Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor

Patent metadata

Field	Value
Publication number	US-9951157-B2
Application number	US-201415030000-A
Country	US
Kind code	B2
Filing date	Oct 17, 2014
Priority date	Oct 18, 2013
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

Spherical carriers for an olefin polymerization catalyst, catalyst components, catalysts, and preparation methods therefor are disclosed. The method for preparing the spherical carriers comprises the following steps: (1) reacting, in the presence of at least one polymeric dispersion stabilizer, a magnesium halide with an organic compound containing active hydrogen to form a complex solution; (2) reacting said complex solution with an alkylene oxide-type compound to directly precipitate solid particles; and (3) recovering the solid particles to obtain spherical carriers. When a catalyst prepared by using the present spherical carrier is used in propylene polymerization, said catalyst exhibits high polymerization activity and high stereo-directing ability.

First claim

What is claimed is:

1. A method for preparing a spherical carrier of an olefin polymerization catalyst, which method comprises reacting at least the following components: (a) a magnesium halide, (b) an organic compound containing active hydrogen, and (c) an epoxide, in the presence of at least one polymeric dispersion stabilizer, to directly precipitate a solid particulate product, wherein the polymeric dispersion stabilizer is at least one chosen from styrene-maleic anhydride copolymers, polystyrene sulfonates, naphthalenesulfonic acid-formaldehyde condensation products, condensed alkyl phenyl ether sulfates, condensed alkylphenol polyoxyethylene ether phosphates, oxyalkyl acrylate copolymer-modified polyethyleneimines, poly(1-dodecyl-4-vinylpyridinium bromide)s, poly(vinylbenzyl trimethyl ammonium salt)s, poly(vinyl alcohol)s, polyacrylamides, ethylene oxide-propylene oxide block copolymers, polyvinylpyrrolidones, poly(vinylpyrrolidone-co-vinyl acetate)s, poly(ethylene glycol)s, alkylphenyl poly oxyethylene ethers and poly(alkyl methylacrylate)s.

2. The method according to claim 1 , wherein the reaction process comprises:
(1) reacting the magnesium halide with the organic compound containing active hydrogen in the presence of the at least one polymeric dispersion stabilizer to form a complex solution; and
(2) reacting the complex solution with the epoxide to directly precipitate the spherical carrier.

3. The method according to claim 2 , having at least one of the following features:
in step (1), the amount of the organic compound containing active hydrogen used ranges from 3 to 30 moles, relative to one mole of the magnesium halide, and the amount of the polymeric dispersion stabilizer used ranges from 0.1 to 10 wt %, based on the total weight of the magnesium halide and the organic compound containing active hydrogen;
reaction conditions of step (1) include: a reaction temperature of from 30 to 160° C.; and a reaction time of from 0.1 to 5 hours;
in step (2), the amount of the epoxide used ranges from 1 to 10 moles, relative to one mole of the magnesium halide; and
reaction conditions of step (2) include: a reaction temperature of from 30 to 160° C.; and a reaction time of from 0.1 to 5 hours.

4. The method according to claim 1 , having at least one of the following features:
the polymeric dispersion stabilizer has a weight average molecular weight of larger than 1,000;
the magnesium halide is at least one chosen from magnesium dichloride, magnesium dibromide and magnesium diiodide;
the organic compound containing active hydrogen is at least one alcohol of formula R 1 OH, wherein R 1 is a C 1 -C 12 linear or branched alkyl; and
no inert dispersion medium is used in both step (1) and (2).

5. The method according to claim 1 , wherein the epoxide has a structure formula (2):

wherein R 2 and R 3 are identical or different, and are each independently hydrogen or unsubstituted or halogen-substituted C 1 -C 5 linear or branched alkyl.

6. The method according to claim 1 , wherein no titanium tetrachloride is introduced in the course of the reaction of the specified components.

7. A spherical carrier prepared by the method according to claim 1 .

8. A process for preparing a solid composition, comprising the steps of:
(a) reacting a magnesium halide of formula MgX 2 with an alcohol of formula R 1 OH in the presence of at least one polymeric dispersion stabilizer at 30 to 160° C., to form a magnesium halide-alcohol adduct solution; and
(b) reacting the magnesium halide-alcohol adduct solution with an epoxide represented by formula (2):

at 30 to 160° C., to directly precipitate particles of the solid composition,
wherein X is halogen; R 1 is a C 1 -C 12 linear or branched alky; and R 2 and R 3 are identical or different, and are each independently hydrogen or unsubstituted or halogen-substituted C 1 -C 5 linear or branched alkyl,
wherein the polymeric dispersion stabilizer is at least one chosen from styrene-maleic anhydride copolymers, polystyrene sulfonates, naphthalenesulfonic acid-formaldehyde condensation products, condensed alkyl phenyl ether sulfates, condensed alkylphenol poly oxyethylene ether phosphates, oxyalkyl acrylate copolymer-modified poly ethyleneimines, poly(1-dodecyl-4-vinylpyridinium bromide)s, poly(vinylbenzyl trimethyl ammonium salt)s, poly(vinyl alcohol)s, polyacrylamides, ethylene oxide-propylene oxide block copolymers, polyvinylpyrrolidones, poly(vinylpyrrolidone-co-vinyl acetate)s, poly(ethylene glycol)s, alkylphenyl polyoxyethylene ethers and poly(alkyl methylacrylate)s, and
wherein, relative to one mole of the magnesium halide, the amount of the alcohol used ranges from 3 to 30 moles and the amount of the epoxide represented by the formula (2) used ranges from 1 to 10 moles; and the polymeric dispersion stabilizer is used in an amount of from 0.1 to 10 wt %, based on the total weight of the magnesium halide and the alcohol.

9. The process according to claim 8 , having at least one of the following features:
step (a) is carried out in a closed vessel;
R 1 is a C 1 -C 8 linear or branched alkyl;
R 2 and R 3 are independently hydrogen or unsubstituted or halogen-substituted C 1 -C 3 linear or branched alkyl;
relative to one mole of the magnesium halide, the amount of the alcohol used ranges from 4 to 20 moles and the amount of the epoxide represented by the formula (2) used ranges from 2 to 6 moles;
the polymeric dispersion stabilizer is used in an amount of from 0.2 to 5 wt %, based on the total weight of the magnesium halide and the alcohol;
the magnesium halide is at least one chosen from magnesium dichloride, magnesium dibromide and magnesium diiodide;
the alcohol is at least one chosen from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol;
the epoxide is at least one chosen from epoxy ethane, epoxy propane, epoxy butane, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane, and epoxy bromobutane;
the polymeric dispersion stabilizer has a weight average molecular weight of larger than 1,000;
and
no inert dispersion medium is used in both step (a) and (b).

10. A solid composition prepared by the process according to claim 8 .

11. The solid composition according to claim 10 , comprising a magnesium compound represented by formula (1) and an epoxide represented by formula (2):

wherein R 1 is a C 1 -C 12 linear or branched alkyl; R 2 and R 3 are identical or different, and are independently hydrogen or unsubstituted or halogen-substituted C 1 -C 5 linear or branched alkyl; X is halogen; m is in a range of from 0.1 to 1.9, n is in a range of from 0.1 to 1.9, and m+n=2; and
wherein the content of the epoxide represented by the formula (2) is in a range of from 0.01 to 0.8 moles per mole of the magnesium compound represented by the formula (1).

12. The solid composition according to claim 11 , having at least one of the following features:
R 1 is a C 1 -C 8 linear or branched alkyl;
R 2 and R 3 are independently hydrogen or unsubstituted or halogen-substituted C 1 -C 3 linear or branched alkyl;
X is chlorine;
m is in a range of from 0.5 to 1.5, n is in a range of from 0.5 to 1.5, and m+n=2;
the content of the epoxide represented by the formula (2) is from 0.02 to 0.5 moles, per mole of

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp

Inventors

• Li Weili
• Xia Xianzhi
• Liu Yuexiang
• Ling Yongtai
• Zhao Jin
• Zhang Jigui
• Gao Futang
• Gao Ping
• Tan Yang
• Peng Renqi
• Zhang Zhihui
• Lin Jie
• Duan Ruilin
• Ma Changyou

Classifications

• C08F4/654

  with magnesium or compounds thereof · CPC title

• C08F4/022

  Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F6/00

  Post-polymerisation treatments (C08F8/00 takes precedence; of conjugated diene rubbers C08C) · CPC title

• C08F10/06 Primary

  Propene · CPC title