Indexed by:
期刊论文
First Author:
Wu, Guang-Peng
Correspondence Author:
Lu, XB (reprint author), Dalian Univ Technol, State Key Lab Fine Chem, Dalian 116024, Peoples R China.
Co-author:
Zu, Yu-Ping,Xu, Peng-Xiang,Ren, Wei-Min,Lu, Xiao-Bing
Date of Publication:
2013-08-01
Journal:
CHEMISTRY-AN ASIAN JOURNAL
Included Journals:
SCIE、EI、PubMed、Scopus
Document Type:
J
Volume:
8
Issue:
8,SI
Page Number:
1854-1862
ISSN No.:
1861-4728
Key Words:
copolymerization; NMR spectroscopy; poylmers; stereochemistry; styrene
oxide
Abstract:
A large amount of interesting information on the alternating copolymerization of CO2 with terminal epoxides has already been reported, such as the regiochemistry of epoxide ring-opening and the stereochemistry of the carbonate unit sequence in the polymer chain. Moreover, the microstructures of CO2 copolymers from propylene oxide and cyclohexene oxide have also been well-studied. However, the microstructure of the CO2 copolymer from styrene oxide (SO), an epoxide that contains an electron-withdrawing group, has not yet been investigated. Herein, we focus on the spectroscopic assignment of the CO2 copolymer from styrene oxide at the diad level by using three kinds of model dimer compounds, that is, T-T, H-T, and H-H. By comparing the signals in the carbonyl region, we concluded that the signals at =154.3, 153.8, and 153.3ppm in the 13CNMR spectrum of poly(styrene carbonate) were due to tail-to-tail, head-to-tail, and head-to-head carbonate linkages, respectively. Moreover, various isotactic and syndiotactic model compounds based on T-T, H-T, and H-H (dimers (R,R)-T-T, (S,S)-T-T, and (R,S)-T-T; (R,R)-H-T, (S,S)-H-T, and (R,S)-H-T; (R,R)-H-H, (S,S)-H-H, and (R,S)-H-H) were synthesized for the further spectroscopic assignment of stereospecific poly(styrene carbonate)s. We found that the carbonate carbon signals were sensitive towards the stereocenters on adjacent styrene oxide ring-opening units. These discoveries were found to be well-matched to the microstructures of the stereoregular poly(styrene carbonate)s that were prepared by using a multichiral CoIII-based catalyst system.
Translation or Not:
no
