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首页> 外文期刊>Journal of Macromolecular Science. Pure and Applied Chemistry >Living carbocationic oligomerization of isobutylene by tertiary alcohol/BCl_3/1-methyl-2-pyrrolidinone initiating systems. kinetic study
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Living carbocationic oligomerization of isobutylene by tertiary alcohol/BCl_3/1-methyl-2-pyrrolidinone initiating systems. kinetic study

机译：叔醇/ BCl_3 / 1-甲基-2-吡咯烷酮引发体系对异丁烯的活性碳阳离子低聚。动力学研究

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摘要

Low molar mass (Mn<4000 g.mol~(-1)), narrow molar mass distribution (Mw | Mn =1.1-1.3) linear #alpha#-(tert-butyl) #omega#-(tert-chloro) and #alpha#-cumyl #omega#-(tert-chloro) oligoisobutylenes (PIBs) were synthesized using two initiating systems: 2,4,4-trimethyl-pentan-2-ol (TMPOH)/BCl_3/-40 deg C and 2-phenylpropan-2-ol (CumOH)/BCl_3/-70 deg C in the presence of an efficient electron-pair donor (ED), 1-methyl-2-pyrrolidinone (NMP) in methyl chloride. The kinetics of oligomerization were investigated. In these two systems, similar polymerization mechanisms were observed with, nevertheless, a slight difference of growing species behavior in the early polymerization steps. The initiation and propagation rate constants were determined; their values are low showing that the addition of NMP to these initiating systems leads to controlled carbocationic polymerizations. Moreover, the living character of the polymerization was demonstrated.
机译：低摩尔质量（Mn <4000 g.mol〜（-1）），窄摩尔质量分布（Mw | Mn = 1.1-1.3）线性#alpha＃-（叔丁基）#omega＃-（叔氯）和使用两个引发系统合成＃alpha＃-枯基#omega＃-（叔氯）低聚异丁烯（PIB）：2,4,4-三甲基戊-2-醇（TMPOH）/ BCl_3 / -40℃和2 -苯基丙-2-醇（CumOH）/ BCl_3 / -70摄氏度，在有效的电子对供体（ED），1-甲基-2-吡咯烷酮（NMP）在氯甲烷中的存在下。研究了低聚反应的动力学。在这两个系统中，观察到相似的聚合机理，但是在早期聚合步骤中，生长物种的行为略有不同。确定了起始和传播速率常数。它们的值低，表明向这些引发体系中添加NMP会导致受控的碳阳离子聚合。另外，对聚合的活性特性进行了说明。

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