packaging organosilicon material which has high refractive index, excellent temperature resistance and better cohesiveness.
In a first aspect of the present invention, there is provided an alkoxyphenyl triethoxysilane compound of formula I:
wherein,
R1is a substituted or unsubstituted C1-C18 alkyl group;
R2is substituted or unsubstituted C1-C4 alkyl.
In another preferred embodiment, the "substituted" refers to substitution with one or more substituents selected from the group consisting of: halogen atom, amido, hydroxyl, carboxyl, sulfydryl, C1-C10 alkyl, C1-C10 alkoxy, C2-C10 ester group, amido, C6-C30 aryl, C1-C30 heteroaryl, C2-C10 acyl, C7-C30 alkyl-aryl, and C2-C30 alkyl-heteroaryl.
In a second aspect of the invention, there is provided a process for the preparation of a compound of formula I as described in the first aspect of the invention, said process comprising the steps of:
reacting a compound of formula Ia with a compound of formula Ib in an inert solvent to obtain a compound of formula I.
In another preferred embodiment, the inert solvent is selected from the group consisting of: toluene, tetrahydrofuran, diethyl ether, or combinations thereof.
In another preferred embodiment, the reaction is carried out in the presence of a metallating agent; preferably, the metallation reagent is selected from the group consisting of: mg, n-butyllithium, or a combination thereof.
In another preferred embodiment, the reaction is carried out under an inert atmosphere; preferably, the reaction is carried out under the protection of argon.
In another preferred embodiment, the reaction is carried out in the presence of an initiator, and preferably, the initiator is elemental iodine.
In another preferred embodiment, the molar ratio of the compound of formula Ia to the compound of formula Ib to the metal catalyst is 1: 0.5-3: 0.6-3.1.
In a third aspect of the present invention, there is provided a silicone material comprising a compound of formula I as described in the first aspect of the present invention, or prepared using a compound of formula I as described in the first aspect of the present invention.
In another preferred embodiment, the organosilicon material is prepared by hydrolytic polymerization of a compound of formula I and one or more compounds selected from the group consisting of: phenyl alkoxy silane, alkyl alkenyl silane.
In another preferred embodiment, the alkyl is C1-C20 alkyl.
In another preferred embodiment, the alkenyl is C1-C20 alkenyl.
In another preferred embodiment, the alkoxy is C1-C20.
In another preferred embodiment, the organosilicon material is prepared by hydrolytic polymerization of a compound of formula I and one or more components selected from the group consisting of: phenyltrimethoxysilane, diphenyldimethoxysilane, and methylvinyldimethoxysilane; preferably, the organic silicon material is prepared by hydrolytic polymerization of a compound shown in the formula I and the following components: phenyltrimethoxysilane, methylvinyldimethoxysilane, and optionally diphenyldimethoxysilane.
In another preferred embodiment, the molar ratio of the compound of formula I to phenyltrimethoxysilane, diphenyldimethoxysilane and methylvinyldimethoxysilane is 2-16: 0 to 14: 0-16: 0 to 15, preferably 2 to 16:0 to 14: 8:7.5, more preferably 2: 14: 8:7.5 or 16:0:8: 7.5.
In another preferred embodiment, the hydrolytic polymerization is carried out under acidic conditions.
In a fourth aspect of the present invention, there is provided a silicone resin comprising or prepared from a silicone material according to the third aspect of the present invention.
In another preferred embodiment, the silicone resin is prepared by reacting the following components: the organosilicon material, the methyl phenyl vinyl silicone resin, the methyl phenyl hydrogen-containing silicone oil and the platinum catalyst according to the third aspect of the invention.
In another preferred embodiment, the silicone resin comprises the following components in parts by weight: the silicone material according to the third aspect of the invention: methyl phenyl vinyl silicone resin: methyl phenyl hydrogen-containing silicone oil: the platinum catalyst = 0-100: 0-10, preferably 100:100:100: 2.5.
In another preferred embodiment, the methyl phenyl vinyl silicone resin is prepared by reacting one or more components selected from the following group: ethyl orthosilicate, phenyltrimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, and vinyltriethoxysilane; preferably, the methyl phenyl vinyl silicone resin is prepared by the reaction of the following components: phenyltrimethoxysilane, methylphenyldimethoxysilane, and optionally a component selected from the group consisting of: ethyl orthosilicate, methylvinyldimethoxysilane, vinyltriethoxysilane, or a combination thereof.
In another preferred embodiment, the molar ratio of the components is: ethyl orthosilicate: phenyltrimethoxysilane: methylphenyl dimethoxy silane: methylvinyldimethoxysilane: vinyltriethoxysilane = 0-10: 40-60: 20-40: 0 to 20: 0 to 20, preferably 5:50:30:10: 10.
In another preferred embodiment, the reaction is hydrolytic polymerization.
In another preferred embodiment, the reaction is carried out under acidic conditions.
In another preferred embodiment, the platinum catalyst is selected from the group consisting of: chloroplatinic acid, chloroplatinic acid-isopropanol solution, methyl vinyl siloxane platinum complex, or combinations thereof.
In another preferred embodiment, the methyl phenyl hydrogen-containing silicone oil is prepared by the following reaction components: diphenyldimethoxysilane, tetramethyltetrahydrocyclotetrasiloxane (D)4 H) And hexamethyldisiloxane.
In another preferred embodiment, the diphenyl dimethoxysilane and the tetramethyltetrahydrocyclotetrasiloxane (D) are4 H) And hexamethyldisiloxane in a molar ratio of 0 to 200:0 to 50:0 to 8, preferably 100:25: 4.
In another preferred embodiment, the reaction is carried out under acidic conditions.
In another preferred embodiment, the reaction is equilibrium polymerization.
In another preferred embodiment, the silicone resin is prepared by reacting the following component A and component B:
the component A comprises: a silicone material, a methyl phenyl vinyl silicone resin, and a platinum catalyst according to the third aspect of the present invention;
the component B comprises: methyl phenyl vinyl silicone resin and methyl phenyl hydrogen-containing silicone oil.
In another preferred embodiment, the reaction comprises: a, B components are uniformly mixed, and then vacuum bubble removal is carried out for 20-30 min, and curing molding is carried out at 80-140 ℃.
In another preferred embodiment, the weight ratio of the component A to the component B is 1-100: 1-100, preferably 1-10: 1-10.
In another preferred example, in the component a, the weight ratio of each component is as follows: the silicone material according to the third aspect of the invention: methyl phenyl vinyl silicone resin: the platinum catalyst = 0-100: 0-50: 0-10, preferably 100:50: 2.5.
In another preferred example, in the component B, the weight ratio of each component is as follows: methyl phenyl vinyl silicone resin methyl phenyl hydrogen silicone oil = 0-50: 0-100, preferably 50: 100.
in a fifth aspect of the present invention, there is provided a silicone resin raw material composition, comprising: the organosilicon material, the methyl phenyl vinyl silicone resin, the methyl phenyl hydrogen-containing silicone oil and the platinum catalyst according to the third aspect of the invention.
In another preferred embodiment, the composition comprises component A and component B, and
the component A comprises: a silicone material, a methyl phenyl vinyl silicone resin, and a platinum catalyst according to the third aspect of the present invention;
the component B comprises: methyl phenyl vinyl silicone resin and methyl phenyl hydrogen-containing silicone oil.
In another preferred embodiment, the raw material composition is used for polymerization to prepare the silicone resin according to the fourth aspect of the present invention.
In a sixth aspect of the present invention, there is provided an article comprising or made with a silicone resin according to the fourth aspect of the present invention.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
The present inventors have conducted extensive and intensive studies for a long time and have unexpectedly found that the incorporation of a flexible oxy-ether bond into a methylphenyl silicone system effectively reduces the rigidity of the methylphenyl silicone, thus improving the adhesion of the silicone encapsulant to the resin substrate while maintaining the heat resistance and high refractive index of the material. The alkoxy phenyl silicone resin can be used as a novel silicone material in the LED packaging industry.
Term(s) for
As used herein, the term "hydrolytic polymerization" refers to the process of reacting silane monomers with water under basic or acidic conditions to remove alkoxy groups and form long chain molecules of siloxysilicon.
The term "equilibrium polymerization" refers to the process by which a cyclic siloxane (typically a four-membered ring) forms a chain siloxysilicon under acidic or basic conditions, which is a reversible process that reaches equilibrium between the linear siloxane and the cyclic siloxane with the addition of an end-capping agent.
The term "methyl silicone resin" refers to a silicone resin in which the pendant groups are entirely methyl.
The term "methylphenyl silicone resin" refers to a silicone resin having methyl and phenyl groups pendant from the silicone resin.
As used herein, the term "C1-C18 alkyl" refers to a straight or branched chain alkyl or cycloalkyl group having 1 to 18 carbon atoms, such as methyl, methylene, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or the like.
Unless otherwise specified, each group described herein includes a case of being substituted or unsubstituted, and the substitution means being substituted with one or more substituents selected from the group consisting of: halogen atom, amido, hydroxyl, carboxyl, sulfydryl, C1-C10 alkyl, C1-C10 alkoxy, C2-C10 ester group, amido, C6-C30 aryl, C1-C30 heteroaryl, C2-C10 acyl, C7-C30 alkyl-aryl, and C2-C30 alkyl-heteroaryl.
Methyl phenyl silicone resin with flexible oxygen ether bond
The invention provides alkoxy phenyl triethoxysilane shown as a formula I:
wherein,
R1is a substituted or unsubstituted C1-C18 alkyl group;
R2is substituted or unsubstituted C1-C4 alkyl.
The alkoxy phenyl triethoxy silane can be prepared by the following method:
reacting a compound of formula Ia with a compound of formula Ib in an inert solvent to obtain a compound of formula I.
The inert solvent is not particularly limited, and may be preferably selected from the group consisting of: toluene, tetrahydrofuran, diethyl ether, or combinations thereof.
The reaction is preferably carried out in the presence of a metal catalyst; more preferably, the metallation reagent is selected from the group consisting of: mg, n-butyllithium, or a combination thereof.
In another preferred embodiment, the reaction is carried out under an inert atmosphere; preferably, the reaction is carried out under the protection of argon.
In another preferred embodiment, the reaction is carried out in the presence of elemental iodine.
In another preferred embodiment, the molar ratio of the compound of formula Ia to the compound of formula Ib to the metal catalyst is 1: 0.5-3: 0.6-3.1.
The compound of the formula I can be used for preparing an organic silicon material and further preparing organic silicon resin. In the present invention, a preferred organosilicon material is prepared by hydrolytic polymerization of a compound of formula I with one or more compounds selected from the group consisting of: phenyl alkoxy silane, alkyl alkenyl silane.
In another preferred embodiment, the alkyl is C1-C20 alkyl.
In another preferred embodiment, the alkenyl is C1-C20 alkenyl.
In another preferred embodiment, the alkoxy is C1-C20.
In another preferred embodiment, the organosilicon material is prepared by hydrolytic polymerization of a compound of formula I and one or more components selected from the group consisting of: phenyltriethoxysilane, diphenyldimethoxysilane, and methylvinyldimethoxysilane; preferably, the organic silicon material is prepared by hydrolytic polymerization of a compound shown in the formula I and the following components: phenyltriethoxysilane, methylvinyldimethoxysilane, and optionally diphenyldimethoxysilane.
The ratio of the components is not particularly limited and can be determined according to actual needs. In a preferred embodiment of the invention, the molar ratio of the compound of formula I to phenyltriethoxysilane, diphenyldimethoxysilane and methylvinyldimethoxysilane is 2-16; 0 to 14; 0 to 16; 0 to 15.
In another preferred embodiment, the hydrolytic polymerization is carried out under acidic conditions.
The invention also provides a silicone resin, wherein the silicone resin comprises the silicone material, or is prepared from the silicone material.
A preferred silicone resin is prepared by reacting: the organic silicon material, methyl phenyl vinyl silicone resin, methyl phenyl hydrogen-containing silicone oil and platinum catalyst.
Wherein the methyl phenyl vinyl silicone resin can be prepared by a common method, for example, by reacting one or more components selected from the following group: ethyl orthosilicate, phenyltrimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, and vinyltriethoxysilane; preferably, the methyl phenyl vinyl silicone resin is prepared by the reaction of the following components: phenyltrimethoxysilane, methylphenyldimethoxysilane, and optionally a component selected from the group consisting of: ethyl orthosilicate, methylvinyldimethoxysilane, vinyltriethoxysilane, or a combination thereof.
In another preferred embodiment, the molar ratio of the components is: ethyl orthosilicate: phenyltrimethoxysilane: methylphenyl dimethoxy silane: methylvinyldimethoxysilane: vinyltriethoxysilane = 0-10: 40-60: 20-40: 0 to 20: 0 to 20.
In another preferred embodiment, the reaction is hydrolytic polymerization.
In another preferred embodiment, the reaction is carried out under acidic conditions.
In another preferred embodiment, the platinum catalyst is selected from the group consisting of: chloroplatinic acid, chloroplatinic acid-isopropanol solution, methyl vinyl siloxane platinum complex, or combinations thereof.
In another preferred embodiment, the methyl phenyl hydrogen-containing silicone oil is prepared by the following reaction components: diphenyldimethoxysilane, tetramethyltetrahydrocyclotetrasiloxane (D)4 H) And hexamethyldisiloxane.
In another preferred embodiment, the diphenyl isMethoxysilane, tetramethyltetrahydrocyclotetrasiloxane (D)4 H) And hexamethyldisiloxane in a molar ratio of 0-200: 0-50: 0-8.
In another preferred embodiment, the reaction is carried out under acidic conditions.
In another preferred embodiment, the reaction is equilibrium polymerization.
In the invention, a more preferable organic silicon resin is prepared by reacting the following component A and component B:
the component A comprises: the organosilicon material, methyl phenyl vinyl silicone resin and platinum catalyst;
the component B comprises: methyl phenyl vinyl silicone resin and methyl phenyl hydrogen-containing silicone oil.
In another preferred embodiment, the reaction comprises: a, B components are uniformly mixed, and then vacuum bubble removal is carried out for 20-30 min, and curing molding is carried out at 80-140 ℃.
The main advantages of the invention include:
(1) the invention provides an organic silicon compound with flexible oxygen ether bond, which can be used as a component of organic silicon resin and is used for reducing the rigidity of the organic silicon resin and enhancing the cohesiveness.
(2) The invention provides an organic silicon material which can be used for preparing a composite component organic silicon resin with excellent performance.
(2) The invention also provides the two-component high-refractive-index organic silicon resin containing the alkoxyl phenyl and the preparation method thereof, and the obtained organic silicon resin has high refractive index, high light transmission, excellent temperature resistance and adhesion and can meet the requirements of the LED packaging industry.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
EXAMPLE 1 preparation of p-methoxyphenyl triethoxysilane
Under the protection of argon, 1.44 g (0.06mol) of magnesium strips, 20.8 g (0.1mol) of ethyl orthosilicate, a small amount of iodine and 100 ml of dried toluene are added into a dry 250 ml three-neck flask, a mixture of 9.35 g (0.05mol) of 4-bromoanisole and 20 ml of dried tetrahydrofuran is stirred and slowly added, after the color of the system fades, the mixture is reacted in an ice-water bath for 24 hours, the solvent is removed after the diatomite filtration, 7.34 g of fraction with the temperature of 80 ℃/10mba is collected by reduced pressure distillation, and the yield is 54%.1H NMR(400MHz,CDCl3,in ppm):7.58～7.60(d,2H),6.89～6.91(d,2H),3.79～3.86(m,9H)，1.20～1.24(t,9H)。
Example 2 preparation of a methyl vinyl silicon resin
50 ml of water, 50 ml of concentrated hydrochloric acid and 30 ml of toluene are added into a clean 500 ml three-neck flask, a mixed solution of 5.2 g (0.025mol) of ethyl orthosilicate, 50.0 g (0.25mol) of phenyltrimethoxysilane, 27.3 g (0.15mol) of methylphenyldimethoxysilane, 6.61 g (0.05mol) of methylvinyldimethoxysilane, 9.5 g (0.05mol) of vinyltriethoxysilane and 20 ml of toluene is added dropwise through a constant-pressure dropping funnel under vigorous stirring, the reaction temperature is controlled below 20 ℃, the reaction is continued for 3h after the dropwise addition is finished, then the reaction is continued for 3h after the heating to 80 ℃, the reaction is cooled to the room temperature, the organic layer is washed to be neutral by water, the anhydrous sodium sulfate is used for drying, the toluene is removed after the filtration, the temperature is increased to 150 ℃/10mba, and the micromolecule compound is removed, 25.5 g of methylphenylvinyl silicone resin is obtained, and the refractive index is 1.1.
Example 3 preparation of p-methoxyphenyl methyl phenyl vinyl silicon resin
Adding 25 ml of water, 25 ml of concentrated hydrochloric acid and 15 ml of toluene into a clean 250 ml three-neck bottle, dropwise adding a mixed solution of 5.4 g (0.02mol) of p-methoxyphenyl triethoxysilane, 27.7 g (0.14mol) of phenyltriethoxysilane, 19.5 g (0.08mol) of diphenyldimethoxysilane, 10.0 g (0.075mol) of methylvinyl dimethoxysilane and 10 ml of toluene through a constant-pressure dropping funnel under vigorous stirring, controlling the reaction temperature below 20 ℃, continuing to react for 3h after the dropwise adding is finished, then heating to 80 ℃ to continue to react for 3h, cooling to room temperature, washing to be neutral by water, drying an organic layer by anhydrous sodium sulfate, filtering to remove toluene, and heating to 150 ℃/10mba under reduced pressure to remove small molecular compounds, thereby obtaining 12.2 g of p-methoxyphenyl methyl phenyl vinyl silicone resin with a refractive index of 1.552.
Example 4 preparation of p-methoxyphenyl methyl phenyl vinyl silicon resin
Adding 25 ml of water, 25 ml of concentrated hydrochloric acid and 15 ml of toluene into a clean 250 ml three-neck flask, dropwise adding a mixed solution of 43.2 g (0.16mol) of p-methoxyphenyl triethoxysilane, 19.5 g (0.08mol) of diphenyldimethoxysilane, 10.0 g (0.075mol) of methylvinyldimethoxysilane and 10 ml of toluene through a constant-pressure dropping funnel under vigorous stirring, controlling the reaction temperature below 20 ℃, continuously reacting for 3h after dropwise adding, then heating to 80 ℃ for continuously reacting for 3h, cooling to room temperature, washing with water to be neutral, drying an organic layer with anhydrous sodium sulfate, filtering, removing toluene, heating to 150 ℃/10mba under reduced pressure, removing small molecular compounds, and obtaining 17.2 g of p-methoxyphenyl methyl phenyl vinyl silicone resin with a refractive index of 1.560.
Example 5 preparation of Methylphenyl Hydrogen-containing Silicone oil
In a clean 100 ml three-necked flask, 48.87 g (0.2mol) of diphenyldimethoxysilane and 12.0 g (0.05mol) of tetramethyltetrahydrocyclotetrasiloxane (D) were placed4 H) 1.29 g (0.008mol) hexamethyldisiloxane (MM) and 2.4 g concentrated sulfuric acid, stirring vigorously to react for 0.5h, adding 3.6 g water, continuing to react for 6h, then adding 3.0 g water and 20 ml toluene, stirring for 1h, adding water to wash until the mixture is neutral, drying the organic layer with anhydrous sodium sulfate, filtering to remove toluene, heating under reduced pressure to 120 ℃/10mba to remove small molecular compounds, and obtaining 19.2 g methylphenyl hydrogen-containing silicone oil with refractive index of 1.543.
EXAMPLE 6 preparation of two-component Silicone resin containing an alkoxyphenyl group
2.0 g of the methyl vinyl silicone resin prepared in example 2 and 4.0 g of the p-methoxyphenyl methyl phenyl vinyl silicone resin prepared in example 3 were uniformly mixed, heat-treated at 120 ℃ for 1 hour, deaerated in vacuum for 30min, and then 0.1 g of methyl vinyl siloxane platinum complex was added, uniformly mixed, and deaerated in vacuum for 30min to obtain component A.
2.0 g of the methyl vinyl silicone resin prepared in example 2 and 4.0 g of the methyl phenyl hydrogen-containing silicone oil prepared in example 5 were mixed uniformly, heat-treated at 120 ℃ for 1 hour, and deaerated in vacuo for 30min to obtain component B.
A, B components are uniformly mixed according to the mass ratio of 1:1, the refractive index is 1.544, vacuum deaeration is carried out for 20min, and then curing is carried out for 1h at 80 ℃ and for 3h at 140 ℃.
The specific data are shown in the following table:
in the above table, the light transmittance is measured by an ultraviolet-visible near-infrared spectrophotometer; the refractive index was measured by abbe refractometer.
Thermal stability was tested using TGA (thermogravimetric analysis) with argon as the carrier gas and a heating rate of 10 deg.C/min.
Adhesion was tested by the red ink experiment. The packaged bracket is soaked in red ink at the temperature of 25 +/-2 ℃, and the presence or absence of permeation is observed under a microscope after 24 hours.
EXAMPLE 7 preparation of a methylphenyl two-component silicone resin
2.0 g of the methyl vinyl silicone resin prepared in example 2 and 4.0 g of a commercially available methyl phenyl vinyl silicone resin (refractive index: 1.540) were uniformly mixed, heat-treated at 120 ℃ for 1 hour, defoamed in vacuum for 30min, then 0.1 g of methyl vinyl siloxane platinum complex was added, uniformly mixed, and defoamed in vacuum for 30min to obtain component A'.
2.0 g of the methyl vinyl silicone resin prepared in example 2 and 4.0 g of the methyl phenyl hydrogen-containing silicone oil prepared in example 5 were mixed uniformly, heat-treated at 120 ℃ for 1 hour, and deaerated in vacuo for 30min to obtain component B.
The A, B components are uniformly mixed according to the mass ratio of 1:1, and are subjected to vacuum defoaming for 20min, then are cured for 1h at 80 ℃, and are cured for 3h at 140 ℃.
The specific data are shown in the following table:
as can be seen from the above examples, after the alkoxy phenyl triethoxysilane provided by the invention is added, the obtained silicone resin has excellent optical properties such as refractive index and light transmittance.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (12)
1. An organosilicon material prepared by hydrolytic polymerization of a compound of formula I with (a) and (b) selected from the group consisting of: (a) a phenylalkoxysilane, and (b) an alkylalkenylsilane and/or an alkylsilane; wherein, the alkyl is C1-C20 alkyl, the alkenyl is C1-C20 alkenyl, and the alkoxy is C1-C20 alkoxy;
the compound of formula I is represented by the following formula:
wherein,
R1is a substituted or unsubstituted C1-C18 alkyl group;
R2is a substituted or unsubstituted C1-C4 alkyl group;
wherein said substitution means substitution with one or more substituents selected from the group consisting of: halogen atom, amido, hydroxyl, carboxyl, sulfydryl, C1-C10 alkyl, C1-C10 alkoxy, C2-C10 ester group, amido, C6-C30 aryl, C1-C30 heteroaryl, C2-C10 acyl, C7-C30 alkyl-aryl, and C2-C30 alkyl-heteroaryl.
2. The silicone material of claim 1, wherein the silicone material is prepared by hydrolytic polymerization of a compound of formula I with one or more components selected from the group consisting of: phenyltrimethoxysilane, diphenyldimethoxysilane, and methylvinyldimethoxysilane.
3. The silicone material of claim 1, wherein said silicone material is prepared by hydrolytic polymerization of a compound of formula I: phenyltrimethoxysilane, methylvinyldimethoxysilane, and optionally diphenyldimethoxysilane.
4. The organosilicon material according to claim 1, wherein the molar ratio of the compound of formula I to phenyltrimethoxysilane, diphenyldimethoxysilane and methylvinyldimethoxysilane is 2-16: 0 to 14: 0-16: 0 to 15.
5. The organosilicon material according to claim 1, wherein the molar ratio of the compound of formula I to phenyltrimethoxysilane, diphenyldimethoxysilane and methylvinyldimethoxysilane is 2-16: 0 to 14: 8: 7.5.
6. the silicone material of claim 1, wherein the molar ratio of the compound of formula I to phenyltrimethoxysilane, diphenyldimethoxysilane, methylvinyldimethoxysilane is 2: 14: 8:7.5 or 16:0:8: 7.5.
7. A silicone resin comprising the silicone material of claim 1, or prepared using the silicone material of claim 1.
8. The silicone resin of claim 7, wherein the silicone resin is prepared by reacting: the silicone material, methyl phenyl vinyl silicone resin, methyl phenyl hydrogen silicone oil, and platinum catalyst of claim 1.
9. The silicone resin of claim 7, wherein the silicone resin is prepared by reacting the following component A and component B:
the component A comprises: the silicone material of claim 1, a methylphenyl vinyl silicone resin, and a platinum catalyst;
the component B comprises: methyl phenyl vinyl silicone resin and methyl phenyl hydrogen-containing silicone oil.
10. A silicone resin raw material composition, characterized in that the composition comprises: the silicone material, methyl phenyl vinyl silicone resin, methyl phenyl hydrogen silicone oil, and platinum catalyst of claim 1.
11. The silicone resin starting composition of claim 10 wherein said composition comprises component a and component B, and
the component A comprises: the silicone material of claim 1, a methylphenyl vinyl silicone resin, and a platinum catalyst;
the component B comprises: methyl phenyl vinyl silicone resin and methyl phenyl hydrogen-containing silicone oil.
12. An article comprising or made from the silicone resin of claim 7.
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