| 蓖麻油基聚氨酯树脂的热降解行为研究 |
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| 引用本文： | 郭建维,欧艺威,马军现,欧华新,王悦辉.蓖麻油基聚氨酯树脂的热降解行为研究[J].华南师范大学学报(自然科学版),2022,54(6):28-36. |
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| 作者姓名： | 郭建维 欧艺威 马军现 欧华新 王悦辉 |
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| 作者单位： | 1.广东工业大学轻工化工学院，广州 510006 |
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| 基金项目： | 国家自然科学基金项目61671140广东省普通高校特色创新项目2020KTSCX179中山市科技计划公益类重点项目2019B2017 |
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| 摘 要： | 利用热重分析仪(TGA)、热重分析-傅里叶变换红外光谱仪(TG-FTIR)及热裂解气相色谱/质谱(PY-GC/MS)联用仪等对蓖麻油基聚氨酯树脂的热降解过程进行测试与表征，采用不同的非等温动力学方法计算树脂的热降解动力学参数，推断树脂的热降解机理。结果表明:蓖麻油基聚氨酯树脂在285 ℃开始降解(质量损失5%)，在450 ℃左右基本降解完全(质量损失95%)。其热降解过程(以升温速率为10 ℃/min为例)分为3个阶段:第一阶段发生285.23~345.25 ℃，其质量损失了60%，主要为树脂氨基甲酸酯键的断裂及部分酯基分解为CO2；第二阶段为345.25~389.17 ℃，质量损失了20%；主要为氨基甲酸酯链段降解为胺类、CO2及含有CH3或-CH2-的小分子有机物；第三阶段为389.17~450.00 ℃，质量损失了20%，主要为小分子有机物进一步降解为CO2和含N易挥发性气体。其降解机理可能有2种途径:第一种是主键氨基甲酸酯结构中酯基-O-左侧碳氧键断裂，形成异氰酸酯和醇，异氰酸酯部分裂解为胺类、二氧化碳等，而醇部分则脱水生成醛或者合成烯烃、烯酸类物质；第二种是氨基甲酸酯结构中-O-右侧碳氧键断裂生成氨基甲酸和醇类，氨基甲酸部分断裂生成伯胺和二氧化碳，醇部分裂解为醛和烯烃等。
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| 关 键 词： | 蓖麻油基聚氨酯树脂 热降解行为 动力学参数 降解机理 |
| 收稿时间： | 2021-11-08 |
Thermal Decomposition Behavior of Castor Oil-based Polyurethane Resin |
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| Affiliation: | 1.School of Light industry and Chemical engineering, Guangdong University of Technology, Guangzhou 511400, China2.University of Electronic Science and Technology of China, Zhongshan Institute, Zhongshan 528402, China3.Zhongshan Xinhui Chemical Products Co. Ltd, Zhongshan 528414, China |
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| Abstract: | The thermogravimetric analyzer (TGA), thermogravimetric analysis-Fourier transform infrared spectrometer (TG-FTIR) and thermal pyrolysis gas chromatography/mass spectrometry (PY-GC/MS) were used for the test and characterization of the thermal degradation process in the castor oil-based polyurethane resin, different non-isothermal kinetic methods were used to calculate the kinetic parameters of the resin and infer the thermal degradation mechanism of the resin. The results show that the castor oil-based polyurethane resin starts to degrade at 285 ℃ (5% mass loss), and the degradation is almost complete around 450 ℃ (95% mass loss). The thermal degradation process (take a heating rate of 10 ℃/min as an example) is divided into three stages: the first stage occurs at 285.23~345.25 ℃, the mass loss is 60%, mainly due to the rupture of the resin urethane bond and parts of the ester group decomposed into CO2; the second stage starts at 345.25~389.17 ℃ with 20% mass loss, the carbamate segment is degraded into amines, CO2 and small molecular organics containing CH3 or -CH2-; the third stage occurs at 389.17~450.00 ℃, the mass loss is 20%, mainly because the small molecular organic matter is further degraded into CO2 and N-containing volatile gas. The degradation mechanism may have two ways: the first is the cleavage of the carbon-oxygen bond on the left side of the ester group -O- in the main bond carbamate structure to form isocyanates and alcohols. The isocyanates are partially split into amines, carbon dioxide, etc., and the alcohol part is dehydrated to generate aldehydes or to synthesize olefins, enoic acids; the second is the cleavage of the -O- right carbon-oxygen bond in the carbamate structure to generate carbamic acid and alcohols. The carbamate partially cracked to generate primary amines and carbon dioxide, and alcohols partially cleft into aldehydes and olefins, etc. |
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