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Partially Renewable Poly(butylene 25-furandicarboxylate-co-isophthalate) Copolyesters Obtained by ROP

机译:通过ROP获得的部分可再生的聚(25-呋喃二甲酸丁二酯-间苯二甲酸丁二酯)共聚酯

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摘要

Cyclic butylene furandicarboxylate (c(BF)n) and butylene isophthalate (c(BI)n) oligomers obtained by high dilution condensation reaction were polymerized in bulk at 200 °C with Sn(Oct)2 catalyst via ring opening polymerization to give homopolyesters and copolyesters (coPBFxIy) with weight average molar masses in the 60,000–70,000 g·mol−1 range and dispersities between 1.3 and 1.9. The composition of the copolyesters as determined by NMR was practically the same as that of the feed, and they all showed an almost random microstructure. The copolyesters were thermally stable up to 300 °C and crystalline for all compositions, and have Tg in the 40–20 °C range with values decreasing almost linearly with their content in isophthalate units in the copolyester. Both melting temperature and enthalpy of the copolyesters decreased as the content in butylene isophthalate units increased up to a composition 30/70 (BF/BI), at which the triclinic crystal phase made exclusively of butylene furanoate units changed to the crystal structure of PBI. The partial replacement of furanoate by isophthalate units decreased substantially the crystallizability of PBF.
机译:通过高稀释度缩合反应获得的环状呋喃甲酸二丁酯(c(BF)n)和间苯二甲酸丁二酯(c(BI)n)低聚物在200°C下与Sn(Oct)2催化剂通过开环聚合反应进行本体聚合,得到均聚酯和重均摩尔质量在60,000–70,000 g·mol -1 范围内且分散度在1.3和1.9之间的共聚酯(coPBFxIy)。通过NMR确定的共聚酯的组成实际上与进料的组成相同,并且它们均显示出几乎随机的微观结构。共聚酯在高达300°C的温度下对所有组合物均具有热稳定性,并具有结晶性,并且Tg在40–20°C范围内,其值与共聚酯中间苯二甲酸酯单元的含量几乎呈线性下降。随着间苯二甲酸丁二酯单元含量的增加,共聚酯的熔融温度和焓均降低,直至组成30/70(BF / BI),此时仅由呋喃甲酸丁二酯单元组成的三斜晶相变为PBI的晶体结构。间苯二甲酸酯单元部分替代呋喃酸酯的方法大大降低了PBF的结晶性。

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