Chromium support-agglomerate-transition metal polymerization catalysts and processes utilizing same
AssigneeW.R. Grace & Co.-Conn.
InventorsKeng-Yu Shih, Dean Alexander Denton, Rimantas Glemza
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Abstract
The present invention is directed to a novel one-step method for forming a supported catalyst complex of high activity by substantially simultaneously contacting a bidentate or tridentate ligand forming compound, a transition metal compound and a chromium immobilized Lewis acid support-agglomerate. The catalyst can be formed prior to polymerization of olefins or within the polymerization reaction zone.
Claims71
A process for forming a coordination catalyst system useful for the polymerization of olefins comprising:
- providing Component I selected from at least one ligand forming compound or precursor compounds for forming at least one ligand forming compound wherein said at least one ligand forming compound is represented by at least one of the following formulas IA or IB:
- wherein in each of formulas IA and IB above:
- each A independently represents an atom of oxygen, sulfur, phosphorous or nitrogen;
- each R independently represents hydrogen, an unsubstituted or substituted C1-C20 hydrocarbyl;
- ------ represents a bond between an A atom and a carbon atom, wherein said bond is selected from a single or double bond;
- and
- each x independently represents an integer of 0, 1 or 2, provided that when A represents a nitrogen or phosphorous atom and --- represents a double bond then x is 1;
- when A represent either a nitrogen or phosphorous atom and ---- represents a single bond, then x is 2;
- when A represents either an oxygen or sulfur atom and ---- represents a double bond, then x is 0;
- and when A represents either an oxygen or sulfur atom and ---- represents a single bond, then x is 1;
- and
- the lines joining each A to each other A represent a C2 to C90 hydrocarbon based group;
- providing as Component II at least one a transition metal compound represented by the formula:
- MXL2L′a II
- wherein
- a is an integer of 0, 1 or 2 such that the sum of a plus 2 equals x,
- M represents at least one of Group 3 to 10 transition metals of the Periodic Table;
- and
- each L and L′, independently represents a member selected from hydrogen, halogen, and hydrocarbon based group associated through a covalent bond to M, or together represent a C3 to C24 hydrocarbon based group, associated through a covalent or dative bond to M, and which, together with M, constitute a ring or fused ring structure;
- and
- providing as Component III a support-agglomerate composite comprising agglomerates of at least two components comprising (A) at least one inorganic oxide component and (B) at least one ion-containing layered component;
- and said support-agglomerate further having from 0.1 to 10 weight percent chromium atoms immobilized thereto;
- or precursor components for said composite selected from (A) at least one inorganic oxide and (B) at least one ion-containing layered component and (C) a chromium compound soluble in an inert liquid in an effective amount to provide 0.1 to 10 weight percent immobilized chromium with respect to the support-agglomerate, said (A) to (B) weight ratio being from 0.25:1 to 99:1;
- contacting Components I, II and III in the presence of an inert liquid, said contacting being conducted under conditions to cause Components I, II and III to form a coordination catalyst composition.
A catalyst useful for the polymerization of olefins formed by contacting substantially simultaneously in an inert liquid:
- Component (I) selected from at least one ligand forming compound or precursor compounds capable of forming at least one ligand forming compound, wherein said at least one ligand forming compound is represented by the general formula:
- wherein in each of formulas IA and IB above:
- each A independently represents an atom of oxygen, sulfur, phosphorous or nitrogen;
- each R independently represents hydrogen, an unsubstituted or substituted C1-C20 hydrocarbyl;
- ------ represents a bond between an A atom and a carbon atom, wherein said bond is selected from a single or a double bond;
- and
- each x independently represents an integer of 0, 1 or 2, provided that when A represents a nitrogen or phosphorous atom and --- represent a double bond then x is 1:
- when A represent either a nitrogen or phosphorous atom and ---- represents a single bond, then x is 2;
- when A represents either an oxygen or sulfur atom and ---- represents a double bond, then x is 0;
- and when A represents either an oxygen or sulfur atom and ---- represents a single bond, then x is 1:
- and
- the lines joining each A to each other A represent a C2 to C90 hydrocarbon based group;
- with
- Component (II) comprising a transition metal compound represented by the formula:
- MXL2L′a II
- wherein
- a is an integer of 0, 1 or 2 such that a plus 2 equals x,
- M represents at least one of Group 3 to 10 transition metals of the Periodic Table;
- and
- each L and L′, independently represents a group selected from hydrogen, halogen, and hydrocarbon based group associated through a covalent bond to M, or together represent a C3 to C24 hydrocarbon based group, associated through a covalent or dative bond to M, and which, together with M, constitute a ring or fused ring structure;
- and with
- (III) a support-agglomerate composite comprising agglomerates of at least two components comprising (A) at least one inorganic oxide component and (B) at least one ion-containing layered component and said support-agglomerate further having chromium atoms immobilized thereto;
- or precursor components for said composite selected from (A) at least one inorganic oxide and (B) at least one ion-containing layered component and (c) a chromium compound soluble in an inert liquid in an effective amount to provide 0.1 to 10 weight percent immobilized chromium with respect to the support-agglomerate.
- said contacting being conducted under conditions sufficient to have Component I, II and II form an activated catalyst composition.
The catalyst of claim 30, 31, 32, 33, 34, 3536, 37 or 38 wherein Component III is derived from the inorganic oxide (A) selected from SiO2, Al2O3, AlPO4, MgO, TiO2, ZrO2, SiO2.Al2O3, MgO.SiO2.Al2O3, SiO2.TiO2.Al2O3, SiO2.Cr2O3.Al2O3 or SiO2.Cr2O3.TiO2 and mixtures thereof.
The catalyst of claim 30, 31, 32, 33, 34, 3536, 37 or 38 wherein Components (I), (II) and (III) are contacted substantially simultaneously in a liquid medium.
The catalyst of claim 30, 31, 32, 33, 34, 3536, 37 or 38 wherein Components (II) and (III) are contacted substantially simultaneously in a liquid medium follows by contact with Component (I).
The catalyst of claim 30, 31, 32, 33, 34, 3536, 37 or 38 wherein Components (I) and (III) are contacted substantially simultaneously in a liquid medium followed by contact with Component (II).
The catalyst of claim 30, 31, 32, 33, 34, 3536, 37 or 38 wherein Component (I) comprises precursor reagents capable of forming said bidentate or tridentate ligand.
A process for the polymerization of olefins comprising contacting in a polymerization zone at least one olefinic compound with the catalyst composition of claim 30, 31, 32, 33, 34, 3536, 37 or 38.
Dependencies are inferred from the claim text.