Supported non-metallocene catalyst used for ethylene polymerization

A non-metallocene and ethylene polymerization technology, which is applied in the field of preparation of supported non-metallocene catalysts, can solve the problems of complex preparation methods of supported catalysts, limited industrial application range, and short activity duration.

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

However, homogeneous catalysts have been proved to have shortcomings such as short activity duration, easy sticking to the kettle, high amount of cocatalyst methylaluminoxane, and too low or too high molecular weight of the obtained polymer in olefin polymerization. The solution polymerization process or high pressure polymerization process of olefins severely limits its industrial application range
[0003] At present, there have been a lot of reports on the support of non-metallocene catalysts in recent years, such as patents CN1539855A, CN1539856A, CN1789291, CN1789292, CN1962702A, CN1769309A, CN1769310A, CN101423573A, CN101798361A, CN102399313A, etc., which provide a variety of ways to obtain non-supported loads Metallocene catalysts, wherein the catalysts using anhydrous magnesium chloride to support non-metallocenes have good particle morphology, such as CN102039186A, CN102039189A, CN102039187A, CN102039185A, CN101942048A, but such catalyst...

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

[0182] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0183] Under the protection of nitrogen, take 2.5 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.

[0184] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / silica gel support

[0185] Under nitrogen protection, take 5.0 grams of the modified silica gel carrier obtained above and add it to a glass reactor, add 60 milliliters of dried toluene, disperse into a suspension, and add 18 milliliters of 10 wt% MAO (methylaluminoxane) toluene solution , heated to 50 ° C, stirred for 4 hours, then washed three times with 50 ml × 3 toluene, then washed with hexane, and dried in vacuum to obtain a solid powder with good fluidity, that is, a silica gel carrier containing meth...

Embodiment 2

[0195] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0196] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0197] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / silica gel support

[0198] Same as step (2) of Example 1.

[0199] (3) Preparation of supported non-metallocene catalyst B

[0200] Same as Example 1 step (4), only 0.168 grams of bis-[N-(3-tert-butyl-o-hydroxybenzylidene) cyclohexylamine] zirconium dichloride in Example 1 is replaced by 0.152 grams [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 Letters, 1999, 1065), and obtain a supported non-metallocene catalyst B. Characterized by ICP, in catalyst B, the weight content of Ti is 0.31%, and the weight content of Al is 11.12%.

[0201]

Embodiment 3

[0203] (1), (2) are the same as the preparation methods of (1) and (2) in Example 2.

[0204] (3) Preparation of supported non-metallocene catalyst C

[0205] Same as Example 1 step (3), only 0.168 grams of bis-[N-(3-tert-butyl-o-hydroxybenzylidene) cyclohexylamine] zirconium dichloride in Example 1 is replaced by 0.198 grams [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 0.36%, and the weight content of Al is 11.19%.

[0206]

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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, alkyl aluminoxane and a silica gel carrier reaction product; the preparation method comprises the following steps: 1) preparation of a chlorinated alkyl silicon modified silica gel carrier, 2)preparation of an alkyl aluminoxane modified silica gel carrier, and 3)preparation of the modified 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 particle 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, homogeneous catalysts have been proved to have shortcomings such as short activity duration, easy sticking to the kettle, high amount of cocatalyst methylaluminoxane, and too low or too high molecular weight of the obtained polymer in olefin polymerization. The solution polymerization process or high pressure polymerization process of ...

Claims

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Application Information

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