高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (11): 2293.

• 研究论文 • 上一篇    下一篇

芳氧基稀土化合物催化ε-己内酯开环聚合的链转移反应及Monte Carlo模拟

李新1, 凌君1, 刘金芝1, 田建创2, 孙维林1, 沈之荃1   

  1. 1. 浙江大学高分子科学研究所, 教育部高分子合成与功能构造重点实验室, 杭州 310027;
    2. 浙江工业大学之江学院, 杭州 310024
  • 收稿日期:2010-01-18 出版日期:2010-11-10 发布日期:2010-11-10
  • 通讯作者: 凌君. E-mail: lingjun@zju.edu.cn; 沈之荃. E-mail: zhiquan_shen@163.com
  • 基金资助:

    国家自然科学基金(批准号: 20804033)、国家“九七三”计划项目(批准号: 2005CB623802)和浙江省人事厅留学人员科技活动项目择优资助经费(批准号: [2008]196)资助.

Monte Carlo Simulation and Chain Transfer Reaction in Ring-opening Polymerization of ε-Caprolactone Initiated by Rare Earth Aryloxides

LI Xin1, LING Jun1*, LIU Jin-Zhi1, TIAN Jian-Chuang2, SUN Wei-Lin1, SHEN Zhi-Quan1*   

  1. 1. Key Laboratory of Macromolecule Synthesis and Functionalization of Ministry of Education, Institute of Polymer Science, Zhejiang University, Hangzhou 310027, China;
    2. Zhijiang College of Zhejiang University of Technology, Hangzhou 310024, China
  • Received:2010-01-18 Online:2010-11-10 Published:2010-11-10
  • Contact: LING Jun. E-mail: lingjun@zju.edu.cn; SHEN Zhi-Quan. E-mail: zhiquan_shen@163.com
  • Supported by:

    国家自然科学基金(批准号: 20804033)、国家“九七三”计划项目(批准号: 2005CB623802)和浙江省人事厅留学人员科技活动项目择优资助经费(批准号: [2008]196)资助.

摘要: 设计了三(2,6-二叔丁基-4-甲基苯氧基)稀土配合物[Ln(OAr)3]催化ε-己内酯(CL)开环聚合反应体系中的链转移反应. 证明存在分子内/分子间酯交换反应, 并验证聚合物在链转移反应过程中发生明显的分子量下降和分子量分布变宽. 用Monte Carlo方法对聚ε-己内酯(PCL)链转移过程进行了计算机模拟, 定量解释了链转移过程中环链分子数量比值的增加、环和链分子的数均分子量下降以及分子量分布变宽等现象, 并发现随着链转移反应的进行, 体系的各项参数先后趋于定值, 最终体系将进入“环链平衡”状态.

关键词: 开环聚合, Monte Carlo模拟, 链转移, 环链平衡

Abstract: Transesterification remains an essential cause of the difficulties to carry out living ring-opening polymerization of ε-caprolactone initiated by rare earth tris(2,6-di-tert-butyl-4-methylphenolate)s. This paper investigates chain transfer reaction which significantly decreases molecular weights and broadens the distributions(Mw/Mn) of the polymers. The intra- and inter-molecular transesterification reactions are demonstrated as well. A Monte Carlo program simulates the chain transfer kinetics and quantitatively reproduces the increase in the cyclic molecule number, the decrease in molecule weights and the broadening of Mw/Mn. A ring-chain equilibrium is reached when the number of cyclic molecules keeps constant after enough reaction time.

Key words: Ring-opening polymerization, Monte Carlo simulation, Chain transfer reaction, Ring-chain equilibrium

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