论文标题:Bottle-grade polyethylene furanoate from ringopening polymerisation of cyclic oligomers
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作者:Massimo Morbidelli et al
发表时间: 2018/07/28
数字识别码:10.1038/s41467-018-05147-y
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《自然-通讯》论文Bottle-grade polyethylene furanoate from ringopening polymerisation of cyclic oligomers报道了一种可以生产出与传统塑料特性相似、但是更可持续的塑料聚合物的方法。该研究表明,瓶级聚乙烯呋喃酸酯——一种基于可再生资源的生物塑料——可在30分钟内获得。
图1:环状低聚物作为合成聚乙烯呋喃酸酯原材料的热性能。图源:Rosenboom et al.
由于我们非常依赖塑料,因此很有必要找到一种可持续的塑料替代品。然而,与常规塑料相比,可持续聚合物通常性能较差(包括变色和热降解),因此无法用于特定的日常应用。聚乙烯呋喃酸酯具有所需的性能,但在形成后便会开始降解,因为它的反应时间非常长。
图2:通过环状低聚物的开环聚合合成瓶级聚乙烯呋喃酸酯。图源:Rosenboom et al.
瑞士苏黎世联邦理工学院的Massimo Morbidelli及其同事提出了一种开环聚合方法,借此形成瓶级聚乙烯呋喃酸酯长直链。根据该方法,首先利用一种高沸点溶剂使初始材料——较小的环状聚乙烯呋喃酸酯链与锡基催化剂混合。一旦聚合物产物开始形成,它就在反应条件下熔化,促进初始材料转化。使用该方法可以在30分钟内完成反应,反应形成的聚乙烯呋喃酸酯具备所需特性,而且降解和变色问题已降至最低。
摘要:Polyethylene furanoate (PEF) represents a promising renewable resource-based bioplastic as replacement for fossil-based polyethylene terephthalate (PET) with improved material properties. However, the synthesis of PEF through conventional polycondensation remains challenging, since the time-intensive reaction leads to degradation and undesired discolouration of the product. Here we show the successful rapid synthesis of bottle-grade PEF via ring-opening polymerisation (ROP) from cyclic PEF oligomers within minutes, thereby avoiding degradation and discolouration. The melting point of such mixture of cyclic oligomers lies around 370 °C, well above the degradation temperature of PEF (~329 °C). This challenge can be overcome, exploiting the self-plasticising effect of the forming polymer itself (which melts around 220 °C) by initiation in the presence of a high boiling, yet removable, and inert liquid plasticiser. This concept yields polymer grades required for bottle applications (Mn > 30 kg mol−1, conversion > 95%, colour-free products), and can be extended to other diffusion-limited polymer systems.
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