Stereoregularity of polystyrene derivatives, 2. Poly(methoxystyrene)s Obtained by Anionic Catalysts.†
Stereoregularity of polystyrene derivatives, 2. Poly(methoxystyrene)s Obtained by Anionic Catalysts.†
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聚苯乙烯衍生物的立构规整性，2. 通过阴离子催化剂获得的聚（甲氧基苯乙烯）。†
DOI：
10.1002/macp.1982.021830112
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发表时间：
1982
期刊：
影响因子：
--
通讯作者：
K. Matsuzaki
中科院分区：
文献类型：
--
作者：
T. Kawamura;T. Uryu;K. Matsuzaki
的立构规整性的聚（甲氧基苯乙烯）的确定从芳香族C1碳的吸收假设一阶马尔可夫统计举行的聚合以及聚苯乙烯。钠、钾、铷等阳离子在THF中催化合成的聚对甲氧基苯乙烯的立构规整性几乎没有变化，得到了富含间同立构的聚合物，而铯-萘则形成了无规聚合物。对甲氧基苯乙烯在甲苯中的聚合，丁基锂催化聚合得到了富间规聚合物，钠、钾离子催化聚合得到了无规聚合物。由钠或钾阳离子在四氢呋喃中制备的聚邻甲氧基苯乙烯的立构规整性随聚合温度的变化而变化，并且在−78°C下形成高度间同立构的聚合物。在甲苯中得到的聚（邻甲氧基苯乙烯）的结构，显着依赖于引发剂;即，随着抗衡离子的离子半径的大小的增加，聚合物的全同立构规整度降低。讨论了聚合反应的机理和立构规整性的取代基效应。
The stereoregularity of poly(methoxystyrene)s was determined from the absorption of the aromatic C1 carbon assuming a first-order Markov statistics holds for the polymerization as well as polystyrenes. The stereoregularity of poly(p-methoxystyrene)s prepared by sodium, potassium, or rubidium cations as catalysts in THF hardly varied and syndiotactic-rich polymers were obtained, whereas a random polymer was formed with cesium-naphthalene. In the polymerization of p-methoxystyrene in toluene, syndiotactic-rich polymers were obtained with butyllithium and random polymers were prepared by sodium or potassium cations as catalysts. The stereoregularity of poly(o-methoxystyrene)s prepared by sodium or potassium cations in tetrahydrofuran changed with the polymerization temperatures, and highly syndiotactic polymers were formed at−78°C. The structure of poly(o-methoxystyrene)s obtained in toluene, markedly depended on the initiators; that is, with increasing the size of the ionic radius of the counterions, the isotacticity of the polymers decreased. The mechanism of the polymerization and the substituent effect of the stereoregularity are discussed.