聚硅烷的合成、表征及光敏性研究

STUDIES ON SYNTHESES AND CHARACTERIZATIONS OF POLYSILANES

研究了不同添加量的二甘醇二甲醚和 15-冠醚 - 5两种助溶剂对聚 (甲基苯乙基硅烷 ) (简记为 PM-PES)合成反应的影响 ,结果表明 ,反应体系中添加 10 %二甘醇二甲醚 (二甘醇二甲醚∶甲苯的体积比 ) ,PMPES的产率明显提高 ,分子量趋于单分散分布。并向聚 (甲基环己基硅烷 ) (简记为 PMCS)和甲基环己基硅烷 -甲基苯乙基硅烷共聚物 (甲基环己基二氯硅烷∶甲基苯乙基二氯硅烷的单体摩尔比为 2 .0、1.0和 0 .5时 ,相应的共聚物分别简记为 Copolymer 1,Copolymer 2和 Copolymer 3)的合成反应中添加10 %二甘醇二甲醚助溶剂 ,其产率分别高达 4 7%和 52 %以上 ,Mw 均达 10 5。并用 1H- NMR、IR谱和 UV吸收光谱对所合成的聚硅烷进行了表征。研究了 PMCS膜在空气中经紫外光辐射前后的 IR谱和高效凝胶渗透色谱 ( GPC) ,表明 ,PMCS经紫外光辐照后发生光降解的同时 。

The effects of adding cosolvents of diglyme and 15 crown 5 to the reaction mixture of Wurtz type coupling of dichlorosilanes upon the yield and molecular weight dispersity of poly(methylphenethylsilane)(PMPES) were discussed. The results show that addition of 10%(diglyme∶toluene by volume) diglyme as a cosolvent to the reaction mixture leads to the yield increase of PMPES with a monomodal distribution of molecular weight. Adding 10% (diglyme∶toluene by volume) diglyme to the reaction mixtures, the yields of poly(methylcyclohexylsilane)(PMCS) and copolymers poly(methylcyclohexylsilane co methylphenethylsilane) (the molar ratios to methylcyclohexyldichlorosilane/methylphenethyldichlorosilane are 2.0 , 1.0 and 0.5 , the copolymers are abbreviated by Copolymers 1, 2 and 3, respectively) are 47% and more than 52% , respectively; their molecular weight ( w) almost reach 0 5. These polysilanes were characterized by 1H NMR , IR and UV absorpton spectrum. The photolysis of PMCS film, Which was exposed on broad band UV light in air for different exposure time, was also investigated by GPC and IR spectrum, the results indicate that the molecular weights to PMCS are decreased and siloxane structure in silicon silicon main chain is formed with the processes of photodegradation and photo oxidation.