Random and Multiblock PBS Copolyesters Based on a Rigid Diol Derived from Naturally Occurring Camphor: Influence of Chemical Microstructure on Thermal and Mechanical Properties

Abstract

(1R,3S)-1,2,2-trimethylcyclopentane-1,3-dimethanol (TCDM) is a rigid alicyclic diol prepared by oxidation and subsequent reduction of naturally occurring camphor. To improve the low glass transition temperature (T g), slow degradation rate, and brittleness of poly­(butylene succinate) (PBS), two series of PBS copolyesters based on TCDM were synthesized using two different methods. Random copolymerization (RC) of a mixture of TCDM, 1,4-butanediol (BDO), and 1,4-succinic acid (SA) afforded random PBS copolyesters, while reactive blending (RB) of pure PBS and PTS (homopolyester based on TCDM and SA) afforded PBS copolyesters with blocklike chemical microstructures. For both series, the insertion of TCDM units resulted in elevated thermal stability and higher T g values compared to those of neat PBS. The RB-prepared copolyesters displayed higher melting points, a higher degree of crystallinity, and higher mechanical properties with respect to those of their random counterparts obtained by RC. The incorporation of TCDM units enhanced the hydrolytic degradation rates for both series, which is more pronounced for the RC-prepared copolyesters. Overall, this work confirmed the effectiveness of the RB technology in preparing high-performance biopolymers such as improving the sustainability of raw materials, achieving high T g values, and promoting the mechanical strength and biodegradability as well.

Synthesis, Crystallization, Structure Memory Effects, and Molecular Dynamics of Biobased and Renewable Poly(n-alkylene succinate)s with n from 2 to 10

“…Poly­( n -alkylene succinate)­s, P n ASs or P n ASu, are biodegradable aliphatic polyesters that have recently attracted considerable attention, mostly in relation to the needs for eco-friendly materials, in the frame of circular and green economy. Next to the polyester synthesis from available renewable resources, the P n ASs are promising polymers for a wide range of applications, wherein thermal stability, processing advantages, and biodegradation are desirable. − The most known P n ASs are those with alkylene number n = 2–4, namely, poly­(ethylene succinate) (PES), − poly­(propylene succinate) (PPS), ,, and poly­(butylene succinate) [PBS or, alternatively, poly­(tetramethylene succinate)]. − …”

Chemical Modification of Poly(butylene trans-1,4-cyclohexanedicarboxylate) by Camphor: A New Example of Bio-Based Polyesters for Sustainable Food Packaging

“…The introduction of rigid TCDM moiety along the PBS polymer chain improved PBS thermal stability, increased glass transition temperature, and improved mechanical properties, the degree of improvement being more significant for block copolymers. The camphor-based diol also enhanced the hydrolytic degradation of PBS [ 37 ].…”

Preparation of biobased poly(propylene 2,5‐furandicarboxylate) fibers: Mechanical, thermal and hydrolytic degradation properties

“…In fact, due to the widespread concerns on environmental protection as well as the depletion of non‐renewable resources, the development of sustainable biobased alternatives to generate polyester fibers has received considerable attention in the last decades because of their potential applications as eco‐friendly fibers contributing to reduction of environmental pollution. Up to now, poly(butylene succinate) (PBS) and polylactide (PLA) as the most intensively studied biobased polyesters have been successfully developed to produce polyester fibers 10–16 . However, such fibers have relatively low glass transition temperature (T g ) and mechanical properties, which significantly limits their industrial application.…”