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OALib Journal期刊
ISSN: 2333-9721
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乙丙共聚物的微结构测定及调控
DOI: 10.3724/SP.J.1105.2013.13111, PP. 1492-1500
Keywords: 共聚合,序列分布,竞聚率,无规共聚物
Abstract:
研究了[N，O]螯合钒（Ⅲ）催化剂（[PhN=C（CH3）CH=C（Ph）O]VCl2（THF）2（2a），[PhN=CHC6H4O]VCl2（THF）2（2b）和[PhN=CHC（Ph）CHO]VCl2（THF）2（2c）催化乙烯和丙烯的共聚合行为.聚合得到了不同丙烯插入率（0mol%~20mol%）和较窄分布（Mw/Mn<3.0）的聚合物.借助高温核磁13C-NMR和高温GPC对所得聚合物的共单体插入率、序列结构、分子量及分布进行测试.研究表明，助催化剂、再活化剂、聚合温度以及反应时间等条件对聚合活性、聚合物分子量以及共单体插入率有重大影响.通过计算亚甲基序列分布（xi）以及聚合物链中连续亚甲基数均序列长度n0和n2+，证实了上述条件还能够对聚合物微结构起到微调作用.此外，虽然催化剂的共聚合活性相当，而且所得聚合物中共单体插入率也很接近，但是通过比较不同催化剂所获的聚合物的xi，n0和n2+，所得聚合物的序列结构却有明显差别，2a催化体系最不容易发生单体的反向插入，而且链结构中存在更多长的亚甲基序列.通过Fineman-Ross方法计算出单体的竞聚率乘积rE×rP≈1.0，说明共单体的插入不受链末端单体单元种类的影响，使得k11/k12=k21/k22，催化剂2a~2c均能催化乙烯与丙烯共聚合得到理想的无规共聚物.
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