Process for making a solid catalyst component for ethylene polymerization and co-polymerization

• US 10,640,584 B2
• Filed: 12/27/2016
• Issued: 05/05/2020
• 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
• Primary Examiner(s): Branch, Catherine S
• Application Number:
  US16/066,494
• Publication Number:
  US 20190002601A1
• Time in Patent Office: 1,225 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 alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group, or 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 is ketone, carboxylic acid, carboxylic acid ester, acyl halide, aldehyde, 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 alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group, or 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 R¹¹ is alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group, or 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 methyl n-propyl ketone, ethyl acetate, n-butyl acetate, acetic acid, isobutyric acid, isobutyraldehyde, ethanoyl chloride, ethanol, or sec-butanol.

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

11. The process according to claim 1 wherein compound (C) is titanium tetraethoxide, titanium tetra-n-butoxide, or 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 obtained by the process according to claim 1.

15. A process, the process comprising for producing polyethylene or copolymer thereof 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, the molar ratio of compound (B) to Mg is from 0.01 to 5, the molar ratio of compound (C) to Mg is from 0.01 to 5, or a combination thereof;

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 methyl n-propyl ketone, ethyl acetate, n-butyl acetate, acetic acid, isobutyric acid, isobutyraldehyde, ethanoyl chloride, ethanol, or sec-butanol;

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

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

the TiX₄ compound is TiCl₄.

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

19. A process, the process comprising producing polyethylene or copolymer thereof in the presence of the solid catalyst component according to claim 17 and a co-catalyst.