Cationic polymerization of vinyl ethers with alkyl or ionic side groups in ionic liquids
Cationic polymerization of vinyl ethers with alkyl or ionic side groups in ionic liquids
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DOI：
10.1002/pola.28039
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发表时间：
2016-06
期刊：
影响因子：
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通讯作者：
Hayato Yoshimitsu;Arihiro Kanazawa;S. Kanaoka;S. Aoshima
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文献类型：
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作者：
Hayato Yoshimitsu;Arihiro Kanazawa;S. Kanaoka;S. Aoshima
在离子液体1-丁基-3-辛基咪唑双（三氟甲磺酰基）酰亚胺中，以乙酸乙酯/TiCl 4为引发体系，乙酸乙酯为外加碱，2，6-二叔丁基吡啶为质子捕获剂，进行了异丁基乙烯基醚的可控阳离子聚合。金属卤化物催化剂，离子液体的抗衡阴离子，和添加剂的明智选择是必不可少的控制聚合。在IL中的聚合进行得比在CH 2Cl 2中快得多，这表明由于高极性，IL中的离子活性物种的数量增加。具有相对较窄的分子量分布的聚合物中得到的IL与双（三氟甲磺酰基）酰亚胺（NTF 2-）阴离子，即使在没有添加的碱，这表明可能的相互作用的抗衡离子的IL与不断增长的碳阳离子。此外，直接阳离子聚合的乙烯基醚与侧咪唑盐，1-（2-乙烯氧基乙基）-3-甲基咪唑双（三氟甲磺酰基）酰亚胺，进行在1-甲基-3-辛基咪唑双（三氟甲磺酰基）酰亚胺在均相状态。所得聚合物的溶解度容易通过抗衡阴离子交换来调节。© 2016 Wiley Periodicals，Inc. J.波利姆科学，A部分：聚合物2016，54，1774-1784
Controlled cationic polymerization of isobutyl vinyl ether was demonstrated to proceed in an ionic liquid (IL), 1-butyl-3-octylimidazolium bis(trifluoromethanesulfonyl)imide, using a 1-(isobutoxy)ethyl acetate/TiCl4 initiating system, ethyl acetate as an added base, and 2,6-di-tert-butylpyridine as a proton trap reagent. Judicious choices of metal halide catalysts, counteranions of ILs, and additives were essential for controlling the polymerization. The polymerization proceeded much faster in the IL than in CH2Cl2, indicating an increased population of ionic active species in the IL due to the high polarity. Polymers with a relatively narrow molecular weight distribution were obtained in the IL with a bis(trifluoromethanesulfonyl)imide ( NTf2–) anion even in the absence of an added base, which suggested possible interactions of the counteranion of the IL with the growing carbocations. Moreover, the direct cationic polymerization of a vinyl ether with pendant imidazolium salts, 1-(2-vinyloxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, proceeded in a homogeneous state in 1-methyl-3-octylimidazolium bis(trifluoromethanesulfonyl)imide. The solubilities of the obtained polymers were readily tuned by counteranion exchange. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1774–1784