Emile Goldbach, Xavier Allonas, Lucile Halbardier, Christian Ley, Céline Croutxé-Barghorn
{"title":"使用吡啶衍生物作为环氧化物光诱导阳离子聚合的抑制剂/缓凝剂","authors":"Emile Goldbach, Xavier Allonas, Lucile Halbardier, Christian Ley, Céline Croutxé-Barghorn","doi":"10.1016/j.reactfunctpolym.2024.105922","DOIUrl":null,"url":null,"abstract":"<div><p>In this study, the cationic photopolymerization of epoxy controlled by pyridine derivative was investigated. Two pyridines were selected in order to explore the impact of the associated pKa and the amine steric hindrance on the polymerization. The inhibition, the polymerization rate, the heat flow and the conversion during dark polymerization were found to be affected depending of the pyridine derivative structure. Two mechanisms seem to be involved. 1) During the initiation step, the proton is trapped by pyridine derivative, a fact which delays the polymerization reaction, because of less growing chains and lower exothermicity. 2) During the propagation reaction, an interaction between the oxonium ion and the pyridine derivative takes place, which results in a decrease of the rate of polymerization. These two mechanisms depend on the concentration, but also on the associated pKa and on the steric hindrance of the amine, which allows a tailorable control over the cationic polymerization kinetics.</p></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":null,"pages":null},"PeriodicalIF":4.5000,"publicationDate":"2024-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Use of pyridine derivatives as inhibitor/retarding agent for photoinduced cationic polymerization of epoxides\",\"authors\":\"Emile Goldbach, Xavier Allonas, Lucile Halbardier, Christian Ley, Céline Croutxé-Barghorn\",\"doi\":\"10.1016/j.reactfunctpolym.2024.105922\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In this study, the cationic photopolymerization of epoxy controlled by pyridine derivative was investigated. Two pyridines were selected in order to explore the impact of the associated pKa and the amine steric hindrance on the polymerization. The inhibition, the polymerization rate, the heat flow and the conversion during dark polymerization were found to be affected depending of the pyridine derivative structure. Two mechanisms seem to be involved. 1) During the initiation step, the proton is trapped by pyridine derivative, a fact which delays the polymerization reaction, because of less growing chains and lower exothermicity. 2) During the propagation reaction, an interaction between the oxonium ion and the pyridine derivative takes place, which results in a decrease of the rate of polymerization. These two mechanisms depend on the concentration, but also on the associated pKa and on the steric hindrance of the amine, which allows a tailorable control over the cationic polymerization kinetics.</p></div>\",\"PeriodicalId\":20916,\"journal\":{\"name\":\"Reactive & Functional Polymers\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.5000,\"publicationDate\":\"2024-04-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Reactive & Functional Polymers\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S138151482400097X\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Reactive & Functional Polymers","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S138151482400097X","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Use of pyridine derivatives as inhibitor/retarding agent for photoinduced cationic polymerization of epoxides
In this study, the cationic photopolymerization of epoxy controlled by pyridine derivative was investigated. Two pyridines were selected in order to explore the impact of the associated pKa and the amine steric hindrance on the polymerization. The inhibition, the polymerization rate, the heat flow and the conversion during dark polymerization were found to be affected depending of the pyridine derivative structure. Two mechanisms seem to be involved. 1) During the initiation step, the proton is trapped by pyridine derivative, a fact which delays the polymerization reaction, because of less growing chains and lower exothermicity. 2) During the propagation reaction, an interaction between the oxonium ion and the pyridine derivative takes place, which results in a decrease of the rate of polymerization. These two mechanisms depend on the concentration, but also on the associated pKa and on the steric hindrance of the amine, which allows a tailorable control over the cationic polymerization kinetics.
期刊介绍:
Reactive & Functional Polymers provides a forum to disseminate original ideas, concepts and developments in the science and technology of polymers with functional groups, which impart specific chemical reactivity or physical, chemical, structural, biological, and pharmacological functionality. The scope covers organic polymers, acting for instance as reagents, catalysts, templates, ion-exchangers, selective sorbents, chelating or antimicrobial agents, drug carriers, sensors, membranes, and hydrogels. This also includes reactive cross-linkable prepolymers and high-performance thermosetting polymers, natural or degradable polymers, conducting polymers, and porous polymers.
Original research articles must contain thorough molecular and material characterization data on synthesis of the above polymers in combination with their applications. Applications include but are not limited to catalysis, water or effluent treatment, separations and recovery, electronics and information storage, energy conversion, encapsulation, or adhesion.