茂金属催化α-烯烃聚合反应动力学
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摘要
对rac-Et(1-Ind)2Zr Cl2/[Me2NHPh]+[B(C6F5)4]-/Al(i Bu)3催化α-烯烃液相聚合的反应体系进行了动力学研究。根据聚合反应机理和具体实验过程,提出了单活性中心模型,并优化确定了模型参数。结果表明,实验数据和模型计算值吻合较好。所得动力学模型参数很好地反映了茂金属体系催化煤制混合α-烯烃聚合反应的变化规律,通过该模型可以预测不同反应条件下的单体浓度、数均分子量和重均分子量,为该聚合反应的工艺设计提供基础数据。
The kinetics of α-olefin polymerization catalyzed by rac-Et(1-Ind)2ZrCl_2/[Me_2NHPh]~+[B(C_6F_5)_4]~-/Al(~iBu)_3 were studied. According to the mechanism of polymerization reaction and experimental procedure, a single active center model was proposed and the model parameters were optimized. The results showed that the experimental data agreed well with the calculated values of the model. The parameters of the kinetic model reflected well the changes in the polymerization of coal-based mixed α-olefins catalyzed by metallocene system. The model can predict monomer concentration, number average molecular weight and weight average molecular weight under different reaction conditions and provide fundamental data for the process design of this polymerization.
The kinetics of α-olefin polymerization catalyzed by rac-Et(1-Ind)2ZrCl_2/[Me_2NHPh]~+[B(C_6F_5)_4]~-/Al(~iBu)_3 were studied. According to the mechanism of polymerization reaction and experimental procedure, a single active center model was proposed and the model parameters were optimized. The results showed that the experimental data agreed well with the calculated values of the model. The parameters of the kinetic model reflected well the changes in the polymerization of coal-based mixed α-olefins catalyzed by metallocene system. The model can predict monomer concentration, number average molecular weight and weight average molecular weight under different reaction conditions and provide fundamental data for the process design of this polymerization.
引文
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[2]Richard F J,Prudence K B,Norman C B,et al.Beta-Agostic interactions in(C5H4Me)2Zr(CH2CH2R)(PMe3)+complexes[J].Journal of the American Chemical Society,1990,112(3):1289-1291.
[3]Breslow D S,Newburg N R.Bis-(cyclopentadienyl)-titanium dichloride-alkylaluminum complexls as catalysts for the polymerization of ethylene[J].Journal of the American Chemical Society,1979,79(18):5072-5073.
[4]Sinn H,Kaminsky W,Vollmer H J,et al.“Living Polymers”on polymerization with extremely productive Ziegler catalysts[J].Angewandte Chemie International Edition,1980,19(5):390-392.
[5]吕春胜,赵俊峰.限制几何构型茂金属/硼化物催化1-癸烯齐聚及其产物表征[J].化工进展,2009,28(8):1371-1375.Lv Chunsheng,Zhao Junfeng.Synthesis and characterization of oligomers from 1-decene catalyzed by metallocene catalyst with constrained geometry[J].Chemical Industry and Engineering Progress,2009,28(8):1371-1375.
[6]Ewen J A.Mechanisms of stereochemical control in propylene polymerizations with soluble group 4B metallocene/methylalumoxane catalysts[J].Journal of the American Chemical Society,1984,106(21):6355-6364.
[7]Kolthammer B W S,Mangold D J,Gifford D R.Polymerization kinetics of octene-1 catalyzed by metallocene methylaluminoxane investigated with attenuated total reflectance fourier transform infrared(ATR-FT-IR)spectroscopy[J].Journal of Polymer Science Part A:Polymer Chemistry,1992,30(6):1017-1026.
[8]Liu Z,Somsook E,White C B,et al.Kinetics of initiation,propagation,and termination for the{rac-[C2H4(1-indenyl)2Zr Me]}[Me B-(C6F5)3]-catalyzed polymerization of 1-hexene[J].Journal of the American Chemical Society,2001,123(45):11193-11207.
[9]Yang Q,Jensen M.Practical synthesis of rac-ethylenebis(η5-indenyl)zirconium dichloride[J].Synlett,1996,(2):147-148.
[10]Ikeda Y,Yamane T,Kaji E,et al.Method of producing tetrakis(pentafluorophenyl)borate derivatives using pentafluorophenyl magnesium derivatives:US,5488169[P].1996-01-30.
[11]郑文,范志强,邵爱凤,等.色谱法用于混合α-烯烃共聚物组份的分析[J].石油化工,1987,(4):39-44.Zheng Wen,Fan Zhiqiang,Shao Aifeng,et al.Determination of the composition of mixed olefin copolymer by gas chromatography[J].Petrochemical Technology,1987,(4):39-44.
[12]徐鑫磊.茂金属催化混合α-烯烃制备高粘度润滑油的研究[D].上海:华东理工大学,2018.
[13]Han J J,Lee H W,Yoon W J,et al.Rate and molecular weight distribution modeling of syndiospecific styrene polymerization over silica-supported metallocene catalyst[J].Polymer,2007,48(22):6519-6531.
[14]Soares J B P.Mathematical modelling of the microstructure of polyolefins made by coordination polymerization:a review[J].Chemical Engineering Science,2001,56(13):4131-4153.