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Title: Synthesis of CO 2-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure

Immortal copolymerization of epoxides/CO 2 using macro-chain-transfer agent (macro-CTA) is a useful method to prepare CO 2-based block copolymers for manufacturing high value-added materials. Despite a variety of CO 2-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] ;  [1] ;  [2] ;  [1] ; ORCiD logo [1] ;  [1] ;  [3] ;  [1] ; ORCiD logo [4] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Zhejiang Univ., Hangzhou (China)
  2. Texas A & M Univ., College Station, TX (United States)
  3. Zhejiang Univ., Hangzhou (China); Univ. of Chicago, Chicago, IL (United States)
  4. Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 3; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
National Natural Science Foundation of China (NNSFC); Welch Foundation; Zhejiang University; National Science Foundation (NSF); USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2; block copolymer; chain transfer agent; immortal polymerization; polycarbonate
OSTI Identifier:
1461348

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., 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. 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., and Xu, Zhi -Kang. 2018. "Synthesis of CO2-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure". United States. doi:10.1021/acs.macromol.7b02231.
@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 = {2018},
month = {2}
}