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化学进展 2010, Vol. 22 Issue (06): 1169-1176 前一篇   后一篇

• 综述与评论 •

六甲基环三硅氧烷（D3）阴离子开环聚合机理与动力学研究

蒋波1**; 詹晓力2; 易玲敏3; 张晓东1; 许敏1; 孙立1   

  1. （1.山东省科学院能源研究所，山东 济南 250014； 2. 浙江大学化学工程与生物工程学系，浙江 杭州 310018； 3. 浙江理工大学 先进纺织材料与制备技术教育部重点实验室，浙江 杭州 310018）
  • 收稿日期:2009-08-11 修回日期:2009-08-28 出版日期:2010-06-24 发布日期:2010-05-05
  • 通讯作者: 蒋波 E-mail:jiangb@sderi.cn
  • 基金资助:

    有机硅氧烷侧链的两亲性梳性接枝共聚物的合成及胶束化行为;自热式生物质热解脱焦脱碳制备高品质燃气技术;生物质气化流化床内焦油脱除催化剂的制备与性能研究

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Advances in the Anionic Ring Opening Polymerization Mechanism and Dynamics of Hexamethylcyclotrisiloxane(D3)

Jiang Bo1; Zhan Xiaoli2; Yi Lingmin3; Zhang Xiaodong1; Xu Min1; Sun Li1   

  1. (1. Energy Research Institute of Shandong Academy of Science, Jinan, 250014, China; 2. Department of Chemical and biochemical Engineering, Zhejiang University，Hangzhou 310027，China; 3. Key Laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China)
  • Received:2009-08-11 Revised:2009-08-28 Online:2010-06-24 Published:2010-05-05
  • Contact: Jiang Bo E-mail:jiangb@sderi.cn

本文从聚合机理和反应动力学两方面综述了近年来六甲基环三硅氧烷（D3）的阴离子开环聚合研究进展。Frye等人提出在非极性的碳氢溶剂中会形成引发剂的的三种加成物质，在不加入促进剂的情况下不会进行D3的开环聚合，这一开环聚合机理成为随后D3阴离子开环聚合机理研究的基础，研究者采用MALDI-TOF研究聚合机理得到的结论证实了这一机理的正确性，促进剂、溶剂、引发剂的类型和聚合步骤会改变活性链末端的缔合和解缔合的平衡能力，对D3开环过程中的反咬和再分布副反应有显著影响。D3开环聚合增长速率对单体浓度为一级，不同的促进剂和引发剂会显著改变活性链末端的缔合能力，从而显著影响聚合动力学。

关键词： 六甲基环三硅氧烷, 活性阴离子聚合, 开环聚合, 聚合机理, 动力学

The advantages in the living anionic polymerization of hexamethylcyclotrisiloxane(D3) in terms of polymerization mechanism and dynamics were summarized. Frye suggested that three kinds of initiation compounds were formed in hydrocarbon solvents and no polymerization proceeded without promotor. The mechanism proposed by Frye was accepted by follower and validated by some researches based on MALDI-TOF technology. During the polymerization, promotors, solvents, initiators and process could change the equilibrium between the association and disassociation of living chains, which could effect the “back-biting” and redistribution side reaction in anionic ring opening polymerization of D3. First-order kinetics was obtained in monomer concentration. Promotors and initiators changed the association ability of living chain end, also the polymerization dynamics.

Contents
1 Anionic ring opening polymerization mechanism of D3
1.1 Anionic ring opening polymerization mechanism of D3 without promotor
1.2 Anionic ring opening polymerization mechanism of D3 with promotor
1.3 Anionic ring opening polymerization mechanism of D3 in different solvents
1.4 The effect of process on anionic ring opening polymerization mechanism of D3
1.5 The effect of initiator type on anionic ring opening polymerization mechanism of D3
2 Anionic ring opening polymerization kinetics of D3
2.1 The effect of impurity on anionic ring opening polymerization kinetics of D3
2.2 The effect of promotors on anionic ring opening polymerization kinetics of D3
3 Conclusions

Key words: hexamethylcyclotrisiloxane, living anion polymerization, ring-opening ploymerization, polymerization mechanism, kinetics

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