美国康奈尔大学Coates, Geoffrey W.研究团队报道了来自C1和C4原料的受天然启发的甲基化聚羟基丁酸盐。相关研究成果于2023年4月6日发表在《自然—化学》。

聚烯烃塑料因其低成本和优异的特性而得到广泛应用，但其环境持久性是一个重大的社会挑战。聚羟基烷酸酯（PHA）是聚烯烃的可生物降解替代品，但其高成本和热不稳定性阻碍了其广泛应用。

该文中，研究人员报道了一系列在结构上受到天然PHA启发的甲基化聚羟基丁酸酯，聚（3-羟基-2-甲基丁酸酯）。顺式均聚物表现出与立构规整度无关的结晶度，这有助于发现高熔点、热稳定性和机械韧性的共聚物，通过调整重复单元的顺反比可以进一步实现全系列聚烯烃类特性。

此外，这些材料可以由廉价的一氧化碳和2-丁烯原料合成，并且可以在其寿命结束时进行化学回收或升级循环使用。这种聚酯系列的多用途特性、丰富的原料和寿命终止用途将为发现可持续的聚烯烃塑料替代品提供强大的平台。

附：英文原文

Title: Nature-inspired methylated polyhydroxybutyrates from C1 and C4 feedstocks

Author: Zhou, Zhiyao, LaPointe, Anne M., Shaffer, Timothy D., Coates, Geoffrey W.

Issue&Volume: 2023-04-06

Abstract: Polyolefin plastics are widely used due to their low cost and outstanding properties, but their environmental persistence presents a major societal challenge. Polyhydroxyalkanoates (PHA) are biodegradable substitutes for polyolefins, but their high cost and thermal instability are impediments to their widespread application. Here we report a series of methylated polyhydroxybutyrates, poly(3-hydroxy-2-methylbutyrate)s, which are structurally inspired by natural PHAs. The cis homopolymers exhibit tacticity-independent crystallinity, which allows for the discovery of high-melting, thermally stable and mechanically tough copolymers, and a full range of polyolefin-like properties can be further achieved by tailoring the cis/trans ratio of the repeating units. Moreover, these materials can be synthesized from inexpensive carbon monoxide and 2-butene feedstocks, and they can be chemically recycled or upcycled at their end of life. The versatile properties, abundant feedstocks and end-of-life utility of this family of polyesters will enable a powerful platform for the discovery of sustainable alternatives to polyolefin plastics.

DOI: 10.1038/s41557-023-01187-0

Source: https://www.nature.com/articles/s41557-023-01187-0