摘要： 【目的】利用硅烷偶联剂改性湿固化聚氨酯，提升材料耐热性，用于潮湿环境文物保护。【方法】以聚醚多元醇（聚乙二醇和聚四亚甲基醚二醇）和脂肪族异氰酸酯（异佛尔酮二异氰酸酯）为前驱物，仲胺基硅烷偶联剂 [三甲氧基 3-（苯氨基）丙基硅烷 ]为有机硅改性剂，合成了部分硅烷封端的有机硅改性湿固化聚氨酯。通过色差仪、紫外 -可见分光光度计、傅立叶变换红外光谱仪、热重分析仪和热氧老化测试等方法对合成的聚氨酯薄膜外观、氢键程度和热稳定性进行表征。【结果】硅烷偶联剂改性湿固化聚氨酯薄膜在可见光范围内透光率为 85%~89%，色差 <0. 4，提高硬段 /软段质量分数和仲胺基硅烷偶联剂用量可以分别增加和减小其微相分离。通过 FWO和 KAS方法计算有机硅改性前后的聚氨酯活化能分别为 77. 33~99. 71 kJ/mol和 104. 02~ 127. 39 kJ/mol，活化能增加 27. 8%~34. 5%，热降解机制符合扩散模型（ D₁，D₂和 D₃）和反应级数模型（ F_n），受热色差变化减小。【结论】制备的硅烷偶联剂改性湿固化聚氨酯具有无色透明的外观，良好的热稳定性，有望应用在潮湿环境出土的脆弱有机质文物保护方面。

关键词: 湿固化聚氨酯, 硅烷偶联剂, 微相分离, 热重分析, 热降解机制

Abstract: ［Objective］To modify moisture-curable polyurethane with silane coupling agents toimprove its thermal resistance for the conservation of cultural relics in humid environments.［Methods］A partially silane-terminated silicone-modified moisture-curable polyurethane was synthesized using polyether polyols（polyethylene glycol and polytetramethylene ether glycol）and aliphatic isocyanates（isophorone diisocyanate） as precursors，with trimethoxy（3-（phenylamino）propyl）silane as the secondary aminosilane coupling agent. The polyurethane films were characterized through chroma meter， UV-Vis spectrophotometry，Fourier-transform infrared spectroscopy（FT-IR）， thermogravimetric analysis（TGA），and thermal-oxidative aging tests to evaluate their appearance，hydrogen bonding degree， and thermal stability.［Results］The results showed that the silicone coupling agent-modified moisture-curable polyurethane films exhibited a visible light transmittance of 85%-89% with a color difference（ΔE）of <0. 4. Increasing the hard segment/soft segment mass ratio enhanced microphase separation， while increasing the dosage of the secondary aminosilane coupling agent reduced it. The activationenergies calculated by the Flynn-Wall-Ozawa（FWO）and Kissinger-Akahira-Sunose（KAS）methods increased from 77. 33-99. 71 kJ/mol to 104. 02-127. 39 kJ/mol before and after silicone modification， showing an increase of 27. 8%-34. 5%. The thermal degradation mechanisms were consistent withdiffusion models（D₁，D₂，and D₃）and the reaction order model（F_n）. The color difference upon heating was reduced.［Conclusion］ The synthesized silicone coupling agent-modified polyurethane is colorless and transparent，exhibits excellent thermal stability，and shows promising potential forapplication in the conservation of fragile organic cultural relics excavated from humid environments.

Key words: moisture-curable polyurethane；silane coupling agent；microphase separation； thermogravimetric analysis；thermal degradation mechanism 

中图分类号: 

• TQ630. 4