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Modulating the Tg of Poly(alkylene succinate)s by Inserting Bio-Based Aromatic Units via Ring-Opening Copolymerization

机译:通过开环共聚插入基于生物的芳香单元来调节聚琥珀酸亚烷基酯的Tg

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摘要

Two series of aliphatic-aromatic copolyesters derived from succinic and 2,5-furandicarboxylic acids, and di-O-2-(hydroxyethyl) resorcinol as diol substituent of either 1,4-butanediol or ethylene glycol, respectively, were obtained by ring opening polymerization(ROP) performed in bulk and catalyzed by Sn(Oct)2. Cyclic oligomers of furandicarboxylate of di-O-2-(hydroxyethyl) resorcinol were successfully synthesized by high-dilution condensation, and then copolymerized with cyclic oligomers of either butylene or ethylene succinate. The synthesized resorcinol-containing succinate-furanoatecopolyesters had Mw oscillating between 50,000 and 30,000 g·mol−1 depending on composition, and they all displayed a nearly random microstructure. They showed an excellent thermal stability with onset decomposition temperatures near 300 °C. They are amorphous with Tg increasing monotonically with the content in resorcinol in both series with values ranging from −30 or −13 °C for butylene and ethylene-based copolyesters, respectively, up to around 45 °C. The resorcinol-containing succinate-furanoate copolyesters showed appreciable hydrolytic degradation when incubated for a few weeks in water under physiological conditions, a behavior that was notably enhanced in the presence of lipases.
机译:通过开环获得分别衍生自琥珀酸和2,5-呋喃二甲酸的两个系列的脂族-芳族共聚酯,以及分别作为1,4-丁二醇或乙二醇的二醇取代基的二-O-2-(羟乙基)间苯二酚Sn(Oct)2催化聚合(ROP)。通过高稀释缩合反应成功合成了二-O-2-(羟乙基)间苯二酚呋喃二甲酸酯的环状低聚物,然后与丁烯或琥珀酸乙烯酯的环状低聚物共聚。合成的含间苯二酚的琥珀酸酯-呋喃酸酯共聚酯,其Mw根据组成在50,000和30,000 g·mol -1 之间振荡,并且都表现出几乎随机的微观结构。它们表现出出色的热稳定性,起始分解温度接近300°C。它们是无定形的,Tg随间苯二酚含量的增加而单调增加,对于丁烯和基于乙烯的共聚酯,其值分别在-30或-13°C范围内,最高约45°C。当在生理条件下于水中孵育数周时,含间苯二酚的琥珀酸-呋喃酸酯共聚酯表现出明显的水解降解,在脂肪酶的存在下这种行为明显增强。

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