Supported late-transition-metal catalyst used for ethylene polymerization and preparation method thereof and application thereof

A late transition metal and ethylene polymerization technology, which is applied in the field of preparation of supported late transition metal catalysts, can solve the problems of limited industrial application, uncontrollable, poor carrier particle shape, etc.

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

Although also many (PCT Int.Appl.99 / 21898; US6,455,647; J.Mol.Catal.A2002,188,123; PCT Int.Appl.2004 / 078804) are also many (PCT Int.Appl.99 / 21898; The cost of carrier preparation and catalyst loading is high, and the particle shape of the carrier is poor and cannot be controlled; although the use of spherical magnesium chloride can ensure that the supported catalyst has a good particle shape, the carrier contains alcohol, water, alkoxy and other components. Complicated, the above shortcomings limit the industrial application of magnesium chloride-supported single-site catalysts

Method used

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  • Supported late-transition-metal catalyst used for ethylene polymerization and preparation method thereof and application thereof
  • Supported late-transition-metal catalyst used for ethylene polymerization and preparation method thereof and application thereof
  • Supported late-transition-metal catalyst used for ethylene polymerization and preparation method thereof and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0067] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0068] Under the protection of nitrogen, take 10.0 g of magnesium chloride 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.

[0069] (2) Preparation of organoaluminum / hydrocarbyl chloride / magnesium chloride carrier

[0070] 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 carr...

Embodiment 2

[0080] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0081] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0082] (2) Preparation of organoaluminum / hydrocarbyl chloride / magnesium chloride carrier

[0083] Same as step (2) of Example 1.

[0084] (3) Preparation of supported transition metal catalyst B

[0085] Same as step (3) of Example 1, only 0.096 grams of [(2,6-bis[1-(2,4,6-trimethylbenimine) ethyl]pyridine ferric dichloride] in Example 1 Replaced with 0.111 grams of [(2,6-bis[1-(2,6-diisopropylphenylimine) ethyl]pyridine ferric dichloride] (see below for its structure, see patent WO9827124A1 for its synthesis, examples 8) to obtain the supported transition metal catalyst B. Characterized by ICP, the weight content of Fe in catalyst B is 0.22%, and the weight content of Al is 11.41%.

[0086]

Embodiment 3

[0088] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0089] Same as (1) preparation method in Example 1.

[0090] (2) Preparation of organoaluminum / hydrocarbyl chloride / magnesium chloride carrier

[0091] Same as step (2) of Example 1, only 18 ml of 10% MAO was replaced with 13 ml of 2M diethylaluminum chloride.

[0092] (3) Preparation of supported transition metal catalyst C

[0093] Same as step (3) of Example 1, only 0.096 grams of [(2,6-bis[1-(2,4,6-trimethylbenimine) ethyl]pyridine ferric dichloride] in Example 1 Replaced with 0.098 g [(2,6-bis[1-(2-methyl 6-chloro-phenylimine) ethyl]pyridine ferric dichloride] (see below for its structure, see patent WO9827124A1 for its synthesis, examples 2) The supported transition metal catalyst C was obtained. Characterized by ICP, the weight content of Fe in catalyst C was 0.20%, and the weight content of Al was 11.92%.

[0094]

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Abstract

The invention relates to a supported late-transition-metal catalyst used for ethylene polymerization and a preparation method thereof. The catalyst comprises a late-transition-metal compound, chlorinated alkyl silicon, an organo aluminium compound and a magnesium chloride 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 organo-aluminium modified magnesium chloride carrier, and 3)preparation of the magnesium chloride supported late-transition-metal catalyst; and the obtained late-transition-metal catalyst has high polymerization activity for catalyzing vinyl polymerization or copolymerization. The preparation method of the magnesium chloride carrier is simple, and the obtained supported catalyst particles have good morphology and have adjustable size. The obtained supported late-transition-metal catalyst is capable of catalyzing copolymerization of ethylene and alpha-alkene, the copolymerization activity is high, the obtained resin powder has good particle morphology, bulk density is high, and the late-transition-metal catalyst is suitable for the polymerization technology of a slurry method and a gas phase method.

Description

technical field [0001] The invention relates to a preparation method of a supported late transition metal catalyst for ethylene polymerization, and the application of the obtained catalyst in olefin polymerization. technical background [0002] In the development of olefin polymerization catalysts, the late transition metal catalysts developed in the 1990s have received great development and attention. Especially Ni, Pd and Fe, Co diimine catalyst system (WO9623010, WO9827124), nickel, palladium catalyst can produce branched even hyperbranched high molecular weight polyethylene with narrow molecular weight distribution through ethylene homogeneous polymerization, iron, cobalt The catalyst can catalyze ethylene to produce linear polyethylene with broad molecular weight distribution. 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 polymer...

Claims

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Application Information

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IPC IPC(8): C08F10/02C08F4/646C08F4/658C08F4/656C08F4/655C08F4/654C08F4/02
Inventor 高榕廖浩瀚李岩周俊领刘东兵黄廷杰
Owner CHINA PETROLEUM & CHEM CORP
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