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Supported non-metallocene catalyst used for ethylene polymerization

A non-metallocene and ethylene polymerization technology, applied in the field of preparation of supported non-metallocene catalysts, can solve the problems of complicated preparation methods of supported catalysts

Active Publication Date: 2014-09-24
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] There are literatures using composite carriers containing magnesium chloride, silica gel, etc. to support non-metallocenes (CN1539856A, CN102399317A, CN102039185A, CN102399331A, CN101423574A, CN1539855A), but the preparation method of the supported catalyst is complicated, and a large amount of MAO needs to be added during polymerization

Method used

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  • Supported non-metallocene catalyst used for ethylene polymerization
  • Supported non-metallocene catalyst used for ethylene polymerization
  • Supported non-metallocene catalyst used for ethylene polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0186] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0187] Under the protection of nitrogen, take 2.50 grams of dry silica gel carrier and put it into a glass reactor, add 100 ml of dried hexane, disperse into a suspension, add 1 ml of SiCl 2 (n-Bu) 2 , start stirring, heat up to 30° C., react for 4 hours, and dry in vacuum to obtain a solid powder with good fluidity.

[0188] (2) Preparation of halogenated hydrocarbyl magnesium / chlorinated hydrocarbyl silicon / silica gel carrier

[0189] Under the protection of nitrogen, take 5.0 grams of the above-mentioned modified silica gel carrier and add it to a glass reactor, add 100 ml of dried toluene, disperse it into a suspension, add 5 ml of 2M ethylmagnesium chloride, start stirring, heat up to 30 ° C, and react After 4 hours, it was vacuum dried to obtain a solid powder with good fluidity.

[0190] (3) Preparation of alkyl aluminoxane / hydrocarbyl magnesium halide / hydrocarbyl chloride silicon / silica g...

Embodiment 2

[0202] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0203] Same as (1) in Example 1, only the SiCl in Example 1 2 (n-Bu) 2 Change to SiCl 4 .

[0204] (2) Preparation of halogenated hydrocarbyl magnesium / chlorinated hydrocarbyl silicon / silica gel carrier

[0205] Same as step (2) of embodiment 1, only ethylmagnesium chloride in embodiment 1 is replaced by ethylmagnesium bromide.

[0206] (3) Preparation of alkyl aluminoxane / hydrocarbyl magnesium halide / hydrocarbyl chloride silicon / silica gel carrier

[0207] Same as step (3) of Example 1.

[0208] (4) Preparation of supported non-metallocene catalyst B

[0209] Same as Example 1 step (4), only 0.168 grams of bis-[N-(3-tert-butyl-o-hydroxybenzylidene) cyclohexylamine] zirconium dichloride in Example 1 was replaced by 0.152 grams of bis- [N-(3-tert-butyl-o-hydroxybenzylidene) aniline] titanium dichloride (L 2 ) 2 TiCl 2 (See below for its structure, see literature for its synthesis, Chemistry...

Embodiment 3

[0212] (1), (2), (3) are the same as the preparation methods of (1), (2), and (3) in Example 2.

[0213] (4) Preparation of supported non-metallocene catalyst C

[0214] Same as step (4) of Example 1, only 0.168 gram of bis-[N-(3-tert-butyl-o-hydroxybenzylidene) cyclohexylamine] zirconium dichloride in Example 1 is replaced by 0.198 gram of bis- [N-(3-phenyl-o-hydroxybenzylidene) aniline] titanium dichloride ((L 3 ) 2 TiCl 2 (see below for its structure), and its synthesis is shown in literature Chemistry Letters, 1999, 1065), and a supported non-metallocene catalyst C is obtained. Characterized by ICP, in catalyst C, the weight content of Ti is 0.38%, the weight content of Al is 11.26%, and the weight content of magnesium is 2.54%.

[0215]

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Abstract

The invention relates to a supported non-metallocene catalyst used for ethylene polymerization and a preparation method thereof. The catalyst comprises a non-metallocene compound, chlorinated alkyl silicon, halogenated alkyl magnesium, alkyl aluminoxane and a silica gel carrier reaction product; the preparation method comprises the following steps: 1) preparation of a chlorinated hydroxyl silicon modified silica gel carrier, 2)preparation of a halogenated alkyl magnesium modified silica gel carrier, 3)preparation of an alkyl aluminoxane modified silica gel carrier, and 4)preparation of the silica gel supported non-metallocene catalyst; and the obtained non-metallocene catalyst has high polymerization activity for catalyzing vinyl polymerization or copolymerization. The preparation method of the silica gel carrier is simple, and the obtained supported catalyst particles have good morphology and have adjustable size.

Description

technical field [0001] The invention relates to a preparation method of a supported non-metallocene catalyst for ethylene polymerization, and the application of the obtained catalyst in olefin polymerization. technical background [0002] In the development of olefin polymerization catalysts, non-metallocene catalysts developed in the 1990s have received great development and attention. In particular, the Group IV transition metal complexes containing phenoxy-imine ligands (EP0874005, WO0155231) have high catalytic olefin polymerization activity, and can obtain functionalized polyolefin resins, which have good applications prospect. However, olefin polymerization is carried out in a homogeneous phase, and the obtained polymer is in an amorphous state, which cannot be used in the widely used slurry method or gas phase polymerization process. [0003] At present, there have been a lot of reports on the support of non-metallocene catalysts in recent years, such as patents CN1...

Claims

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Application Information

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IPC IPC(8): C08F10/02C08F4/646C08F4/02C08F4/658C08F4/656C08F4/655C08F4/654
Inventor 高榕李岩廖浩瀚刘东兵周俊领黄廷杰
Owner CHINA PETROLEUM & CHEM CORP
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