Organic compounds -- part of the class 532-570 series – Organic compounds – Aluminum containing
Reexamination Certificate
1999-04-09
2001-06-19
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Aluminum containing
C556S001000, C556S007000, C556S017000, C556S027000, C556S028000, C556S170000, C556S187000, C502S103000, C502S117000, C526S160000, C526S243000
Reexamination Certificate
active
06248914
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to compositions that are useful as catalyst activators for olefin polymerizations. More particularly the present invention relates to such compositions that are particularly adapted for use in the polymerization of unsaturated compounds having improved activation efficiency and performance. Such compositions are particularly advantageous for use in a polymerization process wherein catalyst, catalyst activator, and at least one polymerizable monomer are combined under polymerization conditions to form a polymeric product.
It is previously known in the art to activate Ziegler-Natta polymerization catalysts, particularly such catalysts comprising Group 3-10 metal complexes containing delocalized &pgr;-bonded ligand groups, by the use of an activator. Generally in the absence of such an activator compound, also referred to as a cocatalyst, little or no polymerization activity is observed.
A class of suitable activators are Lewis acids, especially alumoxanes, which are generally believed to be oligomeric or polymeric alkylaluminoxy compounds, including cyclic oligomers. Examples of alumoxanes (also known as aluminoxanes) include methylalumoxane (MAO) made by hydrolysis of trimethylaluminum as well as modified methylalumoxane (MMAO), wherein a portion of the trimethylaluminum is replaced by a higher alkyl aluminum compound such as triisobutylaluminum. MMAO advantageously is more soluble in aliphatic solvents than is MAO.
Generally alumoxanes contain, on average about 1.5 alkyl groups per aluminum atom, and are prepared by reaction of trialkylaluminum compounds or mixtures of compounds with water (Reddy et al,
Prog. Poly. Sci.,
1995, 20, 309-367). The resulting product is in fact a mixture of various substituted aluminum compounds including especially, trialklyaluminum compounds. The amount of such free trialkylaluminum compound in the mixture generally varies from 1 to 50 percent by weight of the total product.
Although effective in forming an active olefin polymerization catalyst when combined with a variety of Group 3-10 metal complexes, especially Group 4 metal complexes, generally a large excess of alumoxane compared to metal complex, such as, molar ratios from 100:1 to 10,000:1, is required in order to produce adequate rates of polymerization. Unfortunately, the use of such large excesses of cocatalyst is expensive and also results in polymer having an elevated residual aluminum content. This latter factor may adversely affect polymer properties, especially clarity and dielectric constant.
A different type of activator compound is a Bronsted acid salt capable of transferring a proton to form a cationic derivative or other catalytically active derivative of such Group 3-10, metal complex, cationic charge transferring compounds, or cationic oxidizing activators, referred to collectively hereinafter as cationic activators. Preferred cationic activators are ammonium, sullonium, phosphonium, oxonium, ferrocenium, silver, lead, carbonium or silylium compounds containing a cation/anion pair that is capable of rendering the Group 3-10 metal complex catalytically active. Preferred anions associated with this cation comprise fluorinated arylborate anions, more preferably, the tetrakis(pentafluorophenyl)borate anion. Additional suitable anions include sterically shielded, bridged diboron anions. Examples of such cationic activators are disclosed in U.S. Pat. No. 5,198,401, 5,132,380, 5,470,927, 5,153,157, 5,350,723, 5,189,192, 5,626,087 and in 5,447,895.
Further suitable activators for activating metal complexes for olefin polymerization include neutral Lewis acids such as tris(perfluorophenyl)borane and tris(perfluorobiphenyl)borane. The former composition has been previously disclosed for the above stated end use in U.S. Pat. No. 5,721,185, and elsewhere, whereas the latter composition is disclosed in Marks, et al,
J. Am. Chem. Soc.
1996, 118, 12451-12452. Additional teachings of the foregoing activators may be found in Chen, et al,
J. Am. Chem. Soc.
1997,119, 2582-2583, Jia et al,
Organometallics,
1997, 16, 842-857 and Coles et al,
J. Am. Chem. Soc.
1997, 119, 8126-8126.
In U.S. Pat. No. 5,453,410, a strong Lewis acid activator, especially tris-(pentafluorophenyl)borane, was disclosed for use in combination with constrained geometry metal complexes in combination with an alumoxane. This combination beneficially resulted in effective catalyst activation at molar ratios of alumoxane to catalyst that are much lower than required in the absence of the Lewis acid. Suitably, molar ratios from 1:1 to 50:1 could be employed. In U.S. Pat. No. 5,527,929, 5,616,664, 5,470,993, 5,556,928, 5,624,878, the combination of an alumoxane and a strong Lewis acid such as tris-(pentafluorophenyl)boron was disclosed as a suitable activator for use with the metal complexes therein disclosed wherein the metal was in the +2 formal oxidation state. It is known that an exchange reaction between aluminum trialkyl compounds and tris(perfluorophenyl)borane occurs under certain conditions. This phenomenon has been previously described in U.S. Pat. No. 5,602,269.
In U.S. Pat. No. 5,777,120, certain four-coordinate dialkylaluminum amidinate complexes activated with tris(perfluorophenyl)borane were disclosed. The intermediate thought to be formed by the activation was an alumicinium cation derived by Lewis acid abstraction of a methyl group by the borane and stabilized by a Lewis base such as an amine.
It would be desirable to provide activator compositions based on Lewis acids for activation of metal complexes, especially complexes of metals of Group 4 of the Periodic Table of the elements having improved ease of use, cocatalyst properties and efficiency.
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J. Am. Chem. Soc., Marks et al., 1996, 118, 12451-12452.
J. Am. Chem. Soc., Chen et al., 1997, 119, 2582-2583.
Organometallics, Jia et al., 1997, 16, 842-857.
J. Am. Chem. Soc., Coles et al., 1997, 119, 8125-8126.
Schmidbaur et al., Isosteric Organometal Compounds. XII. Small Inorganic Rings. 1. Cycli Alumimosilazane Cation and its Gallium and Indium Ana-logs, Chem. Ber. vol. 102, No. 2, pp. 556-563, 1969 (no translation available).
Bruce et al., Cationic Alkyl Aluminum Ethylene Polymerization Catalysts Based on Monoanionic N, N, N-Pyridyliminoamide Ligands, Chem. Commun. No. 22, pp. 2523-2524, Nov. 10, 1998.
Radzewich et al., Reversible Ethylene Cycloaddition Reactions of Cationic Aluminum.Beta. —Diketiminate Complexes, J. Am. Chem. Soc., vol. 120, No. 36, pp. 9384-9385, Sep. 16, 1998.
Ihara et al., Cationic Aluminum Alkyl Complesex Incorporating Aminotroponimate Ligand, J. Am. Chem. Soc., vol. 120, No. 32, pp. 8277-8278, Aug. 19, 1998.
Jordan et al., Cationic Aluminum Alkyl Complexes. Transition-Metal-Free Olefin Polymerization Catalysts, Polym. Mater. Sci. Eng., vol. 80, pp. 418-419, Mar. 21, 1999.
Nazario-Gonzalez Porfirio
The Dow Chemical Company
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