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苯并恶嗪/胺基类 Vitrimers 中氨基烷基化酚的胺交换作为动态反应

Amine Exchange of Aminoalkylated Phenols as Dynamic Reaction in Benzoxazine/Amine-Based Vitrimers.

作者信息

Wolf Adrian, Pursche Lea, Boskamp Laura, Koschek Katharina

机构信息

Fraunhofer Institute for Manufacturing Technology and Advanced Materials (IFAM), Wiener Straße 12, 28359, Bremen, Germany.

Department 2 Biology/Chemistry, University of Bremen, Leobener Straße 3, 28359, Bremen, Germany.

出版信息

Macromol Rapid Commun. 2024 Dec;45(23):e2400557. doi: 10.1002/marc.202400557. Epub 2024 Oct 10.

DOI:10.1002/marc.202400557
PMID:39388675
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11628363/
Abstract

Bisfunctional benzoxazine and polyether diamine-based polymers show Arrhenius-like stress-relaxation varying with stoichiometry and polymerization temperatures proving vitrimeric behavior. Molecular structural investigations reveal the presence of different aminoalkylated phenols occurring at varying ratios depending on polymer composition and polymerization conditions. The vitrimeric mechanism is found to involve an amine exchange reaction of aminoalkylated phenols in an equilibrium reaction like a nucleophilic substitution reaction. As determined by molecular studies and dissolution experiments in reactive solvents, aliphatic and aromatic primary as well as aliphatic secondary amines in the polybenzoxazine structure can act as nucleophiles in reaction with electrophilic methylene bridges. Thus, aminoalkylated phenols proved to be a relevant structural motif resulting in a vitrimeric polybenzoxazine due to amine exchange reaction.

摘要

基于双功能苯并恶嗪和聚醚二胺的聚合物表现出类似阿累尼乌斯的应力松弛，其随化学计量比和聚合温度而变化，证明了其玻璃态行为。分子结构研究表明，根据聚合物组成和聚合条件的不同，会出现不同比例的不同氨基烷基化酚。发现玻璃态机理涉及氨基烷基化酚的胺交换反应，该反应是一种类似于亲核取代反应的平衡反应。通过分子研究和在反应性溶剂中的溶解实验确定，聚苯并恶嗪结构中的脂肪族和芳香族伯胺以及脂肪族仲胺可作为亲核试剂与亲电亚甲基桥反应。因此，由于胺交换反应，氨基烷基化酚被证明是导致玻璃态聚苯并恶嗪的相关结构基序。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/df383c3134fc/MARC-45-2400557-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/bfa32947ba77/MARC-45-2400557-g001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/94755416b5dd/MARC-45-2400557-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/87d35302072f/MARC-45-2400557-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/f2ce8b02308e/MARC-45-2400557-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/df383c3134fc/MARC-45-2400557-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/bfa32947ba77/MARC-45-2400557-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/5a4fd2db1e8b/MARC-45-2400557-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/d69c3c9f83f6/MARC-45-2400557-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/832bff3f592b/MARC-45-2400557-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/35c5e4d35ee5/MARC-45-2400557-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/94755416b5dd/MARC-45-2400557-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/87d35302072f/MARC-45-2400557-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/f2ce8b02308e/MARC-45-2400557-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2116/11628363/df383c3134fc/MARC-45-2400557-g010.jpg

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本文引用的文献

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Self-Polymerization Promoting Monomers: In Situ Transformation of Disulfide-Linked Benzoxazines into the Thiazolidine Structure.自聚促进单体：二硫键连接的苯并恶嗪原位转化为噻唑烷结构。
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