van der Maas Kevin, Weinland Daniel H, van Putten Robert-Jan, Wang Bing, Gruter Gert-Jan M
Van't Hoff Institute of Molecular Sciences, University of Amsterdam Science Park 904 1098 XH Amsterdam The Netherlands
Avantium Chemicals BV Zekeringstraat 29 1014BV Amsterdam The Netherlands.
Green Chem. 2024 Aug 16;26(22):11182-11195. doi: 10.1039/d4gc02791d. eCollection 2024 Nov 11.
Plastic material performance is strongly correlated to the polymer's molecular weight. Obtaining a sufficiently high molecular weight is therefore a key goal of polymerization processes. The most important polyester polyethylene terephthalate (PET) and the new polyethylene furanoate (PEF) require metal catalysts and time-consuming production processes to reach sufficiently high molecular weights. Metal catalysts, which are typically antimony or tin for polyesters, end up in the plastic products which may result in sustainability and ecological challenges. When the less reactive comonomer isosorbide is introduced to produce (partly) biobased materials with enhanced thermal properties, such as polyethylene--isosorbide furanoate (PEIF), reaching high enough molecular weight becomes even more challenging. This study presents an easily implementable approach to produce high molecular weight PET and PEF polyesters and their isosorbide copolyesters PEIT and PEIF by coupling lower molecular weight polymer chains by the reactive diguaiacyl oxalate (DGO) chain extender. DGO is so reactive, that the use of metal catalysts can be completely avoided and it helps avoiding an extra solid-state polymerization step. In addition, DGO distinguishes itself from typical chain extenders by its ability to be completely removed from the resulting polymer, thereby avoiding the inherent drawbacks associated with typical chain extenders.
塑料材料性能与聚合物的分子量密切相关。因此,获得足够高的分子量是聚合过程的一个关键目标。最重要的聚酯聚对苯二甲酸乙二酯(PET)和新型聚呋喃二甲酸乙二酯(PEF)需要金属催化剂和耗时的生产工艺才能达到足够高的分子量。金属催化剂,聚酯通常使用锑或锡,最终会留在塑料制品中,这可能会带来可持续性和生态挑战。当引入反应活性较低的共聚单体异山梨醇来生产具有增强热性能的(部分)生物基材料,如聚呋喃二甲酸乙二酯-异山梨醇(PEIF)时,达到足够高的分子量变得更具挑战性。本研究提出了一种易于实施的方法,通过使用反应性草酸愈创木酚酯(DGO)扩链剂将较低分子量的聚合物链偶联起来,制备高分子量的PET和PEF聚酯及其异山梨醇共聚酯PEIT和PEIF。DGO反应活性很高,完全可以避免使用金属催化剂,并且有助于避免额外的固态聚合步骤。此外,DGO与典型的扩链剂不同,它能够从所得聚合物中完全去除,从而避免了与典型扩链剂相关的固有缺点。