Method of polymerization

Details Method of polymerization Method of polymerization

1999-05-17

2001-08-07

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S072000, C526S090000, C526S107000, C526S126000, C526S903000, C502S167000, C502S232000, C502S227000

Reexamination Certificate

active

06271325

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to olefin polymerization catalysts containing a metal atom bound to at least two group 15 atoms and their use in gas or slurry phase to produce polyolefins.
BACKGROUND OF THE INVENTION
The intense commercialization of metallocene polyolefin catalysts (metallocene being cyclopentadienyl based transition metal catalyst compounds) has led to widespread interest in the design of non-metallocene, homogeneous catalysts, particularly for use in the economical gas and slurry phase processes. This field is more than an academic curiosity as new, non-metallocene catalysts in gas or slurry phase may provide an easier, more economical pathway to currently available products and may also provide product and process opportunities which are beyond the capability of metallocene catalysts in the gas or slurry phase.
Anionic, multidentate heteroatom ligands have received the most attention in non-metallocene polyolefins catalysis. Notable classes of bidentate anionic ligands which form active polymerization catalysts include N—N
−
and N—O
−
ligand sets. Examples of these types of non-metallocene catalysts include amidopyridines (Kempe, R., “Aminopyridinato Ligands—New Directions and Limitations”, 80
th
Canadian Society for Chemistry Meeting, Windsor, Ontario, Canada, Jun. 1-4, 1997. Kempe, R. et al,
Inorg. Chem.
1996 vol 35 6742.) Likewise, recent reports by Jordan et al. of polyolefin catalysts based on hydroxyquinolines (Bei, X.; Swenson, D. C.; Jordan, R. F.,
Organometallics
1997, 16, 3282) have been interesting even though the catalytic activities of Jordan's hydroxyquinoline catalysts are low.
Schrock et al in U.S. Pat. No. 5,889,128 discloses a process for the living polymerization of olefins in solution using initiators having a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. In particular, the solution phase polymerization of ethylene using {[NON]ZrMe}[MeB(C
6
F
5
)
3
] or {[NON]ZrMe(PhNMe
2
)]}[B(C
6
P
5
)
4
] is disclosed in examples 9 and 10.
EP 893 454 A1 discloses unsupported transition metal amide compounds used in combination with activators to polymerize olefins in the solution phase.
Ethylenebis(salicylideneiminato)zirconium dichloride combined with methyl alumoxane deposited on a support and unsupported versions were used to polymerize ethylene by Repo et al in Macromolecules 1997, 30, 171-175.
Thus there is a need in the art for gas or slurry phase processes to produce polyolefins using new and different supported catalyst systems.
SUMMARY OF THE INVENTION
This invention relates to a catalytic molecule, and a catalyst system comprising a support, an activator, and a metal catalyst compound.
In one aspect, the invention relates to a catalyst system comprising a support, an activator and a metal catalyst compound comprising a group 3 to 14 metal atom bound to at least one anionic leaving group and also bound to at least two group 15 atoms, at least one of which is also bound to a group 15 or 16 atom through another group which may be a C
1
to C
20
hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, phosphorus, or a halogen, wherein the group 15 or 16 atom may also be bound to nothing or a hydrogen, a group 14 atom containing group, a halogen, or a heteroatom containing group, and wherein each of the two group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.
This invention relates to the gas or slurry phase polymerization of olefins using an olefin polymerization catalyst system comprising an activator, a support and a transition metal compound represented by the formula:
wherein
M is a group 3 to 12 transition metal or a group 13 or 14 main group metal, each X is independently an anionic leaving group,
n is the oxidation state of M,
m is the formal charge of the YZL ligand,
Y is a group 15 element,
Z is a group 15 element,
L is a group 15 or 16 element,
R
1
and R
2
are independently a C
1
to C
20
hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, phosphorus, halogen,
R
1
and R
2
may also be interconnected to each other,
R
3
is absent, or is hydrogen, a group 14 atom containing group, a halogen, a heteroatom containing group,
R
4
and R
5
are independently an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, or multiple ring system, and
R
6
and R
7
are independently absent or hydrogen, halogen, heteroatom or a hydrocarbyl group, or a heteroatom containing group.
By “formal charge of the YZL ligand” is meant the charge of the entire ligand absent the metal and the leaving groups X.
By “R
1
and R
2
may also be interconnected to each other” is meant that R
1
and R
2
may be directly bound to each other or may be bound to each other through other groups.
The activator is preferably an aluminum alkyl, an alumoxane, a modified alumoxane, a non-coordinating anion, a borane, a borate or a combination thereof.
In another aspect, the invention relates to a catalytic molecule comprising the transition metal compound represented by the formula set forth above.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a catalytic molecule (metal catalyst), and a catalyst system comprising a support, an activator, and the metal catalyst. The metal catalyst shows surprising ability to be immobilized on a support, activated by an activator, and surprising robustness and catalytic activity when supported and activated. The catalyst molecule itself is described, hereinafter, with reference to its combination with an activator.
In a preferred embodiment the activator is combined with a compound represented by the formula:
wherein
M is a group 3-12 transition metal or a group 13 or 14 main group metal, preferably a group 4, 5, or 6 metal, preferably zirconium or hafnium,
each X is independently an anionic leaving group, preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen,
n is the oxidation state of M, preferably +3, +4, or +5, preferably +4,
m is the formal charge of the YZL ligand, preferably 0, −1, −2 or −3, preferably −2,
L is a group 15 or 16 element, preferably nitrogen,
Y is a group 15 element, preferably nitrogen or phosphorus,
Z is a group 15 element, preferably nitrogen or phosphorus,
R
1
and R
2
are independently a C
1
to C
20
hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, phosphorus, a halogen, preferably a C
2
to C
6
hydrocarbon group, preferably a C
2
to C
20
alkyl, aryl or aralkyl group, preferably a linear, branched or cyclic C
2
to C
20
alkyl group, R
1
and R
2
may also be interconnected to each other,
R
3
is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatom containing group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably R
3
is absent or hydrogen,
R
4
and R
5
are independently an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or multiple ring system, preferably having up to 20 carbon atoms, preferably between 3 and 10 carbon atoms, preferably a C
1
to C
20
hydrocarbon group, a C
1
to C
20
aryl group or a C
1
to C
20
aralkyl group, and
R
6
and R
7
are independently absent, or hydrogen, halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably absent.
An aralkyl group is defined to be a substituted aryl group.
In a preferred embodiment, L is bound to one of Y or Z and one of R
1
or R
2
is bound to L and not to Y or Z.
In an alternate embodiment R
3
and L do not form a heterocyclic ring.
In a preferred embodiment R
4
and R
5
are independently a group represe

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