Catalyst composition and method of polymerization

Details Catalyst composition and method of polymerization Catalyst composition and method of polymerization

2000-12-04

2003-07-15

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...

C526S126000, C526S130000, C526S131000, C526S134000, C526S147000, C526S161000, C526S348300, C526S348400, C526S348500, C526S348600, C526S351000, C526S352000, C526S308000

Reexamination Certificate

active

06593438

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a catalyst system comprising a catalyst compound and an activator used in an olefin polymerization process, preferably in the gas or slurry phase to produce polyolefins. The catalyst system preferably includes an activator, and a catalyst compound comprising a transition metal complexed with a facially coordinating tridentate bisamide ligand.
BACKGROUND OF THE INVENTION
Advances in polymerization and catalysis have resulted in the capability to produce many new polymers having improved physical and chemical properties useful in a wide variety of superior products and applications. With the development of new catalysts the choice of polymerization (solution, slurry, high pressure or gas phase) for producing a particular polymer has been greatly expanded. Also, advances in polymerization technology have provided more efficient, highly productive and economically enhanced processes. Especially illustrative of these advances is the development of technology utilizing bulky ligand metallocene catalyst systems. In a slurry or gas phase process typically a supported catalyst system is used, however, more recently unsupported catalyst systems are being used in these processes. For example, U.S. Pat. Nos. 5,317,036 and 5,693,727 and European publication EP-A-0 593 083 and PCT publication WO 97/46599 all describe various processes and techniques for introducing liquid catalysts to a reactor. There is a desire in the industry using this technology to reduce the complexity of the process, to improve the process operability, to increase product characteristics and to vary catalyst choices. Thus, it would be advantageous to have a process that is capable of improving one or more of these industry needs.
EP 0 893 454 A1 discloses bisamide based catalyst compounds that can be used for ethylene polymerization. WO 98/45039 discloses polymerization catalysts containing electron withdrawing amide ligands combined with group 3-10 or lanthanide metal compounds used with co-catalysts to polymerize olefins.
SUMMARY OF THE INVENTION
This invention relates to a catalyst system and polymerization processes using that catalyst system.
In one aspect, the invention relates to a catalyst system comprising one or more activators and at least one catalyst compound. The catalyst compound preferably comprises a group 3, 4, 5 lanthanide, or actinide metal atom bound to at least one anionic leaving group and also bound to at least three 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, or phosphorus, 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.
In a preferred embodiment, the catalyst compound is represented by the formula:
wherein
M is a group 3, 4 or 5 transition metal or a lanthanide or actinide group metal,
each X is independently an anionic leaving group,
n is the oxidation state of M,
a is 0 or 1,
m is the formal charge of the YZL ligand,
Y is a group 15 element,
Z is a group 15 element,
J is a C
1
to C
20
hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, or phosphorus,
L is a group comprising 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, or phosphorus,
R
1
and R
2
may also be interconnected to each other,
R
3
is hydrogen, a hydrocarbyl group or 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 bound to each other through other groups.
The activator is preferably an alumoxane, a modified alumoxane, a non-coordinating anion, a borane, a borate, a combination thereof or a conventional-type cocatalyst as described below. It appears preferably however, to use the alumoxanes and boranes together as the inventors have observed that alumoxanes alone and boranes alone do not appear activate the catalysts compounds nearly as well.
BRIEF DESCRIPTION OF THE DRAWINGS
DETAILED DESCRIPTION OF THE INVENTION
In a preferred embodiment, one or more activators are combined with a catalyst compound represented by the formula:
M is a group 3, 4, or 5 transition metal or a lanthanide or actinide group metal, preferably a group 4, 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;
J is a C
1
to C
20
hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, preferably a C
1
to C
6
hydrocarbon group, preferably a C
1
to C
20
alkyl, aryl or aralkyl group, preferably a linear, branched or cyclic C
1
to C
20
alkyl or group, wherein the alkyl aryl or aralkyl group may be substituted or un-substituted and may contain heteroatoms, and J may form a ring structure with L;
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, or phosphorus, preferably a C
1
to C
6
hydrocarbon group, preferably a C
1
to C
20
alkyl, aryl or aralkyl group, preferably a linear, branched or cyclic C
1
to C
20
alkyl group,
R
1
and R
2
may also be interconnected to each other,
R
3
is a hydrocarbon group, hydrogen, a halogen, a heteroatom containing group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms;
a is 1;
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, R
4
and R
5
are independently a group represented by the following formula:
wherein
R
8
to R
12
are each independently hydrogen, a C
1
to C
40
alkyl group, a heteroatom, a heteroatom containing group containing up to 40 carbon atoms, preferably a C
1
to C
20
linear or branched alkyl group, preferably a methyl, ethyl, propyl or butyl group, any two R groups may form a cyclic group and/or a heterocyclic group. The cyclic groups may be aromatic. In a preferred embodiment, R
9
and R
10
are independently a methyl, ethyl, propyl or butyl group, in a preferred embodiment, R
9
and R
10
are methyl groups, and R
8
, R
11
and R
12
are hydrogen. In this embodiment, M is preferably zirconium or hafnium, most preferably zirconium; each of L, Y, and Z is nitrogen; each of R
1
and R
2
is —CH
2
—; R
3
is methyl; and R
6
and R

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