Anionic polymerization of <i>N</i>
,<i>N</i>
-dialkyl-2-methylenebut-3-enamide: Effect of alkyl substituents on polymerization behavior
作者:Katsuhiko Takenaka、Natsuyo Shibata、Akihiko Oshikiri、Masamitsu Miya、Hiroki Takeshita、Tomoo Shiomi
DOI:10.1002/pola.24146
日期:2010.9.1
Anionic polymerizations of three 1,3‐butadiene derivatives containing different N,N‐dialkyl amide functions, N,N‐diisopropylamide (DiPA), piperidineamide (PiA), and cis‐2,6‐dimethylpiperidineamide (DMPA) were performed under various conditions, and their polymerization behavior was compared with that of N,N‐diethylamide analogue (DEA), which was previously reported. When polymerization of DiPA was
在不同条件下进行了三种具有不同N,N-二烷基酰胺官能团,N,N-二异丙基酰胺(DiPA),哌啶酰胺(PiA)和顺式-2,6-二甲基哌啶酰胺(DMPA)的1,3-丁二烯衍生物的阴离子聚合并将它们的聚合行为与N,N进行比较先前已报道过二乙酰胺类似物(DEA)。当在-78°C下用钾抗衡离子进行DiPA的聚合时,仅形成痕量的低聚物,而当DiPA在0°C下在LiCl存在下聚合时,以中等收率获得了分子量分布窄的聚合物。 。当在20℃的较高温度下进行聚合时,观察到分子量降低和分子量分布变宽,这大概是由于上限温度的影响。在DMPA的情况下,在0°C时不会形成聚合物,而分子量分布相对较宽的聚合物(M w / M n= 1.2)在20°C下获得。PiA的聚合速率比其他单体的聚合速率快得多,即使在-78°C下24小时仍可以高收率获得聚(PiA)。所得聚合物的微观结构仅对聚(DMPA)为1,4-,而1,2-结构的