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

N-烯丙基-N-叔丁基丙烯酰胺、N-乙烯基-2-吡咯烷酮、N-正丙基-α-氟丙烯酰胺和N-异丙基丙烯酰胺等含酰胺单体形成氢键辅助络合物，不仅在自由基聚合中成功地诱导了立体专一性，而且在阴离子聚合中也成功地诱导了立体专一性。特别是在手性酒石酸酯的存在下，N-烯丙基-N-叔丁基丙烯酰胺的聚合反应中也出现了手性反应。统计二维核磁共振应用于主成分分析，成功地用立体规整性解释了合成聚合物的核磁共振谱图的归属。此外，通过偏最小二乘回归精确地预测了触觉的分布。

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.