非等温DSC法研究聚丁二烯点击化学固化动力学. (Chinese)

In order to apply the click chemical curing system of polybutadiene into the practical process, the non-isothermal differential scanning calorimetry (DSC) method was used to investigate curing reaction kinetics of terminal alkynyl polybutadiene (PTPB)-triazide acetate propane (TAP)-terminal azido polyethylene glycol (APEG) system. The curing temperature and kinetic parameters of this curing system were calculated by the heating rate-temperature extrapolation method, the Kissinger model, the Ozawa model and the Crane model, respectively. The isothermal curing behavior of the curing system was predicted by nth order kinetics model and model free kinetics (MFK). The results indicate that this system has a low curing activity at 60°C and the curing rate constant is only 3.13 X 10 5 min 1. When the mass fraction of the catalyst (CuCO is 0. 1 %, the rate constant is 5.6 X 10 3 min 1, which is two orders of magnitude higher than that of the hydroxyl terminated polybutadiene-toluene di isocyanate (HTPB-TDI) curing system. The MFK prediction result is closer to the measured result. In addition, when the mass fraction of CuCI is 0.1 %, the curing system requires only 10.4h to complete curing at 30°C. [ABSTRACT FROM AUTHOR]

为了更好地将聚丁二烯点击化学固化体系应用到实际工艺中,采用非等温差示扫描量热(DSC)法研究了端炔 基聚丁二烯(PTPB)-三叠氮乙酸酯基丙烷(TAP)-端叠氮基聚乙二醇(APEG)体系的固化反应动力学;利用升温速率-温度 外推法,Kissinger模型,Ozawa模型和Crane模型计算得到该固化体系的固化温度和动力学参数;通过n级固化动力学 模型和非模型动力学(MFK)两种计算方法预测了该固化体系的等温固化行为。结果表明,若不添加催化剂,该体系 60°C下固化反应活性低,固化速率非常缓慢,反应速率常数仅为3.13X W 5 min 1; 当添加催化剂CuCI的质量分数为 0. 1 %时,其反应速率常数为5.6 XW 3 min 1,比端羟基聚丁二烯-甲苯二异氰酸酯(HTP&TOI)固化体系高两个数量 级;MFK预测结果与实测结果更为接近。此外,CuCl质量分数为0.1 %时,该固化体系在30°C下完成固化仅需10.4h. [ABSTRACT FROM AUTHOR]

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