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Vanadium-based catalyst system for olefin polymerization

A technology for olefin polymerization and catalyst, applied in the field of vanadium-based catalyst system

Active Publication Date: 2017-07-25
常州汉韦聚合物有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN103923235A discloses a vanadium-based catalyst obtained by mixing a main catalyst and a cocatalyst, wherein the main catalyst is composed of a vanadium compound or complex and an electron donor, and the electron donor is a single-ring aromatic compound, an acrylate compound, a Acrylic acid ester compound or ether or alcohol compound (formula I-III in the text) without halogen, co-catalyst includes organoaluminum compound and activity accelerator, and pentavalent vanadium plays the main role in this vanadium-based catalyst The role of the electron donor is to stabilize the active center, increase the reactivity, enhance the random copolymerization ability of ethylene and propylene, and reduce the gel formation of EPDM rubber during the polymerization process. However, under the same polymerization conditions, the obtained The propylene content in the ethylene-propylene copolymer is only slightly higher

Method used

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Examples

Experimental program
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Effect test

Embodiment 1

[0030] Propylene and ethylene monomers are in a certain molar ratio (C 3 / C 2 =2.0) was mixed with hexane to form a monomer solution ([M]=57g / L). At -45°C, add VOCl 3 , EtAl 1.5 Cl 1.5 And the catalyst of 2-chloro-2-methylpropane (abbreviated as TB), wherein, the V / M molar ratio is 5.1×10 -4 , the Al / V molar ratio is 20, and the TB / V molar ratio is 5. After 10 minutes of polymerization reaction, 5% hydrochloric acid ethanol solution was added to terminate the reaction, and the obtained polymer was vacuum-dried at 40° C. to constant weight to obtain an ethylene-propylene copolymer. The catalytic activity is 21kg·(mol -1 V), the propylene content in the copolymer is 53mol% (63wt%), and the random sequence distribution content is 67%.

[0031] Compared with Comparative Example 1, under the close situation of obtaining propylene content in the multipolymer, the consumption of propylene in the monomer has reduced by 23%, and the utilization efficiency of propylene has improv...

Embodiment 2

[0033] Propylene and ethylene monomers are in a certain molar ratio (C 3 / C 2 =2.1) was mixed with hexane to form a monomer solution ([M]=59g / L). At -45°C, add VOCl 3 , EtAlCl 2 / Et 2 The catalyst of AlCl and 1,1,1-trichloroethane (abbreviated as TC), wherein the V / M molar ratio is 2.5×10 -4 , the Al / V molar ratio is 15, and the TC / V molar ratio is 20. Polymerization reaction 10 minutes, termination and aftertreatment mode are with embodiment 1, obtain ethylene-propylene copolymerization product, catalytic activity is 52kg (mol -1 V), the propylene content in the copolymer is 34mol% (46wt%), and the random sequence distribution content is 55%.

[0034] Compared with Comparative Example 2, when the propylene content in the obtained copolymer is close, the propylene content in the monomer has decreased by 16%, the propylene utilization efficiency has improved, and the catalytic activity has improved by 27%; co-catalyst consumption (in Al / M ratio Expressed) decreased by 46...

Embodiment 3

[0036] Mix 5-ethylidene-2-norbornene (ENB), propylene, and ethylene monomers in a certain molar ratio (ENB / C 3 / C 2 =0.1 / 4.2 / 1) was mixed with hexane to form a monomer solution ([M]=50g / L). At -45°C, add VOCl 2 (Me 2 C 6 h 3 O), EtAlCl 2 / Et 2 The catalyst of AlCl and TC, wherein, the V / M molar ratio is 6.1×10 -4 , the Al / V molar ratio is 30, and the TC / V molar ratio is 2. Polymerization reaction 10 minutes, termination and aftertreatment mode are with embodiment 1, obtain ethylene-propylene-ENB copolymerization product, catalytic activity is 20kg (mol -1 V), the ethylene conversion rate is 97%, the propylene conversion rate is 20%, the propylene content in the copolymer is 45mol% (55wt%), the ENB content is 4.4mol% (14wt%), and the random sequence distribution content is 72%.

[0037] Compared with Comparative Example 3, under the same polymerization conditions, the utilization efficiency of ethylene, propylene and ENB all increased, and the catalytic activity increa...

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Abstract

The present invention relates to a vanadium-based catalyst system for olefin polymerization, wherein the vanadium-based catalyst system comprises a vanadium compound main catalyst, an organoaluminum compound auxiliary catalyst and a compound regulator containing a carbon-halogen chemical bond. According to the present invention, the vanadium-based catalyst system for olefin homopolymerization and copolymerization of ethylene with other olefins or diolefins has high catalytic activity so as to reduce the catalyst consumption; and the random sequence distribution content in the prepared copolymer is increased, and the comonomer insertion rate is significantly improved.

Description

technical field [0001] The invention relates to a vanadium-based catalyst system for olefin polymerization, in particular to a vanadium-based catalyst system for the copolymerization of ethylene and other olefins or / or dienes. The vanadium-based catalyst system has high catalytic activity, can reduce the amount of catalyst used, and the content of random sequence distribution in the prepared copolymer is increased, the insertion rate of comonomers is increased, and the utilization rate of comonomers is improved. Background technique [0002] Polyolefins are the most important products in synthetic resins, such as polyethylene, polypropylene, polybutene and their copolymers. Copolymers of ethylene and at least one alpha-olefin and / or diene range from crystalline resins to amorphous elastomers and possess unique properties that lend themselves to a variety of uses. For example, linear low density polyethylene or thermoplastic elastomer products can be prepared by copolymerizi...

Claims

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Application Information

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IPC IPC(8): C08F10/00C08F4/68C08F210/16C08F210/02C08F210/06C08F232/08
Inventor 吴一弦张志乾张树何兰霞张腾王云杰
Owner 常州汉韦聚合物有限公司
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