Free-Radical Polymerization and Copolymerization of Acrylimides: Homopolymers of Oxazolidinone Acrylimide and Control of 1,5-Stereochemistry in Copolymers Derived from Isobutylene and an Oxazolidinone Acrylimide
Free-Radical Polymerization and Copolymerization of Acrylimides: Homopolymers of Oxazolidinone Acrylimide and Control of 1,5-Stereochemistry in Copolymers Derived from Isobutylene and an Oxazolidinone Acrylimide
复制标题
丙烯酰亚胺的自由基聚合和共聚：恶唑烷酮丙烯酰亚胺均聚物以及异丁烯和恶唑烷酮丙烯酰亚胺衍生的共聚物中 1,5-立体化学的控制
DOI：
10.1021/jo9914420
复制
发表时间：
2000
影响因子：
3.6
通讯作者：
N. Porter
中科院分区：
文献类型：
--
作者：
Christopher L. Mero and;N. Porter
研究了N-丙烯酰亚胺的聚合和共聚反应。因此，路易斯酸被用来控制恶唑烷酮和异丁烯衍生的N-丙烯酰亚胺的自由基共聚合。适当的Lewis酸(SC(OTf)3)与无手性和手性恶唑烷酮助剂的丙烯酰亚胺络合，可以制备交替的1：1共聚物，通过积分共聚物的1H核磁共振谱确定。以手性恶唑烷酮为原料，在Lewis酸存在的情况下，合成了高等规度的共聚物。核磁共振(~1H和~(13)C)分析表明，某些手性丙烯酰亚胺的m/r二元比率超过95：5。还进行了母体无手性丙烯酰胺的均聚反应。核磁共振分析表明，在−78°C下进行的聚合中，m/r二联体比低至0.25时，均聚物对r二联体具有依赖温度的偏好。
The polymerization and copolymerization of N-acryloyl imides was investigated. Thus, Lewis acids were used to control the free-radical copolymerization of N-acryloyl imides derived from oxazolidinones and isobutylene. Complexation of an appropriate Lewis acid (Sc(OTf)3) to acrylimides of achiral and chiral oxazolidinone auxiliaries allowed the preparation of alternating 1:1 copolymers as determined from integration of the copolymer 1H NMR spectra. Highly isotactic copolymers were made when chiral oxazolidinones were used as starting material if Lewis acid was present in the reaction. NMR analysis (1H and 13C) of the copolymers showed that the m/r dyad ratio was in excess of 95:5 for some of the chiral acrylimides. Homopolymerization of the parent achiral acrylamide was also carried out. NMR analysis of the homopolymer showed a temperature-dependent preference for the r dyad with a m/r dyad ratio as low as 0.25 in polymerizations carried out at −78 °C.