StBA RAFT共聚全程动力学研究

文档编号:HG158  文档字数:9536,页数:33

摘要：可逆加成－断裂链转移(Reversible addition-fragmentation chain transfer polymerization, RAFT)聚合是九十年末兴起的可控/“活性”自由基聚合方法(Controlled/living radical polymerization, CLRP)之一。它结合了传统自由基聚合和活性离子聚合的优点。活性自由基聚合的“活性”特征将单个聚合物链的生长时间延长到小时的量级，这就使得用工程的方法对聚合物的链结构进行控制成为可能。若要能建立一个基于模型的半连续程序进料平台技术，利用这一平台技术实现对聚合物链结构的控制将具有很大的理论和实践意义。
 本文在已有RAFT共聚动力学模型的基础上，首先合成了一种RAFT试剂——苄基二硫代异丁酸酯（BDIB）,然后研究了苯乙烯（St）/丙烯酸丁酯（BA）在BDIB调控下的共聚动力学行为，并根据所得动力学实验数据，优化了RAFT共聚动力学模型参数，从而使得共聚动力学模型能很好地预测St/BA RAFT共聚的动力学，为利用半连续程序进料法，实现对聚合物链结构的精确控制奠定了良好的基础。
关键词：苯乙烯；丙烯酸丁酯；动力学；RAFT聚合

Abstract: Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the controlled/living free radical polymerization techniques.  CLRP combines the advantages of conventional free radical polymerization and living ionic polymerization.  The ‘living’ nature of CLRP gives individual chains a time period of hours to grow and allows us to control chain microstructure by engineering means.  It will be critically important in theoretical and application areas by developing a model-based semi-batch monomer feeding policy to tailor-make copolymer chain structure via CLRP.
 In this paper, we synthesized a kind of RAFT agent----benzyl dithioisobutyrate (BDIB) and investigated the kinetic behavior of St/BA copolymerization mediated by BDIB.  The results of the experiments show that BDIB can well control the styrene (St)/butyl acrylate (BA) copolymerization.  Furthermore, with these experimental data, the adjusted parameters in the kinetic model are optimized.  Thus, the model predictions are in a good agreement with the experimental data in polymerization rate. This will help us to precisely control the chain structure through semi-batch operation.

Keywords：Styrene; Butyl acrylate; Kinetics; RAFT polymerization
目  录
中文摘要 I
英文摘要 II
目录 III
1.绪论 1
  1.1 研究背景、目的及意义 1
  1.2 文献综述 2
   1.3 主要研究内容 8
2.实验部分 9
  2.1 原料来源及精制 9
  2.2 苄基二硫代异丁酸酯（BDIB）的合成 10
  2.3 间歇聚合操作 10
  2.4 分析与表征 10
3.结果与讨论 12
  3.1 RAFT的结构及其选择性 12
  3.2 BDIB调控下St/BA共聚动力学 14
  3.3 BDIB调控下苯乙烯/丙烯酸丁酯共聚全程动力学及参数拟合 16
4.总结 18
致谢 19
参考文献 20
附录A 22
附录B 24

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