Catalyst system and its use in a polymerization process

Details Catalyst system and its use in a polymerization process Catalyst system and its use in a polymerization process

2001-06-18

2003-12-09

Wu, David W. (Department: 1713)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S103000, C502S104000, C502S117000, C502S118000, C526S133000, C526S134000, C526S159000, C526S160000

Reexamination Certificate

active

06660679

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to polymerization catalyst activator complexes, to methods of making these activator complexes, to polymerization catalyst systems containing these activator complexes, and to polymerization processes utilizing same. In one aspect, the present application relates to activator complexes prepared via the reaction of a carbenium salt and a Lewis base, preferably a nitrogen containing Lewis base, having an aromatic group. In another aspect, the present application relates to zwitterionic activator complexes prepared via the reaction of a Group 13 element containing salt including a Lewis base, preferably a nitrogen containing Lewis base, having an aromatic group, and a tritylhalide compound. In another aspect, the invention relates to catalyst systems containing these activator complexes, and to polymerization processes utilizing same.
BACKGROUND OF THE INVENTION
Polymerization catalyst compounds are typically combined with an activator (or co-catalyst) to yield compositions having a vacant coordination site that will coordinate, insert, and polymerize olefins. Typically, methyalumoxane (MAO) is utilized to activate metallocene catalysts. Alternative cocatalysts for metallocenes and other single-site polymerization catalysts have been discovered in recent years. European Patent Application 0 277 004 to Turner describes the reaction of tri(n-butylammonium) tetrakisperfluorophenylborate with methylated metallocenes yielding the activated metallocene salt [Cp
2
ZrMe][B(C
6
F
5
)
4
], methane and tributylamine.
It has been further shown that the choice of amine may affect polymer yields and the quality of the polymer produced. Alternative cations as part of these discrete activators have been explored. For example, the use of triphenylcarbenium tetrakisperfluorophenylaluminate to activate metallocenes in the presence of propylene was disclosed in U.S. Pat. No. 5,763,549. The use of the triphenylcarbenium cation results in an activated catalyst which avoids the presence of an amine. However, in some instances it is desirable to utilize ammonium cations as co-catalyst for practical industrial purposes such as improved solubility as well as in modifications of the polymer properties which weak bases may influence during a polymerization reaction.
U.S. Pat. No. 6,147,173 discloses that anions containing a nitrogen atom in the ring of the perfluorophenyborate activator results in polymers with enhanced molecular weights when compared with the perfluorophenyl borate anion.
WO 99/06449 discloses a zwitterionic catalyst activator including a protonated derivative of a Group 15 element having two hydrocarbyl substituents or having a positively charged derivative of a Group 14 element having three hydrocarbyl substituents.
SUMMARY OF THE INVENTION
It has been discovered that new polymerization catalyst activator complexes may be prepared via the reaction of 1) a carbenium salt and 2) a Lewis base containing an aromatic group. It has also been discovered that new zwitterionic activator complexes may be prepared via the reaction of 1) a Group 13 element containing salt including a Lewis base having an aromatic group, preferably a borate and aluminate salt including a Lewis base having an aromatic group, and 2) a tritylhalide compound.
DETAILED DESCRIPTION
The polymerization catalyst activators of the invention are complexes prepared by combining a Lewis base containing an aromatic group with a carbenium salt and complexes prepared by combining a Group 13 Element containing salt including a Lewis base containing an aromatic group and a trityl halide compound. The resulting complexes have been found to activate polymerization catalyst compounds.
For the purposes of this patent specification, the term “catalyst” refers to a metal compound that when combined with an activator polymerizes olefins, the term “catalyst system” refers to the combination of a catalyst and an activator, and the “activator” is used interchangeably with the term “co-catalyst.”
Activator Compositions
In one embodiment, the activator complex of the invention is represented by the formula [LQ—H
+
][MX
4
]
−
, which, in one embodiment, is prepared by combining a Lewis base containing an aromatic group and a carbenium salt as shown in Reaction I:
Q+L
+
[MX
4
]
−
→[LQ—H
+
][MX
4
]
−
  Reaction (I)
In Reaction I, Q is an aryl substituted neutral Lewis base, preferably an aryl substituted nitrogen, phosphorous, or sulfur containing Lewis base.
L
+
is a positively charged derivative of an element, selected from Group 14 of the Periodic Table of the Elements substituted with three hydrocarbyl substituents, with each substituent having from 1 to 50 carbon atoms. Preferably, L
+
is a stable carbenium ion containing up to 30 non-hydrogen atoms. In another embodiement L
+
is a stable silylium ion containing up to 30 non-hydrogen atoms. Suitable examples of L
+
include tropylium, triphenylmethylium, benzene(diazonium), triethylsilylium, trimethylsilylium and substituted adducts thereof. Preferably, L
+
is triphenyl carbenium.
M is an element selected from Group 13 of the Periodic Table of the Elements. Preferably M is boron or aluminum.
Each X is independently a hydride, a bridged or unbridged dialkylamido, a halide, an alkoxide, an aryloxide, a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or a halosubstituted-hydrocarbyl radical. Each X having up to 20 carbon atoms with the proviso that in not more than one occurrence is X a halide. Preferably, each X is independently an aromatic or substituted aromatic hydrocarbon radical. Non-limiting examples of aromatic radicals include phenyl, napthyl and anthracenyl radicals. Suitable substituents on the substituted aromatic hydrocarbon radical include hydrocarbon, organometalloid, alkoxy, alkylamido, and halide radicals. Preferably, each X is a partially or fully fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each X is a partially or fully fluorinated aryl group, napthyl group or biphenyl group, and most preferably a fluorinated phenyl group.
In one embodiment [MX
4
]
−
is tetra(phenyl)borate, tetra(tolyl)borate, tetra(pentafluorophenyl)borate, tetra(dimethylphenyl)borate, tetra(pentafluorophenyl)-aluminate, tetrafluoroaluminate and the like.
In another embodiment, the activator complex of the invention is represented by the formula [(R″
3
CC
6
H
n−1
R′
x
)ZR
y
H
+
][MX
4
]
−
, which, in one embodiment, is the product of a Lewis base containing an aromatic group and a carbenium salt as shown in Reaction II:
R
y
Z(C
6
H
n
R′
x
)+R″
3
C
+
[MX
4
]
−
→[(R″
3
CC
6
H
n−1
R′
x
)ZR
y
H
+
][MX
4
]
−
  Reaction (II)
In Reaction II, Z is an element from Group 15 or 16 of the Periodic Table of the Elements. Preferably, Z is a Group 15 element or sulfur, more preferably Z is nitrogen, phosphorous or sulfur and most preferably Z is nitrogen.
Each R is independently hydrogen, a hydrocarbyl group, a hydroxyl group, an aryl group, or an alkyl group. Preferably each R is independently an alkyl group containing 1 to 50 carbon atoms, 1 to 20 carbon atoms or 1 to 6 carbon atoms.
Each R′ is independently hydrogen, a hydrocarbyl group, a halogen, a heteroatom, or a heteroatom containing group.
Each R″ is independently a hydrocarbyl group, or a substituted hydrocarbyl group. Preferably, each R″ is an aryl substituted alkyl group, which may be substituted or unsubstituted. For example, R″ may be a hydrocarbyl group substituted with halogens, hydrocarbyl groups, heteroatoms or heteroatom containing groups. More preferably, each R″ is a phenyl group.
In one embodiment R
y
Z(C
6
H
n
R′
x
) is a N,N-dialkylaniline compound, such as for example N,N-dimethylaniline, N,N-

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