MQ樹脂綜述課件

1、姚慧玲姚慧玲20162016年年1212月月MQ硅樹脂 MQ樹脂樹脂 MQ硅樹脂是由單官能連節(jié)（R3SiO1/2即M）和四官能鏈節(jié)（SiO4/2即Q）組成的、結(jié)構(gòu)比特殊的有機/無機雜化聚有機硅氧烷。 MQ硅樹脂外觀為雙層結(jié)構(gòu)緊密球狀體，即球芯部分為Si-O-Si鏈連接，密度較高及聚合度為15-50的籠狀SiO2，球殼是密度較小的M層。李茹等李茹等, MQ, MQ硅樹脂合成及應(yīng)用研究進展硅樹脂合成及應(yīng)用研究進展. . 有機硅材料有機硅材料, 2010(02): , 2010(02): 第第107-112107-112頁頁 根據(jù)不同領(lǐng)域需要，合成出不同功能基團的硅樹脂，如乙烯基、氨基、含氫、苯基硅

2、樹脂等。李茹等李茹等, MQ, MQ硅樹脂合成及應(yīng)用研究進展硅樹脂合成及應(yīng)用研究進展. . 有機硅材料有機硅材料, 2010(02): , 2010(02): 第第107-112107-112頁頁 合成方法合成方法1.硅酸鈉（水玻璃）法硅酸鈉（水玻璃）法以水玻璃作為Q基團原料，六甲基二硅氧烷（MM）或三甲基一氯硅烷（MeSiCl）為單官能團有機硅單元作M基團，在強酸催化劑、醇類溶劑、去離子水的環(huán)境下進行甲硅烷基化反應(yīng)。崔貴銀等崔貴銀等, , 水玻璃法制備水玻璃法制備MQMQ硅樹脂的研究及應(yīng)用進展硅樹脂的研究及應(yīng)用進展. . 化學(xué)工程師化學(xué)工程師, 2013(10): , 2013(10): 第

3、第37-4137-41頁頁. .此法優(yōu)點在于工藝簡單、原料成本低且易得，缺點在于產(chǎn)物分子量分布較寬，M/Q比及結(jié)構(gòu)不易控制，易凝膠化，收率低。許多研究在此基礎(chǔ)上，針對原料、投料順序、催化劑、溶劑、萃取劑及其他工藝條件進行改進。崔貴銀等崔貴銀等, , 水玻璃法制備水玻璃法制備MQMQ硅樹脂的研究及應(yīng)用進展硅樹脂的研究及應(yīng)用進展. . 化學(xué)工程師化學(xué)工程師, 2013(10): , 2013(10): 第第37-4137-41頁頁. . 原料改進原料改進 三甲基氯硅烷水解速度極快，反應(yīng)很難控制，容易產(chǎn)生凝膠，并且反應(yīng)后產(chǎn)生的 HCl，腐蝕性很大，HCl 同時又對水解縮合過程起到催化作用，使反應(yīng)催化

4、劑量很難控制，后期基本被六甲基二硅氧烷取代。 另外將部分Me用乙烯基或氫基、苯基等封端劑代替，可引入乙烯基、氫基和苯基基團，從而提高其性能。 來國橋等采取苯基烷氧基硅烷和乙烯基烷氧基硅烷與六甲基二硅氧烷作M封端劑與水玻璃共同制備了帶有苯基的甲基乙烯基MQ硅樹脂。崔貴銀等崔貴銀等, , 水玻璃法制備水玻璃法制備MQMQ硅樹脂的研究及應(yīng)用進展硅樹脂的研究及應(yīng)用進展. . 化學(xué)工程師化學(xué)工程師, 2013(10): , 2013(10): 第第37-4137-41頁頁. . 投料順序投料順序（1）水玻璃稀釋后加酸中和，然后加MM或Me3SiCl共水解；（2）水玻璃稀釋后同時加酸和MM或Me3SiCl

5、 ；（3）先加酸、MM或Me3SiCl，再加水玻璃共水解。結(jié)論：加料順序?qū)Ψ肿恿亢?M/Q 比值影響較為明顯，先加水玻璃水解到一定程度，再添加六甲基二硅氧烷進行水解縮合的工藝，所得的產(chǎn)物分子量明顯比先加 MM 和乙醇水解后再加水玻璃所得產(chǎn)物的分子量高，M/Q 值差異也很大。 崔貴銀等崔貴銀等, , 水玻璃法制備水玻璃法制備MQMQ硅樹脂的研究及應(yīng)用進展硅樹脂的研究及應(yīng)用進展. . 化學(xué)工程師化學(xué)工程師, 2013(10): , 2013(10): 第第37-4137-41頁頁. . 溶劑溶劑不同溶劑對 MQ 硅樹脂的產(chǎn)能和性能有很大影響，選取乙醇、 甲醇、 丙酮、 異丙醇及甲苯溶劑對 MQ 硅

6、樹脂產(chǎn)率的影響進行了研究。結(jié)論是：以乙醇和異丙醇為溶劑制備的 MQ 硅樹脂的產(chǎn)率較高，摩爾質(zhì)量也較接近；甲醇和丙酮為溶劑制得的 MQ 硅樹脂的產(chǎn)率較低，但摩爾質(zhì)量卻相對較高。采用甲醇和甲苯作溶劑時，容易產(chǎn)生凝膠現(xiàn)象。CN102161765A中溶劑采用由異丙醇和正丁醇質(zhì)量配比為 3 11 1 的配比組成的混合醇。崔貴銀等崔貴銀等, , 水玻璃法制備水玻璃法制備MQMQ硅樹脂的研究及應(yīng)用進展硅樹脂的研究及應(yīng)用進展. . 化學(xué)工程師化學(xué)工程師, 2013(10): , 2013(10): 第第37-4137-41頁頁. . 硅酸酯法硅酸酯法 硅酸鈉法是以正硅酸 作為Q單元，由硅酸酯在酸或堿催化劑作用

7、下水解得到硅酸 , 再進一步縮合 、 加入單官能團有機硅單體 (MM或三甲基氯硅烷等 )封端。 相對于硅酸鈉法而言, 硅酸酯的水解反應(yīng)活性較低、 反應(yīng)較溫和, 因而有利于反應(yīng)的控制。李茹等李茹等, MQ, MQ硅樹脂合成及應(yīng)用研究進展硅樹脂合成及應(yīng)用研究進展. . 有機硅材料有機硅材料, 2010(02): , 2010(02): 第第107-112107-112頁頁 A.Shirahata等人采用先將 MM、 鹽酸 、 水和乙醇的混合物加熱到一定溫度, 再在一定時間內(nèi)滴加正硅酸乙酯的方式 , 獲得了摩爾質(zhì)量分布較窄的 MQ硅樹脂 。因為要保證硅酸酯和三烷基基團之間形成的 Si O- Si 鍵

8、有足夠高的解離速率 , 鹽酸的濃度需在 10%左右 , 這樣正硅酸乙酯水解產(chǎn)物的自縮聚趨勢小, 不易形成凝膠 。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堿催化的方法合成 MQ硅樹脂 。向經(jīng)酸催化縮合的反應(yīng)液加入一定量的甲苯, 調(diào) p H值至堿性, 反應(yīng)

9、一定時間中和 ，然后蒸餾除去甲苯 , 過濾除去析出的固體 NaCl , 得到中性的 MQ硅樹脂甲苯溶液。此法得到的 MQ硅樹脂的烷氧基 、 羥基含量較低 , 而且比較容易控制, 反應(yīng)的產(chǎn)率也比較高 。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