Synthesis of PE with Broad MWD Catalyzed by Supported Ziegler-Natta Catalyst Consisting of Cycloalkoxy Silane as IED
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摘要
Two kinds of cycloalkoxy silane compounds were synthesized and used as the internal electron donors(IEDs) of supported Ziegler-Natta catalyst for ethylene polymerization to produce polyethylene with broader molecular weight distribution(MWD). The effect of the structure and the amount of these IEDs on the polymerization performance was investigated. The results implied that the molecular weight distribution of the obtained polyethylene could be adjusted by the incorporation of IEDs. SEM result showed that the morphology of catalyst particle was spherical and uniform in size distribution. The titanium content of these catalysts was higher, the active TiCl4 species were easily anchored on the support than that without adding IED, which was determined by ICP. The GPC result confirmed that the polyethylene with broader molecular weight distribution in the range of from 23.4 to 25.6 was obtained using triethoxy-(-cyclopentyloxy)-silane(ED1) and triethoxy-(-cyclohexyloxyl)- silane(ED2) as the internal electron donors.
Two kinds of cycloalkoxy silane compounds were synthesized and used as the internal electron donors(IEDs) of supported Ziegler-Natta catalyst for ethylene polymerization to produce polyethylene with broader molecular weight distribution(MWD). The effect of the structure and the amount of these IEDs on the polymerization performance was investigated. The results implied that the molecular weight distribution of the obtained polyethylene could be adjusted by the incorporation of IEDs. SEM result showed that the morphology of catalyst particle was spherical and uniform in size distribution. The titanium content of these catalysts was higher, the active TiCl4 species were easily anchored on the support than that without adding IED, which was determined by ICP. The GPC result confirmed that the polyethylene with broader molecular weight distribution in the range of from 23.4 to 25.6 was obtained using triethoxy-(-cyclopentyloxy)-silane(ED1) and triethoxy-(-cyclohexyloxyl)- silane(ED2) as the internal electron donors.
Two kinds of cycloalkoxy silane compounds were synthesized and used as the internal electron donors(IEDs) of supported Ziegler-Natta catalyst for ethylene polymerization to produce polyethylene with broader molecular weight distribution(MWD). The effect of the structure and the amount of these IEDs on the polymerization performance was investigated. The results implied that the molecular weight distribution of the obtained polyethylene could be adjusted by the incorporation of IEDs. SEM result showed that the morphology of catalyst particle was spherical and uniform in size distribution. The titanium content of these catalysts was higher, the active TiCl4 species were easily anchored on the support than that without adding IED, which was determined by ICP. The GPC result confirmed that the polyethylene with broader molecular weight distribution in the range of from 23.4 to 25.6 was obtained using triethoxy-(-cyclopentyloxy)-silane(ED1) and triethoxy-(-cyclohexyloxyl)- silane(ED2) as the internal electron donors.
引文
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[12]Liu Z,Zhang X L,Huang H B,et al.Synthesis of(co-)polyethylene with broad molecular weight distribution by the heterogenous Ziegler–Natta catalysts via one-pot strategy[J].Journal of Industrial and Engineering Chemistry,2012,18(6):2217-2224
[13]Kong Y,Yi J J,Dou X L,et al.Heterogeneous ZieglerNatta catalysts with different structure of ligands for the preparation of copolymer of ethylene and 1-octene with high comonomer incorporation.Polymer,2010,51(17):3859-3866
[14]Huang Q G,Liu W J,Dou X L,et al.Olefin polymerization catalyst and preparation method:China,CN201010186264.2[P],2010-09-29
[15]Liu Z,Yu M S,Wang J,et al.Preparation and characterization of novel polyethylene/carbon nanotubes nanocomposites with core–shell structure[J].Journal of Industrial and Engineering Chemistry,10.1016/j.jiec.2012.08.034(2013)
[16]Wang J,Yu M S,Jiang W H,et al.The preparation of nanosized polyethylene particles via carbon sphere nanotemplates[J].Industrial&Engineering Chemistry Research,2013,52(49):17691-17694
[17]Huang Q G,Liu Z,Liu W J,et al.Preparation and self-assembly of global nano-particles of MgCl2-CH3CH2OH complex[J].Acta Polymerica Sinica,2012(8):883-886(in Chinese)
[18]Galli P,Luciani L,Gechi G.Advances in the polymerization of polyolefins with coordination catalysts[J].Die Angewandte Macromolekulare Chemie,1981,94(1):63-89
[19]SepplJ V,Auer M.Factors affecting kinetics in slurry type coordination polymerization.Progress in Polymer Science,1990,15(1):147-176
[2]Alt F P,Bohm L L,Enderle H F.Bimodal polyethyleneInterplay of catalyst and process[J].Macromolecular Symposia,2001,163(1):135-144
[3]Zacca J J,Debling J A,Ray W H.Reactor residence-time distribution effects on the multistage polymerization of olefins—II.Polymer properties:bimodal polypropylene and linear low-density polyethylene[J].Chemical Engineering Science,1997,52(12):1941-1967
[4]Loópez-Linares F,Barrios A D,Ortega H,et al.Toward the bimodality of polyethylene,initiated with a mixture of a Ziegler–Natta and a metallocene/MAO catalyst system[J].Journal of Molecular Catalysis A:Chemical,2000,159(2):269-272
[5]Cho H S,Chung J S,Lee W Y.Control of molecular weight distribution for polyethylene catalyzed over Ziegler–Natta/metallocene hybrid and mixed catalysts[J].Journal of Molecular Catalysis A:Chemical,2000,159(2):203-213
[6]Cho K,Lee B H,Hwang K M,et al.Rheological and mechanical properties in polyethylene blends[J].Polymer Engineering&Science,1998,38(12):1969-1975
[7]Premphet K,Paecharoenchai W.Polypropylene/metallocene ethylene-octene copolymer blends with a bimodal particle size distribution:Mechanical properties and their controlling factors[J].Journal of Applied Polymer Science,2002,85(11):2412-2418
[8]Zhang Y,Huang J L,Yang X X,et al.Some mixed cyclopentadienyl–indenyl zirconium complexes with PhCH2 or PhCH2CH2 substituents in ethylene polymerization[J].Journal of Polymer Science Part A:Polymer Chemistry,2005,43(6):1261-1269
[9]Cho H S,Choi Y H,Lee W Y.Characteristics of ethylene polymerization over Ziegler–Natta/metallocene catalysts:Comparison between hybrid and mixed catalysts[J].Catalysis Today,2000,63(2):523-530
[10]Ali A H,Hsieh J T T,Kauffman K J,et al.Producing blown film and blends from bimodal high density high molecular weight film resin using magnesium oxide-supported Ziegler catalyst:The United States,US 5284613[P],1994-02-08
[11]Wang L C,Ren H,Sun J Q.Fe(acac)3-bis(imino)pyridine/MAO:A new catalytic system for ethylene polymerization[J].Journal of Applied Polymer Science,2008,108(1):167-173
[12]Liu Z,Zhang X L,Huang H B,et al.Synthesis of(co-)polyethylene with broad molecular weight distribution by the heterogenous Ziegler–Natta catalysts via one-pot strategy[J].Journal of Industrial and Engineering Chemistry,2012,18(6):2217-2224
[13]Kong Y,Yi J J,Dou X L,et al.Heterogeneous ZieglerNatta catalysts with different structure of ligands for the preparation of copolymer of ethylene and 1-octene with high comonomer incorporation.Polymer,2010,51(17):3859-3866
[14]Huang Q G,Liu W J,Dou X L,et al.Olefin polymerization catalyst and preparation method:China,CN201010186264.2[P],2010-09-29
[15]Liu Z,Yu M S,Wang J,et al.Preparation and characterization of novel polyethylene/carbon nanotubes nanocomposites with core–shell structure[J].Journal of Industrial and Engineering Chemistry,10.1016/j.jiec.2012.08.034(2013)
[16]Wang J,Yu M S,Jiang W H,et al.The preparation of nanosized polyethylene particles via carbon sphere nanotemplates[J].Industrial&Engineering Chemistry Research,2013,52(49):17691-17694
[17]Huang Q G,Liu Z,Liu W J,et al.Preparation and self-assembly of global nano-particles of MgCl2-CH3CH2OH complex[J].Acta Polymerica Sinica,2012(8):883-886(in Chinese)
[18]Galli P,Luciani L,Gechi G.Advances in the polymerization of polyolefins with coordination catalysts[J].Die Angewandte Macromolekulare Chemie,1981,94(1):63-89
[19]SepplJ V,Auer M.Factors affecting kinetics in slurry type coordination polymerization.Progress in Polymer Science,1990,15(1):147-176