MQ树脂综述课件

1、姚慧玲姚慧玲20162016年年1212月月MQ硅树脂 MQ树脂树脂 MQ硅树脂是由单官能连节（R3SiO1/2即M）和四官能链节（SiO4/2即Q）组成的、结构比特殊的有机/无机杂化聚有机硅氧烷。 MQ硅树脂外观为双层结构紧密球状体，即球芯部分为Si-O-Si链连接，密度较高及聚合度为15-50的笼状SiO2，球壳是密度较小的M层。李茹等李茹等, MQ, MQ硅树脂合成及应用研究进展硅树脂合成及应用研究进展. . 有机硅材料有机硅材料, 2010(02): , 2010(02): 第第107-112107-112页页 根据不同领域需要，合成出不同功能基团的硅树脂，如乙烯基、氨基、含氢、苯基硅

2、树脂等。李茹等李茹等, MQ, MQ硅树脂合成及应用研究进展硅树脂合成及应用研究进展. . 有机硅材料有机硅材料, 2010(02): , 2010(02): 第第107-112107-112页页 合成方法合成方法1.硅酸钠（水玻璃）法硅酸钠（水玻璃）法以水玻璃作为Q基团原料，六甲基二硅氧烷（MM）或三甲基一氯硅烷（MeSiCl）为单官能团有机硅单元作M基团，在强酸催化剂、醇类溶剂、去离子水的环境下进行甲硅烷基化反应。崔贵银等崔贵银等, , 水玻璃法制备水玻璃法制备MQMQ硅树脂的研究及应用进展硅树脂的研究及应用进展. . 化学工程师化学工程师, 2013(10): , 2013(10): 第

3、第37-4137-41页页. .此法优点在于工艺简单、原料成本低且易得，缺点在于产物分子量分布较宽，M/Q比及结构不易控制，易凝胶化，收率低。许多研究在此基础上，针对原料、投料顺序、催化剂、溶剂、萃取剂及其他工艺条件进行改进。崔贵银等崔贵银等, , 水玻璃法制备水玻璃法制备MQMQ硅树脂的研究及应用进展硅树脂的研究及应用进展. . 化学工程师化学工程师, 2013(10): , 2013(10): 第第37-4137-41页页. . 原料改进原料改进 三甲基氯硅烷水解速度极快，反应很难控制，容易产生凝胶，并且反应后产生的 HCl，腐蚀性很大，HCl 同时又对水解缩合过程起到催化作用，使反应催化

4、剂量很难控制，后期基本被六甲基二硅氧烷取代。 另外将部分Me用乙烯基或氢基、苯基等封端剂代替，可引入乙烯基、氢基和苯基基团，从而提高其性能。 来国桥等采取苯基烷氧基硅烷和乙烯基烷氧基硅烷与六甲基二硅氧烷作M封端剂与水玻璃共同制备了带有苯基的甲基乙烯基MQ硅树脂。崔贵银等崔贵银等, , 水玻璃法制备水玻璃法制备MQMQ硅树脂的研究及应用进展硅树脂的研究及应用进展. . 化学工程师化学工程师, 2013(10): , 2013(10): 第第37-4137-41页页. . 投料顺序投料顺序（1）水玻璃稀释后加酸中和，然后加MM或Me3SiCl共水解；（2）水玻璃稀释后同时加酸和MM或Me3SiCl

5、 ；（3）先加酸、MM或Me3SiCl，再加水玻璃共水解。结论：加料顺序对分子量和 M/Q 比值影响较为明显，先加水玻璃水解到一定程度，再添加六甲基二硅氧烷进行水解缩合的工艺，所得的产物分子量明显比先加 MM 和乙醇水解后再加水玻璃所得产物的分子量高，M/Q 值差异也很大。 崔贵银等崔贵银等, , 水玻璃法制备水玻璃法制备MQMQ硅树脂的研究及应用进展硅树脂的研究及应用进展. . 化学工程师化学工程师, 2013(10): , 2013(10): 第第37-4137-41页页. . 溶剂溶剂不同溶剂对 MQ 硅树脂的产能和性能有很大影响，选取乙醇、 甲醇、 丙酮、 异丙醇及甲苯溶剂对 MQ 硅

6、树脂产率的影响进行了研究。结论是：以乙醇和异丙醇为溶剂制备的 MQ 硅树脂的产率较高，摩尔质量也较接近；甲醇和丙酮为溶剂制得的 MQ 硅树脂的产率较低，但摩尔质量却相对较高。采用甲醇和甲苯作溶剂时，容易产生凝胶现象。CN102161765A中溶剂采用由异丙醇和正丁醇质量配比为 3 11 1 的配比组成的混合醇。崔贵银等崔贵银等, , 水玻璃法制备水玻璃法制备MQMQ硅树脂的研究及应用进展硅树脂的研究及应用进展. . 化学工程师化学工程师, 2013(10): , 2013(10): 第第37-4137-41页页. . 硅酸酯法硅酸酯法 硅酸钠法是以正硅酸 作为Q单元，由硅酸酯在酸或碱催化剂作用

7、下水解得到硅酸 , 再进一步缩合 、 加入单官能团有机硅单体 (MM或三甲基氯硅烷等 )封端。 相对于硅酸钠法而言, 硅酸酯的水解反应活性较低、 反应较温和, 因而有利于反应的控制。李茹等李茹等, MQ, MQ硅树脂合成及应用研究进展硅树脂合成及应用研究进展. . 有机硅材料有机硅材料, 2010(02): , 2010(02): 第第107-112107-112页页 A.Shirahata等人采用先将 MM、 盐酸 、 水和乙醇的混合物加热到一定温度, 再在一定时间内滴加正硅酸乙酯的方式 , 获得了摩尔质量分布较窄的 MQ硅树脂 。因为要保证硅酸酯和三烷基基团之间形成的 Si O- Si 键

8、有足够高的解离速率 , 盐酸的浓度需在 10%左右 , 这样正硅酸乙酯水解产物的自缩聚趋势小, 不易形成凝胶 。US4707531 Method for producing organ0silicon polymers and the polymers prepared therebyUS4707531 Method for producing organ0silicon polymers and the polymers prepared thereby R.Weidner 等人采用先酸催化后碱催化的方法合成 MQ硅树脂 。向经酸催化缩合的反应液加入一定量的甲苯, 调 p H值至碱性, 反应

9、一定时间中和 ，然后蒸馏除去甲苯 , 过滤除去析出的固体 NaCl , 得到中性的 MQ硅树脂甲苯溶液。此法得到的 MQ硅树脂的烷氧基 、 羟基含量较低 , 而且比较容易控制, 反应的产率也比较高 。US5548053 Process for the preparation of organopolysiloxane US5548053 Process for the preparation of organopolysiloxane resinresinXiaoqiu Xu, Chuan Wu, Preparation, Structure Characterization, and The

10、rmal Performance of Phenyl-Modified MQ Xiaoqiu Xu, Chuan Wu, Preparation, Structure Characterization, and Thermal Performance of Phenyl-Modified MQ Silicone Resins Silicone Resins u INTRODUCTIONMQ type silicone resins are novel silicone materials widely used in many fields. u For example, they can b

11、e used as the reinforcing materials for silicone rubbers to enhance their physical properties.u Used as the tackifiers for silicone pressure-sensitive adhesives, as well as a constituent of deforming agents.u In addition, MQ silicone resins play important roles in other fields such as surfactants, s

12、low-release delivery agents, coatings, and additives.u When MQ resins are used as the fillers for silicone rubbers, they can exhibit the same reinforcing effect produced by traditional fumed or precipitated silica but have little influence on the viscosity of the silicone rubbers. u Once phenyl grou

13、ps are attached to the side chain of the polysiloxane, the modified MQ silicone resins exhibit much better thermal stability, radiation resistance, and higher refractive index compared with other kinds of silicone resins.u In this article, phenyl-modified MQ resins, with an active dimethylvinylsilox

14、yl group, are prepared from the prepolymer of sodium silicate and end capped with the methyldiphenylsiloxyl ordimethylphenylsiloxyl group resulting from the hydrolysis ofmethyldiphenylethoxysilane (MDPES) or dimethylphenylethoxysilane (DMPES). Various factors affecting the properties of the MQ resin

15、s are investigated in detail. uPreparation of MQ Resins MQ resins and the phenyl group-modified MQ resins are prepared by the sodium silicate and the silanols generated from the hydrolysis of end-capping agents, as illustrated in Scheme 1(ah). (a)(b)(d)(c)(e)(f)(f)(g)u Typical process for preparatio

16、n of MQ resins or the phenylgroup-modified MQ resins:u An appropriate amount of concentrated hydrochloric acid and deionized water is added to a three-necked flask and the temperature held constant at 35. u A mixture of sodium silicate and water is quickly added to the flask with vigorous agitation

17、for 1 min. To avoid gelation, the reaction temperature must be held below 40 . u Subsequently, an ethanol solution of mixtures of the required amounts of MM, TMDVS, MDPES, or DMPES or their dimers, such as TMDPS and DMTPS, is added to the flask and allowed to react for 30 min. u Toluene or MM extrac

18、tant are then added to the flask and the temperature is raised to 70C and held for 2 h. u After cooling to room temperature, the mixtures are washed repeatedly with deionized water to neutral pH. u The organic phase is further collected and dehydrated completely using anhydrous calcium chloride. u A

19、fter filtration and removing toluene or MM by evaporation, the MQ silicone resins were obtained. u Detailed experimental conditions are listed in Table 1.Table 1u RESULTS AND DISCUSSION u Determination of M/Q Valueu Me3SiO1/2-Terminated MQ Resins u The total mass percentage of carbon and hydrogen co

20、ntained in thisMQ resin, represented by the symbol GThe total mass percentage G of both carbon and hydrogen can be determined either from elemental analysis or from the 1H-NMR spectrum. u Me2PhSiO1/2-Terminated MQ Resins uthe chemical shifts of the methyl protons in the Me3SiO1/2, Me2ViSiO1/2, and Me2PhSiO1/2 segments overlap each other in the region 0 to about 0.36 ppmuHowever, the chemical shifts of the phenyl protons in the Me2PhSiO1/2 segment and vinyl protons in the Me2ViSiO1/2 segment can be clearly resolved. uThe total content of all the methyl groups in the p