Controlled Cationic Polymerization of Sulfide-Containing Vinyl Ethers
Controlled Cationic Polymerization of Sulfide-Containing Vinyl Ethers
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含硫化物乙烯基醚的受控阳离子聚合
DOI：
10.1007/s13233-022-0004-1
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发表时间：
2021
影响因子：
2.4
通讯作者：
Miki Murata
中科院分区：
文献类型：
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作者：
Takeshi Namikoshi;Yuhei Watanabe;Ayaka Kaneda;Kazuma Ishikawa;Shinji Watanabe;Miki Murata
使用HCl/ZnCl 2 、1-(异丁氧基)乙基乙酸酯(IBEA)/Et研究了含硫化物乙烯基醚的活性阳离子聚合，即含烷基硫醚的2-(乙硫基)乙基乙烯基醚(ESEVE)和含芳基硫醚的2-(苯硫基)乙基和2-[4-(甲硫基)苯氧基]乙基乙烯基醚(分别为PSEVE和MSPEVE)。 1.5 AlCl 1.5 和IBEA /Et 1.5 AlCl 1.5 /SnCl 4 作为引发剂。 ESEVE的聚合在单体转化率为35%时终止，未得到高分子量聚合物；相反，ESEVE 中硫部分的亲核性导致环化，形成五元环锍物种。相比之下，当使用苯环上具有亲核性较低的硫部分的PSEVE时，副反应受到抑制，聚合转化率达到88％，得到具有窄分子量分布的高分子量聚合物（M w = 12,500，M w / Mn = 1.18）。此外，MSPEVE聚合过程中没有生成环状锍，其中硫原子距离生成的碳正离子较远；尽管生长物种的寿命很短，但聚合反应仍定量地进行，产生了具有窄分子量分布的高分子量聚合物。特别地，当使用SnCl 4 作为路易斯酸时，获得了具有最窄分布的高分子量聚合物(M w = 13,500，M w / Mn = 1.08)。
The living cationic polymerizations of sulfide-containing vinyl ethers, namely, alkyl-sulfide-containing 2-(ethylthio)ethyl vinyl ether (ESEVE) and arylsulfide-containing 2-(phenylthio)ethyl and 2-[4-(methylthio)phenoxy]ethyl vinyl ethers ( PSEVE and MSPEVE , respectively), were examined using HCl/ZnCl 2 , 1-(isobutoxy)ethyl acetate (IBEA)/Et 1.5 AlCl 1.5 , and IBEA /Et 1.5 AlCl 1.5 /SnCl 4 as initiators. The polymerization of ESEVE terminated at a 35% monomer conversion, and a high-molecular-weight polymer was not obtained; instead, the nucleophilicity of the sulfur moiety in ESEVE led to cyclization, forming five-membered ring sulfonium species. In contrast, the side reactions were suppressed when PSEVE was used, which has a less-nucleophilic sulfur moiety on its benzene ring, and polymerization proceeded to an 88% conversion, affording a high-molecular-weight polymer with a narrow molecular weight distribution ( M w = 12,500, M w / M n = 1.18). Furthermore, cyclic sulfonium was not produced during the polymerization of MSPEVE , in which the sulfur atom was farther from the generated carbocation; the polymerization proceeded quantitatively producing a high-molecular-weight polymer with a narrow molecular weight distribution, despite the short lifetime of the growing species. In particular, a high-molecular-weight polymer with the narrowest distribution ( M w = 13,500, M w / M n = 1.08) was obtained when SnCl 4 was used as the Lewis acid.
DOI：
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发表时间：
2009
期刊：
Polymer Journal 41
影响因子：
--
作者：
Suzuki;Yasuo;Higashihara;Tomoya;Ando;Shinji;Ueda;Mitsuru
通讯作者：
Mitsuru
醇在活性阳离子聚合中的对立功能：从终止剂/抑制剂到有用的引发剂
DOI：
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发表时间：
2009
期刊：
J.Polym.Sci., Part A : Polym.Chem. 47, No16
影响因子：
--
作者：
中谷和裕;大内誠;澤本光男
通讯作者：
澤本光男