Poly(butylene succinate-co-butylene acetylenedicarboxylate): Copolyester with Novel Nucleation Behavior

Abstract

Big spherulite structure and high crystallinity are the two main drawbacks of poly(butylene succinate) (PBS) and hinder its application. In this work, a new type of copolyester poly(butylene succinate-co-butylene acetylenedicarboxylate) (PBSAD) is synthesized. With the incorporation of acetylenedicarboxylate (AD) units into PBS chains, the crystallization temperature and crystallinity are depressed by excluding AD units to the amorphous region. In contrast, the primary nucleation capability is significantly strengthened, without changing the crystal modification or crystallization kinetics, leading to the recovery of total crystallization rate of PBSAD under the same supercooling condition. The existence of specific interaction among AD units is found to be crucial. Although it is too weak to contribute to the melt memory effect at elevated temperature, the interaction continuously strengthens as the temperature falls down, and the heterogeneous aggregation of AD units keeps growing. When the aggregating process reaches a certain extent, it will induce the formation of a significant amount of crystal nuclei. The unveiled nucleation mechanism helps to design PBS copolymer with good performance.

A Review of Biodegradable Plastics: Chemistry, Applications, Properties, and Future Research Needs

“…However, PBS is comprised of a large spherulite structure with high crystallinity, which results in a brittle physical property. 133 Copolymerization has been used to overcome the weak impact resistance property of PBS. 134 For example, ethylene glycol is substituted for some of the 1.4-butanediol.…”

“…Thus, PBS is a soft, strong, biodegradable material that can replace polyethylene in some applications. However, PBS is comprised of a large spherulite structure with high crystallinity, which results in a brittle physical property . Copolymerization has been used to overcome the weak impact resistance property of PBS .…”

Polybutylene succinate, a potential bio-degradable polymer: synthesis, copolymerization and bio-degradation

“…PBS and poly(butylene succinate-co-butylene acetylenedicarboxylate) (PBSAD) copolymers with M n = 4.45 and 2.48 × 10 4 g mol −1 respectively were synthesized under the same reaction conditions (Scheme 5). 25 A new copolymer, poly(butylene succinate/dithiodipropionate), P(BSBDTDP), was successfully synthesized using 3,3-dithiodiproprionic acid as a comonomeric unit in the presence of the TBT catalyst (Scheme 6). 26 Also, dihydroxyl terminated PBS prepolymers, which are mainly used for chain extension and the copolymerization reaction, were also prepared by the reaction of BD and SA in the presence of the TBT catalyst (Scheme 7).…”

“…PBS and poly(butylene succinate- co -butylene acetylenedicarboxylate) (PBSAD) copolymers with M n = 4.45 and 2.48 × 10 4 g mol −1 respectively were synthesized under the same reaction conditions (Scheme 5). 25…”

“…It was observed that the introduction of AD units enhanced nucleation and at the same time reduced the crystallinity. 25…”