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取代茚基二价稀土配合物催化己内酯开环聚合反应

齐民华1,2, 沈琪2, 沈之荃3   

    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
  • 收稿日期:2007-05-14 修回日期:1900-01-01 出版日期:2007-12-10 发布日期:2007-12-10
  • 通讯作者: 齐民华

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

QI Min-Hua1,2*, SHEN Qi2, SHEN Zhi-Quan3   

    1. Institute of Chemical Engineering, Maoming College, Maoming 525000, China;
    2. Department of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215006, China;
    3. Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
  • Received:2007-05-14 Revised:1900-01-01 Online:2007-12-10 Published:2007-12-10
  • Contact: QI Min-Hua

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.

关键词: 取代茚基, 稀土配合物, 己内酯, 开环聚合

Abstract: The substituted indenyl lanthanide(Ⅱ) complex (C5H9C9H6)2Yb(THF)2 applied to catalyzing the polymerization of ε-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.

Key words: Substituted indenyl, Lanthanide complex, ε-Caprolactone, Ring-opening polymerization

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