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聚(2-烷基/芳基-2-恶唑啉)-咪唑配合物作为环氧树脂的热潜伏性固化剂

Poly(2-alkyl/aryl-2-oxazoline)-Imidazole Complexes as Thermal Latent Curing Agents for Epoxy Resins.

作者信息

Atespare Asu Ece, Behroozi Kohlan Taha, Salamatgharamaleki Saeed, Yildiz Mehmet, Menceloglu Yusuf Ziya, Unal Serkan, Dizman Bekir

机构信息

Integrated Manufacturing Technologies Research and Application Center & Composite Technologies Center of Excellence, Sabanci University, Istanbul, Turkey, 34906.

Faculty of Engineering and Natural Sciences, Materials Science and Nano Engineering, Sabanci University, Istanbul, Turkey, 34956.

出版信息

ACS Omega. 2024 Aug 14;9(34):36398-36410. doi: 10.1021/acsomega.4c03904. eCollection 2024 Aug 27.

Abstract

One-component epoxy resins (OCERs) with improved stability (shelf life) and controlled curing temperatures were prepared using epoxy resins and polyoxazoline-imidazole (POZ-Im) based thermal latent curing agents (TLCs). POZ homopolymers with molar masses of 1000, 2000, and 5000 g/mol were obtained via cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-pentyl-2-oxazoline, and 2-phenyl-2-oxazoline. TLCs were prepared by physically entrapping imidazole, the curing agent, in the POZ matrix at the homopolymer/Im (HP/Im) ratios of 1:1 and 5:1 and characterized by FTIR and TGA. TLCs were then mixed with bisphenol A diglycidyl ether (DGEBA) to obtain OCERs with Im concentrations of 1, 3, and 5 wt %. Dynamic DSC tests were performed to determine the effect of the pendant group and molar mass of POZ, the POZ/Im ratio, and Im concentration on the curing behavior of the OCERs, whereas isothermal DSC tests were carried out to examine their thermal stability and optimal curing temperatures. Optical microscopy was performed to study the compatibility of the TLCs with DGEBA. This study showed that the dispersion quality of TLCs is highly associated with the compatibility of POZs and DGEBA, which affected the release of Im, thus left limit temperatures of curing. In addition, higher left limit temperatures were obtained when the POZ/Im ratio increased. Isothermal DSC results conformed to the improved stability and better thermal latency of the samples with a POZ/Im ratio of 5:1. Moreover, the higher left limit temperatures were obtained with the lowest molar mass of POZ due to the better interaction between the -OH end group of POZ and Im. The shelf life of PEOZ 1K-Im 5:1 1% OCER was predicted at -20, 0, and 20 °C, with an estimated 15.3 days at 20 °C using isothermal DSC and rheology at 50, 60, and 70 °C. Overall, this research contributes to the development of OCERs by introducing POZ-Im complexes as novel TLCs. The findings shed light on the importance of compatibility in achieving optimal dispersion and release of Im and the role of the POZ/Im ratio and POZ molar mass in controlling left limit temperatures, ultimately influencing the curing behavior of OCERs.

摘要

采用环氧树脂和基于聚恶唑啉 - 咪唑(POZ - Im)的热潜伏性固化剂(TLC)制备了具有改善稳定性(保质期)和可控固化温度的单组分环氧树脂(OCER)。通过2 - 乙基 - 2 - 恶唑啉、2 - 丙基 - 2 - 恶唑啉、2 - 戊基 - 2 - 恶唑啉和2 - 苯基 - 2 - 恶唑啉的阳离子开环聚合(CROP)获得了摩尔质量为1000、2000和5000 g/mol的POZ均聚物。通过将固化剂咪唑以1:1和5:1的均聚物/咪唑(HP/Im)比例物理包埋在POZ基质中来制备TLC,并通过FTIR和TGA对其进行表征。然后将TLC与双酚A二缩水甘油醚(DGEBA)混合,以获得Im浓度为1、3和5 wt%的OCER。进行动态DSC测试以确定POZ的侧基和摩尔质量、POZ/Im比例以及Im浓度对OCER固化行为的影响,同时进行等温DSC测试以研究它们的热稳定性和最佳固化温度。通过光学显微镜研究TLC与DGEBA的相容性。该研究表明,TLC的分散质量与POZ和DGEBA的相容性高度相关,这影响了Im的释放,从而影响固化的下限温度。此外,当POZ/Im比例增加时,获得了更高的下限温度。等温DSC结果符合POZ/Im比例为5:1的样品具有改善的稳定性和更好的热潜伏性。此外,由于POZ的 - OH端基与Im之间的相互作用更好,使用最低摩尔质量的POZ获得了更高的下限温度。使用等温DSC以及在50、60和70°C下的流变学预测了PEOZ 1K - Im 5:1 1% OCER在 - 20、0和20°C下的保质期,在20°C下估计为15.3天。总体而言,本研究通过引入POZ - Im配合物作为新型TLC,为OCER的开发做出了贡献。研究结果揭示了相容性在实现Im的最佳分散和释放中的重要性,以及POZ/Im比例和POZ摩尔质量在控制下限温度方面的作用,最终影响OCER的固化行为。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fa8b/11360024/5d56c8c1cffa/ao4c03904_0001.jpg

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