A supported non-metallocene catalyst for ethylene polymerization

A non-metallocene and ethylene polymerization technology is applied in the field of supported non-metallocene catalysts, which can solve the problems of complex preparation methods of supported catalysts, complicated preparation of supports, and limited industrial applications.

Active Publication Date: 2016-08-17
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Catalysts with silica as the carrier have been reported and studied a lot, such as CN102399331A, CN1539855A, CN1769309A, CN1727062A, CN1962702A, but the preparation of the carrier is complicated, and a large amount of methylalumoxane still needs to be introduced during the polymerization process, and the supported catalyst is not effective in catalyzing ethylene polymerization. showed low catalytic activity
And the catalyst that adopts anhydrous magnesium chloride to support non-metallocene shows higher catalytic activity in olefin polymerization process, as CN102039189A, CN102039187A, CN102039185A, CN101942048A, but contains alcohol, water, alkoxy etc. Components and supports are complicated to prepare, and a large amount of methylalumoxane is still introduced during the polymerization process. The above shortcomings limit the industrial application of magnesium chloride-supported non-metallocene catalysts
[0004] There are also literatures that use composite carriers such as magnesium chloride and silica gel to support non-metallocenes (CN1539856A, CN102399317A, CN102039185A, CN102399331A, CN101423574A, CN1539855A), but the preparation method of the supported catalyst is complicated, and MAO needs to be added as a cocatalyst during polymerization

Method used

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  • A supported non-metallocene catalyst for ethylene polymerization
  • A supported non-metallocene catalyst for ethylene polymerization
  • A supported non-metallocene catalyst for ethylene polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0183] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0184] Under the protection of nitrogen, take 5.00 g of magnesium chloride carrier and add 60 ml of dried hexane to 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.

[0185] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0186] Under nitrogen protection, take 5.0 grams of the modified magnesium chloride 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 magnesium chloride carrier containing...

Embodiment 2

[0196] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0197] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0198] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0199] Same as step (2) of Example 1.

[0200] (3) Preparation of supported non-metallocene catalyst B

[0201] Same as step (4) of Example 1, only 0.168 grams of [bis-[N-(3-tert-butyl-o-hydroxybenzylidene) cyclohexylamine] zirconium dichloride] in Example 1 was 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 0.33%, and the weight content of Al is 11.48%.

[0202]

Embodiment 3

[0204] (1), (2) are the same as the preparation methods of (1) and (2) in Example 2.

[0205] (3) Preparation of supported non-metallocene catalyst C

[0206] Same as step (3) of Example 1, only 0.168 grams of [bis-[N-(3-tert-butyl-o-hydroxybenzylidene) cyclohexylamine] zirconium dichloride] in Example 1 was replaced by 0.198 grams 【Bis-[N-(3-phenyl-o-hydroxybenzylidene) aniline] titanium dichloride】(L 3 ) 2 TiCl 2 (Its structure sees below), and its synthesis sees literature Chemistry Letters, 1999, 1065), obtains supporting non-metallocene catalyst C. Characterized by ICP, the weight content of Ti in catalyst C is 0.34%, and the weight content of Al is 11.32%.

[0207]

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Abstract

The invention relates to a supported non-metallocene catalyst for ethylene polymerization and a preparation method thereof, the catalyst comprising (a) a non-metallocene compound; (b) a chlorinated hydrocarbyl silicon modifier; (c) an alkylaluminum oxide (d) magnesium chloride carrier; its preparation method includes: (1) preparation of magnesium chloride carrier modified by hydrocarbyl chloride (2) preparation of magnesium chloride carrier modified by alkyl aluminoxane (3) magnesium chloride supported non-metallocene catalyst Preparation; The obtained catalyst has high activity in ethylene polymerization or copolymerization. The preparation method of the magnesium chloride carrier used is simple, and the particle shape of the obtained loaded catalyst is good, and the size is adjustable; the catalyst catalyzes the copolymerization reaction of ethylene and α-olefin, the copolymerization activity is high, and the obtained resin powder has good particle shape and high bulk density. It can be applied to slurry method and gas phase polymerization process.

Description

technical field [0001] The invention relates to a supported non-metallocene catalyst for ethylene polymerization, a preparation method, 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 CN153...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/02C08F4/646C08F4/02C08F4/658C08F4/656C08F4/655C08F4/654C08F10/00
Inventor 廖浩瀚高榕李岩周俊领刘东兵王丽莎
Owner CHINA PETROLEUM & CHEM CORP
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