Pengwei Xie, Guoqiang Wu, Yubo Liu, Keling Hu, Zhengfeng Ma, Xiaowei Pei, Yang Wu* and Feng Zhou,
{"title":"具有超分子和共价双交联网络的高强度，快速恢复，耐溶剂和可回收的氟化丙烯酸聚氨酯","authors":"Pengwei Xie, Guoqiang Wu, Yubo Liu, Keling Hu, Zhengfeng Ma, Xiaowei Pei, Yang Wu* and Feng Zhou, ","doi":"10.1021/acsapm.5c0031410.1021/acsapm.5c00314","DOIUrl":null,"url":null,"abstract":"<p >High-performance polymer elastomers with high strength, rapid recovery, solvent resistance, and recyclability are desired in engineering fields. The incorporation of supramolecular interactions as sacrificial bonds for energy dissipation is an effective strategy to enhance the mechanical performance of polymers. However, this approach can result in a loss of resilience due to excessive energy consumption. In this study, we developed a kind of noncovalently supramolecular and covalently dual-cross-linked fluorinated acrylic polyurethane (PU-PFOMA) by incorporating adipic acid dihydrazide and acrylate-modified cyclodextrins into the polyurethane main chains and polymerizing perfluorooctyl methacrylate (PFOMA) in the polyacrylate side chains. The resulting PU-PFOMA demonstrated superior mechanical properties (54.36 MPa), elongation at break (1150%), and toughness (248.05 MJ/m<sup>3</sup>) due to the multiple H-bonds formed by adipic acid dihydrazide and the stable covalently cross-linked structure achieved through radical copolymerization. Furthermore, PU-PFOMA exhibited excellent resilience, attributed to the stable interchain cross-linking and the driving force generated by the poly(oxytetramethylene) glycol (PTMG) and PFOMA segments to reform their respective aggregates, owing to their thermodynamically incompatible nature. PU-PFOMA also demonstrated exceptional low-temperature resistance, including high strength (265.62 MPa), high toughness (648.44 MJ/m<sup>3</sup>) at −70 °C, and excellent resilience at −60 °C. More importantly, the PU-PFOMA elastomer has good solvent resistance that compared with PU because of the introduction of fluoroalkyl chains and could be reprocessed by hot pressing (130 °C, 10 MPa) and recover more than 70% of its toughness after reprocessing procedure. This study highlights the prospective uses of PU-PFOMA in fields necessitating robust mechanical characteristics and resistance to low temperatures.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 8","pages":"5058–5069 5058–5069"},"PeriodicalIF":4.4000,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"High-Strength, Rapid-Recovery, Solvent-Resistant, and Recyclable Fluorinated Acrylic Polyurethane with Supramolecular and Covalently Dual-Cross-linked Networks\",\"authors\":\"Pengwei Xie, Guoqiang Wu, Yubo Liu, Keling Hu, Zhengfeng Ma, Xiaowei Pei, Yang Wu* and Feng Zhou, \",\"doi\":\"10.1021/acsapm.5c0031410.1021/acsapm.5c00314\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >High-performance polymer elastomers with high strength, rapid recovery, solvent resistance, and recyclability are desired in engineering fields. The incorporation of supramolecular interactions as sacrificial bonds for energy dissipation is an effective strategy to enhance the mechanical performance of polymers. However, this approach can result in a loss of resilience due to excessive energy consumption. In this study, we developed a kind of noncovalently supramolecular and covalently dual-cross-linked fluorinated acrylic polyurethane (PU-PFOMA) by incorporating adipic acid dihydrazide and acrylate-modified cyclodextrins into the polyurethane main chains and polymerizing perfluorooctyl methacrylate (PFOMA) in the polyacrylate side chains. The resulting PU-PFOMA demonstrated superior mechanical properties (54.36 MPa), elongation at break (1150%), and toughness (248.05 MJ/m<sup>3</sup>) due to the multiple H-bonds formed by adipic acid dihydrazide and the stable covalently cross-linked structure achieved through radical copolymerization. Furthermore, PU-PFOMA exhibited excellent resilience, attributed to the stable interchain cross-linking and the driving force generated by the poly(oxytetramethylene) glycol (PTMG) and PFOMA segments to reform their respective aggregates, owing to their thermodynamically incompatible nature. PU-PFOMA also demonstrated exceptional low-temperature resistance, including high strength (265.62 MPa), high toughness (648.44 MJ/m<sup>3</sup>) at −70 °C, and excellent resilience at −60 °C. More importantly, the PU-PFOMA elastomer has good solvent resistance that compared with PU because of the introduction of fluoroalkyl chains and could be reprocessed by hot pressing (130 °C, 10 MPa) and recover more than 70% of its toughness after reprocessing procedure. This study highlights the prospective uses of PU-PFOMA in fields necessitating robust mechanical characteristics and resistance to low temperatures.</p>\",\"PeriodicalId\":7,\"journal\":{\"name\":\"ACS Applied Polymer Materials\",\"volume\":\"7 8\",\"pages\":\"5058–5069 5058–5069\"},\"PeriodicalIF\":4.4000,\"publicationDate\":\"2025-04-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Polymer Materials\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsapm.5c00314\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Polymer Materials","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsapm.5c00314","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
High-Strength, Rapid-Recovery, Solvent-Resistant, and Recyclable Fluorinated Acrylic Polyurethane with Supramolecular and Covalently Dual-Cross-linked Networks
High-performance polymer elastomers with high strength, rapid recovery, solvent resistance, and recyclability are desired in engineering fields. The incorporation of supramolecular interactions as sacrificial bonds for energy dissipation is an effective strategy to enhance the mechanical performance of polymers. However, this approach can result in a loss of resilience due to excessive energy consumption. In this study, we developed a kind of noncovalently supramolecular and covalently dual-cross-linked fluorinated acrylic polyurethane (PU-PFOMA) by incorporating adipic acid dihydrazide and acrylate-modified cyclodextrins into the polyurethane main chains and polymerizing perfluorooctyl methacrylate (PFOMA) in the polyacrylate side chains. The resulting PU-PFOMA demonstrated superior mechanical properties (54.36 MPa), elongation at break (1150%), and toughness (248.05 MJ/m3) due to the multiple H-bonds formed by adipic acid dihydrazide and the stable covalently cross-linked structure achieved through radical copolymerization. Furthermore, PU-PFOMA exhibited excellent resilience, attributed to the stable interchain cross-linking and the driving force generated by the poly(oxytetramethylene) glycol (PTMG) and PFOMA segments to reform their respective aggregates, owing to their thermodynamically incompatible nature. PU-PFOMA also demonstrated exceptional low-temperature resistance, including high strength (265.62 MPa), high toughness (648.44 MJ/m3) at −70 °C, and excellent resilience at −60 °C. More importantly, the PU-PFOMA elastomer has good solvent resistance that compared with PU because of the introduction of fluoroalkyl chains and could be reprocessed by hot pressing (130 °C, 10 MPa) and recover more than 70% of its toughness after reprocessing procedure. This study highlights the prospective uses of PU-PFOMA in fields necessitating robust mechanical characteristics and resistance to low temperatures.
期刊介绍：
ACS Applied Polymer Materials is an interdisciplinary journal publishing original research covering all aspects of engineering, chemistry, physics, and biology relevant to applications of polymers.
The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrates fundamental knowledge in the areas of materials, engineering, physics, bioscience, polymer science and chemistry into important polymer applications. The journal is specifically interested in work that addresses relationships among structure, processing, morphology, chemistry, properties, and function as well as work that provide insights into mechanisms critical to the performance of the polymer for applications.
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