Helix-Sense-Selective Radical Polymerization of N-(Triphenylmethyl)methacrylamides and Properties of the Polymers
Helix-Sense-Selective Radical Polymerization of N-(Triphenylmethyl)methacrylamides and Properties of the Polymers
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DOI：
10.1295/polymj.pj2006087
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发表时间：
2006-12
期刊：
影响因子：
2.8
通讯作者：
Naohiro Hoshikawa;C. Yamamoto;Y. Hotta;Y. Okamoto
中科院分区：
文献类型：
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作者：
Naohiro Hoshikawa;C. Yamamoto;Y. Hotta;Y. Okamoto
使用自由基引发剂聚合N-（三苯基甲基）甲基丙烯酰胺（TrMAM）和N-[二（4-丁基苯基）-苯基甲基]甲基丙烯酰胺（DBuTrMAM）。聚（TrMAM）不溶于普通有机溶剂，而聚（DBuTrMAM）溶于氯仿和THF。将两种聚合物溶解在浓H2SO 4中，伴随着侧基的裂解，得到聚（甲基丙烯酰胺）（聚（MAM））。聚合物在D_2SO_4中的~ 1H NMR表明，在低温下得到的聚合物接近100%全同立构。全同立构规整度接近100%的聚MAM具有结晶性。聚（DBuTrMAM）在氯仿中形成溶致结晶相。在各种手性添加剂的存在下，单体的自由基聚合产生具有普遍螺旋度的光学活性聚合物。光学活性聚（TrMAM）表现出较低的手性识别。
N-(Triphenylmethyl)methacrylamide (TrMAM) and N-[di(4-butylphenyl)-phenylmethyl]methacrylamide (DBuTrMAM) were polymerized using a radical initiator. The obtained poly(TrMAM) was insoluble in common organic solvents, but poly(DBuTrMAM) was soluble in chloroform and THF. Both polymers were dissolved in conc. H2SO4 accompanied by cleavage of the side groups to give poly(methacrylamide) (poly(MAM)). The 1H NMR of the polymers in D2SO4 indicated that the polymers obtained at low temperature were nearly 100% isotactic. The poly(MAM) with almost 100% isotacticity showed a crystallinity. The poly(DBuTrMAM) formed a lyotropic crystalline phase in chloroform. The radical polymerization of the monomers in the presence of various chiral additives produced optically active polymers having a prevailing helicity. The optically active poly(TrMAM) exhibited a low chiral recognition.