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以聚乙二醇单甲醚(mPEG)、丁二酸酐以及碳酸甘油酯为原料,合成了端基为五元环碳酸酯的聚乙二醇功能性大单体(mPEG-GC);以mPEG-GC为碳酸酯模型化合物,研究了碳酸酯与不同类型的胺在不同温度下反应的速率常数及其动力学活化能。结果表明:碳酸酯的转化率随时间、反应物配比、反应温度增大而增大,随反应物浓度的增大先增加后减少;正庚胺与mPEG-GC反应的活化能最低(Ea=5.63kJ/mol);在相同温度下,环己胺与碳酸酯反应的反应速率常数大于2-氨基庚烷与碳酸酯反应体系的速率常数。
Polyethylene glycol functional macromonomer (mPEG-GC) with 5-membered ring end-capped carbonate was synthesized from polyethylene glycol monomethyl ether (mPEG), succinic anhydride and glycerol carbonate. -GC is a carbonate model compound, and the rate constants and kinetic activation energies of the carbonates reacted with different types of amines at different temperatures were studied. The results showed that the conversion of carbonate increased with time, the ratio of reactants and the reaction temperature, and then increased with the increase of reactant concentration. The reaction energy of n-heptylamine and mPEG-GC was the lowest (Ea = 5.63 kJ / mol). At the same temperature, the reaction rate constant of cyclohexylamine with carbonate is larger than the rate constant of 2-aminoheptane with carbonate reaction system.