Synthetic Biodegradable Polyhydroxyalkanoates (PHAs): Recent Advances and Future Challenges
Synthetic Biodegradable Polyhydroxyalkanoates (PHAs): Recent Advances and Future Challenges
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DOI：
10.1016/j.progpolymsci.2022.101608
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发表时间：
2022-09
影响因子：
27.1
通讯作者：
Andrea H. Westlie;Ethan C. Quinn;Celine R. Parker;E. Chen
中科院分区：
文献类型：
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作者：
Andrea H. Westlie;Ethan C. Quinn;Celine R. Parker;E. Chen
综述了过去50年来合成聚羟基烷酸酯(PHAs)的有效化学催化途径的研究进展，聚羟基烷酸酯是自然界中发现的一类重要的可生物降解聚酯，被认为是石油基不可降解塑料的可持续替代品。本文重点介绍了近年来利用合成的精确度、聚合物立体微结构和单体及分子催化剂结构的可调整性以及化学催化在聚合物生产中的可扩展性和速度等优势来解决生物合成路线所面临的关键挑战。本文按聚(3-羟基丁酸酯)(P3HB)立体微结构(触觉)排列，从全同立构到间同立构再到无规立构P3HB材料，然后是其他PHA均聚物和共聚物。在每种类型的立体化学定义的PHA下，描述了用于合成的单体、催化剂和聚合，以及可能的机械方面。其次，在扩大PHA的范围和开发功能化的、不常见的或非天然的PHA方面，特别是在合成方法和先进的材料性能方面，重点介绍了生物方法无法获得的PHA的最新进展，特别是块状和立体嵌段或立体排列的PHA。最后，讨论了仍然存在的四项关键挑战，以及为应对这些挑战而提出的相应的未来方向。
This article reviews the advances made over the past five decades of research in developing effective chemocatalytic pathways to synthesize polyhydroxyalkanoates (PHAs), a prominent class of biodegradable polyesters found in nature and considered as sustainable alternatives to petroleum-based non-degradable plastics. Focused in this review are recent efforts that seek to address the key challenges facing the biosynthetic routes by taking advantage of precision in synthesis, expedient tunability in polymer stereomicrostructures and structures of monomers and molecular catalysts, as well as scalability and speed in polymer production that chemical catalysis can offer. This article is organized by poly(3-hydroxybutyrate) (P3HB) stereomicrostructures (tacticities), from isotactic to syndiotactic to atactic P3HB materials, followed by other PHA homopolymers and copolymers. Under each type of stereochemically defined PHAs, monomers, catalysts, and polymerizations employed for the synthesis, as well as mechanistic aspects when possible, are described. Next, recent advances in expanding the PHA scope and developing functionalized, uncommon or unnatural PHAs, inaccessible by biological methods, especially block and stereoblock or stereosequenced PHAs, are highlighted in their synthetic methods and advanced materials properties. Lastly, four key remaining challenges, and thus corresponding future directions directed at addressing those challenges, are discussed.