Anionic polymerization of N,N‐dialkyl‐2‐methylenebut‐3‐enamide: Effect of alkyl substituents on polymerization behavior
Anionic polymerization of N,N‐dialkyl‐2‐methylenebut‐3‐enamide: Effect of alkyl substituents on polymerization behavior
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N,N-二烷基-2-亚甲基丁-3-烯酰胺的阴离子聚合：烷基取代基对聚合行为的影响
DOI：
10.1002/pola.24146
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发表时间：
2010
期刊：
影响因子：
--
通讯作者：
T. Shiomi
中科院分区：
文献类型：
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作者：
K. Takenaka;N. Shibata;Akihiko Oshikiri;M. Miya;Hiroki Takeshita;T. Shiomi
在不同条件下进行了N，N-二烷基酰胺、N，N-二异丙酰胺（DiPA）、哌啶酰胺（PiA）和顺式-2,6-二甲基哌啶酰胺（DMPA） 3种1,3-丁二烯衍生物的阴离子聚合，并将其聚合行为与先前报道的N，N-二乙基酰胺类似物（DEA）进行了比较。当DiPA在- 78°C下与钾离子进行聚合时，只形成微量的低聚物，而当DiPA在0°C下与LiCl存在下聚合时，以中等产率获得了分子量分布窄的聚合物。在20℃的较高温度下进行聚合时，分子量下降，分子量分布展宽，可能是由于顶限温度的影响。以DMPA为例，在0℃下未形成聚合物，在20℃下得到相对较宽的分子量分布（Mw/Mn = 1.2）的聚合物。PiA的聚合速度比其他单体快得多，在- 78°C条件下，24 h也能获得高收率的聚（PiA）。所得聚合物的微观结构仅为1,4-聚（DMPA），而聚（DiPA）和聚（PiA）中含有20-30%的1,2-结构。©2010 Wiley期刊公司[J] .高分子材料科学与工程学报，2009,31 (2):444 - 444
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 performed at −78 °C with potassium counter ion, only trace amounts of oligomers were formed, whereas polymers with a narrow molecular weight distribution were obtained in moderate yield when DiPA was polymerized at 0 °C in the presence of LiCl. Decrease in molecular weight and broadening of molecular weight distribution were observed when polymerization was performed at a higher temperature of 20 °C, presumably because of the effect of ceiling temperature. In the case of DMPA, no polymer was formed at 0 °C and polymers with relatively broad molecular weight distributions (Mw/Mn = 1.2) were obtained at 20 °C. The polymerization rate of PiA was much faster than that of the other monomers, and poly(PiA) was obtained in high yield even at −78 °C in 24 h. The microstructure of the resulting polymers were exclusively 1,4- for poly(DMPA), whereas 20–30% of the 1,2-structure was contained in poly(DiPA) and poly(PiA). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3714–3721, 2010