期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 54, 期 7, 页码 2241-2244出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201410692
关键词
carbon dioxide; crystalline; enantiopure polycarbonates; epoxides; polymer stereocomplexes
资金
- National Natural Science Foundation of China (NSFC) [21134002, 21104007]
- Program for Changjiang Scholars and Innovative Research Team in University [IRT13008]
- Chang Jiang Scholars Program from the Ministry of Education of China [T2011056]
Four novel crystalline stereocomplexed polymers are formed by mixing isotactic (R)- and (S)-polycarbonates in 1:1 mass ratio. They show the enhanced thermal stability and new crystalline behavior, significantly distinct from the component enantiomer. Two stereocomplexed CO2-based polycarbonates from meso-3,4-epoxytetrahydrofuran and 4,4-dimethyl-3,5,8-trioxabicyclo[5.1.0]octane have high melting temperatures of up to 300 degrees C, about 30 degrees C higher than the individual enantiomers. Isotactic (R)- or (S)-poly(cyclopentene carbonate) and poly(cis-2,3-butene carbonate) are typical amorphous polymeric materials, however, upon mixing both enantiomers together, a strong interlocked interaction between polymer chains of opposite configuration occurs, affording the crystalline stereocomplexes with melting temperatures of about 200 degrees C and 180 degrees C, respectively. A DFT study suggests that the driving force forming the stereocomplex is the hydrogen-bonding between carbonate units of the opposite enantiomers.
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