WO2016082287A1 - Mdq phenyl vinyl silicone resin and preparation method therefor - Google Patents

Mdq phenyl vinyl silicone resin and preparation method therefor Download PDF

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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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silicone resin
mdq
mass
acid
vinyl
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PCT/CN2014/095701
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French (fr)
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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    • 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

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  • 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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Abstract

The present invention relates to MDQ phenyl vinyl silicone resin. The MDQ phenyl vinyl silicone resin has a structure represented by the following general formula: (Ph2SiO)a(ViMe2SiO0.5)b(Me3SiO0.5)c(SiO2)d, wherein Ph is phenyl, Me is methyl and Vi is vinyl; the value of a ranges from 0.1 to 1; the value of b+c ranges from 0 to 0.1, and b>0; the value of d ranges from 0 to 0.8, and a+b+c+d>0; the value of a/d ranges from 1.6 to 2.5; and the value of (b+c)/d ranges from 1.6 to 2.5. The present invention also provides a method for preparing the MDQ phenyl vinyl silicone resin. According to the method, the viscosity, the refractive index and the vinyl content of a product are controlled through conditions such as the monomer raw material ratio, the reaction time, the temperature and the pH value, the manufacturing conditions are mild, simple and feasible, the raw material source is wide, and the repeatability is good.

Description

一种MDQ类型苯基乙烯基硅树脂及其制备方法  MDQ type phenyl vinyl silicone resin and preparation method thereof 技术领域Technical field
本发明属于高分子材料领域，具体涉及一种MDQ类型苯基乙烯基硅树脂及其制备方法。 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.
背景技术Background technique
有机硅高分子材料如硅凝胶、硅橡胶、硅树脂等具有耐老化、耐高低温、耐紫外光辐射等优点，是目前较为理想的封装材料。其中苯基硅树脂由于具有折光率高、抗透气透水性佳、直接灌注，无需塑料外壳，使用方便等优点，已大量应用于LED贴片、Molding等封装工艺。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.
苯基硅树脂与含硅氢键的有机硅聚合物在铂、钴等金属催化剂作用下发生氢硅化加成反应而交联硫化，硫化条件温和，在中温下即可快速硫化，同时无溶剂、低分子等副产物排出，避免了硫化时产生气泡或沙眼，且固化产物防水防震、耐冲击性、导热性佳，但是有机硅聚合物内聚能密度小，需要补强材料对其进行补强，最常见和用量最大的补强填料是气相法或沉淀法二氧化硅，但其对于硅橡胶增稠效应也非常明显，胶料粘度增大，影响硅橡胶的实际应用范围，且由于折光率不同，加入后影响产品光学透明度，故采用结构类似于气相二氧化硅，折光率高，含Q链节的MDQ类型苯基硅树脂对其进行补强。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. 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.
国内专利CN103360603A公开了一种LED封装用苯基乙烯基硅树脂的制备工艺，该方法采用苯基三甲氧基硅烷或苯基三乙氧基硅烷为T链节来源，以二苯基二甲氧基硅烷和苯基甲基二乙氧基硅烷为D链节来源，1,3-二乙烯基四甲基二硅氧烷为封端剂，合成一种不含Q链节的液体MDT苯基乙烯基硅树脂。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.
国内杭州师范大学伍川等人公开的专利CN102898648中提供了一种可化学交联的MDQ类型苯基乙烯基硅树脂的制备方法，该方法以六甲基二硅氧烷和1，3-二乙烯基四甲基二硅氧烷作为封端剂，甲基苯基二乙氧基硅烷作为D链节来源，正硅酸乙酯作为Q链节来源，以乙醇为溶剂，在盐酸催化下进行水解缩合，得到折光率在1.46～1.50的MDQ硅树脂。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. Vinyl tetramethyldisiloxane as a blocking agent, methylphenyldiethoxysilane as a source of D chain, ethyl orthosilicate as a source of Q chain, ethanol as solvent, catalyzed by hydrochloric acid Hydrolysis condensation gives MDQ silicone resin with a refractive index of 1.46 to 1.50.
中国发明专利CN101805562A公开了烷氧基或含羟基的MDQ苯基硅树脂的合成方法，采用六甲基二硅氧烷、正硅酸甲酯和甲基苯基二氯硅烷、甲苯作为原料，水解缩合制备得含羟基的MDQ苯基硅树脂，固含量为50%，结构式为：[Me3SiO1/2]0.35[MePhSiO2/2]0.2[SiO4/2]0.35[HO]0.06，再将其与含线性羟基硅油组分、气相二氧化硅、交联剂、催化剂、增粘剂混合配制成绝缘型湿气固化涂覆料，应用于各种电子元器伯、线路析及带电工作的器件的防水、防潮、防震、绝缘、防老化、防尘、防腐蚀等。但该苯基MDQ硅树脂不含乙烯基或硅氢键，不能通过硅氢加成固化。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. However, the phenyl MDQ silicone resin does not contain vinyl or silicon hydrogen bonds and cannot be cured by hydrosilylation.
日本专利JP07228701A公开了一种D链节含硅氢的MDQ硅树脂的合成方法，合成工艺为：将甲基MQ硅树脂溶解在有机溶剂中，在酸性催化剂条下进行脱水缩合，再与线性体含氢硅油进行平衡反应，得到结构为(Me3SiO1/2)a(MeHSiO2/2)y(Me2SiO2/2)z(SiO4/2)的D链节含氢的MDQ硅树脂，该发明不含苯基，折光率低，不能用于高光通量需求的LED封装。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.
由于提供Q链节来源的正硅酸乙酯在酸性条件下易发生凝胶化反应，同时各类单体在醇类溶剂中的反应速度不同，正硅酸乙酯与封头剂水解生成甲基MQ硅树脂后，不易与苯基单体继续反应，从而使影响产品最终的透明度。Since the 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.
技术问题technical problem
本发明所要解决的技术问题在于克服现有技术的缺陷，提供一种MDQ类型的苯基乙烯基硅树脂及其制备方法。 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.
技术解决方案Technical solution
本发明是这样实现的，一种MDQ类型的苯基乙烯基硅树脂，其具有如下通式表示的结构：The present invention is achieved by an MDQ type phenylvinyl silicone resin having a structure represented by the following formula:
(Ph2SiO)a (ViMe2SiO0.5)b(Me3SiO0.5)c (SiO2)d (Ph 2 SiO) a (ViMe 2 SiO 0.5 ) b (Me 3 SiO 0.5 ) c (SiO 2 ) d
其中，Ph为苯基，Me为甲基，Vi表示乙烯基；a的取值范围为0.1～1；b+c的取值范围为0～0.1，且b>0；d的取值范围为0～0.8，且a+b+c+d>0；a/d取值范围为1.6～2.5；(b+c)/d取值范围为1.6～2.5。Wherein, 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.
以及，提供上述MDQ类型的苯基乙烯基硅树脂的制备方法，其包括如下步骤：And, a method for preparing a phenylvinyl silicone resin of the above MDQ type, comprising the steps of:
将100～1000质量份的二苯基二甲氧基硅烷和／或二苯基二乙氧基硅烷、10～300质量份的正硅酸乙酯，50～500质量份的有机溶剂混合，室温搅拌，得混合液；100 to 1000 parts by mass of diphenyldimethoxysilane and/or diphenyldiethoxysilane, 10 to 300 parts by mass of ethyl orthosilicate, 50 to 500 parts by mass of an organic solvent, and room temperature Stirring to obtain a mixed solution;
向所述混合液中滴加由20～300质量份的酸性水溶液，滴加完毕后升温至60℃～70℃反应4～6小时，再加入20～200份的乙烯基封头剂和／或甲基封头剂，温度保持60℃～70℃反应6～8小时，得反应液，其中，所述酸性催化剂溶液的质量浓度为5％～15％；20 to 300 parts by mass of an acidic aqueous solution is added dropwise to the mixed solution, and after the dropwise addition is completed, the temperature is raised to 60 ° C to 70 ° C for 4 to 6 hours, and then 20 to 200 parts of a vinyl heading agent and/or 20 to 200 parts are added. The methyl heading agent, the temperature is maintained at 60 ° C ~ 70 ° C for 6 to 8 hours, to obtain a reaction liquid, wherein the acidic catalyst solution has a mass concentration of 5% to 15%;
将所述反应液静置分层，去除上层酸液后加入碱调节pH值至中性，洗涤，得到混合物；The 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;
将所述混合物在真空度等于或大于0.1 Mpa条件下，加热至140℃～160℃保持2～5小时，获得所述MDQ类型苯基乙烯基硅树脂。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.
有益效果Beneficial effect
本发明提供一种MDQ类型的苯基乙烯基硅树脂及其制备方法，所述MDQ类型的苯基乙烯基硅树脂无色透明，折光率高，品质稳定。其制备方法通过单体原料配比、反应时间、温度、pH值等条件来控制产物粘度、折光率、乙烯基含量，从而与相应的苯基含氢交联剂加成得到不同硬度、力学强度的产品。与现有的合成工艺相比，本发明所制备的MDQ类型苯基乙烯基硅树脂折光率高（>1.53/℃），生产工艺条件温和、简单易行，原料来源广泛，重复性好，产品可用于LED封装胶的补强材料、耐热涂料等方面。 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.
附图说明DRAWINGS
图1是本发明实施例1获得的MDQ类型苯基乙烯基硅树脂的红外光谱图。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an infrared spectrum chart of an MDQ type phenylvinyl silicone resin obtained in Example 1 of the present invention.
本发明的实施方式Embodiments of the invention
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
本发明实施例提供一种MDQ类型的苯基乙烯基硅树脂，其具有如下通式表示的结构：Embodiments of the present invention provide a phenylvinyl silicone resin of the MDQ type having a structure represented by the following formula:
(Ph2SiO)a (ViMe2SiO0.5)b(Me3SiO0.5)c (SiO2)d (Ph 2 SiO) a (ViMe 2 SiO 0.5 ) b (Me 3 SiO 0.5 ) c (SiO 2 ) d
其中，Ph为苯基C6H5，Me为甲基CH3，Vi表示乙烯基CH=CH2；a的取值范围为0.1～1；b+c的取值范围为0～0.1，且b>0；d的取值范围为0～0.8，且a+b+c+d>0；a/d取值范围为1.6～2.5； (b+c)/d取值范围为1.6～2.5。所述MDQ类型的苯基乙烯基硅树脂的折光率在1.53～1.55/25℃，粘度在2000～300000 mpa•s/25℃。Wherein, Ph is phenyl C 6 H 5 , Me is methyl CH 3 , Vi represents vinyl CH=CH 2 ; 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 . 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.
本发明实施例还提供上述MDQ类型的苯基乙烯基硅树脂的制备方法，其包括如下步骤：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：将100～1000质量份的二苯基二甲氧基硅烷和／或二苯基二乙氧基硅烷、10～300质量份的正硅酸乙酯，50～500质量份的有机溶剂混合，室温搅拌，得混合液；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;
S02：向所述混合液中滴加由20～300质量份的酸性水溶液，滴加完毕后升温至60℃～70℃反应4～6小时，再加入20～200份的乙烯基封头剂和／或甲基封头剂，温度保持60℃～70℃反应6～8小时，得反应液，其中，所述酸性催化剂溶液的质量浓度为5％～15％；S02: adding 20 to 300 parts by mass of an acidic aqueous solution to the mixed solution, and after heating, heating to 60 ° C to 70 ° C for 4 to 6 hours, and then adding 20 to 200 parts of a vinyl heading agent and / or a methyl heading agent, the temperature is maintained at 60 ° C ~ 70 ° C reaction for 6-8 hours, to obtain a reaction solution, wherein the acidic catalyst solution has a mass concentration of 5% to 15%;
S03：将所述反应液静置分层，去除上层酸液后加入碱调节pH值至中性，洗涤，得到混合物；S03: the 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;
S04：将所述混合物在真空度等于或大于0.1 Mpa条件下，加热至140～160℃保持2～5小时，获得所述MDQ类型苯基乙烯基硅树脂。S04: the mixture is at a vacuum equal to or greater than 0.1 Under the conditions of Mpa, the mixture was heated to 140 to 160 ° C for 2 to 5 hours to obtain the MDQ type phenyl vinyl silicone resin.
具体地，步骤S01中，所述溶剂为甲醇、乙醇、异丙醇等醇类溶剂中的一种或者醇类溶剂的混合物。优选地，所述溶剂为甲醇。Specifically, in the step S01, the solvent is one of an alcohol solvent such as methanol, ethanol or isopropyl alcohol or a mixture of alcohol solvents. Preferably, the solvent is methanol.
步骤S02中，所述滴加优选在20～40分钟内滴加完毕。所述酸性催化剂可选用盐酸、硫酸、硝酸、磷酸、高氯酸、氢溴酸、氢碘酸等质子酸，也可选用三氟甲磺酸、强酸性阳离子树脂等有机酸，其中，优选为盐酸。所述乙烯基封头剂为二乙烯基四甲基二硅氧烷、二苯基二甲基二乙烯基二硅氧烷、二甲基乙烯基硅氧烷、苯基乙烯基硅氧烷中的至少一种，其中，优选为二乙烯基四甲基二硅氧烷。所述甲基封头剂优选为六甲基二硅氧烷。In step S02, 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.
步骤S03具体为，将所述反应液静置分层，去除上层酸液后加入碱性试剂调节pH值至中性，用溶剂洗涤。所述调节pH值至中性的碱可选用氨水、氢氧化钠、氢氧化钾、氢氧化锂、碳酸氢钠中的至少一种。所述洗涤优选用水洗涤。In 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.
步骤S04中，将步骤S03得到的混合物在真空度等于或大于0.1 Mpa条件下，加热至140～160℃，优选地，加热至150℃，蒸馏2～5小时，脱除低沸点物质，获得所述MDQ类型苯基乙烯基硅树脂。In step S04, the mixture obtained in step S03 has a vacuum degree equal to or greater than 0.1. Under the conditions of Mpa, 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.
以下结合具体实施例对本发明的具体实现进行详细描述。The specific implementation of the present invention will be described in detail below with reference to specific embodiments.
实施例1：Example 1:
向装有200质量份甲醇的2 L三口烧瓶中，加入444质量份的二苯基二甲氧基硅烷、189质量份的正硅酸乙酯，在30℃下滴加由45质量份质量分数为25%的盐酸和150质量份的去离子水组成的混合溶液，充分搅拌，半小时内滴加完毕，再升温至60～80℃反应5小时，再加入111.6 g二乙烯基四甲基二硅氧烷封头剂，保持温度在60～80℃，反应7小时后停止，冷却至室温后再分层、加入5 g氢氧化钠中和，水洗至中性，在150℃，真空度0.9 MPa～1.0 MPa的条件下蒸馏3小时，脱除低沸点物质，得到无色透明的MDQ类型苯基乙烯基硅树脂512.0 g，粘度为7800 mPa•s/25℃，折光率1.5495/25℃，乙烯基含量为7.3%（m/m）。2 to 200 parts by mass of methanol In a three-necked flask, 444 parts by mass of diphenyldimethoxysilane and 189 parts by mass of ethyl orthosilicate were added, and 45 parts by mass of 25% by mass of hydrochloric acid and 150 parts by mass were added dropwise at 30 ° C. 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).
实施例2：Example 2:
向装有100质量份甲醇的1 L三口烧瓶中，加入148质量份的二苯基二甲氧基硅烷、63质量份的正硅酸乙酯，在30℃下滴加由30质量份的质量分数为25%的盐酸和100质量份的去离子水的混合溶液，充分搅拌，半小时内滴加完毕，再升温至60～80℃反应5小时，加入56.5 g二乙烯基四甲基二硅氧烷封头剂，保持温度在60～80℃，反应7小时后停止，冷却至室温后再分层、去除上层酸液后加入2.5 g氢氧化钠中和，水洗至中性，在150℃，真空度0.9 MPa～1.0 MPa的条件下蒸馏3小时，脱除低沸点物质，得到无色透明的MDQ类型苯基乙烯基硅树脂186 g，粘度为20000 mPa•s/25℃，折光率1.5503/25℃，乙烯基含量为7.3%（m/m）。To 1 with 100 parts by mass of methanol In a three-necked flask, 148 parts by mass of diphenyldimethoxysilane and 63 parts by mass of ethyl orthosilicate were added, and 30 parts by mass of hydrochloric acid having a mass fraction of 25% and 100 mass were added dropwise at 30 ° C. a mixed solution of deionized water, fully stirred, added dropwise within half an hour, and then heated to 60-80 ° C for 5 hours, added 56.5 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 2.5 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 186. g, viscosity: 20000 mPa•s/25 ° C, refractive index 1.5503/25 ° C, vinyl content 7.3% (m/m).
实施例3：Example 3:
向装有300质量份甲醇的3 L三口烧瓶中，加入888 质量份的二苯基二甲氧基硅烷、378质量份的正硅酸乙酯，在30℃下滴加由90质量份质量分数为25%的盐酸和300质量份的去离子水组成的混合溶液，充分搅拌，半小时内滴加完毕，再升温至60～80℃反应5小时，再加入380 g二乙烯基四甲基二硅氧烷封头剂，保持温度在60～80℃，反应7小时后停止，冷却至室温后再分层、去除上层酸液后加入10 g氢氧化钠中和，水洗至中性，在150℃，真空度0.9 MPa～1.0 MPa的条件下蒸馏3小时，脱除低沸点物质，得到无色透明的MDQ类型苯基乙烯基硅树脂1080 g，粘度为5000 mPa•s/25℃，折光率1.54/25℃，乙烯基含量为8.2%（m/m）。To a 3 L three-necked flask containing 300 parts by mass of methanol, add 888 Parts by mass of diphenyldimethoxysilane, 378 parts by mass of ethyl orthosilicate, and a mixture of 90 parts by mass of 25% by mass of hydrochloric acid and 300 parts by mass of deionized water are added dropwise at 30 ° C The solution is stirred thoroughly, and the addition is completed within half an hour. The temperature is raised to 60-80 ° C for 5 hours, and then 380 is added. 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 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).
实施例4：Example 4:
向装有100质量份甲醇的1 L三口烧瓶中，加入12 质量份的二苯基二甲氧基硅烷、63 质量份的正硅酸乙酯，在30℃下滴加由15质量份质量分数为25%的盐酸和35质量份的去离子水组成混合溶液，充分搅拌，半小时内滴加完毕，再升温至60～80℃反应5小时，再加入56.5 g二乙烯基四甲基二硅氧烷封头剂，保持温度在60～80℃，反应7小时后停止，冷却至室温后再分层、去除上层酸液后加入2 g氢氧化钠中和，水洗至中性，在150℃，真空度0.9 MPa～1.0 MPa的条件下蒸馏3小时，脱除低沸点物质，得到无色透明的MDQ类型苯基乙烯基硅树脂150 g，粘度为4200 mPa•s/25℃，折光率1.54/25℃，乙烯基含量为8.5%（m/m）。To a 1 L three-necked flask containing 100 parts by mass of methanol, 12 parts by mass of diphenyldimethoxysilane, 63 was added. A mass part of ethyl orthosilicate, a mixed solution of 15 parts by mass of 25% hydrochloric acid and 35 parts by mass of deionized water is added dropwise at 30 ° C, thoroughly stirred, and the addition is completed within half an hour, and then the temperature is raised. React to 60-80 ° C for 5 hours, then add 56.5 g divinyltetramethyldisiloxane head sealer, 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 then add 2 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 150. g, viscosity 4200 mPa•s/25 ° C, refractive index 1.54/25 ° C, vinyl content 8.5% (m/m).
实施例5：Example 5:
向装有100质量份甲醇的1 L三口烧瓶中，加入200 质量份的二苯基二甲氧基硅烷、63质量份的正硅酸乙酯，在30℃下滴加由15质量份质量分数为25%的盐酸和35质量份的去离子水组成的混合溶液，充分搅拌，半小时内滴加完毕，再升温至60～80℃反应5小时，再加入71.6 g二乙烯基四甲基二硅氧烷封头剂，保持温度在60～80℃，反应7小时后停止，冷却至室温后再分层、去除上层酸液后加入1 g氢氧化钠中和，水洗至中性，在150℃，真空度0.9 MPa～1.0 MPa的条件下蒸馏3小时，脱除低沸点物质，得到无色透明的MDQ类型苯基乙烯基硅树脂200 g，粘度为300000 mPa•s/25℃，折光率1.55/25℃，乙烯基含量为6.2%（m/m）。To a 1 L three-necked flask containing 100 parts by mass of methanol, add 200 Parts by mass of diphenyldimethoxysilane, 63 parts by mass of ethyl orthosilicate, and a mixture of 15 parts by mass of 25% hydrochloric acid and 35 parts by mass of deionized water is added dropwise at 30 ° C The solution is stirred thoroughly, and the addition is completed within half an hour. The temperature is raised to 60-80 ° C for 5 hours, and then added to 71.6. 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 200. g, viscosity 300,000 mPa•s/25 ° C, refractive index 1.55/25 ° C, vinyl content 6.2% (m/m).
实施例6：Example 6
向装有100 质量份甲醇的1 L三口烧瓶中，加入110质量份二苯基二甲氧基硅烷、63质量份的正硅酸乙酯，在30℃下滴加由15质量份质量分数为25%的盐酸和35质量份的去离子水组成的混合溶液，充分搅拌，半小时内滴加完毕，再升温至60～80℃反应5小时，再加入50 g二乙烯基四甲基二硅氧烷封头剂，保持温度在60～80℃，反应7小时后停止，冷却至室温后再分层、去除上层酸液后加入1 g氢氧化钠中和，水洗至中性，在150℃，真空度0.9 MPa～1.0 MPa的条件下蒸馏3小时，脱除低沸点物质，得到无色透明的MDQ类型苯基乙烯基硅树脂130 g，粘度为20000 mPa•s/25℃，折光率1.55/25℃，乙烯基含量为7.5%（m/m）。To a solution containing 100 parts by mass of methanol In a three-necked flask, 110 parts by mass of diphenyldimethoxysilane and 63 parts by mass of ethyl orthosilicate were added, and 15 parts by mass of 25% by mass of hydrochloric acid and 35 parts by mass were added dropwise at 30 ° C. 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).
采用采用日本SHIMADZU公司的红外光谱仪IRAffinity-1测试实施例1所获得的MDQ类型苯基乙烯基硅树脂，进行红外图谱分析。实施例1获得的MDQ类型苯基乙烯基硅树脂的红外光谱图如图1所示，其中波长3070.81 cm-1是苯环上不饱和碳氢峰，1429.31 cm-1为硅苯基特征峰，1257.64 cm-1为Si-Me峰，1407.13 cm-1为Si-Vi峰，1130 cm-1～1000 cm-1为Si-O-Si峰，说明产品中含有苯基、乙烯基、甲基及Si-O-Si，说明得到的产品为所需要的MDQ类型苯基乙烯基硅树脂。测试25℃下实施例1～6所获得的MDQ类型苯基乙烯基硅树脂的粘度和折光率参考的标准分别为：DIN 53019、GB/T614-2006。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. 1257.64 cm -1 is the Si-Me peak, 1407.13 cm -1 is the Si-Vi peak, and 1130 cm -1 to 1000 cm -1 is the Si-O-Si peak, indicating that the product contains phenyl, vinyl, methyl and Si-O-Si, indicating that the obtained product is the desired MDQ type phenyl vinyl silicone resin. The standards for viscosity and refractive index of the MDQ type phenylvinyl silicone resin obtained in Examples 1 to 6 at 25 ° C were tested as follows: DIN 53019, GB/T614-2006.
采用碘量法测定产品的乙烯基含量，即取0.1 g左右的产品溶于四氯化碳，再加入10 mL 0.1 mol/L的溴化碘试剂，充分振荡后，在暗处放置1小时，然后加入5 mL浓度为10%的碘化钾溶液，再充分振荡，以0.1 mol/L的硫代硫酸钠标准溶液滴定，以淀粉为指标剂，滴至蓝色消失即为终点，同时做空白试验。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.
乙烯基含量按下式计算：The vinyl content is calculated as follows:
乙烯基%＝[ CB×（（V0-V1）/2）×27×100%]/（m×1000）Vinyl %=[ CB×((V 0 -V 1 )/2)×27×100%]/(m×1000)
式中：In the formula:
V0——空白试验硫代硫酸钠用量，mL；V 0 - blank test sodium thiosulfate dosage, mL;
V1——滴定试样硫代硫酸钠用量，mL；V 1 - titration sample sodium thiosulfate dosage, mL;
CB——硫代硫酸钠标准溶液浓度，mol/L；CB - sodium thiosulfate standard solution concentration, mol / L;
m——试样质量，g。m - sample quality, g.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (9)

  1. 一种MDQ类型的苯基乙烯基硅树脂，其特征在于，具有如下通式表示的结构： A phenylvinyl silicone resin of the MDQ type characterized by having a structure represented by the following formula:
    (Ph2SiO)a (ViMe2SiO0.5)b(Me3SiO0.5)c (SiO2)d (Ph 2 SiO) a (ViMe 2 SiO 0.5 ) b (Me 3 SiO 0.5 ) c (SiO 2 ) d
    其中，Ph为苯基，Me为甲基，Vi表示乙烯基；a的取值范围为0.1～1；b+c的取值范围为0～0.1，且b>0；d的取值范围为0～0.8，且a+b+c+d>0；a/d取值范围为1.6～2.5；(b+c)/d取值范围为1.6～2.5。Wherein, 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.
  2. 一种MDQ类型的苯基乙烯基硅树脂的制备方法，其特征在于，包括如下步骤：A method for preparing a phenylvinyl silicone resin of the MDQ type, comprising the steps of:
    将100～1000质量份的二苯基二甲氧基硅烷和／或二苯基二乙氧基硅烷、10～300质量份的正硅酸乙酯，50～500质量份的有机溶剂混合，室温搅拌，得混合液；100 to 1000 parts by mass of diphenyldimethoxysilane and/or diphenyldiethoxysilane, 10 to 300 parts by mass of ethyl orthosilicate, 50 to 500 parts by mass of an organic solvent, and room temperature Stirring to obtain a mixed solution;
    向所述混合液中滴加20～300质量份的酸性水溶液，滴加完毕后升温至60℃～70℃反应4～6小时，再加入20～200份的乙烯基封头剂和／或甲基封头剂，温度保持60℃～70℃反应6～8小时，得反应液，其中，所述酸性催化剂溶液的质量浓度为5％～15％；20 to 300 parts by mass of an acidic aqueous solution is added dropwise to the mixed solution, and after the dropwise addition is completed, the temperature is raised to 60 ° C to 70 ° C for 4 to 6 hours, and then 20 to 200 parts of a vinyl heading agent and/or a group are added. The base heading agent, the temperature is maintained at 60 ° C ~ 70 ° C for 6-8 hours to obtain a reaction liquid, wherein the acidic catalyst solution has a mass concentration of 5% to 15%;
    将所述反应液静置分层，去除上层酸液后加入碱调节pH值至中性，洗涤，得到混合物；The 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;
    将所述混合物在真空度等于或大于0.1 Mpa条件下，加热至140℃～160℃保持2～5小时，获得所述MDQ类型苯基乙烯基硅树脂。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.
  3. 根据权利要求2所述的MDQ类型的苯基乙烯基硅树脂的制备方法，其特征在于，所述溶剂为甲醇、乙醇和异丙醇中的至少一种。The method for producing a phenylvinyl silicone resin of the MDQ type according to claim 2, wherein the solvent is at least one of methanol, ethanol, and isopropyl alcohol.
  4. 根据权利要求2或3所述的MDQ类型的苯基乙烯基硅树脂的制备方法，其特征在于，所述溶剂为甲醇。The method for producing a phenylvinyl silicone resin of the MDQ type according to claim 2 or 3, wherein the solvent is methanol.
  5. 根据权利要求2所述的MDQ类型的苯基乙烯基硅树脂的制备方法，其特征在于，所述酸性催化剂为盐酸、硫酸、硝酸、磷酸、高氯酸、氢溴酸、氢碘酸、三氟甲磺酸和强酸性阳离子树脂中的至少一种。The method for preparing a phenylvinyl silicone resin of the MDQ type according to claim 2, wherein the acidic catalyst is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydrobromic acid, hydroiodic acid, or the like. At least one of fluoromethanesulfonic acid and a strongly acidic cationic resin.
  6. 根据权利要求2或5所述的MDQ类型的苯基乙烯基硅树脂的制备方法，其特征在于，所述酸性催化剂为盐酸。The method for producing a phenylvinyl silicone resin of the MDQ type according to claim 2 or 5, wherein the acidic catalyst is hydrochloric acid.
  7. 根据权利要求2所述的MDQ类型的苯基乙烯基硅树脂的制备方法，其特征在于，所述乙烯基封头剂为二乙烯基四甲基二硅氧烷、二苯基二甲基二乙烯基二硅氧烷、二甲基乙烯基硅氧烷、苯基乙烯基硅氧烷中的至少一种，所述甲基封头剂为六甲基二硅氧烷。The method for preparing a phenylvinyl silicone resin of the MDQ type according to claim 2, wherein the vinyl heading agent is divinyltetramethyldisiloxane or diphenyldimethyldiene. At least one of vinyl disiloxane, dimethyl vinyl siloxane, and phenyl vinyl siloxane, the methyl heading agent being hexamethyldisiloxane.
  8. 根据权利要求2或7所述的MDQ类型的苯基乙烯基硅树脂的制备方法，其特征在于，所述乙烯基封头剂为二乙烯基四甲基二硅氧烷。The method for producing a phenylvinyl silicone resin of the MDQ type according to claim 2 or 7, wherein the vinyl heading agent is divinyltetramethyldisiloxane.
  9. 根据权利要求2所述的MDQ类型的苯基乙烯基硅树脂的制备方法，其特征在于，所述调节pH值至中性的碱为氨水、氢氧化钠、氢氧化钾、氢氧化锂、碳酸氢钠中的至少一种。The method for preparing a phenylvinyl silicone resin of the MDQ type according to claim 2, wherein the pH-to-neutral base is ammonia water, sodium hydroxide, potassium hydroxide, lithium hydroxide or carbonic acid. At least one of sodium hydrogen.
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