摘要
研制了一系列负载型钛系高效催化剂:GZ、ZS、ZE、YJ、CP、STP、SN、HE型等8类,成功地用于乙烯、丙烯、丁烯-1、苯乙烯均聚合,以及乙烯和α-烯烃之间的共聚合反应。研究了催化剂组份、聚合条件、共聚单体配比等对催化活性及多种烯烃聚合反应的影响,聚合反应动力学;并测定了催化剂活性中心浓度及动力学参数等。
Slurry polymerization of ethylene giving high yields of polyethylene under ambient or enchanced pressure with catalyst of TiCl_4/MgCl_2/AlEt_3(named“GZ-Ca- talyst”)prepared by comilling method has been studied. With modified catalyst comprising TiCl_4,Ti(O-n-Bu)_4/MgCl_2/AlEt_3(named “ZS-Catalyst”),the yield of ethylene polymerization or ethylene/propylene copo- lymerization are raised up quite distinctly.For preparation of ultra high molecular weight polyethylene(UHMWPE),a modified catalyst of TiCl_4/MgCl_2/AlEt_3, RMgCl(named“HE-Catalyst”)was found to be especially highly active. With catalyst comprising TiCl_4,Ti(O-n-Bu)_4/MgCl_2,ZnCl_2/AlEt_3(named“YJ-Ca- talyst”)or with catalyst comprising TiCl_4/MgCl_2/AlEt_3,ZnEt_2(named“ZE-Cata- lyst”),ethylene polymerization in absence of hydrogen gives lower molecular weight polymer.A noval modified catalyst of TiCl_4,NdCl_3/MgCl_2/AlEt_3(named “SN-Catalyrs”)is highly active for polymerization of ethylene as well as ster- eospecific polymerzation of styrene and copolymerization of these two monomers. The effects of polymerization conditions and kinetics of ethylene polymerization with each of the above catalysts have been studied. A novel catalyst of TiCl_4,TiCl_3/MgCl_2/EB/Ph_2SiCl_2/Al(i-Bu_3)(named“CP-Cata- lyst”) is highly active as well as stereospecific for polymerization of propylene.It can be further improved by chemical modification with addition of TiCl_4,alumi- num trialkyl,organomagnesium,SiCl_4 and Lewis base to get the “STP-Catalyst” while maintaining highly catalytic activity and high tacticity for polymerization of propylene.The kinetics of propylene polymerization with“CP-Catalyst”and “STP-Catalyst”have been studied.The decay polymarization rate equation deriv- ed in good experimental accordance is expressed as: V_p =V_∞ +(V_o-V_∞ )e^(-βt) or ln(V_p-V_∞)=ln(V_0-V_∞)-βt.
出处
《中山大学学报（自然科学版）》
CAS
CSCD
1990年第3期78-85,共8页
Acta Scientiarum Naturalium Universitatis Sunyatseni
关键词
钛系催化剂
乙烯
-烯烃
聚合反应
titanium catalyst
ethylene
a-olefin
polymerization
copolymerization
