ROMP of n-alkyl norbornene dicarboxyimides:: from classical to well-defined initiators, an overview
ROMP of n-alkyl norbornene dicarboxyimides:: from classical to well-defined initiators, an overview
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DOI：
10.1016/s1381-1169(00)00227-2
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发表时间：
2000-10-23
影响因子：
--
通讯作者：
Leejarkpai, T
中科院分区：
文献类型：
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作者：
Khosravi, E;Feast, WJ;Leejarkpai, T
使用广泛的引发剂的n-烷基异冰片烯二羧酰亚胺的开环易位聚合（ROMP）已被广泛研究。以WCl_6/Me_4Sn（I）和MoCl_5/Me_4Sn（II）为引发剂，外消旋N-烷基双烯二羧酰亚胺的开环聚合分别得到了反式亚乙烯基含量为63%和85%的聚合物。相反，内异构体在几次尝试中的任何一次都不能聚合。使用定义明确的引发剂Mo（CH-t-Bu）（N-2，6-i-Pr 2C 6 H3）（OCMe 3）（2）（III）和Mo（CHCPhMe 2）（N-2，6-i-Pr 2C 6 H3）（OCMe（CF 3）（2））（2）（IV）聚合外-和内-n-烷基异冰片烯二羧酰亚胺。在外型异构体的情况下，III得到具有97%反式亚乙烯基含量的聚合物，IV得到具有约30%反式亚乙烯基含量的聚合物。在内型异构体的情况下，III得到具有93%反式亚乙烯基含量的聚合物，IV得到具有57%反式亚乙烯基含量的聚合物。这些聚合的活性性质通过合成AB二嵌段共聚物通过顺序加入单体来证实。外-和内-n-烷基异冰片烯二羧酰亚胺也使用定义明确的引发剂RuCl 2（CHPh）（PCy 3）（2）（V）聚合。由外型单体和内型单体得到的聚合物中反式亚乙烯基含量分别为82%和100%。使用定义明确的引发剂m-V的聚合反应过程通过H-INMR跟踪，并且引发剂和增长的亚烷基信号都是可观察到的。在所有情况下，C-13 NMR中骨架共振的多重性和加宽与无规微结构相关的重叠环境的多重性是一致的。(C)2000爱思唯尔科技有限公司。保留所有权利。
The ring opening metathesis polymerisation (ROMP) of n-alkyl norbornene dicarboxyimides using a wide range of initiators has been extensively studied. ROMP of exo-n-alkyl norbornene dicarboxyimides with classical initiators WCl6/Me4Sn (I) and MoCl5/Me4Sn (II) gave polymers with 63% and 85% trans vinylene content, respectively. In contrast, the endo-isomer could not be polymerised in any of several attempts. Both exo-and endo-n-alkyl norbornene dicarboxyimides were polymerised using well-defined initiators Mo(CH-t-Bu)(N-2,6-i-Pr2C6H3)(OCMe3)(2) (III) and Mo(CHCPhMe2)(N-2,6-i-Pr2C6H3)(OCMe(CF3)(2))(2) (IV). In the case of exo isomers, III gave polymers with 97% trans vinylene content and IV gave polymers with about 30% trans vinylene content. In the case of endo isomer, III gave polymer with 93% trans vinylene content and IV gave polymer with 57% trans vinylene content. The living nature of these polymerisations was confirmed by synthesising AB diblock copolymers by sequential addition of monomers. Both exo- and endo-n-alkyl norbornene dicarboxyimides were also polymerised using well-defined initiator RuCl2(CHPh)(PCy3)(2) (V). The polymers obtained from exo and endo monomers contain 82% and 100% trans vinylene content respectively. The course of the polymerisation reactions using well-defined initiators m-V were followed by H-1 NMR and both the initiator and propagating alkylidenes signals were observable. The multiplicity and broadening of the backbone resonances in C-13 NMR, in all cases, is consistent with a multiplicity of overlapping environments associated with atactic microstructures. (C) 2000 Elsevier Science B.V. All rights reserved.