Reactivity Ratios of Biobased Dibutyl Itaconate with Conventional and Renewable (Meth)Acrylates: Influence of Depropagation.

IF 5.4 2区化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY

Biomacromolecules Pub Date : 2025-10-13 DOI:10.1021/acs.biomac.5c01505

Jyoti Gupta, Radmila Tomovska, Shaghayegh Hamzehlou, Miren Aguirre

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引用次数: 0

Abstract

The global push for sustainability has driven interest in renewable monomers such as dibutyl itaconate (DBI). Despite its potential for biobased high-performance polymers, DBI's copolymerization with (meth)acrylates is challenging due to low propagation rates, depropagation at moderate temperatures, and unfavorable reactivity ratios. This study investigates the solution copolymerization of DBI with both conventional, butyl acrylate (BA) and methyl methacrylate (MMA), and biobased (2-octyl acrylate (2-OA) and isobornyl acrylate (IBOA)) monomers. Using in situ ¹H NMR and nonlinear least-squares fitting, reactivity ratios were determined: BA/DBI (r_BA = 0.68, r_DBI = 0.68), MMA/DBI (r_MMA = 3.53, r_DBI = 0.38), 2-OA/DBI (r_2-OA = 1.64, r_DBI = 1.44), and IBOA/DBI (r_IBOA = 1.87, r_DBI = 2.0). The study also clarifies discrepancies in literature values for BA/DBI due to uncertainties in DBI's depropagation rates. DBI copolymers with BA, 2-OA, and IBOA showed a lower composition drift than MMA/DBI, which showed a greater disparity in reactivity ratios.

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生物基衣康酸二丁酯与常规和可再生（甲基）丙烯酸酯的反应性比率：退化的影响。

全球对可持续发展的推动推动了对衣康酸二丁酯（DBI）等可再生单体的兴趣。尽管具有生物基高性能聚合物的潜力，但DBI与（甲基）丙烯酸酯的共聚具有挑战性，因为其繁殖速率低，在中等温度下会发生反繁殖，并且反应性比不利。本研究研究了DBI与常规丙烯酸丁酯（BA）和甲基丙烯酸甲酯（MMA）以及生物基丙烯酸2-辛酯（2-OA）和丙烯酸异鸟酯（IBOA）单体的溶液共聚。利用原位1H NMR和非线性最小二乘拟合，确定了BA/DBI （rBA = 0.68, rDBI = 0.68）、MMA/DBI （rMMA = 3.53, rDBI = 0.38）、2-OA/DBI （r2-OA = 1.64, rDBI = 1.44）和IBOA/DBI （rIBOA = 1.87, rDBI = 2.0）的反应性比。该研究还澄清了由于DBI去传播速率的不确定性，BA/DBI的文献值存在差异。与MMA/DBI相比，BA、2-OA和IBOA的DBI共聚物的组分漂移较小，反应性差异较大。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Biomacromolecules 化学-高分子科学

CiteScore

10.60

自引率

4.80%

发文量

417

审稿时长

1.6 months

期刊介绍： Biomacromolecules is a leading forum for the dissemination of cutting-edge research at the interface of polymer science and biology. Submissions to Biomacromolecules should contain strong elements of innovation in terms of macromolecular design, synthesis and characterization, or in the application of polymer materials to biology and medicine. Topics covered by Biomacromolecules include, but are not exclusively limited to: sustainable polymers, polymers based on natural and renewable resources, degradable polymers, polymer conjugates, polymeric drugs, polymers in biocatalysis, biomacromolecular assembly, biomimetic polymers, polymer-biomineral hybrids, biomimetic-polymer processing, polymer recycling, bioactive polymer surfaces, original polymer design for biomedical applications such as immunotherapy, drug delivery, gene delivery, antimicrobial applications, diagnostic imaging and biosensing, polymers in tissue engineering and regenerative medicine, polymeric scaffolds and hydrogels for cell culture and delivery.