Small-scale screening of novel biobased monomers: the curious case of 1,3-cyclopentanediol

• Published in: RSC advances Vol. 8; no. 70; pp. 39818 - 39828
• Main Authors: Noordzij, G J, Dietz, C H J T, Leoné, N, Wilsens, C H R M, Rastogi, S
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 01-01-2018; The Royal Society of Chemistry
• Subjects: Chemical synthesis; Chemistry; Coupling (molecular); Cross coupling; Crosslinking; Dehydration; Molecular weight; Monomers; NMR; Nuclear magnetic resonance; Polyester resins; Polymer films; Polymerization; Thermal stability; Thermogravimetric analysis; Thin films; Trimers; Two dimensional analysis
• ISSN: 2046-2069; 2046-2069
• DOI: 10.1039/C8RA08811J

In this work, we report on the small scale polycondensation and consecutive analysis of novel polyesters based on the potentially renewable 1,3-cyclopentanediol (CPdiol). To avoid evaporation of monomers during thin-film polymerization reactions, trimer pre-polyesters have been synthesized from the corresponding acid-chlorides with diol monomers. Polymerization of these trimers was explored by thermogravimetric analysis to identify potential side reactions, and to assess the ideal polymerization temperature. In general we observe that
-1,3-cyclopentanediol exhibits good thermal stability up to 200 °C, whereas thermal dehydration of the alcohol end-groups occurs upon further heating. In contrast, for
-1,3-cyclopentanediol, the ester bonds of the cyclopentane end-groups become labile, thereby generating carboxylic acid end-groups, and 3-cyclopentenol already at 180 °C. The thermal dehydration reactions yield double bond end-groups, which in turn facilitate cross-linking through cross-coupling and Diels-Alder reactions, leading to an increase in molecular weight. Despite the limited thermal stability of CPdiol, here we demonstrate that polymerization of CPdiol can successfully be achieved in thin-film polycondensation conditions at 180 °C, yielding molecular weights well above 10 kg mol
.