【摘要】 本文设计合成了两种以聚吡唑硼酸盐、吡唑为配体的铜配合物Cu2[μ-pz]2[HB(pz)3]2(1)和Cu[B(pz)4]2(2)(pz:吡唑(C3H4N2))。运用元素分析、红外光谱对配合物进行了表征,并用X-ray衍射测定了它们的晶体结构。非等温热分解动力学研究表明:配合物1的热分解反应分两步,配合物2的热分解反应一步进行。通过计算,配合物1热分解的第一步反应的可能机理为成核与生长,n=1/4;第二步反应的可能机理为化学反应。其非等温动力学方程分别为:dd"T=A#e-RET·41(1-α)[-ln(1-α)]-3和dd"T=A$e-RET(1-α)2。分解反应的表观活化能分别是520.37kJ·mol-1和149.65kJ·mol-1;指前因子lnA分别是118.06s-1和28.10s-1。配合物2热分解的可能机理为化学反应。其非等温动力学方程为:dd"T=A$e-RET(1-α)2。分解反应的表观活化能是111.41kJ·mol-1;指前因子lnA是21.20s-1。更多还原

【Abstract】 Two copper complexes, Cu2 μ-pz2HB(pz)32 (1) and CuB(pz)42 (2) (pz: pyrazole (C3H4N2)), with poly(pyrazolyl)borate and pyrazole as ligands, were synthesized successfully. The two complexes were characterized by IR, elemental analyses, thermal analyses and X-ray diffraction. The study of thermal decomposition kinetics for complex 1 show: the decomposition process is two steps, and the corresponding possible reaction mechanisms are nucleation and growth (n=1/4), and chemical reaction, respectively; the non-isothermal kinetic equations may be expressed ■=■e■·■(1-α)-Ln(1-α)-3 and ■=■e■(1-α)2, respectively; the apparent activation energy is 520.37 kJ·mol-1 and 149.65 kJ·mol-1, respectively; the pre-exponentials are 118.06 s-1 and 28.10 s-1. The study of thermal decomposition kinetics for complex 2 shows: the possible reaction mechanisms of only a step is chemical reaction, the non-isothermal kinetic equations may be expressed as ■=■e■(1-α)2; the apparent activation energy is 111.41 kJ·mol-1; the pre-exponentials is 21.20 s-1. CCDC: 621240, 1.更多还原