聚苯基（聚苄基）甲基硅氧烷的氟烷基化反应研究

通过苯基甲基二乙氧基硅烷和苄基甲基二乙氧基硅烷的缩合反应制备了聚苯基甲基和聚苄基甲基硅氧烷。研究了它们与含氟酰基过氧化物间的反应。经酸碱滴定及ＩＲ、＾１Ｈ ＮＭＲ和＾１９Ｆ ＮＭＲ光谱分析确证反应主要生成苯环上氟烷基取代产物。通过测定经氟烷基化后聚硅氧烷处理的玻璃表面的接触角，初步评价了氟烷基化率对其表现性能变化的影响。

Studies on the Reactions of Polyphenylmethyl-and Polybenzylmethyl-Siloxanes with Fluorinated Acyl Peroxide

Polyphenylmethyl and polybenzylmethyl siloxanes were prepared individually by the condensation of phenylmethyldiethoxysilane or benzylmethyldiethoxysilane,and their reactions with fluorinated acyl peroxide(FAP),carried out under mild conditions,were investigated by the titration,IR,1HNMR and 19F NMR spectrometry.It was found that no detectable fluorinated carboxylic acid was formed during the reactions,and the predominantly formed product was the polysiloxane fluoroalkylated in benzene ring.The utilization ratio of fluoroalkyl group in FAP was obviously dependent upon the molar ratios of the reactants and the solvent used,and it was observed that over one fluoroalkyl group in FAP could be introduced into the benzene ring of polyphenylsiloxane.In addition,the surface tension of the polyphenylsiloxanes was markedly reduced by the introduction of fluoroalkyl group at low fluoroalkylation ratios.Based on the experimental observations,we can consider that the FAP was valuable reagents for introducing fluoroalkyl group into polyphenylsilioxanes conveniently,and the reactions,initiated by the thermal decomposition of FAP,possibly underwent via the fluoroalkyl radical attack on the benzene ring.