The glass transition temperatures of amorphous linear aliphatic polyesters

Jialong Shen, Yavuz Caydamli, Alper Gurarslan, Shanshan Li, Alan E. Tonelli*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

Abstract

A series of wholly amorphous linear aliphatic co- and tetra-polyesters were synthesized via bulk melt step-growth polymerization. Their glass transition temperatures were determined using DSC and were essentially unaffected by crystallinity. The glass transition temperatures of the polyesters increase linearly with the ratio of ester groups per methylene group. Extrapolations of the ratio to zero ester group content gave a reliable value for the Tg of amorphous polyethylene (PE). The experimental Tgs manifest a steeper slope on the Tg vs. ester group content plot compared to those calculated using Van Krevelen's group contribution method. The intramolecular equilibrium flexibilities were evaluated through the calculation of conformational entropies of individual polymer chains approximated by considering solely the short-range interactions between neighboring groups, as embodied in their RIS conformational models. Their calculated conformational entropies, Sconf, decrease linearly with increasing ester group content, leading to the observation that Sconf ∝1/Tg.

Original languageEnglish
Pages (from-to)235-245
Number of pages11
JournalPolymer
Volume124
DOIs
Publication statusPublished - 25 Aug 2017

Bibliographical note

Publisher Copyright:
© 2017 Elsevier Ltd

Keywords

  • Amorphous linear aliphatic polyester
  • Conformational entropy
  • Glass transition

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