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首页> 外文期刊>Journal of Applied Polymer Science >Direct synthesis of highly reactive polyisobutylenes via cationic polymerization of isobutylene co-initiated with TiCl4 in nonpolar hydrocarbon media
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Direct synthesis of highly reactive polyisobutylenes via cationic polymerization of isobutylene co-initiated with TiCl4 in nonpolar hydrocarbon media

机译：在非极性烃介质中通过与TiCl4共引发的异丁烯的阳离子聚合直接合成高反应性的聚异丁烯

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摘要

Living cationic polymerization of isobutylene (IB) with 1-chlorine-2,4,4-trimethyl pentane (TMPCl)/TiCl4/isopropanol (iPrOH) or isoamylol (iAmOH) has been achieved in the presence of 2,6-di-tert-butylpyridine (DtBP) at -80 degrees C. Polyisobutylenes with nearly theoretical M-n based on TMPCl molecules and more than 90% of tert-chlorine-end groups could be obtained at high [TMPCl]. The -proton elimination from CH3 in growing chain ends increased with increasing polymerization temperature and decreasing solvent polarity. A chain-transfer-dominated cationic polymerization process with H2O/TiCl4/iAmOH could be achieved in n-hexane at -30 degrees C. The monomer conversion and content of exo-olefin end groups increased while molecular weight decreased with increasing [iAmOH]. To the best of our knowledge, this is the first example to achieve the direct synthesis of highly reactive polyisobutylene with low M-n of 1200 approximate to 1600, carrying more than 80% of exo-olefin terminals by a single-step process via cationic polymerization co-initiated by TiCl4 in nonpolar hydrocarbon. (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42232.
机译：异丁烯（IB）与1-氯-2,4,4-三甲基戊烷（TMPC1）/ TiCl4 /异丙醇（iPrOH）或异戊醇（iAmOH）的活性阳离子聚合已在2,6-二叔丁基存在下实现-丁基吡啶（DtBP）在-80摄氏度。基于TMPCl分子和90％以上的叔氯端基，可以得到接近理论上的Mn的聚异丁烯。随着聚合温度的升高和溶剂极性的降低，从生长链端中CH3中的-质子消除量增加。在正己烷中，在-30℃下，可以用H2O / TiCl4 / iAmOH进行链转移为主的阳离子聚合过程。随着[iAmOH]的增加，单体转化率和外烯烃端基含量增加。据我们所知，这是第一个通过阳离子聚合反应的一步法直接合成具有1200的低Mn的高反应性聚异丁烯的第一个实例，该低Mn约为1600。 -由非极性烃中的TiCl4引发。 （c）2015 Wiley Periodicals，Inc. J. Appl。 Polym。科学2015，132，42232。

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