苯乙烯衍生物、氧烷和芳香醛的顺序控制阳离子共聚合:酸或氧化可降解三元聚合物的合成

IF 5.2 1区 化学 Q1 POLYMER SCIENCE
Yuto Eguchi, Sadahito Aoshima and Arihiro Kanazawa*, 
{"title":"苯乙烯衍生物、氧烷和芳香醛的顺序控制阳离子共聚合:酸或氧化可降解三元聚合物的合成","authors":"Yuto Eguchi,&nbsp;Sadahito Aoshima and Arihiro Kanazawa*,&nbsp;","doi":"10.1021/acs.macromol.5c0053510.1021/acs.macromol.5c00535","DOIUrl":null,"url":null,"abstract":"<p >In this study, we investigated the cationic terpolymerization of styrene derivatives, oxiranes, and aromatic aldehydes to achieve precise sequence control. Cationic terpolymerization of <i>p</i>-methoxystyrene (pMOS), 1,2-epoxy-4-vinylcyclohexane (VCHO), and benzaldehyde (BzA) proceeded via crossover reactions, yielding terpolymers with high molecular weights (MWs). In addition, selective crossover reactions consisting of pMOS → VCHO, VCHO → BzA, and BzA → pMOS proceeded, resulting in terpolymers with controlled [(pMOS)<sub><i>x</i></sub>–(VCHO)<sub><i>y</i></sub>–BzA]<sub><i>n</i></sub> sequences. The BzA-derived propagating end, which has a structure similar to that of the styrene-derived propagating end, was important for effective terpolymerization as judged by inefficient crossover reactions using methyl ethyl ketone instead of benzaldehyde. By optimizing polymerization conditions, homopropagation reactions of styrene derivatives and oxiranes were almost suppressed in the terpolymerization of 4-<i>tert</i>-butoxystyrene, VCHO, and 2,4-dimethoxybenzaldehyde, resulting in terpolymers with ABC-type periodic sequences. The terpolymers were degraded into low-MW products by acid or oxidant via the cleavage of the crossover reaction-derived, secondary benzylic ether moieties in the main chain.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 9","pages":"4655–4664 4655–4664"},"PeriodicalIF":5.2000,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Sequence-Controlled Cationic Terpolymerization of Styrene Derivatives, Oxiranes, and Aromatic Aldehydes: Synthesis of Acidically or Oxidatively Degradable Terpolymers\",\"authors\":\"Yuto Eguchi,&nbsp;Sadahito Aoshima and Arihiro Kanazawa*,&nbsp;\",\"doi\":\"10.1021/acs.macromol.5c0053510.1021/acs.macromol.5c00535\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In this study, we investigated the cationic terpolymerization of styrene derivatives, oxiranes, and aromatic aldehydes to achieve precise sequence control. Cationic terpolymerization of <i>p</i>-methoxystyrene (pMOS), 1,2-epoxy-4-vinylcyclohexane (VCHO), and benzaldehyde (BzA) proceeded via crossover reactions, yielding terpolymers with high molecular weights (MWs). In addition, selective crossover reactions consisting of pMOS → VCHO, VCHO → BzA, and BzA → pMOS proceeded, resulting in terpolymers with controlled [(pMOS)<sub><i>x</i></sub>–(VCHO)<sub><i>y</i></sub>–BzA]<sub><i>n</i></sub> sequences. The BzA-derived propagating end, which has a structure similar to that of the styrene-derived propagating end, was important for effective terpolymerization as judged by inefficient crossover reactions using methyl ethyl ketone instead of benzaldehyde. By optimizing polymerization conditions, homopropagation reactions of styrene derivatives and oxiranes were almost suppressed in the terpolymerization of 4-<i>tert</i>-butoxystyrene, VCHO, and 2,4-dimethoxybenzaldehyde, resulting in terpolymers with ABC-type periodic sequences. The terpolymers were degraded into low-MW products by acid or oxidant via the cleavage of the crossover reaction-derived, secondary benzylic ether moieties in the main chain.</p>\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":\"58 9\",\"pages\":\"4655–4664 4655–4664\"},\"PeriodicalIF\":5.2000,\"publicationDate\":\"2025-04-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.macromol.5c00535\",\"RegionNum\":1,\"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":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.macromol.5c00535","RegionNum":1,"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

在本研究中,我们研究了苯乙烯衍生物、氧环烷和芳香醛的阳离子共聚合,以实现精确的序列控制。对甲氧基苯乙烯(pMOS)、1,2-环氧-4-乙烯基环己烷(VCHO)和苯甲醛(BzA)通过交叉反应进行阳离子共聚,得到了高分子量(MWs)的三元共聚物。通过pMOS→VCHO、VCHO→BzA、BzA→pMOS的选择性交叉反应,得到了具有可控[(pMOS)x - (VCHO) y-BzA]n序列的三元共聚物。bza衍生的繁殖端具有与苯乙烯衍生的繁殖端相似的结构,通过使用甲基乙基酮代替苯甲醛的低效交叉反应来判断,对于有效的三元聚合很重要。通过优化聚合条件,在4-叔丁基苯乙烯、VCHO和2,4-二甲氧基苯甲醛共聚合过程中,苯乙烯衍生物与氧环烷的同增殖反应几乎被抑制,得到了具有abc型周期序列的共聚合体。在酸或氧化剂的作用下,通过交叉反应衍生的主链上的仲苯醚部分的裂解,三元共聚物被降解成低分子量的产物。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Sequence-Controlled Cationic Terpolymerization of Styrene Derivatives, Oxiranes, and Aromatic Aldehydes: Synthesis of Acidically or Oxidatively Degradable Terpolymers

Sequence-Controlled Cationic Terpolymerization of Styrene Derivatives, Oxiranes, and Aromatic Aldehydes: Synthesis of Acidically or Oxidatively Degradable Terpolymers

In this study, we investigated the cationic terpolymerization of styrene derivatives, oxiranes, and aromatic aldehydes to achieve precise sequence control. Cationic terpolymerization of p-methoxystyrene (pMOS), 1,2-epoxy-4-vinylcyclohexane (VCHO), and benzaldehyde (BzA) proceeded via crossover reactions, yielding terpolymers with high molecular weights (MWs). In addition, selective crossover reactions consisting of pMOS → VCHO, VCHO → BzA, and BzA → pMOS proceeded, resulting in terpolymers with controlled [(pMOS)x–(VCHO)y–BzA]n sequences. The BzA-derived propagating end, which has a structure similar to that of the styrene-derived propagating end, was important for effective terpolymerization as judged by inefficient crossover reactions using methyl ethyl ketone instead of benzaldehyde. By optimizing polymerization conditions, homopropagation reactions of styrene derivatives and oxiranes were almost suppressed in the terpolymerization of 4-tert-butoxystyrene, VCHO, and 2,4-dimethoxybenzaldehyde, resulting in terpolymers with ABC-type periodic sequences. The terpolymers were degraded into low-MW products by acid or oxidant via the cleavage of the crossover reaction-derived, secondary benzylic ether moieties in the main chain.

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
Macromolecules
Macromolecules 工程技术-高分子科学
CiteScore
9.30
自引率
16.40%
发文量
942
审稿时长
2 months
期刊介绍: Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信