用钛系载体催化剂进行1-丁烯聚合的研究

POLYMERIZATION OF 1-BUTENE WITH SUPPORTED TITANIUM CATALYST

研制不同组分的载体钛系高效催化剂,考察在不同聚合条件及外加芳酯的情况下对1-丁烯聚合的影响。用催化剂TiCl_4,Ti(OBu)_4/φ_2SiCI_2/苯甲酸乙酯(EB)/MSCl_2/AlEt_3进行1-丁烯聚合具有高的催化活性(3.2×10~4g·PB/g·Ti·h),外加对-甲基苯甲酸乙酯时可提高聚合物等规度(Ⅰ.Ⅰ％=93.3),分子量可用H_2调节。衰减聚合反应的动力学方程为R_1=R_5+(R_0-R_5)e^(βt)。用DSC、WAXD和^(13)C-NMR等方法表征聚合物。

1-Butene was polymerized with highly active supported titanium catalysts which was developed in this laboratory. The influences of various conditions such as catalyst composition, temperature, triethylaluminum concentration, catalyst concentration, adding ester and H2 on the catalytic activity, decay of polymerization rate,inh value and isotactivity of resulting products were studied in detail. The structure and properties of poly (1-butene) were also studied by WAXD, DSC and 13C-NMR.It was found that TiCl4, Ti (OBu)4/MgCl2 /ethylbenzoate (EB)/(C6H5)2 SiCl2/AlEt3 catalyst had high catalytic activity, i. e. 3.2×104g·PB/g·Ti·h. Isotacticity of products was increased by adding P-CH3C6H4COOEt. i, e. I. I. % =93.3. Molecular weight of products was controlled by H2.The decay of polymerization rate with time fulfills the equation: Rt-Rs=(R0- Rs)e^Bs.