Development of Biodegradable and Biobased Poly(glycerol levulinate-co-glycerol malonate) Copolyesters with Controlled Degradation

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-09-10 DOI:10.1021/acs.macromol.5c00383

Huru Rabia Gulec, , , Zaid Kareem, , , Mete Karaboyun, , and , Ersan Eyiler*,

{"title":"Development of Biodegradable and Biobased Poly(glycerol levulinate-co-glycerol malonate) Copolyesters with Controlled Degradation","authors":"Huru Rabia Gulec, , , Zaid Kareem, , , Mete Karaboyun, , and , Ersan Eyiler*, ","doi":"10.1021/acs.macromol.5c00383","DOIUrl":null,"url":null,"abstract":"<p >Fully biobased oligomers were synthesized from glycerol, levulinic acid, and malonic acid via melt polycondensation. Itaconic acid with a carbon–carbon double bond was incorporated to enable cross-linking using dicumyl peroxide. The effect of the monomer molar ratio on material properties was investigated to understand the structure–property relationships. The addition of malonic acid, acting as both a monomer and a secondary cross-linker, was found to tune the glass-transition temperature, thermal stability, and degradation behavior of the cross-linked random copolyesters. Thermogravimetric analysis (TGA) revealed that malonic acid significantly improved the thermal stability, increasing it by up to 7.6% compared to the neat polymer. The cross-linked copolyesters exhibited excellent degradation profiles, making them suitable for biomedical applications where controlled degradation is essential. Additionally, they demonstrated outstanding shape memory properties, with a nearly 100% shape recovery, offering further potential for biomedical device fabrication.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 18","pages":"9952–9961"},"PeriodicalIF":5.2000,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.macromol.5c00383","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.macromol.5c00383","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

Fully biobased oligomers were synthesized from glycerol, levulinic acid, and malonic acid via melt polycondensation. Itaconic acid with a carbon–carbon double bond was incorporated to enable cross-linking using dicumyl peroxide. The effect of the monomer molar ratio on material properties was investigated to understand the structure–property relationships. The addition of malonic acid, acting as both a monomer and a secondary cross-linker, was found to tune the glass-transition temperature, thermal stability, and degradation behavior of the cross-linked random copolyesters. Thermogravimetric analysis (TGA) revealed that malonic acid significantly improved the thermal stability, increasing it by up to 7.6% compared to the neat polymer. The cross-linked copolyesters exhibited excellent degradation profiles, making them suitable for biomedical applications where controlled degradation is essential. Additionally, they demonstrated outstanding shape memory properties, with a nearly 100% shape recovery, offering further potential for biomedical device fabrication.

Abstract Image

查看原文本刊更多论文

可生物降解和生物基可控降解聚丙二酸甘油-丙二酸甘油共聚酯的研制

以甘油、乙酰丙酸和丙二酸为原料，通过熔融缩聚法合成了全生物基低聚物。采用碳碳双键的衣康酸，通过过氧化二氨基进行交联。研究了单体摩尔比对材料性能的影响，以了解材料的结构-性能关系。丙二酸的加入，作为单体和二级交联剂，被发现可以调整玻璃化转变温度、热稳定性和交联随机共聚酯的降解行为。热重分析（TGA）表明，丙二酸显著改善了聚合物的热稳定性，与纯聚合物相比，其热稳定性提高了7.6%。交联共聚酯表现出优异的降解特性，使其适用于生物医学应用，其中控制降解是必不可少的。此外，它们还展示了出色的形状记忆特性，几乎100%的形状恢复，为生物医学设备制造提供了进一步的潜力。

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.