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

Patent metadata

Field	Value
Publication number	US-10730965-B2
Application number	US-201616066442-A
Country	US
Kind code	B2
Filing date	Dec 23, 2016
Priority date	Dec 30, 2015
Publication date	Aug 4, 2020
Grant date	Aug 4, 2020

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 MgR 1 R 2 ; (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 R 11 f (R 12 O) g SiX h , (C) is a compound having the general formula (R 13 O) 4 M, and (c) contacting the product obtained in step (b) with a titanium halide compound having the general formula TiX 4 , wherein Ti is a titanium atom and X is a halide atom, wherein an organometallic compound is added either before step (a) and/or after step (c). 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 co-catalyst.

First claim

The invention claimed is:

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 MgR 1 R 2 , wherein R 1 and R 2 are the same or different and are independently selected from an 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), (B) and (C), wherein:
(A) is an oxygen and/or nitrogen containing organic compound selected from a ketone, carboxylic acid, carboxylic acid ester, acyl halide, aldehyde, alcohol, or aminoketone,
(B) is a compound having the general formula R 11 f (R 12 O) g SiX 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 R 11 and R 12 are the same or different and are independently selected from an alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group, or alkadienylaryl group;
(C) is a compound having the general formula (R 13 O) 4 M, wherein M is a titanium atom, a zirconium atom or a vanadium atom, O is an oxygen atom and R 13 is selected from 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 TiX 4 , wherein Ti is a titanium atom and X is a halide atom,
wherein an organometallic compound is added before step (a) and/or after step (c).

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 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 molar ratio of organometallic compound to magnesium compound is between 0.04 and 0.7 and/or the molar ratio of organometallic compound to titanium halide compound of between is between 0.04 and 0.8.

5. The process according to claim 1 wherein the molar ratio of the organometallic compound to the magnesium compound is between 0.05 and 1.5 and/or the molar ratio of organometallic compound to titanium halide compound is between 0.15 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 pentan-2-one, methyl n-propyl ketone, ethyl acetate, n-butyl acetate, acetic acid, isobutyric acid, isobutyraldehyde, ethanoyl chloride, ethanol and sec-butanol and/or 4-methylamino-pent-3-en-2-one, 4-n-butylamino-pent-3-en-2-one, 4-tert-butylamino-pent-3-en-2-one, or 4-cyclohexylamino-pent-3-en-2-one.

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

11. The process according to claim 1 wherein compound (C) is selected from 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 TiX 4 to hydroxyl groups is from 0.05 to 1.0.

13. The process according to claim 1 wherein TiX 4 compound is TiCl 4 .

14. A solid catalyst component obtained 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 1 wherein
the molar ratio of Mg to hydroxyl groups is from 0.01 to 10;
the molar ratio of compound (A) to Mg is from 0.01 to 10 and/or 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 molar ratio of organometallic compound to magnesium compound is between 0.04 and 0.7 and/or the molar ratio of organometallic compound to titanium halide compound is between 0.04 and 0.8;
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 pentan-2-one, methyl n-propyl ketone, ethyl acetate, n-butyl acetate, acetic acid, isobutyric acid, isobutyraldehyde, ethanoyl chloride, ethanol and sec-butanol and/or 4-methylamino-pent-3-en-2-one, 4-n-butylamino-pent-3-en-2-one, 4-tert-butylamino-pent-3-en-2-one, or 4-cyclohexylamino-pent-3-en-2-one;
compound (B) is selected from tetraethoxysilane, n-propyltriethoxysilane, isobutyltrimethoxysilane, dimethyldichlorosilane, n-butyltrichlorosilane, or silicon tetrachloride;
compound (C) is selected from titanium tetraethoxide, titanium tetra-n-butoxide, or zirconium tetra-n-butoxide; and
TiX 4 is TiCl 4 .

18. A solid catalyst component obtainable by the process according to claim 17 .

19. A process for producing polyethylene and its copolymers in the presence of the solid catalyst component according to claim 18 and a co-catalyst.

20. The process according to claim 1 , wherein
the molar ratio of Mg to hydroxyl groups is from 0.01 to 10;
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;
the molar ratio of the organometallic compound to the magnesium compound is between 0.04 and 0.7;
the molar ratio of the organometallic compound to the titanium halide compound is between 0.04 and 0.8; and
the molar ratio of the titanium halide compound to Mg is from 0.01 to 10.

21. The process according to claim 20 , wherein the organometallic compound is added before step (a).

22. The process according to claim 21 , wherein the organometallic compound is added after step (c).

Assignees

• Sabic Global Technologies Bv

Inventors

• Moman Akhlaq
• Blackmore Ian

Classifications

• C08F2410/06

  Catalyst characterized by its size · CPC title

• C08F4/6546

  organo-magnesium compounds · CPC title

• C08F110/02

  Ethene · CPC title

• C08F2/34 Primary

  Polymerisation in gaseous state · CPC title

• Y02P20/52

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