Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2000-09-22
2003-05-27
Shaver, Paul F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S088000, C556S402000, C556S431000, C556S435000
Reexamination Certificate
active
06570031
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to novel dendrimeric compounds, to a method for the production thereof and to the use thereof as catalysts for the production of polymers, in particular to the use thereof as co-catalysts for metallocenes for polymerizing unsaturated compounds.
BACKGROUND OF THE INVENTION
It has long been known to use metallocenes in combination with activating co-catalysts, preferably alumoxanes (MAOs), for polymerising olefins and diolefins (c.f. for example EP-A 129 368, 347 128, 347 129, 351 392, 485 821, 485 823).
However, catalyst systems based on metallocenes and alumoxanes have considerable disadvantages. Thus alumoxanes, in particular MAOs, cannot be produced with a high degree of reproducibility either in situ or in a pre-forming process. MAO is a mixture of various species containing aluminum which exist in equilibrium with each other, resulting in a loss of reproducibility during the polymerization of olefinic compounds. Moreover, MAO is not stable in storage and the composition thereof changes on exposure to extreme temperatures. Another serious disadvantage is the considerable excess of MAO which is necessary for the activation of metallocenes. However, this high MAO/metallocene ratio is an absolute prerequisite for achieving high catalyst activities. This results in a crucial processing disadvantage, however, since aluminum compounds must be separated from the polymers during work-up. Furthermore, MAO is a cost-determining factor in the use of catalyst systems containing MAO, meaning that excesses of MAO are uneconomic.
In
J. Am. Chem. Soc
. 1991, 113, 3623, tris(pentafluorophenyl)borane is described as a co-catalyst for metallocene dialkyls. However, the polymerisation activity of catalysts based on tris(pentafluorophenyl)borane is unsatisfactory. EP-A 277 003 and 277 004 describe ionic catalyst systems which are produced by the reaction of metallocenes with ionizing reagents. Perfluorinated, tetraaromatic borate compounds, in particular tetrakis(pentafluorophenyl)borate compounds, are used as ionizing reagents (EP 468 537, EP 561 479). However, the production and introduction of pentafluorophenyl substituents is complex and costly. Using tetrakis(pentafluorophenyl)borate compounds on an industrial scale is thus highly cost-intensive. Another disadvantage of tetrakis(pentafluorophenyl)borate compounds is the poor solubility thereof in hydrocarbons.
WO 93/11172 describes polyanionic activators for metallocenes which consist, for example, of a polystyrene matrix onto which what are termed non-coordinating anions, preferably borate compounds comprising pentafluorophenyl substituents, are chemically bonded. The catalytic activity of the borate compounds described above decreases considerably, however, if the fluoroaromatic substituents on the boron are replaced by other substituents, for example by methyl or butyl substituents.
In comparison with the activators described in EP 468 537, for example N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, the polyanionic activators (God described in WO 93/11172 exhibit lower polymerization activity. Another disadvantage is the poor yield during the production of the polyanionic activators. Costly tris(pentafluorophenyl)borane is used as a starting compound which must be chemically bonded by a complicated method onto a matrix, for example crosslinked polystyrene. The polyanionic activators do not have a uniform surface, wherein accessibility of the molecular surface or the active end groups may be restricted. The precise composition, in particular the number of active end groups of the polyanionic activators is not known. The polyanionic activators have neither a defined molecular size nor dimensional stability. The poor meterability of polyanionic activators is industrially disadvantageous. The sparingly soluble polyanionic activators are used as solids for catalysing polymerization, which is technically disadvantageous in a continuous polymerization process.
SUMMARY OF THE INVENTION
The object thus arose of identifying novel co-catalysts which avoid the above-stated disadvantages. In particular, the object consisted in creating a cost-effective catalyst system which is easy to produce, easy to handle industrially and is capable of polymerizing unsaturated compounds, such as for example olefins and dienes, at a high level of catalytic activity.
It has surprisingly now been found that dendrimeric compounds which contain metals, preferably in combination with metallocenes, are particularly suitable for achieving the above-stated objects.
The present invention accordingly provides novel dendrimeric compounds of the general formula
R
1
4−i
Me
1
[(R
4
)
n
X]i (I),
in which
X represents Me
2
R
2
R
3
(R
y
)
r
,
R
1
, R
2
, R
3
, R
y
are identical or different, may optionally be mono- or polysubstituted and represent hydrogen, C
5
-C
20
cycloalkyl, C
1
-C
20
alkyl, C
7
-C
40
aralkyl, C
6
-C
40
aryl, C
1
-C
10
alkoxy, C
6
-C
40
aryloxy, silyloxy or halogen,
R
4
represents an optionally mono- or polysubstituted alkylene, alkenylene or alkynylene residue, which is optionally interrupted by one or more heteroatoms.
Me
1
represents an element of group IVa of the periodic system of the elements (IUPAC nomenclature),
Me
2
represents an element of group IIIa of the periodic system of the elements (IUPAC nomenclature),
i represents an integer from 2 to 4,
n represents an integer from 1 to 20 and
r represents 0 or 1
wherein, when r=1, the Me
2
residue bears a negative formal charge and in the event of a negative formal charge on Me
2
, this is offset by a cation,
or in which
X represents Me
1
R
5
a
[(R
4
)
m
Me
2
R
2
R
3
(R
y
)
r
]
3−a
,
Me
1
, Me
2
, R
1
, R
2
, R
3
, R
4
, R
y
, i, n, r have the above-stated meanings,
R
5
has the meaning of the residues R
1
, R
2
, R
3
, R
y
,
m is identical to or different from n and represents integers from 1 to 20 and
a represents 0, 1 or 2,
or in which
X represents Me
1
R
5
a
[(R
4
)
m
Me
1
R
6
b
[(R
4
)
p
Me
2
R
2
R
3
(R
y
)
r
]
3−b
]
3−a
,
Me
1
, Me
2
, R
2
, R
3
, R
4
, R
y
, i, n, r, m, a have the above-stated meanings,
R
6
has the meaning of the residues R
1
, R
2
, R
3
, R
y
, R
5
,
b represents 0, 1 or 2 and
p represents integers from 1 to 20,
wherein the compounds described in DE 195 16 200 are excluded, said compounds being produced by the reaction of silicon tetrachloride in a Grignard reaction to form tetraallylsilane, which is subsequently reacted twice or more alternately
a) with trichlorosilane in a quantitative reaction in the presence of a catalyst and then
b) with an allyl compound in a Grignard reaction using a suitable solvent in each case until a dendrimeric skeleton comprising outwardly pointing allyl groups is obtained, the outer allyl groups of which
c) are derivatized in a hydroboration reaction with 9-borabicyclo[3.3.1]nonane.
DETAILED DESCRIPTION OF THE INVENTION
Suitable cations in the event that Me
2
bears a negative formal charge which may be considered are ions of atoms or molecules such as alkali metal ions, for example Li
+
, Na
+
or K
+
, alkaline earth metal ions such as Be
2+
, Mg
2+
, Ca
2+
, Ba
2+
, transition metal ions such as Zn
2+
, Cd
2+
, Mg
2+
, Cu
+
, Cu
2+
, or organic compounds such as ammonium or phosphonium ions of the NR
4
+
or PR
4
+
type, preferably Ph—N(CH
3
)
2
H
+
, or carbocations of the CR
3
+
type, preferably CPh
3
+
.
The nature of the cation NR
4
+
in particular also has an influence on the solubility of the salts, consisting of the dendrimeric compounds according to the invention of the formula (I) which have at least one negative formal charge (r=1) and cations which offset the formal charge. The solubility of the stated salts in non-polar solvents, such as for example toluene and xylene, may, for example, be improved by using ammonium salts NR′R
3
+
which contain a relatively
Becke Sigurd
Denninger Uwe
Mager Michael
Windisch Heike
Bayer Aktiengesellschaft
Cheung Noland J.
Gil Joseph C.
Seng Jennifer R.
Shaver Paul F.
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