PROCESS FOR MAKING A SOLID CATALYST COMPONENT FOR ETHYLENE POLYMERIZATION AND CO-POLYMERIZATION

• US 20190002601A1
• Filed: 12/27/2016
• Published: 01/03/2019
• Est. Priority Date: 12/30/2015
• Status: Active Grant

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Moman, Akhlaq, Blackmore, Ian
• Granted Patent: US 10,640,584 B2
• Time in Patent Office: Days
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 2/14 Organic medium
• CPC Class Codes: C08F 2410/06 Catalyst characterized by its size
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 4/025 Metal oxides
• CPC Class Codes: C08F 4/651 Pretreating with non-metals or metal-free compounds
• CPC Class Codes: C08F 4/6555 and magnesium or compounds thereof

Abstract

The present invention relates to a process for preparing a solid catalyst component suitable for producing polyethylene and its copolymers, said process comprising the steps of: (a) contacting a dehydrated support having hydroxyl groups with a magnesium compound having the general formula MgR¹R²; (b) contacting the product obtained in step (a) with modifying compounds (A) and/or (B) and/or (C), wherein: (A) is at least one oxygen and/or nitrogen comprising organic compound; (B) is a compound having the general formula R¹¹_f(R¹²O)_gSiX_h, (C) is a compound having the general formula (R¹³O)₄M, and (c) contacting the product obtained in step (b) with a titanium halide compound having the general formula TiX₄, wherein Ti is a titanium atom and X is a halide atom, wherein an organometallic compound is added after step (a) and before step (b). The invention also relates to a solid catalyst component obtainable by said process. The invention further relates to a process for producing polyethylene and its copolymers in the presence of the solid catalyst component and a cocatalyst.

Claims

1. A process for preparing a solid catalyst component suitable for producing polyethylene and its copolymers, said process comprising the steps of:

(a) contacting a dehydrated support having hydroxyl groups with a magnesium compound having the general formula MgR¹R², wherein R¹ and R² are the same or different and are independently selected from the group comprising an alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group and alkadienylaryl group;

(b) contacting the product obtained in step (a) with modifying compounds (A) and (B) and (C), wherein;

(A) is an oxygen and/or nitrogen comprising organic compound selected from the group of one ketone, carboxylic acid, carboxylic acid ester, acyl halide, aldehyde and alcohol or aminoketone,

(B) is a compound having the general formula R¹¹_f(R¹²O)_gSiX_h, wherein f, g and h are each integers from 0 to 4 and the sum of f, g and h is equal to 4 with a proviso that when h is equal to 4 then modifying compound (A) is not an alcohol, Si is a silicon atom, O is an oxygen atom, X is a halide atom and R¹¹ and R¹² are the same or different and are independently selected from the group comprising an alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group and alkadienylaryl group;

(C) is a compound having the general formula (R¹³O)₄M, wherein M is a titanium atom, a zirconium atom or a vanadium atom, O is an oxygen atom and R^H is selected from the group comprising an alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group and alkadienylaryl group; and

(c) contacting the product obtained in step (b) with a titanium halide compound having the general formula TiX₄, wherein Ti is a titanium atom and X is a halide atom,

wherein an organometallic compound is added after step (a) and before step (b).

2. The process according to claim 1 wherein the molar ratio of Mg to hydroxyl groups is from 0.01 to 10.

3. The process according to claim 1 wherein the molar ratio of compound (A) to Mg is from 0.01 to 10 and/or the molar ratio of compound (B) to Mg is from 0.01 to 5 and/or the molar ratio of compound (C) to Mg is from 0.01 to 5.

4. The process according to claim 1 wherein the organometallic compound is used in a molar ratio of the organometallic compound to titanium halide compound of between 0.1 and 1.5.

5. The process according to claim 1 wherein the organometallic compound is used in a molar ratio of the organometallic compound to the magnesium compound of between 0.1 and 1.5.

6. The process according to claim 1 wherein the molar ratio of titanium halide compound to Mg is from 0.01 to 10.

7. The process according to claim 1 wherein the support is silica, alumina, magnesia, thoria, zirconia or mixtures thereof.

8. The process according to claim 1 wherein the support is silica.

9. The process according to claim 1 wherein compound (A) is selected from methyl n-propyl ketone, ethyl acetate, n-butyl acetate, acetic acid, isobutyric acid, isobutyraldehyde, ethanoyl chloride, ethanol and sec-butanol.

10. The process according to claim 1 wherein compound (B) is selected from tetraethoxysilane, n-propyltriethoxysilane, isobutyltrimethoxysilane, dimethyldichlorosilane, n-butyltrichlorosilane and silicon tetrachloride.

11. The process according to claim 1 wherein compound (C) is selected from titanium tetraethoxide, titanium tetra-n-butoxide and zirconium tetra-n-butoxide.

12. The process according to claim 1 wherein the total molar ratio of compound (C) and TiX₄ to hydroxyl groups is from 0.05 to 1.0.

13. The process according to claim 1 wherein the TiX₄ compound is TiCl₄.

14. A solid catalyst component obtainable by the process according to claim 1.

15. A process for producing polyethylene and its copolymers in the presence of the solid catalyst component according to claim 14 and a co-catalyst.

16. The process according to claim 2 wherein

the molar ratio of compound (A) to Mg is from 0.01 to 10 and/or the molar ratio of compound (B) to Mg is from 0.01 to 5 and/or the molar ratio of compound (C) to Mg is from 0.01 to 5;

the organometallic compound is used in a molar ratio of the organometallic compound to titanium halide compound of between 0.1 and 1.5;

the molar ratio of titanium halide compound to Mg is from 0.01 to 10.

17. The process according to claim 16, wherein

compound (A) is selected from methyl n-propyl ketone, ethyl acetate, n-butyl acetate, acetic acid, isobutyric acid, isobutyraldehyde, ethanoyl chloride, ethanol and sec-butanol;

compound (B) is selected from tetraethoxysilane, n-propyltriethoxysilane, isobutyltrimethoxysilane, dimethyldichlorosilane, n-butyltrichlorosilane and silicon tetrachloride;

compound (C) is selected from titanium tetraethoxide, titanium tetra-n-butoxide and zirconium tetra-n-butoxide; and

the TiX₄ compound is TiCl₄.

18. A solid catalyst component obtainable by the process according to claim 16.

19. A process for producing polyethylene and its copolymers in the presence of the solid catalyst component according to claim 17 and a co-catalyst.