Synthesis of CO2-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure
Abstract
Immortal copolymerization of epoxides/CO2 using macro-chain-transfer agent (macro-CTA) is a useful method to prepare CO2-based block copolymers for manufacturing high value-added materials. Despite a variety of CO2-based block copolymers that have been reported using distinct macro-CTAs, issues including catalytic activity and blocking efficiency for the immortal polymerization remain superficially understood. Here, we systematically studied the reaction activity and blocking efficiency by using various macro-CTAs (including PPG, PEG, and PS) in the presence of two classical catalyst systems ((BDI)ZnOAc and SalenCoTFA/PPN-TFA). By analysis of the gel permeation chromatograms via mathematical deconvolution, it comes to a conclusion that the size, nature, and ratio of [macro-CTA]/[Cat.] strongly influence the catalytic activity of the reaction and blocking efficiency for the resultant block copolymers. As a result, thin film self-assembly of PS/PPC block copolymers was investigated, and the results were analyzed by SEM to ascertain the impact of blocking efficiency on nanoassembly.
- Authors:
-
[1];
[4];
[2];
[1]
- Zhejiang Univ., Hangzhou (China)
- Texas A & M Univ., College Station, TX (United States)
- Zhejiang Univ., Hangzhou (China); Univ. of Chicago, Chicago, IL (United States)
- Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- National Natural Science Foundation of China (NSFC); Welch Foundation; Zhejiang University; National Science Foundation (NSF); USDOE
- OSTI Identifier:
- 1461348
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 51; Journal Issue: 3; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2; block copolymer; chain transfer agent; immortal polymerization; polycarbonate
Citation Formats
Zhang, Yao -Yao, Yang, Guan -Wen, Wang, Yanyan, Lu, Xin-Yu, Wu, Guang -Peng, Zhang, Ze-Sheng, Wang, Kai, Zhang, Ruo -Yu, Nealey, Paul F., Darensbourg, Donald J., and Xu, Zhi -Kang. Synthesis of CO2-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure. United States: N. p., 2018.
Web. doi:10.1021/acs.macromol.7b02231.
Zhang, Yao -Yao, Yang, Guan -Wen, Wang, Yanyan, Lu, Xin-Yu, Wu, Guang -Peng, Zhang, Ze-Sheng, Wang, Kai, Zhang, Ruo -Yu, Nealey, Paul F., Darensbourg, Donald J., & Xu, Zhi -Kang. Synthesis of CO2-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure. United States. https://doi.org/10.1021/acs.macromol.7b02231
Zhang, Yao -Yao, Yang, Guan -Wen, Wang, Yanyan, Lu, Xin-Yu, Wu, Guang -Peng, Zhang, Ze-Sheng, Wang, Kai, Zhang, Ruo -Yu, Nealey, Paul F., Darensbourg, Donald J., and Xu, Zhi -Kang. Thu .
"Synthesis of CO2-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure". United States. https://doi.org/10.1021/acs.macromol.7b02231. https://www.osti.gov/servlets/purl/1461348.
@article{osti_1461348,
title = {Synthesis of CO2-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure},
author = {Zhang, Yao -Yao and Yang, Guan -Wen and Wang, Yanyan and Lu, Xin-Yu and Wu, Guang -Peng and Zhang, Ze-Sheng and Wang, Kai and Zhang, Ruo -Yu and Nealey, Paul F. and Darensbourg, Donald J. and Xu, Zhi -Kang},
abstractNote = {Immortal copolymerization of epoxides/CO2 using macro-chain-transfer agent (macro-CTA) is a useful method to prepare CO2-based block copolymers for manufacturing high value-added materials. Despite a variety of CO2-based block copolymers that have been reported using distinct macro-CTAs, issues including catalytic activity and blocking efficiency for the immortal polymerization remain superficially understood. Here, we systematically studied the reaction activity and blocking efficiency by using various macro-CTAs (including PPG, PEG, and PS) in the presence of two classical catalyst systems ((BDI)ZnOAc and SalenCoTFA/PPN-TFA). By analysis of the gel permeation chromatograms via mathematical deconvolution, it comes to a conclusion that the size, nature, and ratio of [macro-CTA]/[Cat.] strongly influence the catalytic activity of the reaction and blocking efficiency for the resultant block copolymers. As a result, thin film self-assembly of PS/PPC block copolymers was investigated, and the results were analyzed by SEM to ascertain the impact of blocking efficiency on nanoassembly.},
doi = {10.1021/acs.macromol.7b02231},
journal = {Macromolecules},
number = 3,
volume = 51,
place = {United States},
year = {Thu Feb 01 00:00:00 EST 2018},
month = {Thu Feb 01 00:00:00 EST 2018}
}
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