Olefin polymerization catalyst with double active components and preparation method

An olefin polymerization and catalyst technology, which is applied in the field of dual-active component olefin polymerization catalyst and its preparation, can solve the problems of difficult shape control and low bulk density, and achieve the effects of good material performance, good strength and improved comprehensive performance.

CN105218711AActive Publication Date: 2016-01-06ZIBO XINSU CHEM
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Publication Date
2016-01-06

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Abstract

The present application provides a novel catalyst for olefin polymerization. The catalyst comprises a magnesium-containing composite carrier, a dispersant Ti(OBu)4, a pyrrole ring-containing electron donor compound and active components VCl4 and TiCl4. The magnesium-containing composite carrier of the the catalyst is obtained by spray-drying, has a preferable shape and high ethylene polymerization activity, and is suitable for being used in a gas-phase fluidized bed polymerization process, and is further suitable for being used in a slurry polymerization process; linear polyethylene containing relatively few oligomers with bimodal or wide relative molecular weight distribution can be prepared, and the obtained linear polyethylene has a good material property. The polyethylene resin prepared by using the catalyst has bimodal or broad relative molecular mass distribution, polyethylene resin containing relatively few oligomers can be obtained when polymerization of ethylene and comonomer is catalyzed, a film material blown by the resin has a preferable material property, a good strength and a high dart drop impact quality.
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Description

technical field

[0001] The invention belongs to the field of chemical industry, and in particular relates to a dual active component olefin polymerization catalyst and a preparation method thereof. Background technique

[0002] In the process of producing high-density polyethylene (HDPE) or linear low-density polyethylene (LLDPE), it can be copolymerized with ethylene by adding unsaturated olefin comonomers with more than 3 carbon atoms (such as butene, hexene, etc.) , Reducing the density of the polymer can improve various properties of polyethylene, such as machinability, solubility, heat resistance, corrosion resistance, etc., so as to obtain a polyethylene resin with excellent comprehensive properties.

[0003] Small molecule copolymers in polyethylene can provide plasticization and lubrication for polyethylene resin, reduce the crystallinity of polyethylene resin, and improve the processing performance of polyethylene resin, but at the same time it may cause the problem...

Examples

Embodiment 1

[0044] (1) MgCl 2 Dissolve in ethanol solution, add dehydration activated SiO with particle size less than or equal to 1.0μm 2 , fully dispersed and sprayed to obtain a spherical composite carrier with good shape, the obtained spherical composite carrier is dealcoholized in a fluidized bed to make the MgCl in the spherical composite carrier 2 : SiO 2 : The molar ratio of ethanol is 1:1:0.1;

[0045] (2) The spherical composite carrier obtained by step (1) is dispersed in hexane, and the dispersant Ti(OBu) is added 4 , at 30°C, the carrier was pre-dispersed to obtain a suspension, and the dispersant and MgCl 2 The molar ratio is 0.01;

[0046] (3) Add N-(2,6-dimethylphenyl)-2-pyrrolemethimine to the suspension prepared in step (2), and fully react at 30°C for 0.1 hour. The N-(2 ,6-Dimethylphenyl)-2-pyrrolemethimine and MgCl 2 The molar ratio is 0.001;

[0047] (4) Add TiCl to the carrier suspension prepared in step (3) 4 and VCl 4 At 30°C, reacted for 0.5 hours, the Ti...

Embodiment 2

[0049] (1) MgCl 2 Dissolve in propanol solution, add dehydration-activated SiO with particle size less than or equal to 1.0μm 2 , fully dispersed and sprayed to obtain a spherical composite carrier with good shape, the obtained spherical composite carrier is dealcoholized in a fluidized bed to make the MgCl in the spherical composite carrier 2 : SiO 2 : Propanol molar ratio is 1:5:1;

[0050] (2) The spherical composite carrier obtained by step (1) is dispersed in heptane, and the dispersant Ti(OBu) is added 4 , at 80°C, the carrier was pre-dispersed to obtain a suspension, and the dispersant and MgCl 2 The molar ratio is 1.0;

[0051] (3) Add N-(2,6-diethylphenyl)-2-pyrrolemethimine to the suspension prepared in step (2), and fully react at 150°C for 1.5 hours. The N-(2 ,6-diethylphenyl)-2-pyrrolemethimine and MgCl 2 The molar ratio is 0.1;

[0052] (4) Add TiCl to the carrier suspension prepared in step (3) 4 and VCl 4 At 100°C for 12 hours, the TiCl 4 with MgCl 2...

Embodiment 3

[0054] (1) MgCl 2 Dissolve in butanol solution, add dehydration-activated SiO with particle size less than or equal to 1.0 μm 2 , fully dispersed and sprayed to obtain a spherical composite carrier with good shape, the obtained spherical composite carrier is dealcoholized in a fluidized bed to make the MgCl in the spherical composite carrier 2 : SiO 2 : Butanol molar ratio is 1:3:0.5;

[0055] (2) Disperse the spherical composite carrier obtained in step (1) in octane, add dispersant Ti(OBu) 4 , at 60°C, the carrier was pre-dispersed to obtain a suspension, and the dispersant and MgCl 2 The molar ratio is 0.66;

[0056] (3) Add N-(2,6-diisopropylphenyl)-2-pyrrolemethimine to the suspension prepared in step (2), and fully react at 120°C for 1.3 hours. The N-( 2,6-diisopropylphenyl)-2-pyrrolemethimine and MgCl 2 The molar ratio is 0.009;

[0057] (4) Add TiCl to the carrier suspension prepared in step (3) 4 and VCl 4 At 70°C for 11 hours, the TiCl 4 with MgCl 2 The mo...