Copolymerization of ethylene and 1-octene catalyzed by a modified Ziegler-Natta catalyst

PDF(1690 KB)

Journal of Beijing University of Chemical Technology ›› 2011, Vol. 38 ›› Issue (5) : 56-62.

材料科学与工程

KONG Yuan¹;YI JianJun²;HUANG QiGu¹;GAO KeJing²;ZHANG MingGe²;YANG WanTai¹

Author information +

History +

Abstract

A novel modified supported Ziegler-Natta catalyst(n-BuO)TiCl₃/MgCl₂has been prepared and employed for ethylene/1-octene copolymerization, with AlEt₃as cocatalyst. The influence of varying the polymerization temperature, the Al/Ti molar ratio, the feed molar ratio of ethylene to 1-octene and the ethylene pressure on the copolymerization reaction were investigated. The structure, properties and morphology of the copolymer were characterized by ¹³C-NMR, GPC, DSC and SEM. It was found that the catalytic activity in ethylene/1-octene copolymerization of the modified Ziegler-Natta catalyst was higher than that of the traditional Ziegler-Natta catalyst. The Al/Ti molar ratio and the feed molar ratio of ethylene to 1-octene have obvious effects on the catalytic activity, the comonomer content within the copolymer chain, the molecular weight and molecular weight distribution, and the microstructure of the resulting copolymer. Compared with the traditional Ziegler-Natta catalyst for ethylene/1-octene copolymerization which gives a comonomer content of 0.34%, the modified Ziegler-Natta catalyst showed higher activity for ethylene/1-octene copolymerization, and the comonomer content within the copolymer chain reached as high as 2.26 mol%. The microstructure of the copolymer was determined and the reactivity ratios of the monomers were confirmed by ¹³C-NMR. Values of r_E=55.00 for ethylene and r_O=0.023 for 1-octene with r_E· r_O=1.27 were obtained, suggesting the tendency for random distribution of the comonomers within the copolymer chain.

Cite this article

EndNote

Ris (Procite)

Bibtex

Download Citations

KONG Yuan¹;YI JianJun²;HUANG QiGu¹;GAO KeJing²;ZHANG MingGe²;YANG WanTai¹

. Copolymerization of ethylene and 1-octene catalyzed by a modified Ziegler-Natta catalyst[J]. Journal of Beijing University of Chemical Technology, 2011, 38(5): 56-62

References

［1］ Xu G X, Ruckenstein E. Ethylene copolymerization with 1-octene using a 2-methylbenz[e]indenyl-based ansa-monocyclopentadienylamido complex and methylaluminoxanes catalyst[J]. Macromolecules, 1998, 31: 4724-4729. 
[2] Joung U G, Wu C J, Lee S H. Phenylene-Bridged Cp/Carboxamide Ligands for Titanium Complexes of Various Binding Modes and Their Ethylene/1-Octene Copolymerization[J]. Organometallics, 2006, 25: 5122-5130. 
[3] Rick F, Makot M, Terunori F. Ethylene/Higher α-Olefin Copolymerization Behavior of Fluorinated Bis(phenoxy-imine)titanium Complexes with Methylalumoxane: Synthesis of New PolyethyleneBased Block Copolymers[J]. Macromolecules, 2005, 38: 1546-1552. 
[4] Sarah E R, Alice L L, Robert M W. Amine Bis(phenolate) Zirconium Complexes: Influence of Ligand Structure and Cocatalyst on Copolymerization Behavior[J]. Macromolecules, 2005, 38: 2552-2558. 
[5] Michael R S, Tobin J M. Synthesis, Characterization, and Marked Polymerization Selectivity Characteristics of Binuclear Phenoxyiminato Organozirconium Catalysts[J]. J Am Chem Soc, 2008, 130: 12-13. 
[6] Arriola D J, Carnahan E M, Hustad P D, et al. Catalytic production of olefin block copolymers via Chain shuttling polymerization[J]. Science, 2006, 312: 714-720. 
[7] Mori H, Ohnishi K, Terano M. Ethene polymerization with modifiedpolypropenesupported highly stable Ziegler catalyst[J]. Macromol Rapid Commun, 1996, 17: 25-29. 
[8] Bialk M, Czaja K. The effect of the comonomer on the copolymerization of ethylene with long chain α-olefins using Ziegler-Natta catalysts supported on MgCl₂(THF)₂[J]. Polymer, 2000, 41: 7899-7904. 
[9] Quijada R, Narvaez A, Rojas R, et al. Synthesis and characterization of copolymers of ethylene and 1-octadecene using the rac-Et(Ind)₂ZrCl₂/MAO catalyst system[J]. Macromol Chem Phys, 1999, 200 : 1306-1310. 
[10] Nomura K, Komatus T, Imanish Y. Ligand effect in olefin polymerization catalyzed by (cyclopentadienyl)(aryloxy) titanium(Ⅳ) complexes, Cp*TiCl₂(OAr)-MAO system.: Ethylene/1-hexene copolymerization by (1, 3-tBu₂C₅H₃)TiCl2(O-2, 6-iPr₂C₆H₃)-MAO catalyst system [J]. J Mol Catal, A: Chem, 2000, 159: 17-137. 
[11]Murray M C, Baird M C. Copolymerization of 1-hexene and ethylene catalyzed by the Ziegler catalyst Cp*TiMe₃/B(C₆F₅)₃[J]. J Polym Sci Chem, 2000, 38: 3966-3976. 
[12]Carman C J, Harrington R A, Wilkes C E. Monomer sequence distribution in ethylenepropylene rubber measured by ¹³C-NMR. 3. Use of reaction probability model[J]. Macromolecules, 1977, 10: 536-541. 
[13]Hsieh E T, Randall J C. Monomer sequence distributions in ethylene1hecene copolymers[J]. Macromolecules, 1982, 15: 1402-1406. 

[14]Ko Y S, Han T K, Sadatoshi H, et al. Analysis of microstructure of ethylene-1-hexene copolymer prepared over thermally pretreated MgCl₂/THF/TiCl₄ bimetallic catalyst[J]. J Polym Sci Chem, 1998, 36: 291-300.

PDF(1690 KB)

2815

Accesses

Citation

Detail

Sections

Recommended

Abstract
Cite this article
References

Received	Revised	Published
2011-03-12	1900-01-01	2011-09-20
Issue Date
2011-09-20

Please choose a citation manager

Content to export

Abstract

Cite this article

{{custom_sec.title}}

{{custom_sec.title}}

References

{{custom_fnGroup.title_en}}

Footnotes

模态框（Modal）标题

Please choose a citation manager

Content to export

Abstract

Cite this article

{{custom_sec.title}}

{{custom_sec.title}}

References

{{custom_fnGroup.title_en}}

Footnotes