负载型钛催化剂催化1-十二烯溶液聚合动力学  

Kinetics of α-Dodecene Solution Polymerization on Supported Titanium Catalyst

作　　者：朱永涛[1] 李惠萍[1] 胡子昭[1] 王菁[1] 高小哲[1] 

机构地区：[1]新疆大学化学化工学院石油天然气精细化工教育部,新疆维吾尔自治区重点实验室,新疆乌鲁木齐830008

出　　处：《化学反应工程与工艺》2012年第5期475-480,共6页Chemical Reaction Engineering and Technology

摘　　要：采用TiCl4/MgCl2-Al（i-Bu）3催化剂,溶液聚合法合成了聚1-十二烯烃油溶性减阻剂.使用Brookfield DVⅢ型流变仪对以正已烷、正庚烷和环已烷为溶剂的原料进行流变性研究,以此考察不同溶剂体系对聚合速率的影响,测定了主催化剂TiCl4/MgCl2浓度与助催化剂Al（i-Bu）3浓度的反应级数和聚合反应的表观活化能,并由此建立聚合反应速率方程,探讨了聚合速率对聚合物特性粘数的影响.结果表明,以正已烷、正庚烷和环已烷为溶剂时,聚合速率依次降低,但对单体浓度均呈一级反应；在本研究催化剂加量范围内,聚合速率对主催化剂浓度呈一级关系,而刘助催化剂浓度呈零级关系.聚合速率与特性粘数不成正比关系,需在合适聚合速率下才能得到较高特性粘数.在-5～5℃,聚合的表观活化能为56.64 kJ/mol.An oil-soluble drag reduction agent （DRA） was synthesized from a-dodecene monomers with solution polymerization on supported TiC14/MgC12 catalyst. Rheology study was carried out with Brookfield DV Ⅲ rheometer to measure the polymerization rates in n-hexane, n-heptane and Cyclohexane solvents. Kinetic parameters such as reaction order on concentration of main catalyst TiCIa/MgCI2 and concentration of co-catalyst A1 （i-Bu） as well as reaction apparent activation energy were determined from initial polymerization rate, and the polymerization rate expression was then derived, The effect of chain growth rate on polymer intrinsic viscosity was also discussed. The results show that the polymerization rate is the first order to the concentration of the monomer and main catalyst, and zero order to the concentration of co-catalyst.The polymerization rate decreases successively in n-hexane, n-heptane and cyclohexane solvents. The relationship between the polymerization rate and polymer intrinsic viscosity is non-linear. Polymerization rate should lie in a specific range to obtain the polymer with a higher intrinsic viscosity. The polymerization apparent activation energy is 56.64 k J/tool at -5--5℃.

关 键 词：1-十二烯烃负载钛催化剂溶液聚合影响因素动力学 

分 类 号：O632.12[理学—高分子化学]