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Title: Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters

Abstract

Converting biomass-based feedstocks into polymers not only reduces our reliance on fossil fuels, but also furnishes multiple opportunities to design biorenewable polymers with targeted properties and functionalities. Here we report a series of high glass transition temperature (T g up to 184°C) polyesters derived from sugar-based furan derivatives as well as a joint experimental and theoretical study of substituent effects on their thermal properties. Surprisingly, we find that polymers with moderate steric hindrance exhibit the highest T g values. Through a detailed Ramachandran-type analysis of the rotational flexibility of the polymer backbone, we find that additional steric hindrance does not necessarily increase chain stiffness in these polyesters. We attribute this interesting structure-property relationship to a complex interplay between methyl-induced steric strain and the concerted rotations along the polymer backbone. We believe that our findings provide key insight into the relationship between structure and thermal properties across a range of synthetic polymers.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1];  [3];  [3]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Cornell Univ., Ithaca, NY (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Univ. of Southern Mississippi, Hattiesburg, MS (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543746
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology; Other Topics

Citation Formats

Yu, Xiaopeng, Jia, Junteng, Xu, Shu, Lao, Ka Un, Sanford, Maria J., Ramakrishnan, Ramesh K., Nazarenko, Sergei I., Hoye, Thomas R., Coates, Geoffrey W., and DiStasio, Jr., Robert A. Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters. United States: N. p., 2018. Web. doi:10.1038/s41467-018-05269-3.
Yu, Xiaopeng, Jia, Junteng, Xu, Shu, Lao, Ka Un, Sanford, Maria J., Ramakrishnan, Ramesh K., Nazarenko, Sergei I., Hoye, Thomas R., Coates, Geoffrey W., & DiStasio, Jr., Robert A. Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters. United States. doi:10.1038/s41467-018-05269-3.
Yu, Xiaopeng, Jia, Junteng, Xu, Shu, Lao, Ka Un, Sanford, Maria J., Ramakrishnan, Ramesh K., Nazarenko, Sergei I., Hoye, Thomas R., Coates, Geoffrey W., and DiStasio, Jr., Robert A. Mon . "Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters". United States. doi:10.1038/s41467-018-05269-3. https://www.osti.gov/servlets/purl/1543746.
@article{osti_1543746,
title = {Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters},
author = {Yu, Xiaopeng and Jia, Junteng and Xu, Shu and Lao, Ka Un and Sanford, Maria J. and Ramakrishnan, Ramesh K. and Nazarenko, Sergei I. and Hoye, Thomas R. and Coates, Geoffrey W. and DiStasio, Jr., Robert A.},
abstractNote = {Converting biomass-based feedstocks into polymers not only reduces our reliance on fossil fuels, but also furnishes multiple opportunities to design biorenewable polymers with targeted properties and functionalities. Here we report a series of high glass transition temperature (Tg up to 184°C) polyesters derived from sugar-based furan derivatives as well as a joint experimental and theoretical study of substituent effects on their thermal properties. Surprisingly, we find that polymers with moderate steric hindrance exhibit the highest Tg values. Through a detailed Ramachandran-type analysis of the rotational flexibility of the polymer backbone, we find that additional steric hindrance does not necessarily increase chain stiffness in these polyesters. We attribute this interesting structure-property relationship to a complex interplay between methyl-induced steric strain and the concerted rotations along the polymer backbone. We believe that our findings provide key insight into the relationship between structure and thermal properties across a range of synthetic polymers.},
doi = {10.1038/s41467-018-05269-3},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {7}
}

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