2-（二甲氨基）甲基丙烯酸乙酯/丙烯酸甲酯自由基共聚动力学研究及溶剂溶解反应

IF 6.3 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal Pub Date : 2025-09-02 DOI:10.1016/j.eurpolymj.2025.114253

Opeyemi J. Ajogbeje, Robin A. Hutchinson

{"title":"2-（二甲氨基）甲基丙烯酸乙酯/丙烯酸甲酯自由基共聚动力学研究及溶剂溶解反应","authors":"Opeyemi J. Ajogbeje, Robin A. Hutchinson","doi":"10.1016/j.eurpolymj.2025.114253","DOIUrl":null,"url":null,"abstract":"<div><div>In-situ NMR is used to determine individual monomer conversion profiles and thus comonomer composition drifts vs. overall monomer conversion for the radical copolymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) with methyl acrylate (MA) in dimethyl sulfoxide, toluene, ethanol (EtOH), and an ethanol/water mixture containing 75 wt% EtOH. A faster incorporation of DMAEMA was observed in the copolymer compared to MA in all systems, with the data used to estimate reactivity ratios. In addition, the copolymer composition-averaged propagation rate coefficients (<span><math><msubsup><mi>k</mi><mrow><mi>p</mi></mrow><mrow><mi>c</mi><mi>o</mi><mi>p</mi></mrow></msubsup></math></span>) were obtained using the pulsed laser polymerization – size exclusion chromatography (PLP-SEC) technique for the system in bulk and in EtOH. While the terminal model provided a good representation of copolymer composition, the penultimate model was needed to represent DMAEMA-MA <span><math><msubsup><mi>k</mi><mrow><mi>p</mi></mrow><mrow><mi>c</mi><mi>o</mi><mi>p</mi></mrow></msubsup></math></span> behavior. When DMAEMA and MA were present in water-rich EtOH/water mixtures, the solvolysis of DMAEMA formed methacrylic acid (MAA) and ethyl methacrylate (EMA), potentially leading to formation of a tetrapolymer. While the kinetics of this more complex system was not studied, it was demonstrated that the influence of monomer solvolysis can be important for DMAEMA copolymerization in aqueous solvent mixtures.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"239 ","pages":"Article 114253"},"PeriodicalIF":6.3000,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"An investigation of solvolytic reactions and exploration of 2-(dimethylamino)ethyl methacrylate/methyl acrylate free radical copolymerization kinetics\",\"authors\":\"Opeyemi J. Ajogbeje, Robin A. Hutchinson\",\"doi\":\"10.1016/j.eurpolymj.2025.114253\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>In-situ NMR is used to determine individual monomer conversion profiles and thus comonomer composition drifts vs. overall monomer conversion for the radical copolymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) with methyl acrylate (MA) in dimethyl sulfoxide, toluene, ethanol (EtOH), and an ethanol/water mixture containing 75 wt% EtOH. A faster incorporation of DMAEMA was observed in the copolymer compared to MA in all systems, with the data used to estimate reactivity ratios. In addition, the copolymer composition-averaged propagation rate coefficients (<span><math><msubsup><mi>k</mi><mrow><mi>p</mi></mrow><mrow><mi>c</mi><mi>o</mi><mi>p</mi></mrow></msubsup></math></span>) were obtained using the pulsed laser polymerization – size exclusion chromatography (PLP-SEC) technique for the system in bulk and in EtOH. While the terminal model provided a good representation of copolymer composition, the penultimate model was needed to represent DMAEMA-MA <span><math><msubsup><mi>k</mi><mrow><mi>p</mi></mrow><mrow><mi>c</mi><mi>o</mi><mi>p</mi></mrow></msubsup></math></span> behavior. When DMAEMA and MA were present in water-rich EtOH/water mixtures, the solvolysis of DMAEMA formed methacrylic acid (MAA) and ethyl methacrylate (EMA), potentially leading to formation of a tetrapolymer. While the kinetics of this more complex system was not studied, it was demonstrated that the influence of monomer solvolysis can be important for DMAEMA copolymerization in aqueous solvent mixtures.</div></div>\",\"PeriodicalId\":315,\"journal\":{\"name\":\"European Polymer Journal\",\"volume\":\"239 \",\"pages\":\"Article 114253\"},\"PeriodicalIF\":6.3000,\"publicationDate\":\"2025-09-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"European Polymer Journal\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0014305725005415\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"European Polymer Journal","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0014305725005415","RegionNum":2,"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

摘要

原位核磁共振用于确定单个单体转化谱，从而确定单体组成漂移与整体单体转化2-（二甲氨基）甲基丙烯酸乙酯（DMAEMA）与丙烯酸甲酯（MA）在二甲亚砜、甲苯、乙醇（EtOH）和含有75% EtOH的乙醇/水混合物中的自由基共聚。与所有体系中的MA相比，共聚物中DMAEMA的掺入速度更快，数据用于估计反应性比。此外，利用脉冲激光聚合-粒径排除色谱（PLP-SEC）技术获得了体系在散装和EtOH下的共聚物组成-平均增殖速率系数（kpcop）。虽然末端模型可以很好地表示共聚物的组成，但需要倒数第二个模型来表示DMAEMA-MA kpcop行为。当DMAEMA和MA存在于富水EtOH/水混合物中时，DMAEMA的溶剂解形成甲基丙烯酸（MAA）和甲基丙烯酸乙酯（EMA），可能导致形成四聚物。虽然这个更复杂的体系的动力学没有被研究，但它证明了单体溶剂溶解对DMAEMA在水溶剂混合物中的共聚的影响是重要的。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

An investigation of solvolytic reactions and exploration of 2-(dimethylamino)ethyl methacrylate/methyl acrylate free radical copolymerization kinetics

查看原文本刊更多论文

An investigation of solvolytic reactions and exploration of 2-(dimethylamino)ethyl methacrylate/methyl acrylate free radical copolymerization kinetics

In-situ NMR is used to determine individual monomer conversion profiles and thus comonomer composition drifts vs. overall monomer conversion for the radical copolymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) with methyl acrylate (MA) in dimethyl sulfoxide, toluene, ethanol (EtOH), and an ethanol/water mixture containing 75 wt% EtOH. A faster incorporation of DMAEMA was observed in the copolymer compared to MA in all systems, with the data used to estimate reactivity ratios. In addition, the copolymer composition-averaged propagation rate coefficients (

k_{p}^{c o p}

) were obtained using the pulsed laser polymerization – size exclusion chromatography (PLP-SEC) technique for the system in bulk and in EtOH. While the terminal model provided a good representation of copolymer composition, the penultimate model was needed to represent DMAEMA-MA

k_{p}^{c o p}

behavior. When DMAEMA and MA were present in water-rich EtOH/water mixtures, the solvolysis of DMAEMA formed methacrylic acid (MAA) and ethyl methacrylate (EMA), potentially leading to formation of a tetrapolymer. While the kinetics of this more complex system was not studied, it was demonstrated that the influence of monomer solvolysis can be important for DMAEMA copolymerization in aqueous solvent mixtures.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

European Polymer Journal 化学-高分子科学

CiteScore

9.90

自引率

10.00%

发文量

691

审稿时长

23 days

期刊介绍： European Polymer Journal is dedicated to publishing work on fundamental and applied polymer chemistry and macromolecular materials. The journal covers all aspects of polymer synthesis, including polymerization mechanisms and chemical functional transformations, with a focus on novel polymers and the relationships between molecular structure and polymer properties. In addition, we welcome submissions on bio-based or renewable polymers, stimuli-responsive systems and polymer bio-hybrids. European Polymer Journal also publishes research on the biomedical application of polymers, including drug delivery and regenerative medicine. The main scope is covered but not limited to the following core research areas: Polymer synthesis and functionalization • Novel synthetic routes for polymerization, functional modification, controlled/living polymerization and precision polymers. Stimuli-responsive polymers • Including shape memory and self-healing polymers. Supramolecular polymers and self-assembly • Molecular recognition and higher order polymer structures. Renewable and sustainable polymers • Bio-based, biodegradable and anti-microbial polymers and polymeric bio-nanocomposites. Polymers at interfaces and surfaces • Chemistry and engineering of surfaces with biological relevance, including patterning, antifouling polymers and polymers for membrane applications. Biomedical applications and nanomedicine • Polymers for regenerative medicine, drug delivery molecular release and gene therapy The scope of European Polymer Journal no longer includes Polymer Physics.