Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
1998-03-03
2001-05-08
Bell, Mark L. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S152000, C502S153000, C502S154000, C502S155000, C502S156000, C502S167000, C526S089000, C526S209000, C526S217000
Reexamination Certificate
active
06228794
ABSTRACT:
BACKGROUND OF THE INVENTION
Ziegler-Natta type catalysts for polymerization of unsaturated hydrocarbons, such as alpha olefins, have long been the state of the art catalysts for such reactions. Typically, Ziegler-Natta type catalysts are composed of transition metal salts and aluminum alkyl compounds, e.g., titanium tetrachloride and triethylaluminum. While these catalysts are very effective and have a long-established record of use, they are not without drawbacks. For example, transition metals are expensive, potentially present some toxicity hazards, and to some are environmentally objectionable. Therefore, efforts towards the development of alternative, suitable olefin polymerization catalysts have occurred. For example, metallocene catalysts have been developed for use in alpha olefin polymerization. The polymerization of ethylene using an aluminum-based catalyst but in the absence of a transition metal is known. For example, the formation of polyethylene by the polymerization of ethylene in the presence of catalysts prepared by the reaction of neutral aluminum compounds, such as Cl
2
AlCH(Me)AlCl
2
or (AlR
3
)
2
, with ethylene at a temperature in the range of 25 to 50° C. has been reported by H. Martin and H. Bretinger,
Makromol. Chem.
1992, 193, 1283. However, the reported catalytic activities are very low (1.6×10
−1
-3.8×10
−4
g PE/ (mol*h*atm)).
The present invention has as its primary objective the development of more highly active catalysts useful for the polymerization of unsaturated hydrocarbons which do not require a transition metal compound as a component of the catalyst.
Another objective of the present invention is to prepare such catalysts in high yields using convenient and practical synthetic methods.
A yet further objective of the present invention is a method for polymerizing unsaturated hydrocarbons using the novel, transition metal-free catalysts provided by this invention.
The method and manner of accomplishing each of the above objectives, as well as others, will become apparent from the detailed description of the invention which follows hereinafter.
SUMMARY OF THE INVENTION
This invention relates to novel catalysts, processes of synthesizing the catalysts and to olefin polymerization processes using the catalysts. The catalysts are cationic complexes comprising a Group 13 element and certain ligands. These compounds behave similarly to Ziegler-Natta catalysts but effectively catalyze the polymerization of olefins in the absence of any transition metal.
DETAILED DESCRIPTION OF THE INVENTION
We have discovered that the compositions defined below are effective catalysts for the polymerization of olefins. Therefore, one embodiment of the present invention is represented by a catalyst composition comprising components (1), (2) and (3) wherein component (1) is a Lewis acid having the formula:
wherein
M is an atom selected from the Group 13 elements, i.e., a boron, aluminum, gallium, indium or thallium atom;
X
1
, X
2
and X
3
are the same or different and each is selected from hydrogen and the elements of Groups 14, 15, 16 and 17;
R
1
, R
2
and R
3
are the same or different and each is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, nitrogen or oxygen-containing heterocyclic, silyl, siloxy groups or metallic groups such as Al(III), Mg(II) and two groups (R
1
, R
2
or R
3
) may be combined to form with X
1
, X
2
, or X
3
a cyclic group; and
j, k and m are the same or different and may be 0, 1, 2 or 3 as required to satisfy the valence of each of atoms X
1
, X
2
and X
3
to which R
1
, R
2
and R
3
, respectively, are bound;
component (2) is a Lewis-base having the formula E(R
4
)
n
wherein E is an atom selected from the Group 15 and 16 elements; R
4
represents up to 3 substituents which may be the same or different and are selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, silyl, alkoxy, aryloxy and amino; n is 1, 2 or 3 as required to satisfy the valence of E to which R
4
is bound; and two groups, R
4
, may be attached so as to form a cyclic structure as found in tetrahydrofuran (E═O, (R
4
)
2
═(CH
2
)
4
) or pyridine (E═N, (R
4
)
2
═(CH)
5
); and
component (3) is an activator selected from (a) a salt of a labile, non-coordinating or weakly coordinating anion that is capable of replacing one of the —X
1
—(R
1
)
j
, —X
2
—(R
2
)
k
or —X
3
—(R
3
)
m
groups of component (1); (b) a neutral Lewis-acid that is capable of abstracting one of the —X
1
—(R
1
)
j
, —X
2
—(R
2
)
k
or —X
3
—(R
3
)
m
groups from component (1); (c) an oxidizing agent capable of reacting with component (1) and converting it to a cationic derivative; and (d) alumoxanes.
The hydrocarbyl group which R
1
, R
2
, R
3
and/or R
4
may represent may be a saturated or unsaturated, unsubstituted or substituted, aliphatic, alicyclic, heterocyclic or aromatic group containing up to about 50 carbon atoms, preferably up to about 12 carbon atoms. Examples of the substituents which may be present on the substituted hydrocarbyl groups include methyl, ethyl, isopropyl, isobutyl, t-butyl, neopentyl, alkoxy, and halogen. Examples of the aromatic groups which R
1
, R
2
, R
3
and/or R
4
may represent include, phenyl, naphthyl, and anthracenyl with substituents selected from methyl, ethyl, isopropyl, t-butyl, silyl, aryl, alkoxy, amino, or a halogen. The alkoxy or amino groups which R
1
, R
2
, R
3
and/or R
4
may represent may contain up to about 50 carbon atoms, preferably up to about 12 carbon atoms.
Examples of the groups represented collectively by —X
1
—(R
1
)
j
, —X
2
—(R
2
)
k
and —X
3
—(R
3
)
m
include methoxy, ethoxy, isopropoxy, t-butoxy, phenoxy, thiophenoxy, N-methylanilino, diisopropylamino, bis(trimethylsilyl)amino, dimethylphosphido, dicyclohexylphophido, diphenylphosphido, pivalate, N,N′-diisopropylacetamidinate, N,N′-dicyclohexylacetamidinate, N,N′-diadamantylacetamidinate, N,N′-bis(2,6-dimethylphenyl)acetamidinate, N,N′-diisopropylpivamidinate, N,N′-dicyclohexylpivamidinate, N,N′-diadamantylpivamidinate, N,N′-bis(2,6-dimethylphenyl)pivamidinate, t-butyl-N-isopropylcarbamate, t-butyl-N-isopropylthiocarbamate, diisopropyldithiocarbamate, N,N-dimethyl-N′,N″-diisopropylguanadinate, N,N-diethyl-N′,N″-diisopropylguanadinate, N,N-diisopropyl-N′,N″-diisopropylguanadinate, N,N-bis(trimethylsilyl)-N′,N″-diisopropylguanadinate, 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate, thiopivalate, dithiopivalate, N,N′-diadamantylthioureate, N,N′-bis(2,6-dimethylphenyl)thioureate, N,N′-bis(2,6-diisopropylphenyl)thioureate, and N,N′-bis(t-butyl)thioureate. The groups represented collectively by —X
1
—(R
1
)
j
, —X
2
—(R
2
)
k
and —X
3
—(R
3
)
m
preferably are selected from N,N′-diisopropylacetamidinate, N,N′-dicyclohexylacetamidinate, N,N′-diadamantylacetamidinate, N,N′-diisopropylpivamidinate, N,N′-dicyclohexylpivamidinate, N,N′-diadamantylpivamidinate, N,N-dimethyl-N′,N″-diisopropylguanadinate, N,N-diethyl-N′,N″-diisopropylguanadinate, N,N′-diadamantylthioureate.
The most preferred groups represented by —X
1
—(R
1
)
j
, —X
2
—(R
2
)
k
and —X3—(R
3
)
m
are N,N′-diisopropylpivamidinate, N,N′-dicyclohexylpivamidinate, N,N′-bis(adamantyl)pivamidinate.
Examples of the Lewis-base compounds represented by E(R
4
)
n
include dimethyl ether, tetrahydrofuran, methyl-t-butylether, dimethylsulfide, trimethylamine, triethylamine, tributylamine, 2,6-lutidine, 2,4,6-collidine, N,N-dimethylaniline, 2,6-diisopropylaniline, trimethylphosphine, triethylphosphine, tricyclohexylphosphine, triphenylphosphine, and triphenylphosphite. The Lewis-base is utilized in the range of 0 to 1000 molar equivalents relative to Component (1) with a minimum being preferred to minimize the competitive inhibition of polymerization. The Lewis-base compound represented by E(R
4
)
n
preferably is selected from methyl-t-butylether, 2,6-lu
Coles Martyn P.
Dagorne Samuel
Ihara Eiji
Jordan Richard F.
Bell Mark L.
Morgan & Lewis & Bockius, LLP
Pasterczyk J.
University of Iowa Research Foundation
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