Activator compositions, their preparation, and their use in catalysis
This invention provides activator precursor compositions and activator compositions. The activator precursor compositions are formed from a support material, an organoaluminum compound, and polyfunctional compounds having at least two aromatic groups in which at least two of said aromatic groups each has at least one polar moiety thereon. The activator compositions are formed from a support material, an organoaluminum compound, an aluminoxane, and a polyfunctional compound having at least two aromatic groups in which at least two of said aromatic groups each has at least one polar moiety thereon. Also provided are catalyst compositions, processes for forming catalyst compositions, and polymerization processes utilizing the catalyst compositions of this invention.
1. An activator precursor composition which comprises
i) a support material in contact with an organoaluminum compound, and
ii) a polyfunctional compound which has at least two aromatic groups in which at least two of said aromatic groups each has at least one polar monoprotic group thereon.
2. An activator composition which comprises an aluminoxane and a composition of claim 1 .
3. A composition as in claim 2 which has one or more of the following features:
the support material is silica, alumina, or silica-alumina;
the organoaluminum compound is trimethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, or tri(isobutyl)aluminum;
the polar monoprotic groups of the polyfunctional compound are hydroxy groups, thiol groups, or secondary amino groups.
4. A composition as in any claim 2 which has one or more of the following features:
the organoaluminum compound is trimethylaluminum;
the support material is silica;
the polar monoprotic groups of the polyfunctional compound are hydroxy groups.
5. A composition as in claim 4 wherein the polyfunctional compound is 4,4′-ethylenediphenol, 4,4′-methylenebis(2,6-di(tert-butyl)-phenol), or 1,3,5-trimethyl-2,4,6-tris(3,5-di(tert-butyl)-4-hydroxybenzyl)benzene.
6. A composition as in claim 2 wherein the organoaluminum compound has the formula
Z 3-f AlR f ,
where Al is aluminum;
R is a hydrogen atom or group bound to aluminum via a carbon atom;
Z is an atom other than hydrogen or a group that is bound to aluminum via an atom other than carbon; and
f is a number from 2 to 3.
7. A composition as in claim 2 wherein the polyfunctional compound is represented by the formula
E(ArJH) g
where E is an organic moiety, an atom, or a bond;
Ar is an aromatic moiety;
J is a polar atom or a polar group;
H is a hydrogen atom; and
g is an integer equal to or greater than 2.
8. A composition as in claim 2 wherein the aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or iso-butylaluminoxane.
9. A composition as in claim 8 wherein the aluminoxane is methylaluminoxane and/or wherein the polyfunctional compound is 4,4′-ethylenediphenol, 4,4′-methylenebis(2,6-di(tert-butyl)-phenol), or 1,3,5-trimethyl-2,4,6-tris(3,5-di(tert-butyl)-4-hydroxybenzyl)benzene.
10. A process for forming an activator precursor composition, which process comprises bringing together, in an inert, anhydrous environment,
i) a support material in contact with an organoaluminum compound, and
ii) a polyfunctional compound which has at least two aromatic groups in which at least two of said aromatic groups each has at least one polar monoprotic group thereon,
such that an activator precursor composition is formed.
11. A process for forming an activator composition, which process comprises, in an inert, anhydrous environment,
i) forming an organoaluminum-treated support by contacting a support material and an organoaluminum compound,
ii) contacting said organoaluminum-treated support either
a) with a polyfunctional compound which has at least two aromatic groups in which at least two of said aromatic groups each has at least one polar monoprotic group thereon, forming a mixture, and then contacting said mixture with an aluminoxane, or
b) with an aluminoxane, forming a mixture, and then contacting said mixture with a polyfunctional compound which has at least two aromatic groups in which at least two of said aromatic groups each has at least one polar monoprotic group thereon, or
c) with a portion of a polyfunctional compound, forming a first mixture, contacting said first mixture with the aluminoxane, forming a second mixture, and contacting said second mixture with more polyfunctional compound,
wherein said polyfunctional compound has at least two aromatic groups in which at least two of said aromatic groups each has at least one polar monoprotic group thereon,
such that an activator composition is formed.
12. A process as in claim 11 wherein said organoaluminum-treated support is contacted with the polyfunctional compound and the aluminoxane sequentially.
13. A process as in claim 10 wherein R of the organoaluminum compound is in a molar ratio of about 1:1 or more relative to the polar monoprotic groups of the polyfunctional compound.
14. A process as in claim 11 wherein the aluminoxane is methylaluminoxane and/or wherein the polyfunctional compound is 4,4′-ethylenediphenol, 4,4′-methylenebis(2,6-di(tert-butyl)-phenol), or 1,3,5-trimethyl-2,4,6-tris(3,5-di(tert-butyl)-4-hydroxybenzyl)benzene.
15. A process as in claim 11 wherein
the support material and the organoaluminum compound are brought together to form a first mixture;
the polyfunctional compound is combined with the first mixture to form a second mixture; and
the aluminoxane is combined with the second mixture.
16. A catalyst composition formed from interaction between an activator composition of claim 2 and at least one catalyst compound or complex of a transition metal, lanthanide metal, or actinide metal.
17. A catalyst composition as in claim 16 wherein said catalyst compound or complex is a metallocene.
18. A process for olefin polymerization, which process comprises polymerizing at least one polymerizable olefinic monomer in the presence of a catalyst composition of claim 16 , to form a polyolefin polymer.