Process for preparing solid catalyst components for olefin polymerization

Patent metadata

Field	Value
Publication number	US-12240925-B2
Application number	US-202217824418-A
Country	US
Kind code	B2
Filing date	May 25, 2022
Priority date	Nov 13, 2017
Publication date	Mar 4, 2025
Grant date	Mar 4, 2025

Abstract

A process of preparing a solid catalyst component for the production of polypropylene includes a) dissolving a halide-containing magnesium compound in a mixture, the mixture including an epoxy compound, an organic phosphorus compound, and a hydrocarbon solvent to form a homogenous solution; b) treating the homogenous solution with an organosilicon compound during or after the dissolving step; c) treating the homogenous solution with a first titanium compound in the presence of a first non-phthalate electron donor, and an organosilicon compound, to form a solid precipitate; and d) treating the solid precipitate with a second titanium compound in the presence of a second non-phthalate electron donor to form the solid catalyst component, where the process is free of carboxylic acids and anhydrides.

First claim

What is claimed is:

1. A process of preparing a solid catalyst component for olefin polymerization, the process comprising:
dissolving a halide-containing magnesium compound in a mixture comprising an epoxy compound, an organic phosphorus compound, and a hydrocarbon solvent to form a homogenous solution;
treating the homogenous solution with a first titanium compound in the presence of a supportive electron donor to form a solid precipitate;
treating the solid precipitate with a second titanium compound, optionally in the presence of a non-phthalate electron donor, to form the solid catalyst component;
wherein:
the process is free of carboxylic acids and anhydrides;
the first titanium compound and the second titanium compound are independently represented by:
Ti(OR) g X 4-g ;

each R is independently a C 1 -C 4 alkyl;
X is Br, Cl, or I;
g is 0, 1, 2, or 3;
the supportive donor comprises an ether, a succinate, a monoaryl ester, a polycarboxylic acid ester, a polyhydroxy ester, a heterocyclic polycarboxylic acid ester, a polyhydroxy ester, a heterocyclic polycarboxylic acid ester, an acrylate, an inorganic acid ester, an alicyclic polycarboxylic acid ester, or a hydroxy-substituted carboxylic acid ester compound having 2 to 30 carbon atoms; and
the catalyst component comprises particles having a granular, or a substantially spherical or a spherical shape and exhibiting a D 50 from about 3 μm to about 150 μm.

2. The process of claim 1 , wherein the non-phthalate electron donor is different from the supportive donor, and the non-phthalate electron donor comprises an aryl diester, a diether, a succinate, an organic acid ester, a polycarboxylic acid ester, a polyhydroxy ester, a heterocyclic polycarboxylic acid ester, an inorganic acid ester, an alicyclic polycarboxylic acid ester, a hydroxy-substituted carboxylic acid ester compound having 2 to 30 carbon atoms, or a compound having at least one ether group and at least one ketone group, or a mixture of any two or more thereof.

3. The process of claim 1 , wherein the non-phthalate electron donor is added prior to or after the solid precipitate is formed, and the process incorporates using two or more the non-phthalate internal donors.

4. The process of claim 1 , wherein the process is conducted without the non-phthalate electron donor.

5. The process of claim 1 , wherein the treating the homogenous solution is conducted in the presence of a halogenating agent containing at least one halogen atom capable of transfer to the magnesium compound.

6. The process of claim 5 , wherein the halogenating agent comprises an aryloyl chloride, an alkanoyl chloride, an alkyl chloride, HCl, TiCl 4 , RnTiCl 4-n , CCl 4 , R n SiCl 4-n , or R n A1C1 3-n , wherein R is alkyl, cycloalkyl, aryl, or alkoxy, and n is a whole number satisfying the formula 0<n<4 and a ratio of halogenating agent to magnesium compound is at least 1:1 on a mol basis.

7. The process of claim 1 , wherein the solid precipitate is formed in presence of a polyacrylate.

8. The process of claim 1 , wherein the treating the homogenous solution is conducted in the presence of a di-(C 1 -C 12 )-alkylether.

9. The process of claim 1 wherein the treating of the homogenous solution is conducted in the presence of a hydrocarbon solvent, an aromatic solvent, or a mixture of any two or more thereof.

10. The process of claim 1 , wherein the supportive electron donor is represented as:

wherein:
each of R 1 through R 34 is independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and
q is an integer from 0 to 12.

11. The process of claim 1 wherein the supportive electron donor is methyl formate, butyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexy acetate, ethyl propionate, methyl butyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl p-methoxybenzoate, methyl p-methylbenzoate, ethyl p-t-butylbenzoate, ethyl naphthoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbezoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, or a mixture of any two or more thereof.

12. The process of claim 1 , wherein the epoxy compound is a glycidyl-containing compound represented by Formula:

wherein:
a is 1, 2, 3, 4, or 5;
X is alkyl, F, Cl, Br, I; and
R a is H, alkyl, aryl, or cyclyl.

13. The process of claim 1 , wherein the organic phosphorus compound is represented as:

wherein: R 1 , R 2 , and R 3 are each independently C1-C10 alkyl.

14. The process of claim 1 , wherein an organosilicon compound is added during the process and the organosilicon compound contains O—Si—O, Si—O—Si groups, or both O—Si—O and Si—O—Si groups.

15. The process of claim 14 wherein the organosilicon compound is a silane, siloxane or polysiloxane represented as:
R n Si(OR′) 4-n

wherein:
each R is H, alkyl, or aryl;
each R′ is H, alkyl, aryl, or a SiR n′ (OR′) 3-n ; and
n is 0, 1, 2, or 3.

16. The process of claim 1 , wherein the halide-containing magnesium halide compound is magnesium chloride.

17. A polymerization process comprising polymerizing an olefin in the presence of the solid catalyst component produced according to the process of claim 1 , an organoaluminum compound, and, optionally, an external electron donor, an activity limiting agent, or both an external electron donor and an activity limiting agent.

18. A process for polymerizing or copolymerizing an olefinic monomer, the process comprising contacting an olefinic monomer, and optionally a comonomer, with the solid catalyst component produced according to the process of claim 1 , an organoaluminum compound, and at least one selectivity control agent to form a polyolefin, wherein the at least one selectivity control agent comprises a silane compound, and, optionally, an activity limiting agent.

19. The process of claim 18 , wherein the polyolefin comprises polymer particles having a granular, a substantially spherical shape, or a spherical shape, and exhibiting an aspect ratio B/L3 greater than about 0.6.

Assignees

• Grace W R & Co

Inventors

• Marin Vladimir P
• Hintolay Ahmed

Classifications

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C08F2410/06

  Catalyst characterized by its size · CPC title

• B01J35/23

  in a colloidal state · CPC title

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• C08F10/02

  Ethene · CPC title