IP Library Granted Patent US 10,221,259
Granted Patent B2
US 10,221,259 · App. 15/541,663 · Granted Mar 5, 2019

SiO

Inventors: Dermot O'Hare (Oxford, GB); Jean-Charles Buffet (Oxford, GB); Chunping Chen (Oxford, GB)
Assignee: SCG CHEMICALS CO., LTD.
C08F10/02B01J21/08B01J27/236B01J35/002B01J35/008B01J35/0013B01J35/0086B01J35/023B01J35/08B01J35/1014B01J35/1019B01J37/035B01J37/06B01J37/343C08F4/02C08F4/65916B01J31/1608B01J31/1616B01J31/2295C08F4/65912C08F4/65925C08F4/65927
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Quick Facts
Patent No.
US 10,221,259
App. No.
15/541,663
Granted
Mar 5, 2019
Kind
B2
Abstract

A catalyst system is provided which comprises a solid support material having, on its surface, one or more catalytic transition metal complex wherein the solid support material comprises SiO 2 @AMO-LDH microspheres having the formula I: (i) wherein, M z+ and M′ y+ are two different charged metal cations; z=1 or 2; y=3 or 4; 0<x<0.9; b is 0 to 10; c is 0.01 to 10, preferably >0.01 and <10; p>0 q>0; X n− is an anion with n>0, preferably 1−5a=z(1−x)+xy−2; and the AMO-solvent is an 100% aqueous miscible organic solvent. Preferably, M′ in the formula I is Al. Preferably, M in the formula I is Li, Mg or Ca. The catalyst system has use in the polymerization and/or copolymerization of at least one olefin to produce a homopolymer and/or copolymer.

Claims (56)

1. A catalyst system comprising a solid support material having, on its surface, one or more catalytic transition metal complex wherein the solid support material comprises SiO 2 @AMO-LDH microspheres having the formula I

(SiO 2 ) p @{[M z+ (1−x) M′ y+ x (OH) 2 ] a+ (X n− ) a/n⋅b H 2 O⋅c (AMO-solvent)} q

wherein,

M z+ and M′ y+ are two different charged metal cations;

z=1 or 2;

y=3 or 4;

0<x<0.9;

b is 0 to 10;

c is 0.01 to 10;

p>0;

q>0;

X n− is an anion with n>0;

a=z(1−x)+xy−2; and

the AMO-solvent is an 100% aqueous miscible organic solvent.

2. The catalyst system according to claim 1 , wherein the solid support material has the formula I in which M′ is one or more trivalent metal cations.

3. The catalyst system according to claim 1 , wherein the solid support material has the formula I in which M is one or more divalent cation.

4. The catalyst system according to claim 1 , wherein the solid support material has the formula I in which X n− is selected from CO 3 2− , OH − , F − , Cl − , Br − , I − , SO 2− , NO 3 − and PO 4 3− , or a mixture thereof.

5. The catalyst system according to claim 1 , wherein the solid support material has the formula I in which M is Mg, M′ is Al and X n− is CO 3 − .

6. The catalyst system according to claim 1 , wherein the solid support material has the formula I in which the AMO-solvent is ethanol, acetone or methanol.

7. The catalyst system according to claim 1 , wherein the catalytic transition metal complex is at least one complex of a metal selected from zirconium, iron, chromium, cobalt, nickel, titanium and hafnium, the complex containing one or more aromatic or heteroaromatic ligands.

8. The catalyst system according to claim 1 , wherein the catalytic transition metal complex is a metallocene containing zirconium or hafnium.

9. The catalyst system according to claim 1 , wherein the catalytic transition metal complex is at least one compound selected from.

10. The catalyst system according to claim 1 , wherein the system is obtained by a process comprising the step of activating the solid support material with an alkylaluminoxane, triisobutylaluminium (TIBA), triethylaluminium (TEA) or diethylaluminium chloride (DEAC).

11. The catalyst system according to claim 10 , wherein the alkylaluminoxane is methylaluminoxane (MAO) or modified methylaluminoxane (MMAO).

12. A method of making the catalyst system of claim 1 which comprises

(a) providing a solid support material comprising SiO 2 @AMO-LDH microspheres having the formula (I)

(SiO 2 ) p @{[M z+ (1−x) M′ y+ x (OH) 2 ] a+ (X n− ) a/n .b H 2 O. c (AMO-Solvent)} q   (I)

wherein,

M z+ and M′ y+ are two different charged metal cations;

z=1 or 2;

y=3 or 4;

0<x<0.9;

b is 0 to 10;

c is 0.01 to 10;

p>0,

q>0;

X n− is an anion with n>0;

a=z(1−x)+xy−2; and

the AMO-solvent is an aqueous miscible organic solvent,

(b) treating the SiO 2 @AMO-LDH microspheres with at least one catalytic transition metal complex having olefin polymerisation catalytic activity.

13. The method according to claim 12 , wherein the solid support material has the formula I in which M′ is one or more trivalent metal cations.

14. The method according to claim 12 , wherein the solid support material has the formula I in which M is one or more divalent metal cations.

15. The method according to claim 12 , wherein the solid support material has the formula I in which X n− is selected from CO 3 2− , OH − , F, Cl − , Br − , I − , SO 2− , NO 3 − and PO 4 3− , or a mixture thereof.

16. The method according to claim 12 , wherein the solid support material has the formula I in which M z+ is Mg, M′ y+ is Al and X n− is CO 3 − .

17. The method according to claim 12 , wherein the solid support material has the formula I in which AMO-solvent is ethanol, acetone or methanol.

18. The method according to claim 12 , wherein the catalytic transition metal complex is at least one complex of a metal selected from zirconium, iron, chromium, cobalt, nickel, titanium and hafnium, the complex containing one or more aromatic or heteroaromatic ligands.

19. The method according to claim 12 , wherein the catalytic transition metal complex is a metallocene containing zirconium or hafnium.

20. The method according to claim 12 , wherein the catalytic transition metal complex is at least one compound selected from.

21. The method according to claim 12 , further comprising a step of calcining the SiO 2 @AMO-LDH microspheres, before the treating step (b).

22. The method according to claim 21 , further comprising a step of treating the calcined SiO 2 @AMO-LDH with an alkylaluminoxane before the treating step (b).

23. The method according to claim 22 , wherein the alkylaluminoxane is methylaluminoxane (MAO) or modified methylaluminoxane (MMAO).

24. A process for forming a polyethylene homopolymer or a polyethylene copolymer which comprises reacting olefin monomers in the presence of a system according to claim 1 .

25. A process for producing a polymer of an olefin which comprises contacting the olefin with the solid catalyst system according claim 1 .

26. The process according to claim 25 , wherein the olefin is ethylene.

27. The process according to claim 25 , wherein the process is performed at a temperature of 50-100° C.

28. The process according to claim 24 , wherein the copolymer comprises 1-10 wt % of a (4-8 C) α-olefin.

Assignments (3)
CHANGE OF NAME Recorded Sep 23, 2024
From: SCG CHEMICALS CO., LTD.
To: SCG CHEMICALS PUBLIC CO. LTD.
Reel/Frame 069025/0394 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 23, 2024
From: SCG CHEMICALS PUBLIC CO. LTD.
To: OXFORD UNIVERSITY INNOVATION LIMITED
Reel/Frame 068666/0759 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 30, 2017
From: O'HARE, DERMOT; BUFFET, JEAN-CHARLES; CHEN, CHUNPING
To: SCG CHEMICALS CO., LTD.
Reel/Frame 044556/0064 →
Priority Claims (1)
GB 1500111.8 · Jan 6, 2015 · national
Continuity (1)
Related Publication 20180022839A1 · Jan 25, 2018