Effect of 1,4‐cyclohexylene units on thermal properties of poly(1,4‐cyclohexylenedimethylene adipate) and similar aliphatic polyesters

Abstract

In the field of aliphatic polyesters there is a great interest in building novel macromolecular structures that may effectively feature the required properties for specific applications. For this reason, it is extremely important to understand the correlations between chemical structure and final performance. Monomers based on the 1,4‐cyclohexylene unit are interesting as they are potentially bio‐based and rigid enough to improve glass transition and melting temperatures. The present paper describes the preparation of samples of poly(1,4‐cyclohexylenedimethylene adipate), characterized by different cis/trans isomeric ratio of the cyclic units, the analysis of their thermal properties and the comparison with the properties of similar polymers such as poly(butylene adipate), poly(butylene‐1,4‐cyclohexanedicarboxylate) and poly(1,4‐cyclohexylenedimethylene‐1,4‐cyclohexanedicarboxylate). The effect of the rigidity and of the stereochemistry of the 1,4‐cyclohexylene unit on the thermal properties was analysed. Such an effect reaches its maximum level when the cyclic‐containing monomers are the diacid or the diester and when the trans isomers predominate. Starting from such a result, the combination of specific cyclic building blocks with the correct cis/trans ratio makes it possible to build macromolecular structures with the required final properties.

Use of ionic liquids based on phosphonium salts for preparing biocomposites by in situ polymerization

“…The homopolymer sample was prepared following the literature, by a two‐stage process, from dimethyl adipate and 1,4‐cyclohexanedimethanol with 66 mol % of trans isomer content.…”

“…A new polymeric matrix was chosen for this study: the poly(1,4‐dimethylcyclohexane adipate), an aliphatic polyester prepared from dimethyl adipate and 1,4‐cyclohexanedimethanol (CHDM), potentially biobased and biodegradable . Indeed, although such monomers are now petro‐derived, the processes to prepare them from biomass are available .…”

“…A new polymeric matrix was chosen for this study: the poly(1,4-dimethylcyclohexane adipate), an aliphatic polyester prepared from dimethyl adipate and 1,4-cyclohexanedimethanol (CHDM), potentially biobased and biodegradable. 5,6 Indeed, although such monomers are now petro-derived, the processes to prepare them from biomass are available. 7 The polymer, whose structure is reported in Figure 1, might prove interesting for future applications also because it contains the 1,4-cyclohexylene unit, that is rigid enough to notably improve thermal stability and thermal properties.…”

Manipulating the Properties of Poly(1,4‐Cyclohexylenedimethylene Terephthalate) (PCT) Just by Tuning Steric Configuration of 1.4‐Cyclohexanedimethanol (CHDM)

“…For instance, Celli et al. synthesized a series of poly(1,4‐cyclohexylenedimethylene‐1,4‐cyclohexanedicarboxylate) (PCCD) and found that the T m of PCCD could be varied from 128 °C for the polyester containing 99% trans ‐CHDA (1,4‐cyclohexanedicarboxylic acid) to 104 °C for the polyester synthesized from 70% cis ‐CHDA . They also changed the amorphous poly(butylene 1,4‐cyclohexanedicarboxylate) (PBCHD) to highly crystalline polyester only by increasing the trans ‐CHDA content from 26% to 100% .…”

Solid‐state polymerization process for the preparation of poly(cyclohexane‐1,4‐dimethylene cyclohexane‐1,4‐dicarboxylate) polymers with high melting temperature and crystallinity

“…Indeed, the glass transition ( T g ) and melting ( T m ) temperatures of polymers containing 1,4‐cyclohexylene moieties are higher with respect to those of the corresponding polyesters with linear aliphatic groups like poly(butylene adipate). Both CHDA and CHDM are obtained from terephthalic acid that can be prepared starting from renewable resources, making these monomers attracting from an environmental point of view .…”