The Synthesis of Acrylate-Based Macromonomers and Structured Copolymers by High-Temperature Semi-Batch Radical Polymerization: The Impact of Acrylate vs. Methacrylate Monomer Choice

IF 3.9 3区化学 Q2 POLYMER SCIENCE

Journal of Polymer Science Pub Date : 2025-02-18 DOI:10.1002/pol.20240980

Elizabeth G. Bygott, David Pahovnik, Ema Žagar, Robin A. Hutchinson

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Abstract

High-temperature starved-feed semi-batch radical polymerization is used to produce an isobornyl acrylate (iBoA) polymer solution with high macromonomer content without a mediating agent. The p(iBoA) macromonomer solution serves as an addition-fragmentation agent to synthesize a blocky copolymer in a single-pot sequential feeding process, as has been demonstrated using n-butyl acrylate (BA) as the second monomer. The impact of monomer selection on the copolymer product is investigated by switching the second monomer to n-butyl methacrylate (BMA) while keeping all other aspects of the operating strategy unchanged. Methodologies developed to verify macromonomer incorporation are used to compare the iBoA-BA and iBoA-BMA systems, with two-dimensional liquid chromatography providing a clear contrast between the acrylate and methacrylate (co)polymer products. The comparison demonstrates the effect of monomer structure on the macromonomer addition-fragmentation kinetics, with a blocky copolymer produced using the acrylate macromonomer only when an acrylate is used as the second monomer feed.

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高温半间歇自由基聚合合成丙烯酸酯基大单体及结构共聚物：丙烯酸酯与甲基丙烯酸酯单体选择的影响

采用高温喂料半间歇自由基聚合法，在不添加中间剂的情况下制备了高单体含量的丙烯酸异鸟酯（iBoA）聚合物溶液。以丙烯酸正丁酯（BA）为第二单体，p（iBoA）大单体溶液可作为添加-破碎剂，在单锅连续加料过程中合成嵌段共聚物。在保持所有其他操作策略不变的情况下，通过将第二种单体转换为甲基丙烯酸正丁酯（BMA），研究了单体选择对共聚物产品的影响。用于验证大单体掺入的方法被用于比较iBoA-BA和iBoA-BMA体系，二维液相色谱提供了丙烯酸酯和甲基丙烯酸酯（co）聚合物产品之间的清晰对比。比较表明单体结构对大单体加成-破碎动力学的影响，只有当丙烯酸酯作为第二单体进料时，才用丙烯酸酯大单体制得块状共聚物。

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来源期刊

Journal of Polymer Science POLYMER SCIENCE-

CiteScore

6.30

自引率

5.90%

发文量

264

期刊介绍： Journal of Polymer Research provides a forum for the prompt publication of articles concerning the fundamental and applied research of polymers. Its great feature lies in the diversity of content which it encompasses, drawing together results from all aspects of polymer science and technology. As polymer research is rapidly growing around the globe, the aim of this journal is to establish itself as a significant information tool not only for the international polymer researchers in academia but also for those working in industry. The scope of the journal covers a wide range of the highly interdisciplinary field of polymer science and technology.