Unveiling chain-chain interactions in CO2-based crystalline stereocomplexed polycarbonates by solid-state NMR spectroscopy and DFT calculations
发表时间：2019-03-11
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- 论文类型：
- 期刊论文
- 第一作者：
- Zhao, Zhenchao
- 通讯作者：
- Zhang, WP (reprint author), Dalian Univ Technol, Sch Chem Engn, State Key Lab Fine Chem, Dalian 116024, Liaoning, Peoples R China.
- 合写作者：
- Ren, Pengju,Liu, Ye,Zhao, Kangbo,Lu, Xiao-Bing,Zhang, Weiping
- 发表时间：
- 2018-03-01
- 发表刊物：
- JOURNAL OF ENERGY CHEMISTRY
- 收录刊物：
- SCIE、EI
- 文献类型：
- J
- 卷号：
- 27
- 期号：
- 2
- 页面范围：
- 361-366
- ISSN号：
- 2095-4956
- 关键字：
- Stereocomplexed polycarbonates; Crystalline carbonate polymers; Stacking interaction; Solid-state NMR; DFT
- 摘要：
- CO2-based stereocomplexed polycarbonates derived from the intermolecularly interlocked interaction between the enantiopure polymers with the opposite configuration exhibit high crystallinity, excellent thermal and mechanical stabilities. Deep insights into the mechanism of stereocomplexation are of particular importance to the design and manufacture of new promising and sustainable polycarbonates with enhanced physicochemical properties. Our solid-state NMR experiments linking with DFT computations clearly reveal the specific chain-chain interactions in a typical stereocomplexed poly (4,4-dimethyl3,5,8-trioxabicyclo[5.1.0] octane carbonate) (PCXC). C-13 CP/MAS NMR, H-1 DUMBO MAS NMR and C-13/H-1 relaxation-time measurements indicate that the formation of stereocomplex reduces the local mobilities of carbonyl, methine and methylene groups in each chain of PCXC significantly. Through a combination of two-dimensional H-1-C-13 HETCOR NMR and DFT calculation analysis, the cis-/trans-conformations and packing models of PCXC chains in the amorphous, enantionpure isotactic and stereocomplexed polycarbonates are identified. The splitting of C-13 and H-1 NMR chemical shifts of methine groups in the backbone carbon region demonstrates the ordered interlock interactions between the R- and S-chain in the stereocomplexed PCXC. (C) 2018 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
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- 否
