CN101215381B - Method for preparing methylphenyl hydrogen-containing silicone oil - Google Patents
Method for preparing methylphenyl hydrogen-containing silicone oil Download PDFInfo
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- CN101215381B CN101215381B CN2008100591167A CN200810059116A CN101215381B CN 101215381 B CN101215381 B CN 101215381B CN 2008100591167 A CN2008100591167 A CN 2008100591167A CN 200810059116 A CN200810059116 A CN 200810059116A CN 101215381 B CN101215381 B CN 101215381B
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- polymerization
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- phenyl
- monomer
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 44
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- -1 methylphenyl hydrogen Chemical compound 0.000 title claims description 35
- 238000000034 method Methods 0.000 title abstract description 20
- 229920002545 silicone oil Polymers 0.000 title description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 48
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003729 cation exchange resin Substances 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 3
- YFCGDEUVHLPRCZ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C YFCGDEUVHLPRCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 229920001296 polysiloxane Polymers 0.000 abstract description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 239000002981 blocking agent Substances 0.000 abstract 1
- 238000009835 boiling Methods 0.000 abstract 1
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 38
- 235000019198 oils Nutrition 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000005855 radiation Effects 0.000 description 7
- 229920002521 macromolecule Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000005046 Chlorosilane Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- DESGIDRJCLIWRS-UHFFFAOYSA-N [SiH]Cl Chemical compound [SiH]Cl DESGIDRJCLIWRS-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920000260 silastic Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- VTMOWGGHUAZESJ-UHFFFAOYSA-N chloro(diphenyl)silane Chemical class C=1C=CC=CC=1[SiH](Cl)C1=CC=CC=C1 VTMOWGGHUAZESJ-UHFFFAOYSA-N 0.000 description 1
- YCITZMJNBYYMJO-UHFFFAOYSA-N chloro(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](Cl)C1=CC=CC=C1 YCITZMJNBYYMJO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention discloses a process for preparing organosilicon oil which contains hydrogen, in particular to a process for preparing organosilicon oil which contains hydrogen and methyl-phenyl silica chain link. The invention utilizes dimethyl silicone cyclic siloxane(Dn), polymethyl hydrogen cyclic siloxane(DmH), hybrid ring body of methyl and phenyl (DpPh), hydrolysis hybrid ring body of methyl and phenyl (D'qPh) to be polymerization reaction monomer, the process comprises adding the polymerization reaction monomer and blocking agent into organic solvent under the protection of N2 gas, controlling the reaction temperature and the reaction time, reacting under the function of catalyst, distilling to remove dissolvent in ordinary pressure after reacting, decompressing to withdraw low-boiling residue to get target product, purifying the product with activated carbon, and then the degree of purity of the product is high. The invention has the advantages of low cost, moderate contiditon, simple technology, simple and convenient operation and no pollution, and raw material are easily obtained, and the invention is suitable for industrialization. Products which are prepared by the invention have an excellent effect in the process of sealing and packing of LED.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogeneous organic silicone oil, specifically be meant a kind of preparation method who contains the hydrogeneous organic silicone oil of aminomethyl phenyl silica chain link.
Technical background
Power type light-emitting diode (Light Emitting Diode, LED) through the development of decades, be widely used in the big area picture and text and show that full-color screen, state indication, sign illumination, signal show, Backlight For Liquid Crystal Display Panels, aspects such as automobile combined tail lamp and room light.LED has a lot of distinct advantages, as " China illumination " 2007 (1-2): 54-59 is described, LED has energy-saving and environmental protection, safe life length, low consumption, low-heat, shockproof, waterproof, miniature, high brightness, easily light modulation, light beam is concentrated and reduce advantage such as maintenance, utilize above-mentioned a certain or multiple advantages or all advantage can develop various semiconductor lightings application product innovations.Therefore, the research that lot of manpower and material resources is carried out LED has been dropped in countries in the world, has made significant headway, make LED be expected to become after incandescent light, luminescent lamp, high-intensity gas discharge lamp the 4th generation light source.
Traditional LED packaged material is a Resins, epoxy.Because the specific refractory power between semi-conductor and the epoxy resin encapsulating material differs bigger, cause the critical angle of inner full-reflection very little, the light that active layer produces has only sub-fraction to be removed, and major part is absorbed through multiple reflection at chip internal, thereby influences the optical efficiency of getting of semiconductor material.On the other hand, the early stage thermal resistance of Resins, epoxy, will raise rapidly and the Resins, epoxy flavescence because of the bad junction temperature of chip that cause of heat radiation with its packaged material as the power type white light LED device up to 250～300 ℃/W, thereby quickens the light decay of device; Meanwhile, the stress that produces because of thermal expansion also can cause open circuit, thereby causes the LED component failure.In addition, the major reason that light output reduces rapidly is because blue light and ultraviolet radiation and temperature rising, the transparency of packaged material seriously descend (IEEE Proc.SPIE, 1998,3279:259-262; Microelectronics reliability, 1999,39 (8): 1219-1227).
Main in the world power-type LED illuminating device manufacturer competitively drops into huge fund and research and development strength, strengthen the research and development of organosilicon encapsulating material, attempt to utilize advantages such as organosilicon material high-low temperature resistant, ageing-resistant, UV resistant, radiation hardness to solve the technological deficiency that the power type white light LED encapsulating epoxy resin is faced, obtained very great achievement, existing procucts are put on market now.WO2004107458 has reported under a kind of platinum catalyst effect, chlorosilane with the band active hydrogen functional groups, diphenyl chlorosilanes etc. are raw material, prepare the containing hydrogen silicone oil that contains phenylbenzene silica chain link of different phenyl contents and prepare the method for LED packaged material through hydrolysis condensation reaction with its cross-linked vinyl end-blocking silicone resin, behind the packaged material sulfidization molding, shrinking percentage is low, fast light Good Heat-resistance, do not ftracture and transmittance reaches 95%, if adopting YX-8000 Resins, epoxy is packaged material, under acid anhydrides vulcanizing agent MH-700 and vulcanization accelerator SA-102 effect, after 100 ℃ * 4h and two sections sulfurations of 150 ℃ * 6h, the shrinking percentage of packaged material is 10 times of organosilicon material, transmittance only is 80%, and the xanthochromia phenomenon occurs.Japanese Patent JP2004002809 has reported in the silicoorganic compound that contain a Si-H key in a kind of molecule under the platinum catalytic condition and have carbon-to-carbon double bond simultaneously and another kind of each molecule and has contained the silicoorganic compound of two Si-H keys at least through addition reaction of silicon with hydrogen, make the LED packaged material that second-order transition temperature is higher than 100 ℃, do not have the xanthochromia phenomenon after this material package.U.S. Pat 20050212008 (its equating patent EP1424363) has been reported to adopt and has been contained silicon hydride chlorid and alkyl chlorosilane, diphenyl chlorosilane contains the methyl and phenyl hydrogen-containing silicon oil of dimethyl-silicon hydrogen chain link and phenylbenzene silica chain link by the preparation of hydrolytie polycondensation method, then silicone oil and ethenyl blocking silicon rubber are obtained the packaged material of power-type LED by the catalytic silicon hydrogen of platinum addition vulcanization prepared, the refractive index of packaged material reaches 1.51 behind the sulfidization molding, behind 400nm light source irradiation 100h, transmittance drops to 92% from initial 95%, irradiation still is 92% behind the 500h, and the transmittance of epoxy resin encapsulating material then drops to 78% and 65% respectively from initial 97%.U.S. Pat 20050006794 has been reported and has been used dimethyl containing hydrogen silicone oil that contains silicon hydride chlorid and the preparation of not hydrogenous chlorosilane hydrolytie polycondensation or the methyl and phenyl hydrogen-containing silicon oil that contains phenylbenzene silica chain link, adopt silicon hydrogen additive process, the end capped organo-silicone rubber of cross-linked vinyl prepares the method for LED packaged material.Packaged material behind the sulfidization molding has excellent mechanical property and non-viscosity energy, can stand the cold cycling impact between 1000 times-50 ℃ to 150 ℃ and does not ftracture.U.S. Pat 20060134440 has been reported with ring-type, hydrogen-containing siloxane oligopolymer and vinyl organosilicon oligopolymer under the platinum catalyst effect, add filler (oxide compounds such as boron, silicon, titanium, aluminium, zinc), 50 ℃～200 ℃ sulfurations make LED encapsulation organosilicon matrix material.This material is at 140 ℃, 450～470nm wavelength light irradiation 1000h, and transmittance is declined by less than 10%.Wherein, ring-type, hydrogen-containing siloxane oligopolymer be by contain silicon hydride chlorid with alkyl chlorosilane hydrolysis, condensation, become ring to make.
Above-mentioned studies show that, the organosilicon encapsulating material performance is far superior to Resins, epoxy, is the desirable packaged material of power type white light LED device.External semiconductor lighting company and main organosilicon material manufacturing enterprise have all carried out research and have applied for patent the optical grade organosilicon encapsulating material, and that domestic correlative study is still owed is active.Have only the report of three pieces of Chinese patents at present relevant for LED, they are respectively one piece of patent " a kind of white light LEDs and method for packing thereof " (Chinese invention patents of Zhongshan University's application, CN1838440A), reported the method that adopts silicon rubber encapsulation white light LEDs, and the structure and the preparation method of organosilicon material do not made reports; One piece of patent " with the method for nano mattisolda low temp sintering, packaging and connecting high power LED " (Chinese invention patent of University Of Tianjin's application, CN1870310), method in this invention is to adopt particle diameter less than the 100nm nano silver particles, prepare the nano mattisolda of gained, low temp sintering, packaging and connecting high power LED with dispersion agent fish oil, binding agent alpha-terpineol and solvent acetone uniform mixing under ultrasonic water bath is assisted; One piece of patent (Chinese invention patent that is entitled as " transparent composite composition " of SUMITOMO CHEMICAL bakelite Co., Ltd. application, CN1649966), this patent report a kind ofly use general glass filler, in very wide wavelength region, has high transmitance, can be applicable to purposes such as LED packaged material, replace the optical material of glass.These two patents do not relate to organosilicon encapsulating material.
The exploitation and the production domesticization of high refractive index, clear, radiation hardness, high thermal conductivity, the flexible organosilicon encapsulating material of optical grade that can eliminate stress are that China's semiconductor lighting engineering is badly in need of one of gordian technique that solves.A very crucial link is exactly the containing hydrogen silicone oil of synthetic high transmission rate, high refractive index in the research and development of organosilicon LED packaged material, as the liquid silicone macromolecule crosslink agent.Though containing hydrogen silicone oil all has production marketing both at home and abroad, as the liquid silicone macromolecule crosslink agent of LED packaged material, require to contain two reactive hydrogens at least in the purity height, molecule of containing hydrogen silicone oil, have suitable viscosity simultaneously.For reaching the purpose of crosslinked liquid organosilicon macromolecule material, obtain even structure, highly transparent and refractive index greater than 1.5 packaged material, require containing hydrogen silicone oil should with packaged material structural similitude or close.This containing hydrogen silicone oil is not seen sale on the market, the LED methyl and phenyl hydrogen-containing silicon oil for packaging of foreign patent report mostly is the containing hydrogen silicone oil that contains phenylbenzene silica chain link, and LED encapsulation of the present invention does not appear in the newspapers with the methyl and phenyl hydrogen-containing silicon oil that contains aminomethyl phenyl silica chain link, and the containing hydrogen silicone oil of domestic and foreign literature report all is by containing silicon hydride chlorid and the non-silicon hydride chlorid hydrolytie polycondensation that contains forms basically.This patent has been reported a kind of method that adopts hydrogeneous cyclosiloxane and methyl cyclosiloxane, methyl phenyl ring siloxane ring-opening copolymerization, preparation LED encapsulates the methyl and phenyl hydrogen-containing silicon oil that contains aminomethyl phenyl silica chain link with high refractive index, clear, the reaction conditions gentleness, easy and simple to handle, pollution-free, be convenient to industrialization.Methyl and phenyl hydrogen-containing silicon oil of the present invention has good performance, as high refractive index, clear, radiation hardness, high-low temperature resistant, weather-proof, can be used as liquid macromolecule crosslink agent in the LED packaged material, also be expected efficient linking agent as other liquid silastic, seal gum, joint sealant and tackiness agent.
Summary of the invention
The present invention is directed to deficiency of the prior art, provide a kind of and do not appear in the newspapers, high refractive index, clear, contain the preparation method of the methyl and phenyl hydrogen-containing silicon oil of aminomethyl phenyl silica chain link.
Another object of the present invention is to provide a kind of methyl and phenyl hydrogen-containing silicon oil with high refractive index, clear, radiation hardness, high-low temperature resistant, characteristic such as weather-proof, as liquid macromolecule crosslink agent in the LED packaged material, this containing hydrogen silicone oil also is expected the efficient linking agent as other liquid silastic, seal gum, joint sealant and tackiness agent.
The present invention is achieved by following technical proposals:
A kind of preparation method of methyl and phenyl hydrogen-containing silicon oil, undertaken by following step:
(1) with polydimethylcyclosil.xane (D
n), poly-methyl hydrogen cyclosiloxane (D
m H), aminomethyl phenyl mixed methylcyclosiloxane (D
p Ph), aminomethyl phenyl hydrolysis mixed methylcyclosiloxane (D '
q Ph) in one or more be polymerization reaction monomer; D wherein
n, D
m H, D
p Ph, D '
q PhChemical structural formula as follows
In the said structure formula n, m, p, q be respectively greater than, equal 3 integer;
(2) at N
2Under the protection of gas, polymerization reaction monomer, end-capping reagent are joined in toluene, tetrahydrofuran (THF), sherwood oil, normal hexane, the methylene dichloride one or more in the solvent;
(3) be the reaction mixture control reaction temperature 40 ℃～80 ℃, polymerization reaction time is 1～20h;
(4) after reaction finished, air distillation removed and desolvates, and decompression withdrawing low-boiling-point substance can get target product.
As preferably, the polymerization degree n of the polymerization reaction monomer described in the above-mentioned preparation method, m are 3,4,5 or 6.As better selection, the polymerization degree n of above-mentioned polymerization reaction monomer, m are 4; The polymerization degree of p, q is 3,4,5 or 6.Be octamethylcyclotetrasiloxane (D
4), tetramethyl-tetrahydrochysene cyclotetrasiloxane (D
4 H), aminomethyl phenyl mixed methylcyclosiloxane (D
p Ph, p=3,4,5,6), aminomethyl phenyl hydrolysis mixed methylcyclosiloxane (D '
q Ph, q=3,4,5,6).
As preferably, the polymerization single polymerization monomer aminomethyl phenyl mixed methylcyclosiloxane (D described in the above-mentioned preparation method
n Ph) in methyl and phenyl mol ratio be 1: 1.Described polymerization single polymerization monomer D '
q PhBe the hybrid ring siloxane of dimethyldichlorosilane(DMCS) and dichloromethyl phenylsilane cohydrolysis condensation prepared, wherein methyl and phenyl mol ratio (a: be 10～20: 1 b).
As preferably, the end-capping reagent described in the above-mentioned preparation method is 1,1,3,3-tetramethyl--1,3-dihydro sily oxide, hexamethyldisiloxane, decamethyl tetrasiloxane, 1,3-dimethyl-1,1,3, one or more in 3-tetraphenyl-sily oxide.As better selection, described end-capping reagent is 1,1,3,3-tetramethyl--1,3-dihydro sily oxide.
As preferably, add 98% vitriol oil, 70% vitriol oil, acidic white earth, HClO in the polyreaction described in the above-mentioned preparation method
4Or a kind of in the strongly acidic cation-exchange is catalyzer.As better selection, described catalyzer is the wide aperture storng-acid cation exchange resin, and wide aperture storng-acid cation exchange resin consumption is 5% of a polymerization single polymerization monomer total mass.In the present invention, the wide aperture storng-acid cation exchange resin adopts ordinary method to handle before use, and sealing is kept in the dry environment.
Solvent described in the present invention is that toluene has effect preferably.
As preferably, the temperature of reaction among the above-mentioned preparation method is 55 ℃～65 ℃, and polymerization reaction time is 4.5～5.5h.As better selection, described temperature of reaction is 60 ℃, and polymerization reaction time is 5h.
As preferably, the decompression withdrawing low-boiling-point substance described in the above-mentioned preparation method is warming up to 205 ℃ simultaneously.Can make the purity of target product higher, in order further to obtain methyl and phenyl hydrogen-containing silicon oil, in target product, add gac and stir, suction filtration then, filtrate is the water white transparency methyl and phenyl hydrogen-containing silicon oil.The gac of above-mentioned adding accounts for the 0.5-2wt% powdered active carbon of target product, can obtain effect preferably.Among the present invention, polymerisate removes low molecular compound through decompression, be chilled to room temperature after, the powdered active carbon that adds about 1wt% also stirs, and filters then, all has good result from economy, technical standpoint.
Reaction formula of the present invention can be expressed as:
D ' in the present invention
q PhPreparation:
With dimethyldichlorosilane(DMCS) and dichloromethyl phenylsilane in 50 ℃～70 ℃ hydrolysis, 110 ℃ of condensations, depolymerize to ring, make aminomethyl phenyl hydrolysis mixed methylcyclosiloxane.By changing two kinds of hydrolysis chlorosilane proportion of raw materials, regulate the ratio of methyl and phenyl in the hydrolysis mixed methylcyclosiloxane, identify its structure with nucleus magnetic resonance.Preferable methyl of the present invention and phenyl ratio are 10～20: 1 aminomethyl phenyl hydrolysis mixed methylcyclosiloxane.
Beneficial effect:, contain methyl and phenyl hydrogen-containing silicon oil aminomethyl phenyl silica chain link, high refractive index, clear with the methyl and phenyl hydrogen-containing silicon oil of method of the present invention preparation.The phenyl of prepared methyl and phenyl hydrogen-containing silicon oil and the mol ratio of silicon (Ph/Si) are between 0.30～0.60, hydrogen quality percentage composition is between 0～0.5%, viscosity is between 10mpas～1000mpas, have high refractive index, clear, radiation hardness, high-low temperature resistant, advantage such as weather-proof, be especially suitable for use as liquid macromolecule crosslink agent in the LED packaged material, also be expected efficient linking agent as other seal gum, joint sealant and tackiness agent.Present method raw material is easy to get, and cost is low, mild condition, and technology is simple, and is easy and simple to handle, pollution-free, is convenient to industrialization.
Embodiment
The present invention can further specify by following embodiment, but embodiment is not a limiting the scope of the invention.
Embodiment 1
At N
2Protection adds polymerization single polymerization monomer 63.8gD down in 500mL exsiccant there-necked flask
p PhAnd 36.2gD
4 H35 ℃～45 ℃/-remove the moisture content in the polymerization single polymerization monomer under the 0.096MPa, add 2.6g end-capping reagent 1,1,3 then, 3-tetramethyl--1,3-dihydro sily oxide, 5.0g catalyzer (wide aperture storng-acid cation exchange resin), 100mL toluene solvant, 65 ℃ of following polymerization 5h, suction filtration reclaims the wide aperture storng-acid cation exchange resin.Normal pressure leads to N
2Protection is steamed down and is removed most of toluene; be decompressed to then-0.096MPa; be warming up to 205 ℃ gradually and remove remaining solvent and low molecular compound; be cooled to room temperature; the powdered active carbon and the stirring that add mixture total mass 1wt%; suction filtration reclaims Powdered Activated Carbon then, and filtrate is the water white transparency methyl and phenyl hydrogen-containing silicon oil.Methyl and phenyl hydrogen-containing silicon oil refractive index n
D 25=1.5050, the about 150mpas of rotary viscosity (25 ℃, down together), warp
1H-NMR records Si-H quality percentage composition 0.45%, and Ph/Si (mol ratio) is 0.49, and it is 3.5 * 10 that GPC records number-average molecular weight (Mn)
3G.mol
-1, molecular weight distribution width (MWD) is 2.31.
Embodiment 2
Adopt the method identical, with 37.1gD with embodiment 1
p Ph, 27.7gD
4 H, 35.2g D '
q PhBe polymerization single polymerization monomer, 1.8g 1,1,3,3-tetramethyl--1, and 3-dihydro sily oxide is an end-capping reagent, and 5.0g wide aperture storng-acid cation exchange resin is a catalyzer, and 100mL toluene is solvent, after polymerization and aftertreatment finish, gained methyl and phenyl hydrogen-containing silicon oil refractive index n
D 25=1.4720,25 ℃ of about 150mpas of rotary viscosity.Warp
1H-NMR records Si-H quality percentage composition 0.4%, and Ph/Si (mol ratio) is 0.33, and it is 2.7 * 10 that GPC records number-average molecular weight (Mn)
3G.mol
-1, MWD is 1.69.
Embodiment 3
Adopt the method identical, with 42.5gD with embodiment 1
p Ph, 15.1gD
4 H, 42.5g D '
q PhBe polymerization single polymerization monomer, 2.5g 1,1,3,3-tetramethyl--1, and 3-dihydro sily oxide is an end-capping reagent, and 5.0g wide aperture storng-acid cation exchange resin is a catalyzer, and 100mL toluene is solvent, after polymerization and aftertreatment finish, gained methyl and phenyl hydrogen-containing silicon oil refractive index n
D 25=1.4898,25 ℃ of about 120mpas of rotary viscosity, warp
1H-NMR records Si-H quality percentage composition 0.24%, and Ph/Si (mol ratio) is 0.43, and it is 2.4 * 10 that GPC records number-average molecular weight (Mn)
3G.mol
-1, MWD is 2.27.
Embodiment 4
With 62.5gD
p Ph, 22.4gD
4 H, 11.1g D '
q Ph, 4.0gD
4Be polymerization single polymerization monomer, 2.7g 1,1,3,3-tetramethyl--1, and 3-dihydro sily oxide is an end-capping reagent, 100mL toluene is solvent, under the different catalysts effect, products therefrom such as following table.If use sulfuric acid to make catalyzer, then monomer, end-capping reagent, solvent and catalyzer are added the 250mL there-necked flask, under the mechanical stirring, 80 ℃ of following polymerization 5h; Polymerization finishes, and standing demix removes lower floor's acid solution, uses deionized water wash until neutrality.If use the wide aperture storng-acid cation exchange resin to make catalyzer, then implementation step is with embodiment 1.
| Catalyzer | Outward appearance | Refractive index (n D 25) | Ph/Si (mol ratio) | H (W％) |
| 98% vitriol oil | Muddy | - | - | - |
| 70% vitriol oil | Transparent | 1.5456 | ≈1.0 | 0 |
| The wide aperture storng-acid cation exchange resin | Transparent | 1.5050 | 0.53 | 0.3 |
Embodiment 5
Adopt the identical feed ratio of the method identical with embodiment 1 and embodiment 4, the wide aperture storng-acid cation exchange resin is a polymerizing catalyst, and its add-on is the 5wt% of comonomer total mass, product for preparing under differing temps such as following table:
| The polymerization temperature | Outward appearance | Refractive index | Ph/Si | H | Rotary viscosity | Mn | ?MWD |
| Degree/℃ | n D 25 | (molar | (wt％) | (/mpa·s) | (/g.mol -1) |
ratio)
| 40 | Muddy | - | - | - | - | - | - |
| 50 | Transparent | 1.5011 | 0.52 | 0.33 | 120 | 3.3×10 3 | 2.37 |
| 65 | Transparent | 1.5050 | 0.53 | 0.30 | 120 | 3.2×10 3 | 2.06 |
| 80 | Muddy | - | - | - | - | - | - |
Embodiment 6
Adopt the method identical and embodiment 4 identical feed ratio and catalyzer with embodiment 1, at 65 ℃ of following polymerization different times, the product of preparation such as following table:
| Polymerization time/h | Outward appearance | Refractive index n D 25 | Ph/Si (molar ratio) | H (wt％) | Rotary viscosity (/ mpas) | Mn (/ g.mol -1) | MWD |
| 2 | Transparent | 1.5050 | 0.51 | 0.33 | ?120 | 2.6×10 3 | 3.01 |
| 5 | Transparent | 1.5050 | 0.53 | 0.30 | ?120 | 3.2×10 3 | 2.06 |
| 10 | Transparent | 1.5042 | 0.50 | 0.31 | ?190 | 3.2×10 3 | 1.92 |
| 20 | Transparent | 1.5022 | 0.48 | 0.32 | ?550 | 6.6×10 3 | 1.34 |
Claims (7)
1. the preparation method of a methyl and phenyl hydrogen-containing silicon oil is characterized in that being undertaken by following step:
(1) with polydimethylcyclosil.xane D
n, poly-methyl hydrogen cyclosiloxane D
m H, aminomethyl phenyl mixed methylcyclosiloxane D
p Ph, aminomethyl phenyl hydrolysis mixed methylcyclosiloxane D '
q PhIn one or more be polymerization reaction monomer, be catalyzer with the wide aperture storng-acid cation exchange resin, wide aperture storng-acid cation exchange resin consumption is 5% of a polymerization single polymerization monomer total mass; D wherein
n, D
m H, D
p Ph, D '
q PhChemical structural formula as follows
In the said structure formula n, m, p, q be respectively greater than, equal 3 integer, a: b=10～20: 1;
(2) at N
2Protection joins polymerization reaction monomer, end-capping reagent in the solvent down, and described solvent is one or more in toluene, tetrahydrofuran (THF), sherwood oil, normal hexane, the methylene dichloride;
(3) be the reaction mixture control reaction temperature 55 ℃～65 ℃, polymerization reaction time is 4.5～5.5h;
(4) after reaction finished, air distillation removed and desolvates, and decompression withdrawing low-boiling-point substance can get target product.
2. preparation method according to claim 1 is characterized in that polymerization degree n, the m of described polymerization reaction monomer is 3,4,5 or 6.
3. preparation method according to claim 2 is characterized in that polymerization degree n, the m of described polymerization reaction monomer is 4; The polymerization degree of p, q is 3,4,5 or 6.
4. preparation method according to claim 1 is characterized in that described polymerization single polymerization monomer aminomethyl phenyl mixed methylcyclosiloxane D
p PhMiddle methyl and phenyl mol ratio are 1: 1.
5. preparation method according to claim 1 is characterized in that described end-capping reagent is 1,1,3,3-tetramethyl--1,3-dihydro sily oxide, hexamethyldisiloxane, decamethyl tetrasiloxane, 1,3-dimethyl-1,1,3, one or more in 3-tetraphenyl-sily oxide.
6. preparation method according to claim 5 is characterized in that described end-capping reagent is 1,1,3,3-tetramethyl--1,3-dihydro sily oxide.
7. preparation method according to claim 1 is characterized in that described decompression withdrawing low-boiling-point substance, is warming up to 205 ℃ simultaneously.
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| CN101475689B (en) * | 2008-12-03 | 2011-01-12 | 杭州师范大学 | Preparation of methyl phenyl vinyl silicon resin |
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