Catalyst system with aluminum fluoride activator

Details Catalyst system with aluminum fluoride activator Catalyst system with aluminum fluoride activator

2000-10-11

2002-12-31

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...

C502S104000, C502S117000, C502S103000, C502S132000, C502S155000, C526S134000, C526S160000, C526S161000, C526S169000, C526S170000, C526S172000, C526S943000

Reexamination Certificate

active

06500907

ABSTRACT:

The present invention relates to a catalyst system suitable for polymerizing unsaturated monomers and comprising active constituents obtainable by reacting
A) a transition metal compound with
B) aluminum trifluoride,
C) a cation-forming compound and, if desired,
D) further components.
The present invention also relates to the use of aluminum trifluoride as activator in a catalyst system, to a process for preparing a catalyst system, to a process for preparing polymers based on monomers having C—C double bond and/or C—C triple bond, and to the use of a catalyst system for forming carbon-carbon covalent bonds or carbon-heteroatom covalent bonds.
It is known that the following reactions, for example, can be performed in preparing metal compounds that are active in polymerization, such as metallocenium ion catalysts:
a) metallocenedialkyl+strong cation-forming compound (Lewis acid), X. Yang, C. L. Stern. T. F. Marks, J. Am. Chem. Soc. 1991, 113, 3623-5
b) metallocenedialkyl+Brönsted acid with non-nucleophilic anion, EP 0 591 756 (Idemitsu Kosan)
c) metallocene compound+aluminoxane EP 0 035 242 (BASF AG)
Reactions a) and b) have the common feature that they are severely restricted in terms of the choice of activator; that is, of the strong cation-forming compound and of the Brönsted acid with non-nucleophilic anion. Only very specific, preferably perfluoroaromatic, boron compounds lead to a usable activator. Reaction c) requires large amounts of expensive aluminoxane, which is a disruptive factor in the resulting polymer.
There is therefore a desire to prepare active catalysts based on inexpensive, readily available and widely applicable activators. R. Taube in DD 265 150 A1 describes the polymerization of 1,3-butadiene in the presence of a mixture of nickel cyclodecatriene or nickel acetylacetonate with aluminum triethyl and aluminum trifluoride. The polymerization of other monomers, especially alkenes or styrene and its derivatives, and other catalysts, comprising aluminum trifluoride plus a cation-forming compound, are not mentioned.
It is an object of the present invention to provide a catalyst system which is not severely restricted in terms of the choice of activator. This means that even customary cation-forming compounds commonly employed in preparative organic chemistry, such as hexafluoroantimonic acid HSbF
6
, antimony pentafluoride SbF
5
, and trifluoromethanesulfonic acid CF
3
SO
3
H, could be used to generate transition metal catalysts. In addition, the catalyst system ought to be able to function per se as a supported catalyst or to be convertible to such a catalyst.
We have found that this object is achieved by the catalyst system defined at the outset, by the use of aluminum trifluoride in the catalyst system defined at the outset, by a process for preparing the catalyst system defined at the outset, by a process for preparing polymers using the catalyst system defined at the outset, and by the use of the catalyst system defined at the outset for forming carbon-carbon covalent bonds or carbon-heteroatom covalent bonds.
Suitable transition metal compounds A) are in principle all those which react with components B), C) and, if used, D) chemically to form an active catalyst.
Examples of highly suitable transition metal compounds A) are transition metal complexes with a ligand of the formulae F-I to F-IV
where the transition metal is selected from the elements Ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mo, W, Fe, CO, Ni, Pd and Pt or from an element of the rare earth metals. Preference is given here to compounds of nickel and palladium as the central metal.
E is an element from group 15 of the Periodic Table of the Elements (5th main group), preferably N or P and, with particular preference, N. The two atoms E in a molecule can be the same or different.
The radicals R
1A
to R
18A
, which can be the same or different, are as follows:
R
1A
and R
4A
are independently of one another hydrocarbon radicals or substituted hydrocarbon radicals, preferably those where the carbon adjacent to the element E is attached to at least two carbon atoms.
R
2A
and R
3A
are independently of one another hydrogen, hydrocarbon or substituted hydrocarbon radicals or else together form a ring system which may also include one or more heteroatoms.
R
6A
is hydrocarbon or substituted hydrocarbon radicals,
R
5A
is hydrogen, hydrocarbon or substituted hydrocarbon radicals,
R
6A
and R
5A
may also together form a ring system.
R
8A
is hydrocarbon or substituted hydrocarbon radicals,
R
9A
is hydrogen, hydrocarbon or substituted hydrocarbon radicals,
R
8A
and R
9A
may also together form a ring system.
R
7A
each independently of the others is hydrogen, hydrocarbon or substituted hydrocarbon radicals, it also being possible for two radicals R
7A
to form a ring system. n is an integer between 1 and 4, preferably 2 or 3.
R
10A
and R
14A
independently of one another are hydrogen, hydrocarbon or substituted hydrocarbon radicals.
R
11A
, R
12A
and R
13A
independently of one another are hydrogen, hydrocarbon or substituted hydrocarbon radicals, where two or more radicals R
11A
, R
12A
and R
13A
may also together form a ring system.
R
15A
and R
18A
independently of one another are hydrogen, hydrocarbon or substituted hydrocarbon radicals.
R
16A
and R
17A
independently of one another are hydrogen, hydrocarbon or substituted hydrocarbon radicals.
Examples of particularly suitable compounds F-I to F-IV are:
Di(2,6-di-i-propylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride Di(di-i-propylphenyl)-2,3-dimethyldiazabutadienenickel dichloride Di(2,6-di-i-propylphenyl)-dimethyldiazabutadienepalladium dimethyl Di(2,6-di-i-propylphenyl)-2,3-dimethyldiazabutadienenickel dimethyl Di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride Di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienenickel dichloride Di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienepalladium dimethyl Di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienenickel dimethyl Di(2-methylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride Di(2-methylphenyl)-2,3-dimethyldiazabutadienenickel dichloride Di(2-methylphenyl)-2,3-dimethyldiazabutadienepalladium dimethyl Di(2-methylphenyl)-2,3-dimethyldiazabutadienenickel dimethyl Diphenyl-2,3-dimethyl-diazabutadienepalladium dichloride Diphenyl-2,3-dimethyl-diazabutadienenickel dichloride Diphenyl-2,3-dimethyl-diazabutadienepalladium dimethyl Diphenyl-2,3-dimethyl-diazabutadienenickel dimethyl Di(2,6-dimethylphenyl)-azanaphthenepalladium dichloride Di(2,6-dimethylphenyl)-azanaphthenenickel dichloride Di(2,6-dimethylphenyl)-azanaphthenepalladium dimethyl Di(2,6-dimethylphenyl)-azanaphthenenickel dimethyl 1,1′-Dipyridylpalladium dichloride 1,1′-Dipyridylnickel dichloride 1,1′-Dipyridylpalladium dimethyl 1,1′-Dipyridylnickel dimethyl
Further particularly suitable transition metal compounds A) are those having at least one cyclopentadienyl-type ligand, which are commonly known as metallocene complexes (two or more cyclopentadienyl-type ligands) or half-sandwich complexes (one cyclopentadienyl-type ligand).
Particularly suitable metallocene complexes are those of the formula
where
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum or an element from subgroup III of the Periodic Table or from the lanthanoids,
X is fluorine, chlorine, bromine, iodine, hydrogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl, alkylaryl having 1 to 10 carbons in the alkyl radical and 6 to 20 carbons in the aryl radical, —OR
6
or —NR
6
R
7
,
n is an integer between 1 and 3, n corresponding to the valence of M minus 2,
and where
R
6
and R
7
are C
1
-C
10
-alkyl, C
6
-C
15
-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl having in each case 1 to 10 carbons in the alkyl radical and 6 to 20 carbons in the aryl radical,
R
1
to R
5
are hydrogen, C
1
-C
10
-alkyl, 5-7 membered cycloalkyl which can in turn carry a C
1
-C
10
-alkyl as substituent, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals may if desired together be saturated or unsaturated cyclic groups havin

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