{"title":"热响应性可降解共聚物的设计与合成:羟基功能化乙烯基醚与环烯酮缩醛的整合","authors":"Shinji Sugihara, Atsushi Endo, Komal Raje, Atsushi Matsumoto, Satoshi Fujita and Yasushi Maeda","doi":"10.1039/D5PY00398A","DOIUrl":null,"url":null,"abstract":"<p >Degradable copolymers with adjustable thermoresponsive characteristics are synthesized through radical copolymerization of hydroxy-functional vinyl ethers (OH-VEs), such as 2-hydroxyethyl vinyl ether (HEVE) or di(ethylene glycol) vinyl ether (DEGV), with 2-methylene-1,3-dioxepane (MDO). Mechanistic investigations, including reactivity ratio determination and <small><sup>1</sup></small>H NMR spectroscopy, reveal that hydrogen bonding from the hydroxy groups in vinyl ethers affects both radical vinyl polymerization of OH-VEs and radical ring-opening polymerization of MDO. The resulting poly(HEVE-<em>co</em>-MDO) and poly(DEGV-<em>co</em>-MDO) copolymers exhibit LCST-type thermoresponsive behavior in aqueous solutions within specific MDO composition ranges (23–28 mol% and 35–37 mol%, respectively), whereas poly(vinyl alcohol-<em>co</em>-MDO) without oxyethylene moieties remains either fully soluble or insoluble, irrespective of temperature. Poly(DEGV-<em>co</em>-MDO) uniquely forms coacervates in turbid solutions due to its enhanced hydrophilicity, a phenomenon not observed with poly(HEVE-<em>co</em>-MDO). RAFT polymerization facilitates molar mass control, demonstrating an inverse relationship between molar mass and cloud point temperature. The copolymers exhibit selective degradability of MDO units under alkaline conditions and are expected to demonstrate good biocompatibility, as suggested by cytotoxicity assays.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 26","pages":" 3059-3069"},"PeriodicalIF":3.9000,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Design and synthesis of thermoresponsive degradable copolymers: integrating hydroxy-functional vinyl ethers with cyclic ketene acetals†\",\"authors\":\"Shinji Sugihara, Atsushi Endo, Komal Raje, Atsushi Matsumoto, Satoshi Fujita and Yasushi Maeda\",\"doi\":\"10.1039/D5PY00398A\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Degradable copolymers with adjustable thermoresponsive characteristics are synthesized through radical copolymerization of hydroxy-functional vinyl ethers (OH-VEs), such as 2-hydroxyethyl vinyl ether (HEVE) or di(ethylene glycol) vinyl ether (DEGV), with 2-methylene-1,3-dioxepane (MDO). Mechanistic investigations, including reactivity ratio determination and <small><sup>1</sup></small>H NMR spectroscopy, reveal that hydrogen bonding from the hydroxy groups in vinyl ethers affects both radical vinyl polymerization of OH-VEs and radical ring-opening polymerization of MDO. The resulting poly(HEVE-<em>co</em>-MDO) and poly(DEGV-<em>co</em>-MDO) copolymers exhibit LCST-type thermoresponsive behavior in aqueous solutions within specific MDO composition ranges (23–28 mol% and 35–37 mol%, respectively), whereas poly(vinyl alcohol-<em>co</em>-MDO) without oxyethylene moieties remains either fully soluble or insoluble, irrespective of temperature. Poly(DEGV-<em>co</em>-MDO) uniquely forms coacervates in turbid solutions due to its enhanced hydrophilicity, a phenomenon not observed with poly(HEVE-<em>co</em>-MDO). RAFT polymerization facilitates molar mass control, demonstrating an inverse relationship between molar mass and cloud point temperature. The copolymers exhibit selective degradability of MDO units under alkaline conditions and are expected to demonstrate good biocompatibility, as suggested by cytotoxicity assays.</p>\",\"PeriodicalId\":100,\"journal\":{\"name\":\"Polymer Chemistry\",\"volume\":\" 26\",\"pages\":\" 3059-3069\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-06-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/py/d5py00398a\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/py/d5py00398a","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Design and synthesis of thermoresponsive degradable copolymers: integrating hydroxy-functional vinyl ethers with cyclic ketene acetals†
Degradable copolymers with adjustable thermoresponsive characteristics are synthesized through radical copolymerization of hydroxy-functional vinyl ethers (OH-VEs), such as 2-hydroxyethyl vinyl ether (HEVE) or di(ethylene glycol) vinyl ether (DEGV), with 2-methylene-1,3-dioxepane (MDO). Mechanistic investigations, including reactivity ratio determination and 1H NMR spectroscopy, reveal that hydrogen bonding from the hydroxy groups in vinyl ethers affects both radical vinyl polymerization of OH-VEs and radical ring-opening polymerization of MDO. The resulting poly(HEVE-co-MDO) and poly(DEGV-co-MDO) copolymers exhibit LCST-type thermoresponsive behavior in aqueous solutions within specific MDO composition ranges (23–28 mol% and 35–37 mol%, respectively), whereas poly(vinyl alcohol-co-MDO) without oxyethylene moieties remains either fully soluble or insoluble, irrespective of temperature. Poly(DEGV-co-MDO) uniquely forms coacervates in turbid solutions due to its enhanced hydrophilicity, a phenomenon not observed with poly(HEVE-co-MDO). RAFT polymerization facilitates molar mass control, demonstrating an inverse relationship between molar mass and cloud point temperature. The copolymers exhibit selective degradability of MDO units under alkaline conditions and are expected to demonstrate good biocompatibility, as suggested by cytotoxicity assays.
期刊介绍:
Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.