Metallocene and constrained geometry catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation
OwnerKeng-Yu Shih, Dean Alexander Denton +1inventors
InventorsKeng-Yu Shih, Dean Alexander Denton, Michael John Carney
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Abstract
The present invention is directed to a coordinating catalyst system comprising at least one metallocene or constrained geometry pre-catalyst transition metal compound, (e.g., di-(n-butylcyclopentadienyl) zirconium dichloride), 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 catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer having very good morphology.
Claims70
A coordinating catalyst system capable of polymerizing olefins comprising:
- (I) as a pre-catalyst, at least one metallocene or constrained geometry, transition metal compound capable of (A) being activated upon contact with the support-activator of (II)(B) or (B) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with the support-activator of (II)(B), wherein the transition metal is at least one member selected from Groups 3, 4 or the Lanthanide metals, of the Periodic Table of Elements;
- in intimate contact with
- (II) catalyst support-activator agglomerate comprising a composite of (A) at least one inorganic oxide component selected from SiO2, Al2O3, MgO, AlPO4, TiO2, ZrO2, Cr2O3 and (B) at least one ion containing layered material having interspaces between the layers and sufficient Lewis acidity, when present within the support-activator, to activate the pre-catalyst when the pre-catalyst is in contact with the support-activator, said layered material having a cationic component and an anionic component, wherein said an anionic component is present within the interspace of the layered material, said layered material being intimately dispersed with said inorganic oxide component within the agglomerate in an amount sufficient to improve the activity of the coordinating catalyst system for polymerizing ethylene monomer, expressed as Kg of polyethylene per gram of catalyst system per hour, relative to the activity of a corresponding catalyst system employing the same pre-catalyst but in the absence of either Component A or B of the support-activator;
- 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 1:1 to about 500:1.
The catalyst system of claim 11 wherein the layered material of the support-activator is at least one of clay or clay minerals having a negative charge of below 0.
The catalyst system of claim wherein the layered material is a smectite clay, the weight ratio of inorganic oxide to clay in the support activator agglomerate is from about 0.25:1 to about 99:1, and the ratio of micromoles of pre-catalyst to grams of support-activator is from about 5:1 to about 200:1.
A coordinating catalyst system formed by the process comprising:
- (I) agglomerating to form a support-activator:
- (A) at least one inorganic oxide component selected from SiO2, Al2O3, MgO, AlPO4, TiO2, ZrO2, Cr2O3 with
- (B) at least one ion containing layered material having interspaces between the layers and sufficient Lewis acidity, when present within the support-activator, to activate the transition metal of the pre-catalyst of II when the pre-catalyst is in contact with the support-activator, said layered material, having a cationic component and an anionic component, wherein said anionic component is present within the interspace of the layered material, said layered material being intimately dispersed with said inorganic oxide component within said agglomerate in an amount sufficient to improve the activity of the coordinating catalyst system for polymerizing ethylene monomer, expressed as Kg of polyethylene per gram of catalyst system per hour, relative to the activity of a corresponding catalyst system employing the same pre-catalyst but in the absence of either Component A or B of the support-activator;
- (II) providing as a pre-catalyst, at least one metallocene, or constrained geometry, transition metal compound capable of (A) being activated upon contact with the support-activator of (I), or (B) 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 Groups 3, 4 or the Lanthanlide metals, of the Periodic Table of Elements;
- (III) contacting the support-activator and pre-catalyst 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 1:1 to about 500:1.
A process for preparing a catalyst system capable of polymerizing at least one olefin comprising:
- (I) agglomerating to form a support-activator:
- (A) at least one inorganic oxide component selected from SiO2, Al2O3, MgO, AlPO4, TiO2, ZrO2, Cr2O3 with
- (B) at least one ion containing layered material having interspaces between the layers and sufficient Lewis acidity, when present within the support-activator, to activate the pre-catalyst compound of (II) when the pre-catalyst is in contact with the support-activator, said layered material having a cationic component and an anionic component, wherein said anionic component is present within the interspace of the layered material, said layered material being intimately dispersed with said inorganic oxide component within the agglomerate in amounts sufficient to improve the activity of the coordinating catalyst system for polymerizing ethylene monomer, expressed as Kg of polyethylene per gram of catalyst system per hour, relative to the activity of a corresponding catalyst system employing the same pre-catalyst but in the absence of either Component A or B of the support-activator;
- (II) providing as a pre-catalyst, at least one metallocene, or constrained geometry transition metal compound capable of (A) being activated upon contact with the support-activator, or (B) 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 member selected from Groups 3, 4 or Lanthamide metals, of the Periodic Table of Elements;
- (III) contacting the support-activator and pre-catalyst in the presence of at least one inert liquid hydrocarbon in a manner sufficient to provide in the liquid hydrocarbon, a ratio of micromoles of pre-catalyst to grams of support-activator of from about 1:1 or to about 500:1, and to cause at least one of absorption and adsorption of the pre-catalyst by the support-activator.
Dependencies are inferred from the claim text.