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A Kinetic Study of Thermal Decomposition of Glycidyl Azide Polymer (GAP)-based Energetic Thermoplastic Polyurethanes

机译:缩水甘油基叠氮化物聚合物(GAP)基高能热塑性聚氨酯热分解的动力学研究

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摘要

Energetic thermoplastic polyurethane elastomers (ETPUs) of glycidyl azide polymer (GAP) were synthesized on GAP/poly(caprolactone)(PCL) (100/0, 50/50) as a soft segment and methylenebis(phenylisocyanate) (MDI) extended 1,5-pentanediol as a hard segment by solution polymerization in dimethyl formamide (DMF). Differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA) were used to examine the thermal decomposition behavior. Kinetic analysis was performed with model fitting and a model-free method to obtain the activation energy as a function of the extent of conversion. ETPU decomposition was divided into two stages with different activation energies. The first main weight loss step corresponds to the elimination of N2 from the decomposition of-N3 bonds within azide polymers. The activation energy of the main decomposition of GAP ETPU and GAP/PCL ETPU was approximately 190 kJ/mol. The second weight loss step coincides with the decomposition of the skeleton. The activation energy of those showed an increasing trend.
机译:缩水甘油基叠氮化物聚合物(GAP)的高能热塑性聚氨酯弹性体(ETPU)是在GAP /聚己内酯(PCL)(100/0,50/50)和亚甲基双(苯基异氰酸酯)(MDI)扩展1,通过在二甲基甲酰胺(DMF)中进行溶液聚合,将5-戊二醇作为硬链段。差示扫描量热法(DSC)和热重分析(TGA)用于检查热分解行为。用模型拟合和无模型方法进行动力学分析,以获得活化能随转化程度的变化。 ETPU分解分为具有不同活化能的两个阶段。第一个主要的失重步骤对应于叠氮化物聚合物中-N3键的分解消除N2。 GAP ETPU和GAP / PCL ETPU主要分解的活化能约为190 kJ / mol。第二个减肥步骤与骨架分解相吻合。那些的活化能显示出增加的趋势。

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