Fully Isohexide-Based Polyesters: Synthesis, Characterization, and Structure鈥揚roperties Relations
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- 作者：Jing Wu ; Pieter Eduard ; Lidia Jasinska-Walc ; Artur Rozanski ; Bart A. J. Noordover ; Daan S. van Es ; Cor E. Koning
- 刊名：Macromolecules
- 出版年：2013
- 出版时间：January 22, 2013
- 年：2013
- 卷：46
- 期：2
- 页码：384-394
- 全文大小：501K
- 年卷期：v.46,no.2(January 22, 2013)
- ISSN：1520-5835
文摘
Here we present a novel series of biobased polyesters solely based on renewable isohexide building blocks, synthesized via melt polymerization. The recently developed isoidide dicarboxylic acid (IIDCA) was polymerized with rigid renewable diols such as isosorbide (IS), isomannide (IM), isoidide (II), and the novel 2,5-methylene-extended isoidide dimethanol (IIDML). Both IIDCA and IIDML were developed to increase the reactivity of the isohexide building block, while retaining rigidity and hence the beneficial effects on Tg. Compared to the parent isohexides, IIDML showed a markedly higher reactivity, resulting in three to four times higher weight-average molecular weight (Mw) values of the synthesized polyesters. The molecular structure of the novel polyesters was analyzed by 1H, 13C and 2D-COSY NMR techniques, confirming that the stereoconfigurations of the isohexide moieties were preserved under the applied polymerization conditions. The II/IS-based polyesters have high Tg values noted of 70 and 85 掳C, respectively, while the IIDML-based polyester has a lower Tg of approximately 45 掳C, yet with an higher degree of crystallinity than the parent isohexide-based polyesters. A systematic study on structure-thermal properties relations comparing these novel polyesters with, e.g., aliphatic polyesters reveals that, when incorporated into polyesters, both IIDCA and IIDML are able to increase the Tg by approximately 70 掳C, which is comparable to the parent isohexides. Given the enhanced reactivity, high thermal stability and the retained ability to increase the Tg, IIDML is a promising renewable building block for performance polymers.