生物基 2,5-双（羟甲基）呋喃聚酯的酶促批量合成、表征、流变性和生物降解性

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry Pub Date : 2024-05-29 DOI:10.1039/d4gc01512f

Cornelis Post, Dina Maniar, Jesse A. Jongstra, Daniele Parisi, Vincent S. D. Voet, Rudy Folkersma, Katja Loos

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引用次数: 0

摘要

由于 2,5-双（羟甲基）呋喃 (BHMF) 这种有趣的呋喃单体稳定性有限，因此合成基于这种单体的生物基聚酯具有挑战性。在这项工作中，通过使用酶（iCALB）或市售催化剂（DBTO），采用绿色高效的大体积聚合工艺生产了一系列基于 BHMF 的聚酯。对这两种聚合方法进行了比较，结果表明这两种方法都很成功，聚合值最高可达 14 000 g mol-1。脂肪族共聚单体中的亚甲基单元数目从 2 个到 8 个不等，研究了这一数目对聚合物热行为和稳定性的影响。研究发现，压缩成型盘的结晶度在 13% 到 27% 之间，接触角在 63° 到 73° 之间，这证实了这些聚酯具有亲水性。振荡剪切流变学研究表明，基于 BHMF 的聚酯的熔体行为存在显著差异，从牛顿液体到剪切稀化材料，其复合粘度高出 3 个数量级。低频复合粘度与脂肪族段中亚甲基单元的数量之间存在明显的反比关系。最后，生物降解性测试表明，合成的 BHMF 基聚酯随着时间的推移具有可生物降解的特性，其中观察到不同的生物降解率与重复单元中脂肪族段的长度有关。根据原子经济性 (AE)、反应质量效率 (RME)、E 因子和 EcoScale 分析了这两种合成路线的可持续性。这项研究强调，可再生的 BHMF 基聚酯可通过无溶剂和可持续的工艺生产，具有可生物降解的特性，并且可通过改变脂肪族单元中亚甲基的数量来定制其热学和流变学特性。

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Enzymatic bulk synthesis, characterization, rheology, and biodegradability of biobased 2,5-bis(hydroxymethyl)furan polyesters

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Enzymatic bulk synthesis, characterization, rheology, and biodegradability of biobased 2,5-bis(hydroxymethyl)furan polyesters

The synthesis of biobased polyesters based on 2,5-bis(hydroxymethyl)furan (BHMF) is challenging due to the limited stability of this interesting furanic monomer. In this work, a series of BHMF-based polyesters were produced via a green and efficient bulk polymerization process, by using either an enzyme (iCALB) or a commercially available catalyst (DBTO). The polymerization methods were compared and shown to both be successful, with Image ID:d4gc01512f-t1.gif

values up to 14 000 g mol⁻¹. The number of methylene units in the aliphatic comonomer was varied from 2 to 8, and the influence of this on the thermal behavior and stability of the polymers was investigated. The degree of crystallinity of compression molded discs was found to be in the range from 13 to 27%, and the contact angles were determined to be in the region from 63 to 73°, confirming that these polyesters are hydrophilic. An oscillatory shear rheology investigation demonstrated significant differences between the melt behavior of the BHMF-based polyesters, ranging from a Newtonian liquid to a shear thinning material with a 3 orders of magnitude higher complex viscosity. A clear inversely proportional correlation between the low-frequency complex viscosity and the number of methylene units in the aliphatic segment was observed. Finally, a biodegradability test revealed that the synthesized BHMF-based polyesters had a biodegradable character over time, wherein different biodegradation rates were observed related to the length of aliphatic segments in the repeating units. The sustainability of both synthesis routes was analyzed based on atom economy (AE), reaction mass efficiency (RME), E-factor and EcoScale. This work emphasizes that renewable BHMF-based polyesters can be produced via a solvent-free and sustainable process, which show biodegradable behavior and that their thermal and rheological properties can be tailored by varying the number of methylene groups in the aliphatic unit.

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来源期刊

Green Chemistry 化学-化学综合

CiteScore

16.10

自引率

7.10%

发文量

677

审稿时长

1.4 months

期刊介绍： Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.