WO2016082287A1 - Résine mdq de phénylvinylsilicone et son procédé de préparation - Google Patents

Résine mdq de phénylvinylsilicone et son procédé de préparation Download PDF

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Publication number
WO2016082287A1
WO2016082287A1 PCT/CN2014/095701 CN2014095701W WO2016082287A1 WO 2016082287 A1 WO2016082287 A1 WO 2016082287A1 CN 2014095701 W CN2014095701 W CN 2014095701W WO 2016082287 A1 WO2016082287 A1 WO 2016082287A1
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Prior art keywords
silicone resin
mdq
mass
acid
vinyl
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PCT/CN2014/095701
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English (en)
Chinese (zh)
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李彦民
罗建立
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深圳市森日有机硅材料有限公司
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Publication of WO2016082287A1 publication Critical patent/WO2016082287A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the invention belongs to the field of polymer materials, and particularly relates to a MDQ type phenyl vinyl silicone resin and a preparation method thereof.
  • Silicone polymer materials such as silicone gel, silicone rubber, silicone resin, etc. have the advantages of aging resistance, high temperature resistance, ultraviolet radiation resistance, etc., and are currently ideal packaging materials. Among them, phenyl silicone resin has many advantages such as high refractive index, good resistance to gas permeability and water permeability, direct perfusion, no plastic casing, convenient use, etc., and has been widely used in LED chip, Molding and other packaging processes.
  • the phenyl silicone resin and the silicon-hydrogen-bonded silicone polymer undergo a hydrosilation addition reaction under the action of a metal catalyst such as platinum or cobalt to crosslink and vulcanize, the vulcanization condition is mild, and the vulcanization can be rapidly vulcanized at a medium temperature without solvent. Low molecular and other by-products are discharged, avoiding bubbles or trachoma during vulcanization, and the cured product is waterproof, shockproof, impact resistant, and thermally conductive, but the cohesive energy density of the silicone polymer is small, and the reinforcing material is required to reinforce it.
  • a metal catalyst such as platinum or cobalt
  • the most common and most used reinforcing filler is gas phase or precipitated silica, but its thickening effect on silicone rubber is also very obvious, the viscosity of the rubber increases, affecting the practical application range of silicone rubber, and due to the refractive index Differently, after adding, it affects the optical transparency of the product, so the structure is similar to fumed silica, and the refractive index is high, and the QQ type phenyl silicone resin containing Q chain is used for reinforcing.
  • the domestic patent CN103360603A discloses a preparation process of a phenyl vinyl silicone resin for LED packaging, which uses phenyltrimethoxysilane or phenyltriethoxysilane as a source of T-links, and diphenyldimethoxy Silyl group and phenylmethyldiethoxysilane are the source of D chain, 1,3-divinyltetramethyldisiloxane is the terminal blocking agent, and a liquid MDT phenyl group without Q chain is synthesized.
  • Vinyl silicone resin used to prepare a preparation process of a phenyl vinyl silicone resin for LED packaging, which uses phenyltrimethoxysilane or phenyltriethoxysilane as a source of T-links, and diphenyldimethoxy Silyl group and phenylmethyldiethoxysilane are the source of D chain, 1,3-divinyltetramethyldisiloxane is the terminal blocking agent
  • a preparation method of a chemically crosslinkable MDQ type phenyl vinyl silicone resin is provided in the patent CN102898648 disclosed by Wuchuan et al., which is a method of preparing hexamethyldisiloxane and 1,3-two.
  • Chinese invention patent CN101805562A discloses a method for synthesizing an alkoxy group or a hydroxyl group-containing MDQ phenyl silicone resin, which uses hexamethyldisiloxane, methyl orthosilicate and methylphenyldichlorosilane, toluene as a raw material to hydrolyze
  • the hydroxyl group-containing MDQ phenyl silicone resin was prepared by condensation, and the solid content was 50%.
  • the structural formula was: [Me 3 SiO 1/2 ] 0.35 [MePhSiO 2/2 ] 0.2 [SiO 4/2 ] 0.35 [HO] 0.06 , It is mixed with linear hydroxyl silicone oil component, fumed silica, crosslinker, catalyst and tackifier to form insulating moisture curing coating material, which is applied to various electronic components, line analysis and live working.
  • the device is waterproof, moisture proof, shockproof, insulated, anti-aging, dustproof, anti-corrosive, etc.
  • the phenyl MDQ silicone resin does not contain vinyl or silicon hydrogen bonds and cannot be cured by hydrosilylation.
  • Japanese Patent No. JP07228701A discloses a method for synthesizing a D-chain containing silicon-hydrogen-containing MDQ silicone resin by dissolving methyl MQ silicone resin in an organic solvent, dehydrating condensation under an acidic catalyst strip, and linear body.
  • the hydrogen-containing silicone oil is subjected to an equilibrium reaction to obtain D-link hydrogen-containing MDQ silicon having a structure of (Me 3 SiO 1/2 ) a (MeHSiO 2/2 ) y (Me 2 SiO 2/2 ) z (SiO 4/2 ) Resin, the invention does not contain phenyl, has a low refractive index, and cannot be used for LED packages requiring high luminous flux.
  • ethyl orthosilicate source from the Q-linkage is prone to gelation under acidic conditions, and the reaction speed of various monomers in the alcohol solvent is different, ethyl orthosilicate and the heading agent are hydrolyzed to form a After the base MQ silicone resin, it is not easy to continue to react with the phenyl monomer, thereby affecting the final transparency of the product.
  • the technical problem to be solved by the present invention is to overcome the defects of the prior art, and to provide a phenyl vinyl silicone resin of the MDQ type and a preparation method thereof.
  • the present invention is achieved by an MDQ type phenylvinyl silicone resin having a structure represented by the following formula:
  • Ph is a phenyl group
  • Me is a methyl group
  • Vi represents a vinyl group
  • a ranges from 0.1 to 1
  • b+c ranges from 0 to 0.1, and b>0
  • d ranges from 0 to 0.8, and a+b+c+d>0
  • a/d ranges from 1.6 to 2.5
  • (b+c)/d ranges from 1.6 to 2.5.
  • a method for preparing a phenylvinyl silicone resin of the above MDQ type comprising the steps of:
  • reaction solution is allowed to stand layering, the upper layer acid solution is removed, the alkali is added to adjust the pH to neutrality, and the mixture is washed to obtain a mixture;
  • the mixture is at a vacuum equal to or greater than 0.1 Under the conditions of Mpa, the mixture was heated to 140 ° C to 160 ° C for 2 to 5 hours to obtain the MDQ type phenyl vinyl silicone resin.
  • the invention provides an MDQ type phenyl vinyl silicone resin and a preparation method thereof, wherein the MDQ type phenyl vinyl silicone resin is colorless and transparent, has high refractive index and stable quality.
  • the preparation method controls the viscosity, refractive index and vinyl content of the product by the ratio of monomer raw materials, reaction time, temperature and pH, thereby adding different hardness and mechanical strength to the corresponding phenyl hydrogen-containing crosslinking agent.
  • the product Compared with the existing synthetic process, the MDQ type phenyl vinyl silicone resin prepared by the invention has high refractive index (>1.53/° C.), the production process condition is mild, simple and easy, the raw material source is wide, and the repeatability is good. It can be used as a reinforcing material for LED packaging adhesives, heat-resistant coatings, etc.
  • Fig. 1 is an infrared spectrum chart of an MDQ type phenylvinyl silicone resin obtained in Example 1 of the present invention.
  • Ph is phenyl C 6 H 5
  • Me is methyl CH 3
  • the MDQ type phenylvinyl silicone resin has a refractive index of 1.53 to 1.55/25 ° C and a viscosity of 2,000 to 300,000 mpa•s/25 °C.
  • the embodiment of the invention further provides a method for preparing the above-mentioned MDQ type phenyl vinyl silicone resin, which comprises the following steps:
  • S01 100 to 1000 parts by mass of diphenyldimethoxysilane and/or diphenyldiethoxysilane, 10 to 300 parts by mass of ethyl orthosilicate, and 50 to 500 parts by mass of an organic solvent are mixed. Stir at room temperature to obtain a mixed solution;
  • reaction solution is allowed to stand layering, the upper layer acid solution is removed, the alkali is added to adjust the pH to neutrality, and the mixture is washed to obtain a mixture;
  • the solvent is one of an alcohol solvent such as methanol, ethanol or isopropyl alcohol or a mixture of alcohol solvents.
  • the solvent is methanol.
  • the dropwise addition is preferably completed within 20 to 40 minutes.
  • the acidic catalyst may be selected from protic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydrobromic acid, hydroiodic acid, and the like, and organic acids such as trifluoromethanesulfonic acid and strongly acidic cationic resin may also be used. hydrochloric acid.
  • the vinyl heading agent is divinyltetramethyldisiloxane, diphenyldimethyldivinyldisiloxane, dimethylvinylsiloxane, phenylvinylsiloxane At least one of them is preferably divinyltetramethyldisiloxane.
  • the methyl heading agent is preferably hexamethyldisiloxane.
  • step S03 the reaction solution is allowed to stand still, the upper layer acid solution is removed, and an alkaline reagent is added to adjust the pH to neutrality, and the solvent is washed.
  • the base for adjusting the pH to neutral may be at least one selected from the group consisting of ammonia water, sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogencarbonate. The washing is preferably washed with water.
  • step S04 the mixture obtained in step S03 has a vacuum degree equal to or greater than 0.1.
  • the mixture is heated to 140 to 160 ° C, preferably, heated to 150 ° C, and distilled for 2 to 5 hours to remove the low-boiling substance to obtain the MDQ type phenylvinyl silicone resin.
  • the mixed solution consisting of deionized water, fully stirred, added dropwise within half an hour, and then heated to 60-80 ° C for 5 hours, then added 111.6 g divinyltetramethyldisiloxane heading agent, keep the temperature at 60-80 ° C, stop after 7 hours of reaction, cool to room temperature, then layer, add 5 g of sodium hydroxide to neutralize, wash to neutral , at 150 ° C, vacuum 0.9 Distillation for 3 hours under conditions of MPa to 1.0 MPa, and removal of low-boiling substances, to obtain 512.0 g of colorless and transparent MDQ type phenyl vinyl silicone resin, viscosity 7800 mPa•s/25° C., refractive index 1.5495/25° C., vinyl content 7.3% (m/m).
  • Divinyltetramethyldisiloxane heading agent keep the temperature at 60-80 ° C, stop after 7 hours of reaction, cool to room temperature, then layer, remove the upper layer of acid and add 10 g sodium hydroxide neutralized, washed to neutral, at 150 ° C, vacuum 0.9 MPa ⁇ 1.0 Distillation under MPa for 3 hours to remove low-boiling substances, to obtain a colorless and transparent MDQ type phenyl vinyl silicone resin 1080 g, viscosity 5000 mPa•s/25° C., refractive index 1.54/25° C., vinyl content 8.2% (m/m).
  • Mixture solution consisting of deionized water, stir well, add dropwise within half an hour, then heat up to 60-80 ° C for 5 hours, then add 50 g divinyltetramethyldisiloxane heading agent, keep the temperature at 60-80 ° C, stop after 7 hours of reaction, cool to room temperature, then layer, remove the upper layer of acid and add 1 g sodium hydroxide is neutralized, washed with water to neutrality, distilled at 150 ° C, vacuum degree of 0.9 MPa to 1.0 MPa for 3 hours, and the low-boiling substance is removed to obtain a colorless and transparent MDQ type phenyl vinyl silicone resin 130. g, viscosity of 20,000 mPa•s/25 ° C, refractive index of 1.55/25 ° C, and vinyl content of 7.5% (m/m).
  • the MDQ type phenyl vinyl silicone resin obtained in Example 1 was tested by an infrared spectrometer IRAffinity-1 of Japan SHIMADZU Co., and infrared spectrum analysis was performed.
  • the infrared spectrum of the MDQ type phenyl vinyl silicone resin obtained in Example 1 is shown in Fig. 1.
  • the wavelength of 3070.81 cm -1 is the unsaturated hydrocarbon peak on the benzene ring, and the 1429.31 cm -1 is the characteristic peak of the silicon phenyl group.
  • the iodometric method is used to determine the vinyl content of the product, that is, about 0.1 g of the product is dissolved in carbon tetrachloride, and then 10 mL is added.
  • Mol/L iodine bromide reagent after fully shaking, place in the dark for 1 hour, then add 5 mL of 10% potassium iodide solution, and then fully shake to 0.1
  • the mol/L sodium thiosulfate standard solution is titrated, and the starch is used as an indicator. The drop to the blue disappearance is the end point, and a blank test is performed at the same time.
  • the vinyl content is calculated as follows:
  • Vinyl % [ CB ⁇ ((V 0 -V 1 )/2) ⁇ 27 ⁇ 100%]/(m ⁇ 1000)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne une résine MDQ de phénylvinylsilicone. La résine MDQ de phénylvinylsilicone présente une structure représentée par la formule générale suivante : (Ph2SiO)a(ViMe2SiO0.5)b(Me3SiO0.5)c(SiO2)d, dans laquelle Ph représente phényle, Me représente méthyle et Vi représente vinyle ; la valeur de a se situe dans la plage de 0,1 à 1 ; la valeur de b + c se situe dans la plage de 0 à 0,1, et b > 0 ; la valeur de d se situe dans la plage de 0 à 0,8 et a + b + c + d > 0 ; la valeur de a/d se situe dans la plage de 1,6 à 2,5 ; et la valeur de (b + c)/d se situe dans la plage de 1,6 à 2,5. La présente invention concerne également un procédé de préparation de la résine MDQ de phénylvinylsilicone. Selon le procédé, la viscosité, l'indice de réfraction et la teneur en vinyle d'un produit sont régulés par des conditions telles que le rapport matière première monomère, le temps de réaction, la température et la valeur du pH, les conditions de fabrication sont douces, simples et faisables, la source de matière première est grande et la répétabilité est bonne.
PCT/CN2014/095701 2014-11-27 2014-12-30 Résine mdq de phénylvinylsilicone et son procédé de préparation WO2016082287A1 (fr)

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CN201410707591.6A CN104448318B (zh) 2014-11-27 2014-11-27 一种mdq类型苯基乙烯基硅树脂及其制备方法
CN201410707591.6 2014-11-27

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CN109369916A (zh) * 2018-09-05 2019-02-22 惠州瑞德新材料科技股份有限公司 一种耐超高温有机硅中间体的制备方法
CN113563590A (zh) * 2021-08-09 2021-10-29 中国工程物理研究院化工材料研究所 一种新型耐高温硼-硅树脂及其合成方法
CN114539922A (zh) * 2020-11-26 2022-05-27 海洋化工研究院有限公司 一种钛合金用抗冲刷辐射防热涂层及其制备方法和应用
CN115678012A (zh) * 2022-11-01 2023-02-03 中科院广州化学有限公司 一种多端烯烃基支化聚硅氧烷及其制备方法和应用
CN117625118A (zh) * 2023-11-28 2024-03-01 广东鼎立森新材料有限公司 一种led用封装胶水的制备方法

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CN104892938A (zh) * 2015-06-26 2015-09-09 深圳市森日有机硅材料有限公司 一种mdq类型苯基含氢硅树脂及其制备方法
CN108697592B (zh) 2016-03-14 2021-04-27 美国陶氏有机硅公司 硅氧烷组合物
CN109722218B (zh) * 2018-12-25 2021-05-04 烟台德邦科技股份有限公司 一种耐电解液密封胶及其制备方法
CN110698674A (zh) * 2019-02-18 2020-01-17 杭州师范大学 一种可化学交联固化的含氟mdq类型硅树脂及其制备方法

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CN102952271A (zh) * 2012-06-07 2013-03-06 安徽众星新材料有限公司 高折射率硅树脂及其制备方法和应用
CN103834012A (zh) * 2014-02-25 2014-06-04 江苏三木化工股份有限公司 大规模集成电路用有机硅树脂及其制备方法

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CN101891893B (zh) * 2010-07-23 2012-01-04 深圳市安品有机硅材料有限公司 Led封装用苯基氢基硅树脂的制备方法
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JPH05125191A (ja) * 1991-11-06 1993-05-21 Kanegafuchi Chem Ind Co Ltd ケイ素系ハイブリツド材料
CN101717512A (zh) * 2009-11-20 2010-06-02 苏州大学 一种甲基苯基乙烯基硅树脂的制备方法
CN102898648A (zh) * 2012-05-11 2013-01-30 杭州师范大学 一种可化学交联固化的苯基mdq类型硅树脂及其制备方法
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CN103834012A (zh) * 2014-02-25 2014-06-04 江苏三木化工股份有限公司 大规模集成电路用有机硅树脂及其制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109369916A (zh) * 2018-09-05 2019-02-22 惠州瑞德新材料科技股份有限公司 一种耐超高温有机硅中间体的制备方法
CN114539922A (zh) * 2020-11-26 2022-05-27 海洋化工研究院有限公司 一种钛合金用抗冲刷辐射防热涂层及其制备方法和应用
CN114539922B (zh) * 2020-11-26 2023-06-23 海洋化工研究院有限公司 一种钛合金用抗冲刷辐射防热涂层及其制备方法和应用
CN113563590A (zh) * 2021-08-09 2021-10-29 中国工程物理研究院化工材料研究所 一种新型耐高温硼-硅树脂及其合成方法
CN115678012A (zh) * 2022-11-01 2023-02-03 中科院广州化学有限公司 一种多端烯烃基支化聚硅氧烷及其制备方法和应用
CN115678012B (zh) * 2022-11-01 2023-07-14 中科院广州化学有限公司 一种多端烯烃基支化聚硅氧烷及其制备方法和应用
CN117625118A (zh) * 2023-11-28 2024-03-01 广东鼎立森新材料有限公司 一种led用封装胶水的制备方法

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