Stereospecific radical and anionic polymerization utilizing hydrogen bonding and characterization by statistical 2D NMR

通过形成氢键辅助的酰胺类单体配合物，如n-烯丙基-n-叔丁基丙烯酰胺、n-乙烯基-2-吡啶酮、n-正丙基- α -氟丙烯酰胺和n-异丙基丙烯酰胺，不仅在自由基聚合中，而且在阴离子聚合中都成功地诱导了立体特异性。特别是，在手性酒石酸盐存在下，n -烯丙基- n -叔丁基丙烯酰胺的聚合也会引起手性。应用主成分分析的统计二维核磁共振，成功地解释了合成聚合物在立体规则方面的核磁共振谱分配。此外，利用偏最小二乘回归对战术分布进行了精确预测。

Stereospecificities were successfully induced not only in radical polymerization but also in anionic polymerization, with the aid of formation of hydrogen-bond-assisted complexes of amide-containing monomers, such as N-allyl-N-tert-butylacrylamide, N-vinyl-2-pyrrolidone, N-n-propyl-alpha-fluoroacrylamide, and N-isopropylacrylamide. In particular, chirality was also induced in the polymerization of N-allyl-N-tert-butylacrylamide in the presence of chiral tartrates.Statistical 2D NMR, in which principle component analysis was applied, successfully interpreted assignments of NMR spectra of synthetic polymers in terms of stereoregularities. In addition, tacticities distributions were precisely predicted by partial least squares regression.