Despite the commercial availability of 3,4-epoxycyclohexylmethyl acrylate (ECMA), its homopolymerization is not reported. In this study, liquid viscous poly(3,4-epoxycyclohexylmethyl acrylate) (PECMA) is synthesized via free radical polymerization and fractionated to obtain samples with varying molecular weights. After casting with a cationic photoinitiator and photocuring of the resultant film to cross-link the epoxide groups via ring-opening polymerization, a hard solid coating is formed. For fully cured coatings, hardness (H) increases with the molecular weight of PECMA. At a weight-average molecular weight (M_w) of 14.5 kDa, the H value of the fully cured coating reached 0.78 ± 0.02 GPa, over five times that of poly(ethylene terephthalate) (PET) and three times that of polystyrene (PS), representing the highest H value reported for an organic material. This exceptional hardness correlates with excellent wear resistance, as no wear tracks are observed after 250 abrasion cycles with steel wool under 13 kPa. The coating also exhibits high transparency, with 97% transmittance at 500 nm for a 50 μm-thick film, and remains thermally stable up to 300 °C. These properties indicate that PECMA holds significant potential for diverse applications.

中文翻译：

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聚（3,4-环氧环己基丙烯酸酯）的合成和用于制备极硬但柔韧的有机聚合物涂层


尽管 3,4-环氧环己基丙烯酸甲酯 （ECMA） 已上市，但其均聚反应尚未见报道。在本研究中，通过自由基聚合合成液体粘性聚（3,4-环氧环己基丙烯酸酯）（PECMA），并分馏以获得不同分子量的样品。使用阳离子光引发剂浇铸并光固化所得薄膜后，通过开环聚合使环氧化物基团交联，形成坚硬的固体涂层。对于完全固化的涂层，硬度 （H） 随着 PECMA 的分子量而增加。当重均分子量 （M_w） 为 14.5 kDa 时，完全固化涂层的 H 值达到 0.78 ± 0.02 GPa，是聚对苯二甲酸乙二醇酯 （PET） 的五倍多，是聚苯乙烯 （PS） 的三倍，是有机材料报道的最高 H 值。这种出色的硬度与出色的耐磨性相关，因为在低于 13 kPa 的钢丝绒中，经过 250 次磨损循环后，不会观察到磨损痕迹。该涂层还表现出高透明度，对于 50 μm 厚的薄膜，在 500 nm 处的透射率为 97%，并且在高达 300 °C 的温度下仍保持热稳定性。 这些特性表明 PECMA 在多种应用中具有巨大的潜力。