Catalyst support, production and use thereof in the polymerization of olefins

• US 20040014917A1
• Filed: 04/24/2003
• Published: 01/22/2004
• Est. Priority Date: 10/24/2000
• Status: Abandoned Application

• Current Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Original Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Inventors: Eberle, Thomas, Kohler, Katrin, Lubda, Dieter, Eichhorn, Jens
• Application Number:
  US10/399,992
• Publication Number:
  US 20040014917A1
• Time in Patent Office: Days
• US Class Current: 526/160
• CPC Class Codes: B01J 21/00 Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
• CPC Class Codes: B01J 21/12 Silica and alumina
• CPC Class Codes: B01J 2531/46 Titanium
• CPC Class Codes: B01J 2531/48 Zirconium
• CPC Class Codes: B01J 2531/49 Hafnium
• CPC Class Codes: B01J 31/14 of aluminium or boron
• CPC Class Codes: B01J 31/143 of aluminium
• CPC Class Codes: B01J 31/1616 Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts catalysts comprising molecular sieves B01J29/00
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 2500/01 High molecular weight, e.g. >800,000 Da.
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/24 Polymer with special particle form or size
• CPC Class Codes: C08F 4/025 Metal oxides
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65925 two cyclopentadienyl rings being mutually non-bridged

Abstract

The present invention relates to a support for catalysts which has a content of physisorbed water of at least 2.5% by weight. Further subject-matters of the application are a process for preparing heterogeneous catalysts containing these supports and the use of these catalysts for olefin polymerization and also a polymerization process using the catalysts.

Claims

1. Support for catalysts, characterized in that it has a content of physisorbed water of at least 2.5% by weight.

2. Support for catalysts according to claim 1, characterized in that it has a water content in the range from 3 to 8% by weight and is an oxidic material which is preferably selected from among the oxides of the elements of main groups 3 and 4 and transition groups 3 to 8 of the Periodic Table and is particularly preferably an aluminium, silicon, boron, germanium, titanium, zirconium or iron oxide or a mixed oxide or an oxide mixture of the specified compounds.

3. Support for catalysts according to claim 1 or 2, characterized in that it is a mixed aluminium-silicon oxide which is preferably obtainable by a process in which

a) separate gels of aluminium (hydr)oxide and silicon (hydr)oxide are prepared first,

b) the two gels are subsequently mixed with one another and homogenized,

c) the homogenized mixture is spray dried.

4. Support according to at least one of claims 1 to 3, characterized in that the support has a particle surface area, determined by the BET method, in the range from 50 to 500 m²/g, preferably in the range from 150 to 450 m²/g, and a pore volume, likewise measured by the BET method, in the range from 0.5 to 4.5 ml/g, preferably above 0.8 ml/g and particularly preferably in the range from 1.5 to 4.0 ml/g, and the ratio of SiO₂ to Al₂O₃ is in the range from 100:

1 to 1;

2, preferably in the range from 20;

1 to 5;

1.

5. Support according to at least one of claims 1 to 4, characterized in that it consists of spherical particles in which all ratios of the means of the three mutually perpendicular diameters are in the range from 1.5:

1 to 1;

1.5 and the mean particle size of the catalyst particles is in the range from 1 to 100 μ

m, preferably in the range from 3 to 50 μ

m.

6. Heterogeneous catalyst suitable for the synthesis of polyolefins, comprising

a) at least one support according to at least one of claims 1 to 5,

b) at least one compound of a transition metal of transition groups 3 to 8 of the Periodic Table and

c) at least one organometallic compound of a (semi)metal of main group 3 or 4 of the Periodic Table,

where the components b) and c) are absorbed on the support a) and together form the catalytically active species.

7. Heterogeneous catalyst according to claim 6, characterized in that the compound of a transition metal of transition groups 3 to 8 of the Periodic Table is a complex, particularly preferably a metallocene compound, where the central metal is preferably selected from among the elements titanium, zirconium, hafnium, vanadium, palladium, nickel, cobalt, iron and chromium, with titanium and especially zirconium being particularly preferred central atoms, and the organometallic compound of a (semi)metal of main group 3 or 4 of the Periodic Table is a compound of one of the elements boron, aluminium, tin or silicon, preferably a compound of boron or aluminium, particularly preferably an aluminoxane, in particular methylaluminoxane.

8. Heterogeneous catalyst according to claim 6 or 7, characterized in that it consists of particles having a mean particle size in the range from 1 to 150 μ

m, preferably in the range from 3 to 75 μ

m.

9. Process for preparing a heterogeneous catalyst suitable for the synthesis of polyolefins, characterized in that

a) a support according to at least one of claims 1 to 5 is reacted with at least one organometallic compound of a (semi)metal of main group 3 or 4 of the Periodic Table and

b) with at least one compound of a transition metal of transition groups 3 to 8 of the Periodic Table to give the heterogeneous catalyst.

10. Process according to claim 9, characterized in that the cocatalyst is absorbed on the support first and the catalyst is subsequently added.

11. Process according to claim 9, characterized in that a mixture of catalyst and cocatalyst is absorbed on the support.

12. Process according to at least one of claims 9 to 11, characterized in that the compound of a transition metal of transition groups 3 to 8 of the Periodic Table which is used is a complex, particularly preferably a metallocene compound, where the central metal is preferably selected from among the elements titanium, zirconium, hafnium, vanadium, palladium, nickel, cobalt, iron and chromium, with titanium and especially zirconium being particularly preferred central atoms, and the organometallic compound of a (semi)metal of main group 3 or 4 of the Periodic Table which is used is a compound of one of the elements boron, aluminium, tin or silicon, preferably a compound of boron or aluminium, particularly preferably an aluminoxane, in particular methylaluminoxane.

13. Process according to at least one of claims 9 to 12, characterized in that either no further drying of the support apart from the spray drying takes place prior to the reaction of the support with the (co)catalyst or the drying is carried out at temperatures below 400°

C., preferably below 250°

C. and particularly preferably at not more than 180°

C.

15. Use of a heterogeneous catalyst according to at least one of claims 6 to 8 or a heterogeneous catalyst prepared by a process according to any of claims 9 to 13 for the preparation of polyolefins.

16. Process for preparing polyolefins, characterized in that a heterogeneous catalyst according to at least one of claims 6 to 8 or a heterogeneous catalyst prepared by a process according to any of claims 9 to 13 and an olefin of the formula R¹CH═

CHR², where R¹ and R² may be identical or different and are selected from the group consisting of hydrogen and cyclic and acyclic alkyl radicals having from 1 to 20 carbon atoms, are used.

17. Process for preparing polyolefins according to claim 16, characterized in that the polymerization is carried out as a gas-phase or suspension polymerization.

18. Use of a heterogeneous catalyst according to at least one of claims 6 to 8 or a heterogeneous catalyst prepared by a process according to any of claims 9 to 13 for preparing polyolefins having a spherical particle structure.

14. Process for producing a support for catalysts, characterized in that

a) separate gels of aluminium (hydr)oxide and silicon (hydr)oxide are prepared first,

b) the two gels are subsequently mixed with one another and homogenized,

c) the homogenized mixture is spray dried.