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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (22): 2547-2552. 上一篇    下一篇

研究论文

非等速率自缩合乙烯基聚合反应产物的支化度

周志平*,a 张际亮a 盛维琛a 颜德岳b

  

  1. (a江苏大学材料科学与工程学院 镇江 212013)
    (b上海交通大学金属基复合材料国家重点实验室 上海 200240)

  • 投稿日期:2008-01-29 修回日期:2008-07-03 发布日期:2008-11-28
  • 通讯作者: 周志平

Degree of Branching of Products Formed from General Self-Condensing Vinyl

ZHOU, Zhi-Ping *,a ZHANG, Ji-Liang a SHENG, Wei-Chen a YAN, De-Yue b   

  1. (a School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013)
    (b State Key Laboratory of Metal Matrix Composites, Shanghai Jiaotong University, Shanghai 200240)
  • Received:2008-01-29 Revised:2008-07-03 Published:2008-11-28
  • Contact: ZHOU, Zhi-Ping

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被引次数

15 | 3

分析了一般的非等速率自缩合乙烯基聚合反应(SCVP)所生成的超支化聚合物体系的结构单元和支化度. 详细计算了支化度随反应进程(A基团转化率x)、活性的A*和B*基团反应速率比(r)和活化剂/单体物质的量比(α)的变化关系. 对任何指定的r和α组合, 随x的增加而单调增加, 对确定的x, 当α＜x/(1＋ )时, 随r的增加而单调减少, 当 α＞x/(1＋ )时, 随r的变化不再是单调的, 有极大值, 但无论怎样的r和α组合, 最大的支化度都只有0.5. 要想进一步提高产物的支化度, 可以在反应终了时, 在体系中再加入适当的其它单体, 使活化基团全部反应掉, 从而可使支化度达到2α/(1＋α).

关键词: 超支化聚合物, 自缩合乙烯基聚合反应(SCVP), 支化度, 动力学

The structural units and degree of branching of the hyperbranched polymers formed from general self-condensing vinyl polymerization (SCVP) with non-equal reactivities were investigated by the mechanism of kinetics. The dependent relationships of the average degree of branching ( ) on the conversion of group A (x), reactivity ratio of A* to B* (r), and activator/monomer ratio (α) were calculated, respectively. For any specified r and α, increases monotonously with increasing x. For a specified x, decreases monotonously with increasing r under the condition of α＜x/(1＋ ) and has a maximum under the condition of α＞x/(1＋ ). However, the maximum degree of branching does not exceed 0.5 for the SCVP. If some suitable monomers were added into the reaction system at the end of SCVP and all active groups were consumed, a higher value of , 2α/(1＋α), could be obtained.

Key words: hyperbranched polymer, self-condensing vinyl polymerization (SCVP), degree of branching, kinetics