Cooperative Semi-Interpenetrating Polymerization toward Boroxine-Based Dynamic Covalent Networks with Tunable Properties and Chemical Recyclability

IF 5.7 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2026-10-13 DOI:10.1021/acs.macromol.6c01784

Fan Zhang,Hui Zhou,Tian-Jun Yue,Wei-Min Ren,Xiao-Bing Lu

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Abstract

The dynamic chemistry of covalent boron-oxygen bonds has been extensively leveraged to construct cutting-edge dynamic covalent polymer networks (DCPNs) with self-healing, repairable, and reprocessable properties. However, the inherent poor water resistance of the resulting structural units, such as boronic esters or boroxines, severely limits the widespread application of boron-containing DCPNs. Herein, a novel and effective H2O-induced cooperative semi-interpenetrating polymerization (sIPP) was successfully developed by using diisocyanates (DIC) and linear boronic acid-contained polyesters (P-BA) as starting materials, thus constructing a series of well-mixed and water-resistant dynamic covalent semi-interpenetrating polymer networks (P-sIPNs-DIC) composed of boroxine-based DCPNs and linear polyureas. Additionally, precise control over structural unit composition, sequence distribution, and carbon–carbon double-bond geometry enables tunable mechanical properties of the resultant P-sIPNs-DIC between thermoplastic elastomers and robust plastics. Impressively, P-sIPNs-DIC enable effective acidic depolymerization to selectively recover the pristine P-BA with excellent yield, which can be directly employed to regenerate P-sIPNs-DIC with performance matching the original, thus achieving a closed-loop lifecycle from linear polymers to polymer networks and back to linear polymers.

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具有可调性质和化学可回收性的基于硼氧辛的动态共价网络的半互穿聚合

共价硼氧键的动态化学已被广泛用于构建具有自修复、可修复和可再加工特性的前沿动态共价聚合物网络（dcpn）。然而，由此产生的结构单元（如硼酯或硼氧化合物）固有的较差的耐水性严重限制了含硼DCPNs的广泛应用。本文以二异氰酸酯（DIC）和含线性硼酸聚酯（P-BA）为原料，成功制备了一种新型的、有效的h2o诱导的协同半互穿聚合物（sIPP），从而构建了一系列由硼氧基dcpn和线性聚氨酯组成的混合良好、耐水的动态共价半互穿聚合物网络（p - sIPP -DIC）。此外，通过对结构单元组成、序列分布和碳-碳双键几何形状的精确控制，可以在热塑性弹性体和坚固塑料之间调节p - sips - dic的机械性能。令人印象深刻的是，p - sins - dic能够有效的酸性解聚，选择性地恢复原始的P-BA，收率很高，可以直接用于再生性能与原始性能匹配的p - sins - dic，从而实现从线性聚合物到聚合物网络再回到线性聚合物的闭环生命周期。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.