有机硅聚合物过渡金属络合催化剂的合成与活性——Ⅴ 聚—4—氧杂—6—羟基—7—二苯膦基庚基硅氧烷钯络合物的合成及其在烯烃氢化中的催化活性

有机硅聚合物过渡金属络合催化剂的合成与活性——Ⅴ 聚—4—氧杂—6—羟基—7—二苯膦基庚基硅氧烷钯络合物的合成及其在烯烃氢化中的催化活性 THE SYNTHESIS AND ACTIVITY OF SILICONE SUPPORTED TRANSITION METAL COMPLEX CATALYSTS Ⅴ. THE SYNTHESIS OF POLY—OXA—7—DIPHENYLPH—OSPHINO—6—HYDROXYHEPTYLSILOXANE PALLADI—UM COMPLEX AND ITS CATALYTIC ACTIVITY FOR HYDROGENATION OF OLEFINS 陈远萌 first-author 刘基万 林颐庚 肖超勃 麦才淞 以烟雾法二氧化硅为载体的聚—4—氧杂—6—羟基—7—二苯膦基庚基硅氧烷和氯亚钯酸钠四水合物作用制备的高分子钯络合物,在30—50℃和适当的溶剂中对烯烃的常压加氢具有良好的活性和选择性。苯乙烯、α—甲基苯乙烯、丙烯酸及其酯可在1.5—2.5小时内平稳地氢化完全,环戊二烯、α—蒎烯、芳基、羧基和酯基在同样条件下不能氢化。甲醇、异丙醇、醋酸等质子溶剂对其催化活性有显著的促进作用,但某些非质子溶剂,如二甲基甲酰胺、苯也有良好效果。水也可以作为反应介质。因此,这一聚合物催化剂特别适用于和芳基、氰基、羧基及酯基直接相连的双键的氢化。除此之外,它还可以回收再用而催化活性没有显著降低。 A polymer-palladium complex prepared from sodium chloropalladate tetrahydrate and poly-oxa-7-diphenylphosphino-6-hydroxyheptylsiloxane supported on fumed silica was described. The title catalyst displayed a high activity and selectivity for hydrogenation of olefins in proper solvents under an atmospheric pressure of hydrogen at 30—50℃. Styrene, α-methylstyrene, acrylonitrile, acrylic acid and its ester could be hydrogenated smoothly within 1.5—2.5 hours, cyclopentadiene, α-pinene, aromatic, cyano, carboxy and ester groups could not be hydrogenated under same conditions. Protic solvents, such as methanol, i-propanol, acetic acid, remarkably promoted the catalytic activity of the palladium complex, but some nonprotic solvents, such as DMF, benzene, also exhibited good behaviour. It was interesting to note that water could be used as reaction medium. Thus, the polymer catalyst was especially suitable for the hydrogenation of the ethylenic double bonds which are linked to aromatic, cyano, carboxy and ester groups. Furthermore, it could be reused several times without serious loss of activity. 1982-03-01 2021-04-01 3