{"title":"复合引发体系下target - atrp制备丙烯酸酯的乳液及动力学研究","authors":"Xingbing Yang, Wei Li, Qian Wu, Qin Zhang, Jingyi Li, Tingting Jiang, Qin Xiao","doi":"10.1134/S1560090425600445","DOIUrl":null,"url":null,"abstract":"<p>Acrylate emulsions were prepared through atom transfer radical polymerization (ARGET-ATRP) with methyl methacrylate (MMA), ethyl acrylate (EA) and butyl acrylate (BA) as monomers using electron transfer-activated regenerative catalysts, with benzyl bromide (BBB) and ethyl 2-bromoisobutyrate (EBIB) as a complex initiation system and copper bromide and bipyridine as a catalytic system. The effects of the temperature, the compound initiator ratio, the compound emulsifier ratio, the ligand type and the content on the polymerization dynamics were examined, and the polymer was characterized by infrared spectroscopy and 1H NMR. This study revealed that the monomer conversion rate and the apparent polymerization rate are positively correlated with the reaction temperature, and the apparent activation energy of the reaction was <i>E</i><sub>a</sub> = 57.63 KJ/mol. When benzyl bromide was used as the initiator alone, the initiation efficiency of the system was low. After EBIB was added, the initiation effect was greater for benzyl bromide : EBIB = 7 : 3, and the conversion rate and polymerization rate were positively correlated with the amount of reducing agent. The monomer conversion rate and apparent growth rate constant were the greatest when the mass ratio of the emulsifier sodium dodecyl sulfate and sodium dodecyl benzene sulfonate was 7 : 3. Different ligands affected the monomer conversion rate and apparent growth rate constant, and with increasing ligand content, the monomer conversion rate and apparent polymerization rate constant increased. According to the results of infrared spectroscopy and nuclear magnetic hydrogen spectroscopy, the compound initiator successfully triggered the polymerized monomer to generate the ternary copolymer.</p>","PeriodicalId":739,"journal":{"name":"Polymer Science, Series B","volume":"66 6","pages":"684 - 692"},"PeriodicalIF":1.0000,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Emulsion and Dynamics of Acrylate Prepared by ARGET-ATRP under a Compound Initiation System\",\"authors\":\"Xingbing Yang, Wei Li, Qian Wu, Qin Zhang, Jingyi Li, Tingting Jiang, Qin Xiao\",\"doi\":\"10.1134/S1560090425600445\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Acrylate emulsions were prepared through atom transfer radical polymerization (ARGET-ATRP) with methyl methacrylate (MMA), ethyl acrylate (EA) and butyl acrylate (BA) as monomers using electron transfer-activated regenerative catalysts, with benzyl bromide (BBB) and ethyl 2-bromoisobutyrate (EBIB) as a complex initiation system and copper bromide and bipyridine as a catalytic system. The effects of the temperature, the compound initiator ratio, the compound emulsifier ratio, the ligand type and the content on the polymerization dynamics were examined, and the polymer was characterized by infrared spectroscopy and 1H NMR. This study revealed that the monomer conversion rate and the apparent polymerization rate are positively correlated with the reaction temperature, and the apparent activation energy of the reaction was <i>E</i><sub>a</sub> = 57.63 KJ/mol. When benzyl bromide was used as the initiator alone, the initiation efficiency of the system was low. After EBIB was added, the initiation effect was greater for benzyl bromide : EBIB = 7 : 3, and the conversion rate and polymerization rate were positively correlated with the amount of reducing agent. The monomer conversion rate and apparent growth rate constant were the greatest when the mass ratio of the emulsifier sodium dodecyl sulfate and sodium dodecyl benzene sulfonate was 7 : 3. Different ligands affected the monomer conversion rate and apparent growth rate constant, and with increasing ligand content, the monomer conversion rate and apparent polymerization rate constant increased. According to the results of infrared spectroscopy and nuclear magnetic hydrogen spectroscopy, the compound initiator successfully triggered the polymerized monomer to generate the ternary copolymer.</p>\",\"PeriodicalId\":739,\"journal\":{\"name\":\"Polymer Science, Series B\",\"volume\":\"66 6\",\"pages\":\"684 - 692\"},\"PeriodicalIF\":1.0000,\"publicationDate\":\"2025-06-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Science, Series B\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S1560090425600445\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Science, Series B","FirstCategoryId":"1","ListUrlMain":"https://link.springer.com/article/10.1134/S1560090425600445","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Emulsion and Dynamics of Acrylate Prepared by ARGET-ATRP under a Compound Initiation System
Acrylate emulsions were prepared through atom transfer radical polymerization (ARGET-ATRP) with methyl methacrylate (MMA), ethyl acrylate (EA) and butyl acrylate (BA) as monomers using electron transfer-activated regenerative catalysts, with benzyl bromide (BBB) and ethyl 2-bromoisobutyrate (EBIB) as a complex initiation system and copper bromide and bipyridine as a catalytic system. The effects of the temperature, the compound initiator ratio, the compound emulsifier ratio, the ligand type and the content on the polymerization dynamics were examined, and the polymer was characterized by infrared spectroscopy and 1H NMR. This study revealed that the monomer conversion rate and the apparent polymerization rate are positively correlated with the reaction temperature, and the apparent activation energy of the reaction was Ea = 57.63 KJ/mol. When benzyl bromide was used as the initiator alone, the initiation efficiency of the system was low. After EBIB was added, the initiation effect was greater for benzyl bromide : EBIB = 7 : 3, and the conversion rate and polymerization rate were positively correlated with the amount of reducing agent. The monomer conversion rate and apparent growth rate constant were the greatest when the mass ratio of the emulsifier sodium dodecyl sulfate and sodium dodecyl benzene sulfonate was 7 : 3. Different ligands affected the monomer conversion rate and apparent growth rate constant, and with increasing ligand content, the monomer conversion rate and apparent polymerization rate constant increased. According to the results of infrared spectroscopy and nuclear magnetic hydrogen spectroscopy, the compound initiator successfully triggered the polymerized monomer to generate the ternary copolymer.
期刊介绍:
Polymer Science, Series B is a journal published in collaboration with the Russian Academy of Sciences. Series B experimental and theoretical papers and reviews dealing with the synthesis, kinetics, catalysis, and chemical transformations of macromolecules, supramolecular structures, and polymer matrix-based composites (6 issues a year). All journal series present original papers and reviews covering all fundamental aspects of macromolecular science. Contributions should be of marked novelty and interest for a broad readership. Articles may be written in English or Russian regardless of country and nationality of authors. All manuscripts are peer reviewed