Method of polymerization and polymer produced therefrom

Details Method of polymerization and polymer produced therefrom Method of polymerization and polymer produced therefrom

2002-05-16

2004-02-24

Harlan, Robert (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S161000, C526S348600, C502S152000

Reexamination Certificate

active

06696537

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to olefin polymerization catalysts containing a metal atom bound to at least two group 15 atoms fed in solution or slurry into a gas phase or slurry phase reactor to produce polyolefins and the polyolefins produced therefrom.
BACKGROUND OF THE INVENTION
Metallocene polymerization catalysts (i.e. transition metals, typically groups 4, 5 or 6, having at least one pi bonded ligand, preferably a cyclopentadienyl, indenyl or fluorenyl group) have recently been used to produce resins having a desirable product properties.
Furthermore, there is always a need in the art for a method to introduce catalysts into a gas or slurry phase reactor in such a way as to reduce fouling and/or increase activity. Catalysts used in the gas phase are typically supported because in the past liquid catalysts severely fouled the reactor. Some supported catalysts however have the disadvantages of reduced activity. Thus there is a need in the art of gas or slurry phase processes to find efficient, cost effective reduced fouling means to feed catalysts into a gas or slurry phase reactor. For more information on the disadvantages of using liquid catalysts in a gas phase reactor see the background sections of U.S. Pat. No. 5,317,036 and U.S. Pat. No. 5,693,727 which relates to introducing unsupported catalysts into a gas phase reactor.
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
F
5
)
4
] is disclosed in examples 9 and 10.
Mitsui Chemicals, Inc. in EP 0 893 454 A1 discloses transition metal amides combined with activators to polymerize olefins in the solution phase. 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.
U.S. Ser. No. 09/312,878, filed May 17, 1999 discloses novel supported catalysts used in the gas or slurry phase to polymerize olefins.
SUMMARY OF THE INVENTION
This invention relates to a catalyst system comprising a liquid carrier, 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 liquid carrier and a transition metal compound as described below.
The activator is preferably an aluminum alkyl, an alumoxane, a modified alumoxane, a non-coordinating anion, a borane, a borate or a combination thereof.
The carrier is preferably an alkane.
DETAILED DESCRIPTION OF THE INVENTION
In a preferred embodiment the activator is combined with a compound represented by the formulae:
wherein
M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, preferably a Group 4, 5, or 6 metal, and more preferably a Group 4 metal, and most preferably zirconium, titanium or hafnium,
each X is independently a leaving group, preferably, an anionic leaving group, and more preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and most preferably an alkyl.
y is 0 or 1 (when y is 0 group L′ is absent),
n is the oxidation state of M, preferably +3, +4, or +5, and more preferably +4,
m is the formal charge of the YZL or the YZL′ ligand, preferably 0, −1, −2 or −3, and more preferably −2,
L is a Group 15 or 16 element, preferably nitrogen,
L′ is a Group 15 or 16 element or Group 14 containing group, preferably carbon, silicon or germanium,
Y is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen,
Z is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen,
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, or phosphorus, preferably a C
2
to C
20
alkyl, aryl or aralkyl group, more preferably a linear, branched or cyclic C
2
to C
20
alkyl group, most preferably a C
2
to C
6
hydrocarbon group.
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, hydrogen or an alkyl group, and most preferably hydrogen
R
4
and R
5
are independently an alkyl group, an aryl group, 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, more preferably between 3 and 10 carbon atoms, and even more 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, or a heteroatom containing group, for example PR
3
, where R is an alkyl group,
R
1
and R
2
may be interconnected to each other, and/or R
4
and R
5
may be interconnected to each other,
R
6
and R
7
are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably absent, and
R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, a heteroatom containing group.
By “formal charge of the YZL or YZL′ ligand”, it 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” it 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. By “R
4
and R
5
may also be interconnected” it is meant that R
4
and R
5
may be directly bound to each other or may be bound to each other through other groups.
An alkyl group may be a linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof. 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 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 cycli

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