US 6,271,165 B1Granted

Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same

AssigneeThe Dow Chemical Company

InventorsGrant B. Jacobsen, Pierre H. H. Loix, Theo J. P. Stevens

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Abstract

This invention relates to supported and nonsupported catalyst components comprising (a) an ionic compound comprising (a)(1) a cation and (a)(2) an anion having up to 100 nonhydrogen atoms and the anion containing at least one subtituent comprising a moiety having an active hydrogen reacted with (c) an organometal or metalloid compound wherein the metal or metalloid is selected from Groups 2, 12, 13, or 14 of the Periodic Table of the Elements, and, optionally, (b) a transition metal compound, (d) a support material, and/or a diluent. Included are methods for preparation of the catalyst components, catalysts, reaction products and dispersions thereof, as well as polymerization process using the catalyst.

Claims48

Dependent claims

A compound that is the reaction product of:

(a) an ionic compound comprising (a)(1) a cation and (a)(2) an anion having up to 100 nonhydrogen atoms and containing at least one substituent comprising a moiety having an active hydrogen,
wherein the cation (a)(1) is represented by the following general formula:
[L*—H]+, wherein:
L* is a nitrogen, oxygen, sulfur or phosphorus containing Lewis base containing from one to three C10-40 alkyl groups with a total of from 12 to 100 carbons, and the anion (a)(2) corresponds to Formula (II):
[M′m+Qn(Gq(T—H)r)z]d− (II)
wherein:
M′ is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements;
Q independently in each occurrence is selected from the group consisting of hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl, and substituted-hydrocarbyl radicals, including halo-substituted hydrocarbyl radicals, and hydrocarbyl- and halohydrocarbyl-substituted organo-metalloid radicals, the hydrocarbyl portion in each of these groups preferably having from 1 to 20 carbons, with the proviso that in not more than one occurrence is Q halide;
G is a polyvalent hydrocarbon radical having r+1 valencies bonded to M′ and r groups (T—H);
the group (T—H) is a radical wherein T comprises O, S, NR, or PR, the O, S, N or P atom of which is bonded to hydrogen atom H wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl germyl radical or hydrogen;
m is an integer from 1 to 7;
n is an integer from 0 to 7;
q is an integer of 0 or 1;
r is an integer from 1 to 3;
z is an integer from 1 to 8;
d is an integer from 1 to 7;
and
n+z−m=d, and
(c) an organometal or metalloid compound corresponding to the formula:
MoRcxXay,
wherein
Mo is a metal or metalloid selected from Groups 2, 12, 13 or 14 of the Periodic Table of the Elements,
Rc independently each occurrence is hydrogen or a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, trihydrocarbylsilyl, trihydrocarbylgermyl or hydrocarbylsilylhydrocarbyl;
Xa is a noninterfering group having from 1 to 100 nonhydrogen atoms which is halo-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy or halide;
x is a nonzero integer which may range from 1 to an integer equal to the valence of Mo;
y is zero or a nonzero integer which may range from 1 to an integer equal to 1 less than the valence of Mo;
and
x+y equals the valence of Mo.

25 more elements

A supported solid catalyst comprising (a) an ionic compound comprising (a)(1) a cation and (a)(2) an anion having up to 100 nonhydrogen atoms and the anion containing at least one substituent comprising a moiety having an active hydrogen, (b) a transition metal compound, (c) an organometal or metalloid compound wherein the metal or metalloid is selected from the Groups 1-14 of the Periodic Table of the Elements, and (d) a support material, wherein,

(i) the support material is a pretreated support material and in the supported catalyst component the anion (a)(2) is not chemically bonded to the support (d), or
(ii) the ionic compound has a solubility in toluene at 22° C. of at least 0.1 weight percent, the support material used is a support material containing tethering groups and in the supported catalyst component the anion (a)(2) is chemically bonded to the support (d);
and,
wherein the solid catalyst is obtained by combining components (a), (b), (c), and (d) in any order, and wherein, during at least one step in the preparation of the solid catalyst, component (a) is dissolved in a diluent in which (a) is soluble, optionally in the presence of one or more of components (b), (c), and (d) or the contact product of (a) with such one or more of (b), (c), and (d), and then is converted into solid form.

1 more element

A method for preparing a dispersion of a supported catalyst component comprising (a) an ionic compound comprising (a)(1) a cation and (a)(2) an anion having up to 100 nonhydrogen atoms and the anion containing at least one substituent comprising a moiety having an active hydrogen, and (d) a support material, where the supported catalyst component is in solid form dispersed in a diluent in which both (a) and (d) are insoluble or sparingly soluble, the method comprising converting a solution of the ionic compound (a) in a diluent in which (a) is soluble in the presence of the support material into a dispersion comprising component (a) in solid form, and wherein,

(i) the support material used is a pretreated support material and, in the supported catalyst component, the anion (a)(2) is not chemically bonded to the support (d), or
(ii) the ionic compound used has a solubility in toluene at 22° C. of at least 0.1 weight percent, the support material used is a support material containing tethering groups and, in the supported catalyst component, the anion (a)(2) is chemically bonded to the support (d).

A method for preparing a solid catalyst comprising combining, in any order, (a) an ionic compound comprising (a)(1) a cation and (a)(2) an anion having up to 100 nonhydrogen atoms and the anion containing at least one substituent comprising a moiety having an active hydrogen, (b) a transition metal compound, (c) an organometal or metalloid compound wherein the metal or metalloid is selected from the Groups 1-14 of the Periodic Table of the Elements, and (d) a support material, wherein during at least one step in the preparation of the solid catalyst, component (a) is dissolved in a diluent in which (a) is soluble to produce a solution of (a), optionally in the presence of one or more of components (b), (c), and (d) or the contact product of (a) with such one or more of (b), (c), and (d), and then is converted into solid form, optionally followed by recovering the solid catalyst in dry particulate form, wherein,

(i) the support material used is a pretreated support material and in the supported catalyst the anion (a)(2) is not chemically bonded to the support (d), or
(ii) the ionic compound used has a solubility in toluene at 22° C. of at least 0.1 weight percent, the support material used is a support material containing tethering groups and in the supported catalyst the anion (a)(2) is chemically bonded to the support (d).

Dependencies are inferred from the claim text.

Facts

Application: 09/297,422Filed 21 Jun 1999 · continuation in part
Priority: 18 Dec 1996
Granted: 7 Aug 2001
Term ends: Not estimatedThe source records don’t support an estimate.

Classification12 codes

C08F 10/00
Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double
C07F 17/00
Metallocenes
C08F 4/61912
Component covered by group C08F4/60 containing a transition metal-carbon bond: in combination with an organoaluminium compound
C08F 4/6192
Component covered by group C08F4/60 containing a transition metal-carbon bond: containing at least one cyclopentadienyl ring, condensed or not,…