Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
2000-05-25
2004-04-20
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S117000, C502S152000, C502S155000, C502S156000, C526S161000, C526S172000
Reexamination Certificate
active
06723675
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to a family of novel catalyst compounds and compositions for the polymerization of olefins. The catalyst compounds and compositions of the invention are especially useful for the production of copolymers of ethylene and alpha olefins, copolymers of ethylene and cyclic olefins, or copolymers of ethylene and alpha olefin-dienes.
BACKGROUND OF THE INVENTION
A variety of metallocenes and single site-like catalysts have been developed to prepare olefin polymers. Metallocenes are organometallic coordination complexes containing one or more &pgr;-bonded moieties (i.e., cyclopentadienyl groups) in association with a transition metal atom. Catalyst compositions containing metallocenes and single site-like catalysts are used in the preparation of polyolefins, producing relatively homogeneous copolymers at acceptable polymerization rates while allowing one to tailor closely the final properties of the polymer as desired.
For instance, Döhring et al., “Donor-Ligand-Substituted Cyclopentadienyl-chromium(III) Complexes: A New Class of Alkene Polymerization Catalyst. 1. Amino-substituted Systems”
Organometallics
, 2000, 19, 388-402 discloses complexes which, according to the reference, when treated with MAO, lead to formation of active catalysts for the oligomerization, polymerization and copolymerization of ethylene. One example of such a complex is (cyclo-C
4
H
8
NC
2
H
4
C
5
—Me
4
)CrCl
2
and another is (cyclo-C
4
H
8
NC
2
H
4
C
5
Me
4
)CrMe
2
.
Despite these efforts, a need has remained for catalyst compounds and compositions which enable olefin polymerization reactions to be performed more efficiently, in particular, with enhanced activity. In addition, there has remained a need for catalyst compounds and compositions which enable olefin polymerization reactions to be more closely tailored so as to provide polymer product having desired molecular weight distribution. The catalyst compounds of the present invention, as well as catalyst compositions which contain the catalyst compounds of the present invention, and olefin polymerization reactions which employ the catalyst compounds of the present invention, as described below, satisfy these needs.
SUMMARY OF THE INVENTION
The present invention provides catalyst precursors for use in olefin polymerization reactions. The precursors of the present invention provide high activity for these polymerization reactions, and can be used to produce polyolefins having desired molecular weight distribution, e.g., a narrow molecular weight distribution or a desired range of molecular weight distribution. The present invention also provides catalyst compositions and catalyst systems which comprise the catalyst precursors of the present invention and a co-catalyst, as well as polymerization reactions conducted in the presence of such catalyst precursors, compositions and systems.
The catalyst precursors according to the present invention include those having the formula:
wherein:
R
1
, R
2
, R
3
and R
4
are each independently selected from among hydrogen and C
1
-C
8
hydrocarbyl groups, wherein none, one or two pairs of substituents selected from the group consisting of R
1
, R
2
, R
3
and R
4
are linked to form saturated or unsaturated rings;
M is an atom selected from among the elements of Groups IV, V and VI;
m is 1, 2, 3 or 4;
the or each X is selected from among halide elements, C
1
-C
8
hydrocarbyl groups, C
1
-C
8
alkoxy groups, C
1
-C
8
carboxylate groups and C
1
-C
8
carbamate groups;
n is 1, 2 or 3;
the or each L is an organic compound containing at least one lone pair of electrons;
Q is a divalent radical of the formula YR
5
R
6
, wherein Y is a Group 14 atom, wherein R
5
and R
6
are each independently selected from among hydrogen and C
1
-C
8
hydrocarbyl groups, and wherein R
5
and R
6
are not linked or are linked to form a saturated or unsaturated ring;
E is a Lewis basic group having formula (i) or (ii) below:
—C(R
7
)=Z
1
R
8
, (i)
wherein R
7
and R
8
are each independently selected from among hydrogen and C
1
-C
8
hydrocarbyl groups, and wherein R
7
and R
8
are not linked or are linked to form a saturated or unsaturated ring; and
Z
1
is a nitrogen atom or a phosphorus atom, which bonds to M;
wherein:
Z
2
is an oxygen atom, a sulphur atom or a selenium atom, which bonds to M; and
R
9
, R
10
and R
11
are each independently selected from among hydrogen and C
1
-C
8
hydrocarbyl groups, wherein no pair or one pair of substituents selected from R
9
, R
10
and R
11
are linked to form a saturated or unsaturated ring.
The invention also provides a catalyst composition comprising a catalyst precursor according to the present invention and an activating co-catalyst, as disclosed below.
The invention also provides a catalyst system comprising a catalyst precursor according to the present invention and an activating co-catalyst as described above, in which the catalyst precursor and the activating co-catalyst are introduced to a reaction system at different locations.
The invention further provides a process for producing an olefin polymer, which comprises contacting at least one olefin monomer under polymerization conditions with a catalyst precursor, and/or a catalyst composition as described above.
The invention further provides olefin polymers, such as ethylene polymers, produced by a process as described in the preceding paragraph, and products, e.g., blow-molded articles, high density films, etc., made from such olefin polymers.
DETAILED DESCRIPTION OF THE INVENTION
In this specification, the term “olefinically unsaturated hydrocarbons” is often represented for convenience by “olefins”.
The expression “copolymer” (and other terms incorporating this root), as used herein, refers to polymers containing two or more comonomers, i.e, it encompasses copolymers, terpolymers, etc.
The Group element notation in this specification is as defined in the Periodic Table of Elements according to the IUPAC 1988 notation (IUPAC Nomenclature of Inorganic Chemistry 1960, Blackwell Publ., London). Therein, Group IV, V, XIII, XIV and XV correspond respectively to Groups IVB, VB, IIIA, IVA and VA of the Deming notation (Chemical Rubber Company's Handbook of Chemistry & Physics, 48th edition) and to Groups IVA, VA, IIIB, IVB and VB of the IUPAC 1970 notation (Kirk-Othmer Encyclopedia of Chemical Technology, 2nd edition, Vol. 8,p. 94).
As mentioned above, the catalyst precursor of the present invention has the following formula:
wherein:
R
1
, R
2
, R
3
and R
4
are each independently selected from among hydrogen and C
1
-C
8
hydrocarbyl groups (e.g., preferably methyl), wherein none, one or two pairs of substituents selected from the group consisting of R
1
, R
2
, R
3
and R
4
are linked to form saturated or unsaturated rings (e.g., R
2
and R
3
are preferably linked to provide an indenyl group);
M is an atom selected from among the elements of Groups IV, V and VI, preferably a transition metal in an oxidation state of +3;
m is 1, 2, 3 or 4;
the or each X is selected from among halide elements, C
1
-C
8
hydrocarbyl groups, C
1
-C
8
alkoxy groups, C
1
-C
8
carboxylate groups and C
1
-C
8
carbamate groups;
n is 1, 2 or 3;
the or each L is an organic compound containing at least one lone pair of electrons;
Q is a divalent radical of the formula YR
5
R
6
, wherein Y is a Group 14 atom, wherein R
5
and R
6
are each independently selected from among hydrogen and C
1
-C
8
hydrocarbyl groups, and wherein R
5
and R
6
are not linked or are linked to form a saturated or unsaturated ring;
E is a Lewis basic group having formula (i) or (ii) below:
—C(R
7
)=Z
1
R
8
, (i)
wherein R
7
and R
8
are each independently selected from among hydrogen and C
1
-C
8
hydrocarbyl groups, and wherein R
7
and R
8
are not linked or are linked to form a saturated or unsaturated ring; and
Z
1
is a nitrogen atom or a phosphorus atom, which bonds to M;
wherein:
Z
2
is an oxigen atom, a sulphur atom or a selenium atom, which bonds to M; and
R
Bell Mark L.
McKinney Osborne K.
Pasterczyk J.
Univation Technologies LLC
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