US 6,686,306 B2Granted

Supported dual transition metal catalyst systems

AssigneeW.R. Grace & Co.-Conn.

InventorKeng-Yu Shih

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Abstract

A coordination catalyst system comprising at least one metallocene or constrained geometry pre-catalyst transition metal compound, (e.g., rac-ethylene bis(indenyl)zirconium dichloride), at least one non-metallocene, non-constrained geometry, bidentate transition metal compound or tridentate transition metal compound (e.g., tridentate 2,6-diacetylpyridine-bis(2,4,6-trimethylanaline)FeCl2), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting dual transition metal catalyst system is suitable for addition polymerization of ethylenically and acetylenically unsaturated monomers into polymers; for example, polymers having a broad molecular weight distribution, Mw/Mn, and good polymer morphology.

Claims81

Dependent claims

A coordination polymerization catalyst system comprising:

(I) as a pre-catalyst, at least one each of a Group (1) material and a Group (2) material wherein said Group (1) material is at least one metallocene or constrained geometry transition metal compound capable of (i) being activated upon contact with a support-activator (II)(B) or (ii) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with said support-activator (II)(B), wherein the transition metal is at least one metal selected from the group consisting of Groups 3, 4 and the Lanthanide metals of the Periodic Table of Elements;
and wherein said Group (2) material is at least one non-metallocene, non-constrained geometry, bidentate transition metal compound or tridentate transition metal compound capable of (i) being activated upon contact with said support-activator (II)(B) or (ii) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with said support-activator (II)(B), wherein the transition metal is at least one member selected from Groups 3 to 10 of the Periodic table;
in intimate contact with
(II) catalyst support-activator agglomerate particles comprising a composite of (A) at least one inorganic oxide component selected from SiO2, Al2O3, MgO, AlPO4, TiO2, ZrO2, or Cr2O3 and (B) at least one ion containing layered material having interspaces between the layers, said support-activator having sufficient Lewis acidity to activate said pre-catalyst when said pre-catalyst is in contact with said support-activator, said layered material having a cationic component and an anionic component, wherein said cationic component is present within the interspace of the layered material, said layered material being intimately dispersed with said inorganic oxide component within said agglomerate particle in an amount sufficient to provide a coordination catalyst system having the ability to polymerize at least one unsaturated monomer;
wherein the amount of the pre-catalyst and support-activator which is in intimate contact is sufficient to provide a ratio of micromoles of pre-catalyst to grams of support-activator of from about 5:1 to about 500:1.

2 more elements

A coordination catalyst system formed by the process comprising:

(I) agglomerating to form particles of a support-activator:
(A) at least one inorganic oxide component selected from SiO2, Al2O3, MgO, AlPO4, TiO2, ZrO2, or Cr2O3 with
(B) at least one ion containing layered material having interspaces between the layers, said support-activator having sufficient Lewis acidity to activate the transition metal of the pre-catalyst of II when said pre-catalyst is in contact with the support-activator, said layered material, having a cationic component and an anionic component, wherein said cationic component is present within the interspace of said layered material, said layered material being intimately dispersed with said inorganic oxide component within said agglomerate particle in an amount sufficient to provide a coordination catalyst system having the ability to polymerize at least one unsaturated monomer;
(II) providing as a pre-catalyst, at least one each of a Group (1) material and a Group (2) material, wherein said Group (1) material is at least one metallocene, or constrained geometry, transition metal compound capable of (i) being activated upon contact with the support-activator of (I), or (ii) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with the support-activator, wherein the transition metal is at least one element selected from the group consisting of Groups 3, 4 and the Lanthanide metals of the Periodic Table of Elements;
and wherein said Group (2) material is at least one non-metallocene, non-constrained geometry, bidentate transition metal compound or tridentate transition metal compound capable of (i) being activated upon contact with said support-activator (II)(B) or (ii) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with said support-activator (II)(B), wherein the transition metal is at least one member selected from Groups 3 to 10 of the Periodic table;
(III) contacting pre-catalyst component Group (1) and Group (2) materials, separately or together with said support-activator, in the presence of at least one inert liquid hydrocarbon in a manner sufficient to provide a ratio of micromoles of pre-catalyst to grams of support-activator of from about 5:1 to about 500:1.

3 more elements

A process for preparing a catalyst system capable of polymerizing at least one unsaturated monomer comprising:

(I) agglomerating to form particles of a support-activator:
(A) at least one inorganic oxide component selected from SiO2, Al2O3, MgO, AlPO4, TiO2, ZrO2, or Cr2O3 with
(B) at least one ion containing layered material having interspaces between the layers, said suppprt-activator having sufficient Lewis acidity to activate the pre-catalyst compound of (II) when said pre-catalyst is in contact with said support-activator, said layered material having a cationic component and an anionic component, wherein said cationic component is present within the interspace of the layered material, said layered material being intimately dispersed with said inorganic oxide component within the agglomerate particle in amounts sufficient to provide a coordination catalyst system having the ability to polymerize said at least one unsaturated monomer;
(II) providing as a pre-catalyst, at least one each of a Group (1) material and a Group (2) material wherein said Group (1) material is at least one metallocene or constrained geometry transition metal compound capable of (i) being activated upon contact with said support-activator, or (ii) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with said support-activator, wherein said transition metal is at least one metal selected from the group consisting of Groups 3, 4 and the Lanthanide metals of the Periodic Table of Elements;
and wherein said Group (2) material is at least one non-metallocene, non-constrained geometry, bidentate transition metal compound or tridentate transition metal compound capable of (i) being activated upon contact with said support-activator or (ii) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with said support-activator, wherein said transition metal is at least one member selected from Groups 3 to 10 of the Periodic table;
(III) contacting each of said pre-catalyst component Group (1) and Group (2) materials, separately or together, with said support-activator in the presence of at least one inert liquid hydrocarbon in a manner sufficient to provide in said liquid hydrocarbon, a ratio of micromoles of pre-catalyst to grams of support-activator of from about 5:1 to about 500:1, and to cause at least one of absorption and adsorption of said pre-catalyst by said support-activator.

3 more elements

A polymerization process comprising contacting at least one unsaturated monomer under polymerization conditions with a coordination catalyst system comprising:

(I) as a pre-catalyst, at least one each of a Group (1) material and a Group (2) material wherein said Group (1) material is at least one metallocene or constrained geometry transition metal compound capable of:
(i) being activated upon contact with support-activator (II);
or (ii) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with said support-activator (II), wherein said transition metal is at least one metal selected from the group consisting of Groups 3, 4 and the Lanthanide metals of the Periodic Table of Elements;
and wherein said Group (2) material is at least one non-metallocene, non-constrained geometry, bidentate transition metal compound or tridentate transition metal compound capable of:
(i) being activated upon contact with said support-activator (II);
or (ii) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with said support-activator (II), wherein said transition metal is at least one member selected from Groups 3 to 10 of the Periodic table;
in intimate contact with
(II) catalyst support-activator agglomerate particles comprising a composite of:
(A) at least one inorganic oxide component selected from SiO2, Al2O3, MgO, AlPO4, TiO2, ZrO2, or Cr2O3;
and (B) at least one ion containing layered material having interspaces between the layers, said support-activator having sufficient Lewis acidity to activate said pre-catalyst when said pre-catalyst is in contact with said support-activator, said layered material having a cationic component and an anionic component, wherein said cationic component is present within the interspace of said layered material, said layered material being intimately dispersed with said inorganic oxide component within said agglomerate particles in an amount sufficient to provide a coordination catalyst system having the ability to polymerize said at least one unsaturated monomer;
wherein the amount of the pre-catalyst and support-activator which is in intimate contact is sufficient to provide a ratio of micromoles of pre-catalyst to grams of support-activator of from about 5:1 to about 500:1.

8 more elements

Dependencies are inferred from the claim text.

Facts

Application: 10/120,317Filed 10 Apr 2002 · us provisional application
Priority: 30 Apr 2001
Published: US 2003/0225225 A14 Dec 2003
Granted: 3 Feb 2004
Term ends: Not estimatedThe source records don’t support an estimate.

Classification7 codes

C08F 10/00
Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double
C08F 4/65912
Component covered by group C08F4/64 containing a transition metal-carbon bond: in combination with an organoaluminium compound
C08F 4/6592
Component covered by group C08F4/64 containing a transition metal-carbon bond: containing at least one cyclopentadienyl ring, condensed or not,…
C08F 4/65927
Containing at least two cyclopentadienyl rings, fused or not: two cyclopentadienyl rings being mutually bridged