Glyoxal-Based Bi-Oxazine Benzoxazines: Formaldehyde-Free Biothermosets

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-11-12 DOI:10.1021/acs.macromol.4c01358

Vaishaly Duhan, Bimlesh Lochab

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Abstract

Natural abundant resources and safe chemicals are attractive feedstocks for achieving circular sustainability. A wide variety of biophenols and greener amines offered interesting avenues in the evolution of the upcoming class of phenolic thermosets, polybenzoxazines (PBZ). High dependence on formalin as a starting material for monomer synthesis has prompted exploration of alternative safe chemicals. In this study, we designed a family of glyoxal-based benzoxazine (BZ) monomers to synthesize formaldehyde-free biothermosets, leveraging a proximity and promiscuity oxazine–oxazine dependent polymerization. The bi-oxazine functionality at the reactive C₂ center in the monomers demanded significantly low temperature for ring-opening polymerization with high polymerization enthalpy favoring an ease in polymer growth, overcoming challenges posed by earlier generation BZ monomers. Current work demonstrates the proof-of-concept for a highly efficient methodology for formaldehyde replacement in benzoxazine chemistry and holds promise for the exploration of a new platform chemical, glyoxal, toward the next generation of benzoxazine with unique reactivities.

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乙二醛基双噁嗪苯并噁嗪：无甲醛生物发热体

丰富的天然资源和安全的化学品是实现循环可持续性的诱人原料。各种生物酚和更环保的胺为即将出现的酚类热固性塑料--聚苯并噁嗪（PBZ）的发展提供了有趣的途径。由于单体合成的起始原料对福尔马林的依赖性很高，这促使我们探索其他安全的化学品。在这项研究中，我们设计了一系列乙二醛基苯并恶嗪（BZ）单体，利用恶嗪-恶嗪依赖性聚合的接近性和杂合性合成不含甲醛的生物热固性塑料。单体中反应性 C2 中心的双噁嗪官能团对开环聚合的温度要求很低，聚合焓很高，有利于聚合物的生长，克服了早一代 BZ 单体带来的挑战。目前的工作证明了苯并恶嗪化学中甲醛置换的高效方法的概念，并有望探索出一种新的平台化学品乙二醛，从而开发出具有独特反应活性的下一代苯并恶嗪。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.