{"title":"亚胺炔单击聚合:X-炔单击聚合工具箱中的多功能新工具","authors":"Oguzhan Aslanturk, Gokhan Sagdic, Emrah Cakmakci, Hakan Durmaz, Ufuk Saim Gunay","doi":"10.1039/d4py00918e","DOIUrl":null,"url":null,"abstract":"The Michael reaction, a cornerstone in organic chemistry, continues to revolutionize the field with its unparalleled versatility in forming carbon-carbon, carbon-oxygen, carbon-nitrogen, and carbon-sulfur bonds, paving the way for groundbreaking advancements in complex molecule and macromolecule construction. In this study, imide-yne reaction was employed at the macromolecular level for the first time for the preparation of linear poly(imide ester)s. A wide range of bisimides and dipropiolates were reacted through imide-yne click polymerization in the presence of 1,4-diazabicyclo[2.2.2] octane (DABCO) at room temperature. The polymerizations proceed in an anti-Markovnikov fashion, yielding the E-isomer as the major product. Polymers were obtained in high yields and their molecular weights were found to be in the range of 5.64-12.67 kDa. The remaining unreacted double bonds in the linear polymers were found to undergo further functionalization with thiols using a strong organocatalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), which was also supported by a model study. Post-polymerization modification study prompted us to prepare imide-yne monomers that can react with dithiols to synthesize poly(imide thioether)s through nucleophilic thiol-ene click reaction using TBD as the catalyst. The obtained polymers displayed a wide range of glass transition temperatures and thermal stability. Thus, it can be said that the proposed method enables the synthesis of new polyimide-based structures with tailorable thermal properties. It is believed that the proposed strategy will make a significant contribution to expanding the versatility of active alkyne chemistry at the macromolecular level.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.1000,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Imide-Yne Click Polymerization: A New and Versatile Tool for the Toolbox of X-Yne Click Polymerization\",\"authors\":\"Oguzhan Aslanturk, Gokhan Sagdic, Emrah Cakmakci, Hakan Durmaz, Ufuk Saim Gunay\",\"doi\":\"10.1039/d4py00918e\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The Michael reaction, a cornerstone in organic chemistry, continues to revolutionize the field with its unparalleled versatility in forming carbon-carbon, carbon-oxygen, carbon-nitrogen, and carbon-sulfur bonds, paving the way for groundbreaking advancements in complex molecule and macromolecule construction. In this study, imide-yne reaction was employed at the macromolecular level for the first time for the preparation of linear poly(imide ester)s. A wide range of bisimides and dipropiolates were reacted through imide-yne click polymerization in the presence of 1,4-diazabicyclo[2.2.2] octane (DABCO) at room temperature. The polymerizations proceed in an anti-Markovnikov fashion, yielding the E-isomer as the major product. Polymers were obtained in high yields and their molecular weights were found to be in the range of 5.64-12.67 kDa. The remaining unreacted double bonds in the linear polymers were found to undergo further functionalization with thiols using a strong organocatalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), which was also supported by a model study. Post-polymerization modification study prompted us to prepare imide-yne monomers that can react with dithiols to synthesize poly(imide thioether)s through nucleophilic thiol-ene click reaction using TBD as the catalyst. The obtained polymers displayed a wide range of glass transition temperatures and thermal stability. Thus, it can be said that the proposed method enables the synthesis of new polyimide-based structures with tailorable thermal properties. It is believed that the proposed strategy will make a significant contribution to expanding the versatility of active alkyne chemistry at the macromolecular level.\",\"PeriodicalId\":100,\"journal\":{\"name\":\"Polymer Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.1000,\"publicationDate\":\"2024-09-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4py00918e\",\"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://doi.org/10.1039/d4py00918e","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Imide-Yne Click Polymerization: A New and Versatile Tool for the Toolbox of X-Yne Click Polymerization
The Michael reaction, a cornerstone in organic chemistry, continues to revolutionize the field with its unparalleled versatility in forming carbon-carbon, carbon-oxygen, carbon-nitrogen, and carbon-sulfur bonds, paving the way for groundbreaking advancements in complex molecule and macromolecule construction. In this study, imide-yne reaction was employed at the macromolecular level for the first time for the preparation of linear poly(imide ester)s. A wide range of bisimides and dipropiolates were reacted through imide-yne click polymerization in the presence of 1,4-diazabicyclo[2.2.2] octane (DABCO) at room temperature. The polymerizations proceed in an anti-Markovnikov fashion, yielding the E-isomer as the major product. Polymers were obtained in high yields and their molecular weights were found to be in the range of 5.64-12.67 kDa. The remaining unreacted double bonds in the linear polymers were found to undergo further functionalization with thiols using a strong organocatalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), which was also supported by a model study. Post-polymerization modification study prompted us to prepare imide-yne monomers that can react with dithiols to synthesize poly(imide thioether)s through nucleophilic thiol-ene click reaction using TBD as the catalyst. The obtained polymers displayed a wide range of glass transition temperatures and thermal stability. Thus, it can be said that the proposed method enables the synthesis of new polyimide-based structures with tailorable thermal properties. It is believed that the proposed strategy will make a significant contribution to expanding the versatility of active alkyne chemistry at the macromolecular level.
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.