Novel Poly(butylene fumarate) and Poly(butylene succinate) Multiblock Copolymers Bearing Reactive Carbon–Carbon Double Bonds: Synthesis, Characterization, Cocrystallization, and Properties

Abstract

Widespread application of biodegradable polyesters is restrained by inferior mechanical properties, higher cost, and lack of reactive functional sites for further modification. A new class of multiblock copolymers bearing reactive sites on the main chains, composed of poly(butylene fumarate) (PBF) and poly(butylene succinate) (PBS), has been designed and synthesized to enhance the biodegradability of PBF and expand its application, while retaining the mechanical properties. The chemical structures of the copolymers were confirmed by 1 H NMR spectra and GPC. The two segments are compatible in both the amorphous and crystalline region, and form cocrystals because of their similar nature. The multiblock copolymers possess satisfactory thermal and mechanical properties. The degradation rate of copolymers is substantially accelerated by the copolymerization with PBS. The novel polymer may be directly used as biodegradable materials or be postfunctionalized to modify the physicochemical properties or to endow the polymers with special properties.

Sulfonated poly(butylene succinate) as a pseudo‐random copolymer: effect of sulfonate groups on microstructure and thermal behavior

“…By measuring the area under the e, e′ and e″ peaks, the chain randomness and sequence length values can be determined. Chemical shifts at 3.6–3.7 ppm and 1.6–1.7 ppm can be assigned to the protons of terminal methylene groups . Analyzing the signals obtained revealed that, while the polycondensation temperature during copolyester synthesis was about 245 °C, no side reaction such as butanediol etherification (the Ordelt reaction) or crosslinking has occurred and unsaturated polymers have been successfully synthesized.…”

“…Therefore, a new strategy has been developed to efficiently synthesize ionic polyesters, such that unsaturated polymers containing carbon–carbon double bonds along their backbones are modified by reactive substances . Carbon–carbon double bonds are provided by poly(butylene fumarate) (PBF) and poly(butylene succinate‐ ran ‐fumarate) (PBSF) copolyesters, which are modified in the next stage through post‐polymerization modification due to the Michael addition of sodium bisulfite. In the majority of these studies, the amount of sulfonate groups along the polymer chain has not been considerable (being less than 50 mol% of sulfonate groups) and their effects have not been clearly explained.…”

Biobased Thermoplastic Poly(ester urethane) Elastomers Consisting of Poly(butylene succinate) and Poly(propylene succinate)

“…XXXX, XXX, XXX−XXX thermore, new signals of MDI residue appeared at shifts of 7.30 (δH g ), 7.10 (δH h ), and 3.88 (δH i ) ppm. Therefore, the structures of the target polymers are confirmed.Weight fractions of PPS, PBS and MDI in PEUs can be deduced from the integral areas of corresponding protons by the following equations:23,24 …”

A facile and versatile strategy to efficiently synthesize sulfonated poly(butylene succinate), self-assembly behavior and biocompatibility

“…27 Therefore, it is reasonable to deduce that esterification and polycondensation just proceeded in the way as designed. The average molecular weight and molecular weight distribution of the copolyesters were determined by GPC, and the results were also summarized in Table 1.…”

“…[26][27][28] The copolyesters possess excellent biodegradability, thermal properties and mechanical properties. In addition, the abundant carbon-carbon double bonds on the backbone provide many reactive sites for further modification and introduction of functional groups.…”