Electron donors in carbocationic polymerization
Electron donors in carbocationic polymerization
复制标题
碳阳离子聚合中的电子给体
DOI：
10.1007/bf01153431
复制
发表时间：
1988
期刊：
影响因子：
3.2
通讯作者：
J. Kennedy
中科院分区：
文献类型：
--
作者：
M. Zsuga;J. Kennedy
概述低分子量（<$Mn = 900-5000）窄分子量分布（MWD;<$Mw/Mn = 1.1-1.2）以反式-2，5-二甲基-2，5-二乙酰氧基-3-己烯（DiOAcDMeH 6）/BCl 3为引发体系，在给电子体（艾德）二甲基亚砜（DMSO）存在下，于-30 °C的氯甲烷稀释液中合成了氯遥爪聚异丁烯（PIB）。聚合的活性特征通过线性Mn对Wp（聚合物的重量）图证明，该线性Mn对Wp（聚合物的重量）图从原点开始，斜率为1/[Io]（其中[Io] =引发剂浓度）。DMSO降低了聚合的总速率，然而，它将引发剂效率（Ieff）提高到约100%。数字平均值- 1H NMR测得氯端官能度为-Fn=1.97±0.04。聚合机理的细节进行了讨论。这是第一次窄MWDtert。氯遥爪PIB已经在接近氯甲烷的回流温度下制备。
SummaryLow molecular weight (¯Mn ∼900–5000) narrow molecular weight distribution (MWD; ¯Mw/Mn = 1.1–1.2)tert.-chlorine telechelic polyisobutylenes (PIBs) have been synthesized by the use of thetrans-2,5-dimethyl-2,5-diacetoxy-3-hexene (DiOAcDMeH6)/BCl3 initiating system in the presence of the electron donor (ED) dimethyl sulfoxide (DMSO) in methyl chloride diluent at −30°C. The living character of the polymerization was demonstrated by linear Mn versus Wp (weight of polymer) plots starting at the origin with the slope of 1/[Io] (where [Io] = initiator concentration). DMSO reduces the overall rate of polymerization, however, it increases the initiator efficiency (Ieff) to ∼100%. The number averagetert.-chlorine end functionality is -Fn=1.97±0.04, by1H NMR spectroscopy. Polymerization mechanistic details are discussed. This is the first time narrow MWDtert.-chlorine telechelic PIB has been prepared close to the reflux temperature of methyl chloride.