Abstract This work is focused on the development of sustainable stone conservation materials, based on BPA-free epoxy-silica hybrid resins, with consolidating and hydrophobic properties, for long-term treatments. For this purpose, a cycloaliphatic diol, with minor health and environmental associated issues with respect to classic phenolic derivatives, was selected to synthesize a BPA-free bio-based epoxy resins precursor, 2,2,4,4-tetramethyl-1,3-cyclobutanediol diglycidylether (CBDO-DGE). Fourier transform infrared (FT-IR) and Raman spectroscopies were employed to assess the synthesis and clean-up procedures. In addition, both 1H-NMR and 13C-NMR in solution were used to ascertain the structure and purity of the bio-based epoxy. The development of the epoxy thermosets by 1,8- diaminooctane (DAO), triethylenetetramine (TETA) and 5-amino-1,3,3-trimethylcyclohexanemethylamine (IPDA) curing agents was followed by attenuated total reflection infrared (ATR FT-IR) and Raman spectroscopies, whereas their suitability as organic counterpart of the hybrids was established by differential scanning calorimetry (DSC) and thermogravimetric (TGA) measurements. In addition, epoxy-silica hybrids were obtained by exploiting sol-gel technology, carrying out the epoxy hardening reactions also in the presence of (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and octyltriethoxysilane (OcTES), as silica-forming additives. To investigate the properties of the resulting hybrid materials imparted by the selection of the different reactants, various blends were studied by a combination of scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDS), ATR FT-IR and Raman analysis. Furthermore, the assessment of the hybrids tunability as materials for stone conservation was ascertained in terms of thermostability and hydrophobicity by TG-DTA, DSC, dynamic mechanical analysis (DMA) and contact angle measurements.

中文翻译：

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基于天然来源的脂环族二醇的环氧-二氧化硅杂化物的设计，用于保护岩土材料

摘要 这项工作的重点是开发可持续的石材保护材料，该材料基于不含 BPA 的环氧-二氧化硅杂化树脂，具有固结和疏水特性，可用于长期处理。为此，选择了与经典酚类衍生物相比具有较小健康和环境相关问题的脂环族二醇来合成不含 BPA 的生物基环氧树脂前体 2,2,4,4-四甲基-1,3 -环丁二醇二缩水甘油醚 (CBDO-DGE)。傅里叶变换红外 (FT-IR) 和拉曼光谱被用来评估合成和净化程序。此外，溶液中的 1H-NMR 和 13C-NMR 都用于确定生物基环氧树脂的结构和纯度。由 1,8-二氨基辛烷 (DAO)、三亚乙基四胺 (TETA) 和 5-氨基-1,3 开发的环氧热固性树脂，3-三甲基环己烷甲胺 (IPDA) 固化剂之后是衰减全反射红外 (ATR FT-IR) 和拉曼光谱，而它们作为杂化物的有机对应物的适用性是通过差示扫描量热法 (DSC) 和热重 (TGA) 测量确定的。此外，通过利用溶胶-凝胶技术，在（3-缩水甘油氧基丙基）三甲氧基硅烷（GPTMS）和辛基三乙氧基硅烷（OcTES）作为二氧化硅形成添加剂存在下进行环氧硬化反应，获得了环氧-二氧化硅杂化物。为了研究通过选择不同反应物而产生的混合材料的性质，通过扫描电子显微镜/能量色散 X 射线光谱 (SEM-EDS)、ATR FT-IR 和拉曼分析的组合研究了各种共混物. 此外，