具有混合双齿配位基的有机硅聚合物负载硅氢化配位催化剂  

Polysiloxane-Bound Hydrosilylation Coordinate Catalyst with Mixed Bidentate Ligands

作　　者：卢雪然[1] 方国庆[1] 陈远荫[1] 

机构地区：[1]武汉大学化学系,武汉430072

出　　处：《分子催化》1993年第1期1-8,共8页Journal of Molecular Catalysis(China)

基　　金：高等学校博士学科专项科研基金资助课题

摘　　要：4-硫杂-6-氯庚基三甲氧基硅烷以气相法二氧化硅固载化,或以二苯基膦锂膦化再以气相法二氧化硅固载化,合成了具有S、Cl、S、P混合双齿配体的二氧化硅固载聚硅氧烷.二者与氯亚铂酸钾反应,得到相应的铂配合物Si—S,Cl—Pt,Sil—S,P—Pt.研究了它们对烯烃硅氢加成反应的催化性能.Two new type of polysiloxane - bound mixed bidentate metal complexes , silica - bound poly - 4 -thia-6-chlorohexylsilsesquioxane and silica bound poly- 4-thia- 6-diphenylphosphinohexylsesquioxane platinumcomplexes, have been synthesized from 3- mercaptopropyl- trimethoxysilane via thioetherif ication with 2-chloroethyl tosylate, followed by immobilization on silica directly, or further reacting with lithium diphenyl phosphide and then immobilization on silica, followed by treating with potassium chloroplatinite in acetone under Ar atmosphere. The structures of the platinum complexes were characterized by elemental analysis and XPS. It was found that the platinum complexes are efficient catalysts for the hydrosilylation of olefins with triethoxysilane. Six α-olefins: styrene, dec-1-ene, dodec-1-ene, allyl glycidyl ether, allyl benzene, and allyl phenyl ether were used as substrate to evaluate the catalytic activity and selectivity of the complexes. Terminal addition products were obtained from all olefins except for styrene. The yields of adducts varied from 66 to 89%. No induction period has been observed at the reaction temperature. Mercury was used as a selective poison to explore the nature of the catalytic reaction, i. e. it is heterogeneous or homogeneous in nature. The results showed that the hydrosilylation proceeded smoothly in spite of the addition of mercury. Furthermore changing the sequence of adding reaction mass had little influence on hydrosilylation. The platinum complexes could be recovered and reused, but the reaction velocity decreased gradually in the sequential runs. Based on the above experiments, the reaction mechanism was discussed.

关 键 词：催化剂 硅氢化催化剂 聚硅氧烷 

分 类 号：O643.36[理学—物理化学]