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

被引:35
作者
Mero, CL
Porter, NA [2 ]
机构
[1] Duke Univ, Dept Chem, Durham, NC 27708 USA
[2] Vanderbilt Univ, Dept Chem, Nashville, TN 37235 USA
关键词
D O I
10.1021/jo9914420
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
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 H-1 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 (H-1 and C-13) 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 mlr dyad ratio as low as 0.25 in polymerizations carried out at -78 degrees C.
引用
收藏
页码:775 / 781
页数:7
相关论文
共 32 条
[1]  
[Anonymous], ANGEW CHEM INT EDIT
[2]  
ENDO T, 1969, MAKROMOLEKUL CHEM, V123, P46
[3]  
EVANS, 1990, ORGANIC SYNTHESIS, V68, P77
[4]  
FELDMAN KS, 1988, J AM CHEM SOC, V110, P330
[5]  
FLORJANCZYK Z, 1983, MAKROMOL CHEM, V184, P2457
[6]  
FLORJANCZYK Z, 1982, MAKROMOL CHEM, V183, P1081
[7]  
FLORJANCZYK Z, 1978, MAKROMOL CHEM, V179, P287
[8]   STEREOSELECTIVE CHELATION-CONTROLLED REDUCTION OF ALPHA-IODO-BETA-ALKOXY ESTERS UNDER RADICAL CONDITIONS [J].
GUINDON, Y ;
LAVALLEE, JF ;
LLINASBRUNET, M ;
HORNER, G ;
RANCOURT, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (25) :9701-9702
[9]   STEREOSELECTIVE REDUCTION OF ACYCLIC ALPHA-BROMO ESTERS [J].
GUINDON, Y ;
YOAKIM, C ;
LEMIEUX, R ;
BOISVERT, L ;
DELORME, D ;
LAVALLEE, JF .
TETRAHEDRON LETTERS, 1990, 31 (20) :2845-2848
[10]   POLY[2,2-DIMETHYL-4-(METHOXYLCARBONYL)BUTYLENE] - SYNTHESIS WITH AN ETHYLALUMINUM SESQUICHLORIDE-PEROXIDE INITIATOR AND NMR CHARACTERIZATION [J].
KUNTZ, I ;
CHAMBERLAIN, NF ;
STEHLING, FJ .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 1978, 16 (07) :1747-1753