Living carbocationic polymerization
Living carbocationic polymerization
复制标题
活性碳正离子聚合
DOI：
10.1007/bf00718919
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发表时间：
1989
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. Mishra;C. C. Charles Chen;J. Kennedy
单官能和双官能交替醇，即，枯基醇（CumOH）、2，4，4-三甲基-2-戊醇（TMOH）、2，6-二羟基-2，4，4，6-四甲基庚烷（TMHDiOH）与BCl 3结合已被证明是异丁烯（IB）在CH 3Cl或CH 2Cl 2溶剂中在−10°至−80°C范围内活性聚合的有效引发体系。聚合的活性性质通过从原点开始的线性Mn相对于形成的聚异丁烯（PIB）的量（WPIB）的图和相应的形成的PIB摩尔数（N）相对于WPIB的水平图来证明。用甲醇产物-氯封端的PIB淬灭。后者产物的定量脱氯化氢产生外烯烃（异亚丙基）端基。这些实验表明，活性碳阳离子聚合实际上很久以前就在这些实验室中进行了（1），但还没有被认识到。
Mono- and bifunctionaltert-alcohols, i.e., cumyl alcohol (CumOH), 2,4,4-trimethyl-2-pentanol (TMPOH), 2,6-dihydroxy-2,4, 4, 6-tetramethylheptane (TMHDiOH), in conjunction with BCl3 have been shown to be efficient initiating systems for the living polymerization of isobutylene (IB) in CH3Cl or CH2Cl2 solvents in the −10° to −80°C range. The living nature of the polymerizations was demonstrated by linear Mn versus amount of polyisobutylene (PIB) formed (WPIB) plots starting at the origin and corresponding horizontal number of PIB moles formed (N) versus WPIB plots. Quenching with methanol producestert-chlorine terminated PIBs. Quantitative dehydrochlorination of the latter products yields exo-olefin (isopropylidene) end groups. These experiments demonstrate that living carbocationic polymerizations have in fact been conducted in these laboratories long ago (1) without having been recognized as such.