含硫氮双齿配位体有机硅聚合物负载的铂络合物的催化作用

THE SYNTHESIS AND ACTIVITY OF POLY γ N (β PHENSULFIDE) ETHYLAMINOPROPYLSILOXANE PLATINUM COMPLEX

含硫氮双齿配位体的有机硅聚合物和Ｋ２ＰｔＣｌ６反应，得到固载在二氧化硅上的聚－γ－Ｎ（β－苯硫基）乙基胺丙基硅氧烷铂络合物，并用ＸＰＳ研究其结构．选用十二烯、癸烯、苯基烯丙醚、烯丙基苯、氯代十一烯、丁烯腈等７种底物与三乙氧基硅烷进行硅氢加成反应，另用丁烯进行氢化，均选用铂络合物为催化剂，实验结果表明铂络合物显示出良好的催化活性．在１．２～２．２ｈ之间，含有４．９×１０－６ｍｏｌ铂络合物可将苯基烯丙醚、十二烯、癸烯、烯丙基苯、氯代十一烯５种底物硅氢化，产率均在７９％以上，其选择性在９８％～１００％之间．对丁烯的催化加氢效果也很好，第一次脉冲氢化时，直接形成０．０４５～０．

The poly γ N (β phensulfide) ethylamino propylsiloxane platinum complex has been synthesized. The structures of the platinum complex were characterized by analysis and XPS. It was found that the platinum complex is efficient catalyst for the hydrosilylation of olefins with triethoxysilane. Seven α olefins:decene, dodecene, allyl benzene,allyl phenyl enter,chlorundecene, methyl butyl acrylate, allyl cyanide were used as substrate to evaluate the catalytic activity and selectivity of the complex. Terminal addition products were obtained from all olefins.More than 79 of decene, dodecene, chlorundecene, metyl butyl acrylate, allyl phenyl ether (10×10 -3 mol) were hydrosilylation with complex containing 4.9×10 -6 mol platinum with in 1.2 2.2 h. Tne selectivity reaches 96% to 100%. On the other hand, platinum complex was subjected to single turnover (STO) reaction characterization and displayed the higher activity for the hydrogenation of I butene,butane was formed on direct hydrogenation sites (0.045 mol to 0.049 mol butane/mol Pt).