A supported late transition metal catalyst for ethylene polymerization

A late transition metal and ethylene polymerization technology, applied in the field of supported late transition metal catalysts, can solve the problems of restricting the industrial application of late transition metal catalysts and increasing the cost of catalyst preparation

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

It is also possible to functionalize the catalyst ligand structure and load the late transition metal catalyst on silica gel by chemical bonding (CN10169111; CN101173012; CN101531724) to improve the loading efficiency of the catalyst, but the cost of catalyst preparation in this method is greatly increased, and the above disadvantages Limiting the Industrial Applications of Silica-Supported Post-Transition Metal Catalysts

Method used

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  • A supported late transition metal catalyst for ethylene polymerization
  • A supported late transition metal catalyst for ethylene polymerization
  • A supported late transition metal catalyst for ethylene polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062] (1) Preparation of chlorinated alkyl silicon / silica gel carrier

[0063] Under the protection of nitrogen, take 10.0 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.

[0064] (2) Preparation of alkyl magnesium chloride / alkyl silicon chloride / silica gel carrier

[0065] Under the protection of nitrogen, take 10.0 g of the modified silica gel carrier obtained in step (1) and put it into a glass reactor, add 100 ml of dried toluene, disperse it into a suspension, add 10 ml of 2M ethylmagnesium chloride, and start stirring. Raise the temperature to 30° C., react for 4 hours, and dry in vacuum to obtain a solid powder with good fluidity.

[0066] (3) Preparation of organoaluminum / alkyl magnesium chloride / alkyl silicon chloride / silica gel carrier

[0067] U...

Embodiment 2

[0078] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0079] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0080] (2) Preparation of halogenated hydrocarbyl magnesium / chlorinated hydrocarbyl silicon / silica gel carrier

[0081] Same as step (2) of embodiment 1, only ethylmagnesium chloride in embodiment 1 is replaced by ethylmagnesium bromide.

[0082] (3) Preparation of organoaluminum / hydrocarbyl magnesium halide / chlorinated hydrocarbyl silicon / silica gel carrier

[0083] Same as step (3) of Example 1.

[0084] (4) Preparation of supported transition metal catalyst B

[0085] Same as Example 1 step (4), only 0.096 grams of (2,6-bis[1-(2,4,6-trimethylbenimine) ethyl]pyridine ferric dichloride in Example 1 is replaced by 0.111 g of [2,6-bis[1-(2,6-diisopropylphenylimine) ethyl]pyridine ferric dichloride] (see below for its structure, see Patent WO9827124A1, Example 8 for its synthesis), The supported transi...

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 halogenated hydrocarbyl magnesium / chlorinated hydrocarbyl silicon / silica gel carrier

[0091] Same as Example 2 step (2) preparation method.

[0092] (3) Preparation of organoaluminum / hydrocarbyl magnesium halide / chlorinated hydrocarbyl silicon / silica gel carrier

[0093] Same as step (2) of Example 1, only 18 ml of 10% MAO was replaced with 13 ml of 2M diethylaluminum chloride.

[0094] (4) Preparation of supported transition metal catalyst C

[0095] Same as Example 1 step (4), only 0.096 grams of (2,6-bis[1-(2,4,6-trimethylbenimine) ethyl]pyridine ferric dichloride in Example 1 is replaced by 0.098 g [2,6-bis[1-(2-methyl 6-chloro-phenylimine) ethyl]pyridine ferric dichloride] (see below for its structure, see patent WO9827124A1, Example 2 for its synthesis), The supported transition metal catalyst C was obtained....

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Abstract

The invention relates to a supported late transition metal catalyst for ethylene polymerization and a preparation method thereof, the catalyst comprising (a) a late transition metal compound; (b) a chlorinated hydrocarbyl silicon modifier; (c) a hydrocarbyl magnesium halide; (d) organoaluminum compound; (e) reaction product of silica gel carrier; its preparation method includes: (1) preparation of chlorinated hydrocarbyl silicon modified silica gel carrier, (2) preparation of halogenated hydrocarbyl magnesium modified silica gel carrier, (3 ) Preparation of organoaluminum-modified silica gel carrier, (4) preparation of late transition metal catalyst supported on silica gel, the obtained late transition metal catalyst catalyzes ethylene polymerization or copolymerization with high polymerization activity. The preparation method of the silica gel carrier used is simple, and the obtained loaded catalyst particle has good shape and easy adjustment in size.

Description

technical field [0001] The invention relates to a supported late transition metal catalyst for ethylene polymerization, a preparation method thereof, and an 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 series catalyst can generate branched even hyperbranched high molecular weight polyethylene with narrow molecular weight distribution through ethylene homogeneous polymerization, iron, Cobalt-based catalysts produce linear polyethylene with a 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 polymerization...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/02C08F4/70
Inventor 高榕廖浩瀚李岩刘东兵周俊领傅捷
Owner CHINA PETROLEUM & CHEM CORP
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