A supported single metallocene catalyst for ethylene polymerization

A single metallocene and ethylene polymerization technology, applied in the field of preparation of modified silica gel supported single metallocene catalysts, can solve the problems of limiting the industrial application of silica gel supported single metallocene catalysts, low catalyst loading efficiency, large amount of MAO, etc., to achieve high Ethylene polymerization catalytic activity, good shape, adjustable particle size effect

Active Publication Date: 2016-09-21
CHINA PETROLEUM & CHEM CORP +1
View PDF17 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Because the homogeneous single metallocene catalyst requires a large amount of MAO to achieve high activity, the production cost is high, and the obtained polymer is amorphous, which cannot be used in the widely used slurry method or gas phase polymerization process to overcome the above problems The most effective way is to support the soluble mono-metallocene catalyst
[0003] At present, there are a lot of research reports on metallocene loading, among which the catalyst using spherical magnesium chloride (containing alcohol) to support metallocene has good particle morphology, such as PCT Int.Appl.99 / 21898; US6,455,647; J.Mol.Catal .A2002,188,123; PCT Int.APP1.2004 / 078804; CN 101817892; CN 101172988, but the carrier contains alcohol, water, alkoxy and other components, and the preparation of the carrier is complicated; 2 CN 102286114; CN 1174848; CN 1174849; CN 1356343; US 4,808,561; US ​​5,026,797; US 5,763,543; The loading efficiency of the catalyst is low, and a large amount of methylalumoxane is still introduced during the polymerization process. The above shortcomings limit the industrial application of silica gel-loaded single metallocene catalysts.
[0004] There are also literatures that use carriers containing magnesium chloride, silica gel, etc. to load mono-metallocenes (Polymer International, 2002, 51, 417-423; US5962360), but the activity is very low, and a large amount of MAO needs to be added during polymerization

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • A supported single metallocene catalyst for ethylene polymerization
  • A supported single metallocene catalyst for ethylene polymerization
  • A supported single metallocene catalyst for ethylene polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0053] 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.

[0054] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / silica gel support

[0055] 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 met...

Embodiment 2

[0064] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0065] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0066] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / silica gel support

[0067] Same as step (2) of Example 1.

[0068] (3) Preparation of supported metallocene catalyst B

[0069] Same as step (3) of Example 1 to obtain supported metallocene catalyst B. Characterized by ICP, the weight content of Ti in catalyst B is 0.30%, and the weight content of Al is 11.18%.

Embodiment 3

[0071] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0072] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to CH 3 SiCl 3 .

[0073] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / silica gel support

[0074] Same as step (2) of Example 1.

[0075] (3) Preparation of supported metallocene catalyst C

[0076] Same as step (3) of Example 1 to obtain supported metallocene catalyst C. Characterized by ICP, the weight content of Ti in catalyst C is 0.31%, and the weight content of Al is 11.22%.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The present invention relates to a supported mono-metallocene catalyst for ethylene polymerization, and a preparation method thereof. The catalyst comprises (a) a mono-metallocene compound; (b) a chlorinated hydrocarbyl silicon modifier; (c) an alkylaluminum oxide alkane; (d) reaction product of silica gel carrier; its preparation method includes: (1) preparation of chlorinated hydrocarbyl silicon modified silica gel carrier, (2) preparation of alkyl aluminoxane modified silica gel carrier, (3) modification The preparation of silica gel supported single metallocene catalyst, the obtained single metallocene catalyst catalyzes ethylene polymerization or copolymerization and has high polymerization activity. The preparation method of the silica gel carrier used is simple, and the obtained loaded catalyst particle has good shape and adjustable size.

Description

technical field [0001] The invention relates to a preparation method of a modified silica gel supported mono-metallocene catalyst and the application of the obtained catalyst in olefin polymerization. Background technique [0002] The development and application of metallocene catalysts is another major breakthrough in the field of olefin polymerization catalysts after the traditional Ziegler-Natta catalysts, especially in the 1980s, Kaminsky and Sinn et al. (Angew.Chem., 1980, 19, 390; Adv. Organoment.Chem., 1980, 18, 99) developed a high-efficiency cocatalyst methylaluminoxane (MAO), making the research on metallocene catalysts enter a stage of rapid development. In recent years, in the study of olefin polymerization catalysts, single metallocene catalysts with electron-donating ligands have received more and more attention. Many catalysts with unique properties have been reported in the literature, such as those with aryloxy groups (Organometallics, 1998,17(11):2152-2154...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/02C08F4/6592
Inventor 高榕廖浩瀚李岩周俊领刘东兵王丽莎
Owner CHINA PETROLEUM & CHEM CORP
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap