Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters

Xiaopeng Yu, Junteng Jia, Shu Xu, Ka Un Lao, Maria J. Sanford, Ramesh K. Ramakrishnan, Sergei I. Nazarenko, Thomas R. Hoye, Geoffrey W. Coates, Robert A. DiStasio

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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.

Original languageEnglish (US)
Article number2880
JournalNature communications
Issue number1
StatePublished - Dec 1 2018

Bibliographical note

Funding Information:
Funding for this project was provided by the Center for Sustainable Polymers, a National Science Foundation (NSF) Center for Chemical Innovation (CHE-1413862). J.J., K.U.L. and R.A.D. acknowledge partial support from Cornell University through start-up funding. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This work also made use of the NMR Facility at Cornell University, which is supported, in part, by the NSF under award number CHE-1531632.

Publisher Copyright:
© 2018, The Author(s).


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