Sustainable Terephthalic Polyesters with Medium/Long Methylene Sequence: Structure–Property Relationships and Closed-Loop Chemical Recycling

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-12-23 DOI:10.1021/acs.macromol.4c01793

Junfeng Liu, Jianfei Xia, Chang Zeng, Chengtao Yu, Ying Zheng, Bao Wang, Shanshan Xu, Pengju Pan

{"title":"Sustainable Terephthalic Polyesters with Medium/Long Methylene Sequence: Structure–Property Relationships and Closed-Loop Chemical Recycling","authors":"Junfeng Liu, Jianfei Xia, Chang Zeng, Chengtao Yu, Ying Zheng, Bao Wang, Shanshan Xu, Pengju Pan","doi":"10.1021/acs.macromol.4c01793","DOIUrl":null,"url":null,"abstract":"Traditional short-chain terephthalic polyesters such as poly(ethylene terephthalate) (PET) are among the most produced plastics in today’s polymer industry, while their large-scale chemical recycling has been a long-standing challenge. The long-chain polyesters have shown good recyclability under mild conditions, whereas the structure–property relationships and chemical recycling performance of long-chain terephthalic polyesters are still unclear. Herein, we synthesized a series of medium/long-chain terephthalic polyesters with different methylene sequence lengths (CH2 number in diol monomer nCH2 = 6, 8, 10, 12) and investigated their thermal properties, crystallization behavior, mechanical properties, and chemical recycling performance. All terephthalic polyesters show good crystallizability; their melting temperature decreases, and melting enthalpy increases gradually as nCH2 increases from 2 to 12. All polyesters adopt a triclinic crystal lattice while slightly different crystalline lamellar structures. The medium/long-chain terephthalic polyesters exhibit improved ductility and good melt processability, enabling them to be used as three-dimensional (3D) printing materials. In addition, the medium- and long-chain terephthalic polyesters are chemically recyclable and can depolymerize under mild conditions (e.g., 140 °C in methanol). The monomers obtained by depolymerization can be reused to synthesize again the according polyesters. This study provides new inspiration for developing sustainable high-performance polyesters with great industrial potential.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"149 1","pages":""},"PeriodicalIF":5.1000,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c01793","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}

引用次数: 0

Abstract

Traditional short-chain terephthalic polyesters such as poly(ethylene terephthalate) (PET) are among the most produced plastics in today’s polymer industry, while their large-scale chemical recycling has been a long-standing challenge. The long-chain polyesters have shown good recyclability under mild conditions, whereas the structure–property relationships and chemical recycling performance of long-chain terephthalic polyesters are still unclear. Herein, we synthesized a series of medium/long-chain terephthalic polyesters with different methylene sequence lengths (CH₂ number in diol monomer n_CH₂ = 6, 8, 10, 12) and investigated their thermal properties, crystallization behavior, mechanical properties, and chemical recycling performance. All terephthalic polyesters show good crystallizability; their melting temperature decreases, and melting enthalpy increases gradually as n_CH₂ increases from 2 to 12. All polyesters adopt a triclinic crystal lattice while slightly different crystalline lamellar structures. The medium/long-chain terephthalic polyesters exhibit improved ductility and good melt processability, enabling them to be used as three-dimensional (3D) printing materials. In addition, the medium- and long-chain terephthalic polyesters are chemically recyclable and can depolymerize under mild conditions (e.g., 140 °C in methanol). The monomers obtained by depolymerization can be reused to synthesize again the according polyesters. This study provides new inspiration for developing sustainable high-performance polyesters with great industrial potential.

Abstract Image

查看原文本刊更多论文

可持续发展的中/长亚甲基对苯二甲酸聚酯：结构-性能关系和闭环化学回收

传统的短链对苯二甲酸聚酯，如聚对苯二甲酸乙酯（PET），是当今聚合物工业中产量最大的塑料之一，而它们的大规模化学回收一直是一个长期的挑战。长链聚酯在温和条件下表现出良好的可回收性，但长链对苯二甲酸聚酯的结构-性能关系和化学回收性能尚不清楚。本文合成了一系列不同亚甲基序列长度（二醇单体中CH2数nCH2 = 6、8、10、12）的中/长链对苯二甲酸聚酯，并研究了它们的热性能、结晶行为、力学性能和化学回收性能。所有对苯二甲酸聚酯均表现出良好的结晶性；随着nCH2从2增加到12，它们的熔化温度逐渐降低，熔化焓逐渐增大。所有聚酯都采用三斜晶格，而晶体层状结构略有不同。中/长链对苯二甲酸聚酯具有更好的延展性和良好的熔融加工性，使其能够用作三维（3D）打印材料。此外，中链和长链对苯二甲酸聚酯是化学可回收的，可以在温和的条件下（例如，在甲醇中140°C）解聚。解聚得到的单体可重复利用，再合成相应的聚酯。该研究为开发具有巨大工业潜力的可持续高性能聚酯提供了新的启示。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.