取代茚基二价稀土配合物催化己内酯开环聚合反应  

Ring-open Polymerization of ε-Caprolactone Catalyzed by Substituted Indenyl Complexes

作　　者：齐民华[1] 沈琪[2] 沈之荃[3] 

机构地区：[1]茂名学院化工学院,茂名525000 [2]苏州大学化学化工系,苏州215006 [3]浙江大学高分子科学与工程系,杭州310027

出　　处：《高等学校化学学报》2007年第12期2418-2421,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20072027)资助

摘　　要：研究了1-环戊烷基茚基二价镱配合物(1-C5H9C9H6)2Yb(THF)2作为单组分催化剂催化己内酯开环聚合反应,考察了催化剂用量、聚合反应时间、聚合反应温度对己内酯聚合反应的影响.结果表明,配合物(1-C5H9C9H6)2Yb(THF)2对己内酯聚合有较高的催化活性;温度升高,聚合反应的转化率增加,但产物的数均分子量及分子量分布无明显变化;所得聚合物分子量分布较窄.其它几种取代茚基稀土配合物也显示出较高的催化活性,其活性有下列次序:(1-C2H5C9H6)2Sm(THF)2>(1-C5H9C9H6)2Sm(THF)>KSm(1-C5H9C9H6)3(THF)3>(1-PhCH2C9H6)2Sm(THF)2>(1-C5H9C9H6)2Yb(THF)2,二价钐配合物较二价镱配合物具有较高的催化活性.通过凝胶渗透色谱法测定了聚合产物的数均分子量及其分布.Abstract The substituted indenyl lanthanide （ Ⅱ ） complex （ C5H9 C9H6 ） 2Yb （THF） 2 applied to catalyzing the polymerization of ^-caprolactone was investigated. The results indicate that the complex （C5H9C9H6）2 Yb（THF）2 as single component catalyst showed a high activity, the conversion of the polymerization and the number-average molecular weight of the polymers were affected by temperature and time of polymerization, and using dose of the catalyst in polymerization process. The number-average molecular weight and molecular weight distribution of the polymer were not sensitive to temperature. But the conversion increased to increasing the polymerization temperature; molecular weight distribution of PCL gained was narrow. Other modified substituted indenyl lanthanide （ Ⅱ ） complexes also showed a good catalytic activity. The order of catalytic activity of the substituted indenyl lanthanide （ Ⅱ ） complexes was as follows： （1-C2H5C9H6）2Sm（THF）2〉（1-C5H9C9H6）2Sm（THF）〉KSm（1-C5H9C9H6）3（THF）3〉（1-PhCH2C9H6）2Sm（THF）2〉（1-C5H9C9H6）2Yb（THF）2, The number-average molecular weight and molecular weight distribution of PCL was measured by GPC.

关 键 词：取代茚基 稀土配合物 己内酯 开环聚合 

分 类 号：O632.62[理学—高分子化学] O614.33[理学—化学]