{"title":"双重氮化合物热裂解合成双卡宾的聚合行为","authors":"Xiaosong Liu , Mark G. Moloney , Koji Okuda","doi":"10.1039/d4py01474j","DOIUrl":null,"url":null,"abstract":"<div><div>A study of the collapse of bisdiazo compounds with different terminal groups upon heating to generate reactive biscarbene intermediates has provided evidence for homopolymerization in a process that proceeds in the absence of catalysts and is tolerant of oxygen. This polymerization behaviour was monitored spectroscopically through UV-vis kinetic analysis with various combinations of temperature and solvent, and clear evidence for dimer and trimer formation was found by field desorption mass spectrometry. Oligomerization may involve the formation of CC and CN–NC linkages, as studied and validated by molecular dynamics (MD) calculations, before reaching macromolecular size. In the presence of terminal NH<sub>2</sub> groups, cross-linking resulting from carbene insertion is also observed. This unusual polymerization of diazo monomers, when conducted on a polyvinyl alcohol (PVA) surface in the open-air upon heating, creates a highly cross-linked structure that changes surface properties.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 21","pages":"Pages 2480-2493"},"PeriodicalIF":3.9000,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Polymerization behaviour of biscarbenes derived by thermolysis of bisdiazo compounds†\",\"authors\":\"Xiaosong Liu , Mark G. Moloney , Koji Okuda\",\"doi\":\"10.1039/d4py01474j\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>A study of the collapse of bisdiazo compounds with different terminal groups upon heating to generate reactive biscarbene intermediates has provided evidence for homopolymerization in a process that proceeds in the absence of catalysts and is tolerant of oxygen. This polymerization behaviour was monitored spectroscopically through UV-vis kinetic analysis with various combinations of temperature and solvent, and clear evidence for dimer and trimer formation was found by field desorption mass spectrometry. Oligomerization may involve the formation of CC and CN–NC linkages, as studied and validated by molecular dynamics (MD) calculations, before reaching macromolecular size. In the presence of terminal NH<sub>2</sub> groups, cross-linking resulting from carbene insertion is also observed. This unusual polymerization of diazo monomers, when conducted on a polyvinyl alcohol (PVA) surface in the open-air upon heating, creates a highly cross-linked structure that changes surface properties.</div></div>\",\"PeriodicalId\":100,\"journal\":{\"name\":\"Polymer Chemistry\",\"volume\":\"16 21\",\"pages\":\"Pages 2480-2493\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-05-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1759995425001615\",\"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://www.sciencedirect.com/org/science/article/pii/S1759995425001615","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Polymerization behaviour of biscarbenes derived by thermolysis of bisdiazo compounds†
A study of the collapse of bisdiazo compounds with different terminal groups upon heating to generate reactive biscarbene intermediates has provided evidence for homopolymerization in a process that proceeds in the absence of catalysts and is tolerant of oxygen. This polymerization behaviour was monitored spectroscopically through UV-vis kinetic analysis with various combinations of temperature and solvent, and clear evidence for dimer and trimer formation was found by field desorption mass spectrometry. Oligomerization may involve the formation of CC and CN–NC linkages, as studied and validated by molecular dynamics (MD) calculations, before reaching macromolecular size. In the presence of terminal NH2 groups, cross-linking resulting from carbene insertion is also observed. This unusual polymerization of diazo monomers, when conducted on a polyvinyl alcohol (PVA) surface in the open-air upon heating, creates a highly cross-linked structure that changes surface properties.
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.