Thermo-reversible self-healing of a partially fluorinated crosslinked polymer was achieved by utilizing reversible Diels–Alder (DA) chemistry. Copolymers (PHFBA-co-PFMA) of perfluorobutyl acrylate (HFBA) and furfurylmethacrylate (FMA) with controlled stoichiometric ratios were synthesized by microwave-assisted radical polymerization by controlling the individual components. The microstructures and stoichiometries of these copolymers of PHFBA and PFMA were analyzed by ¹H, ¹⁹F, ¹³C, and DOSY NMR spectroscopy and their molecular weights were analyzed by GPC. The glass transitions (T_g) of the different stoichiometric copolymers correlate well with the estimated T_g values from the Fox equation. A thermo-reversible crosslinked polymer network was achieved via Diels–Alder (DA) and retro-DA reactions between the furan moiety of the copolymer (PHFBA-co-PFMA) and bismaleimide; the self-healing ability of this network was investigated using ¹H NMR, DSC and solution experiments. The self-healing process and recovery of the crosslinked polymers was screened by microscopic visualization and stress–strain tensile studies. The surface properties of the fluorous copolymers and crosslinked polymers were studied by water contact angle measurements, and their mechanical properties were investigated by nanoindentation and DMA.

中文翻译：

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氟交联共聚物中的热可逆自修复†

通过使用可逆的Diels-Alder（DA）化学方法，可实现部分氟化的交联聚合物的热可逆自愈。通过控制组分的微波辅助自由基聚合反应，合成了化学计量比受控的丙烯酸全氟丙烯酸丁酯（HFBA）和甲基丙烯酸糠基酯（FMA）的共聚物（PHFBA- co -PFMA）。通过¹ H，¹⁹ F，¹³ C和DOSY NMR光谱分析了这些PHFBA和PFMA共聚物的微观结构和化学计量，并通过GPC分析了它们的分子量。不同化学计量的共聚物的玻璃化转变温度（T _g）与估计的T _g很好地相关Fox方程中的值。通过Diels–Alder（DA）和共聚物的呋喃部分（PHFBA- co -PFMA）与双马来酰亚胺之间的Retro-DA反应，实现了热可逆交联的聚合物网络。使用¹ H NMR，DSC和溶液实验研究了该网络的自我修复能力。交联聚合物的自愈过程和回收率通过显微镜可视化和应力-应变拉伸研究进行筛选。通过水接触角测量研究了含氟共聚物和交联聚合物的表面性能，并通过纳米压痕和DMA研究了它们的机械性能。