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

Yi Li,Guoyong Huang,Xi Dong,Hai-Mu Ye,Xue-Wei Wei,Wei Zhao,Cong Chen

doi:10.3390/polym13030365

Yi Li, Guoyong Huang + Show 5 more

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https://doi.org/10.3390/polym13030365

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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.

Highlights

Poly(butylene succinate) (PBS) as one of the promising biodegradable polyesters, can exhibit comparable mechanical properties with traditional polyolefins [1,2], showing great potential in diversified applications of packing materials, clothing, biomedical engineering, etc., [3,4]
poly(butylene succinate) (PBS) and poly(butylene succinate-co-butylene acetylenedicarboxylate) (PBSAD) were synthesized through a two-stage reaction
It is clear that the incorporation of acetylenedicarboxylic (AD) units into PBS chains would decrease the intensity of peak 3# when compared with peak 1# or peak 2#

Summary

Introduction

Poly(butylene succinate) (PBS) as one of the promising biodegradable polyesters, can exhibit comparable mechanical properties with traditional polyolefins [1,2], showing great potential in diversified applications of packing materials, clothing, biomedical engineering, etc., [3,4]. PBS suffers some severe drawbacks, including large spherulite structure, high crystallinity, and serious post-crystallization, which make it brittle and weak in impact resistance [5]. Nucleating agent is usually blended into PBS matrix to improve the heterogeneous nucleation that contributes to the reduction of spherulite size. Various nucleating agents including organic molecules [6,7], inorganic particles [8,9], nanofillers [10,11] have been used to effectively decrease the spherulite size and improve the mechanical performance. The problem of high crystallinity or post-crystallization behavior cannot be avoided [12,13], which makes the PBS composites still brittle in character. Copolymerization is an effective approach to resolve the high crystallinity and postcrystallization problems of PBS. Like adipic acid [14], terephthalic acid [15], 1,3-propane diol [16], and ethane diol [17], are copolymerized with PBS, the crystallinity of copolymer can be notably decreased depending on the comonomer content

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