双重氮化合物热裂解合成双卡宾的聚合行为

IF 3.9 2区 化学 Q2 POLYMER SCIENCE
Xiaosong Liu , Mark G. Moloney , Koji Okuda
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引用次数: 0

摘要

对具有不同末端基团的双重氮化合物在加热时坍塌生成活性双卡宾中间体的研究,为均聚提供了证据,该过程在没有催化剂的情况下进行,并且耐氧。通过不同温度和溶剂组合的UV-Vis动力学分析对聚合行为进行了光谱监测,并通过场解吸质谱法发现了二聚体和三聚体形成的明确证据。正如分子动力学(MD)计算所证实的那样,在达到大分子大小之前,寡聚化可能涉及C=C和C=N-N=C键的形成。在末端NH2基团存在的情况下,还观察到由碳插入引起的交联。这种不寻常的重氮单体聚合在聚乙烯醇(PVA)表面上进行,在露天加热时,会产生高度交联的结构,从而改变表面性质。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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.
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来源期刊
Polymer Chemistry
Polymer Chemistry POLYMER SCIENCE-
CiteScore
8.60
自引率
8.70%
发文量
535
审稿时长
1.7 months
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.
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