SiO2-layered double hydroxide microspheres and their use as catalyst supports in ethylene polymerisation

Patent metadata

Field	Value
Publication number	US-10221259-B2
Application number	US-201615541663-A
Country	US
Kind code	B2
Filing date	Jan 6, 2016
Priority date	Jan 6, 2015
Publication date	Mar 5, 2019
Grant date	Mar 5, 2019

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 SiO2@AMO-LDH microspheres having the formula I: (i) wherein, Mz+ 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; Xn− 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.

First claim

The invention claimed is:

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.

Assignees

• Scg Chemicals Co Ltd

Inventors

• O'Hare Dermot
• Buffet Jean-Charles
• Chen Chunping

Classifications

• C08F110/02 Primary

  Ethene · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• B01J37/06

  Washing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title