Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-08-16
2002-05-21
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...
C526S130000, C526S170000, C526S943000, C526S123100, C502S120000, C502S121000, C502S128000, C502S152000, C502S155000
Reexamination Certificate
active
06391989
ABSTRACT:
The present invention relates to catalyst systems, a process for preparing them and their use in the polymerization of olefins.
Ziegler-type catalysts based on angled metallocenes containing metals of group 4 form a new generation of catalysts which can be used industrially for the polymerization of &agr;-olefins (H. H. Brintzinger, D. Fischer, R. Mülhaupt, R. Rieger, R. Waymouth, Angew. Chem. 1995, 107, 1255-1283).
To obtain an active catalyst system, the metallocene complex is treated with a large excess of methylaluminoxane (MAO) (H. Sinn, W. Kaminsky, Adv. Organomet. Chem., 1980, 18, 99). Apart from the high cocatalyst costs, this has the disadvantage of a high aluminum content in the resulting polymer. For this reason, new activation methods which make do without a superstoichiometric amount of activator have been developed. The synthesis of “cation-like” metallocene polymerization catalysts is described in J. Am. Chem. Soc. 1991, 113, 3623. In this synthesis, the alkyl group is abstracted from an alkyl-metallocene compound by means of trispentafluorophenylborane which is used in a stoichiometric amount based on the metallocene.
EP-A-0,427,697 claims this synthetic principle and a corresponding catalyst system comprising an uncharged metallocene species (e.g. Cp
2
ZrMe
2
), a Lewis acid (e.g. B(C
6
F
5
)
3
) and aluminum alkyls. A process for preparing salts of the formula LMX
+
XA
−
according to the above-described principle is claimed in EP-A-0,520,732.
EP-A-0,558,158 describes zwitterionic catalyst systems prepared from dialkyl-metallocene compounds and salts of the formula [R
3
NH]
+
[BPh
4
]
−
. The reaction of such a salt with, for example, Cp
2
*ZrMe
2
results in protolysis and elimination of methane to give a methyl-zirconocene cation as an intermediate. This reacts via C—H activation to form the zwitterion Cp
2
*Zr
+
-(m-C
6
H
4
)-BPh
3
−
. In this zwitterion, the Zr atom is covalently bound to a carbon atom of the phenyl ring and is stabilized by means of an agostic hydrogen bond.
US-A-5,384,299 claims corresponding systems in which dimethylanilinium salts with perfluoriated tetraphenylborates are used.
Apart from the activating action of the borate salts, their ligand sphere has an important effect on reaction equilibrium. Large bulky ligands substantially prevent dimerization of the metallocenium fragments and thus displace the position of the equilibrium to the side of the catalytically active species. The mononuclear borate anions described hitherto have four aryl ligands and can, by incorporation of bulky groups on the ligand, exercise an influence on the reaction equilibrium (WO 95/24268). Disadvantages of these systems are the complicated syntheses and also the extreme sensitivity of the resulting metallocenium complexes.
It is an object of the present invention to provide an inexpensive catalyst system which has the advantages of bulky ligands but avoids the disadvantages of the existing bulky aryl ligands.
We have found that this object is achieved by a catalyst system comprising
a) at least one support,
b) at least one metallocene and
c) at least one compound of the formula (I)
where
M
1
is an element of group IIa, IIIa, IVa or Va of the Periodic Table of the Elements,
x is 0 or 1,
y is 0 or 1,
z is 0 or 1,
A is a cation of group Ia, IIa, IIIa of the Periodic Table of the Elements, a carbenium, oxonium, phosphonium or sulfonium cation or a quaternary ammonium compound,
Q
1
, Q
2
, Q
3
are each a ligand system based on a biphenyl framework bound to M
1
via the positions 2 and 12 and having the formula (II),
where
R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
and R
8
are identical or different and are each a hydrogen atom, a halogen atom, a C
1
-C
40
group, preferably C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
40
-aryl, C
6
-C
40
-haloaryl, C
6
-C
40
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl or C
7
-C
40
-haloalkylaryl, or an OSiR
3
9
group, where R
9
are identical or different and are each a hydrogen atom, a halogen atom, a C
1
-C
40
group, preferably C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
40
-aryl, C
6
-C
40
-haloaryl, C
6
-C
40
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl or C
7
-C
40
-haloalkylaryl, and two or more radicals R
1
to R
8
may be joined to one another so as to form a monocyclic or polycyclic ring system which may be substituted.
The compounds of the formula (I) are particularly preferably ones in which M
1
is boron. Such compounds have the formula (III)
where
A is a cation of group Ia, IIa, IIIa of the Periodic Table of the Elements, a carbenium, oxonium, phosphonium or sulfonium cation or a quaternary ammonium compound,
Q
1
and Q
2
are identical or different and are each a ligand system based on a biphenyl framework bound to B via the positions 2 and 12, where Q corresponds to the formula (II).
A similarly preferred compound of the formula (I) is a compound in which M
1
is phosphorus. Such compounds have the formula (IV)
where
A is a cation of group Ia, IIa, IIIa of the Periodic Table of the Elements, a carbenium, oxonium, phosphonium or sulfonium cation or a quaternary ammonium compound,
Q
1
, Q
2
, Q
3
are identical or different and are each a ligand system based on a biphenyl framework bound to P via the positions 2 and 12, where Q corresponds to the formula (II).
Particularly preferred but nonlimiting examples of chemical compounds of the formulae (III) and (IV) according to the present invention are:
The catalyst system of the present invention comprises at least one metallocene, where this can be ionized by the cation A and an ion pair of metallocene cation and a noncoordinating or only weakly coordinating anion is formed.
The chemical compounds of the formula (II) according to the present invention can be used together with an organometallic transition metal compound as catalyst system. Organometallic transition metal compounds used are, for example, metallocene compounds. These can be, for example, bridged or unbridged biscyclopentadienyl complexes as described, for example, in EP-A-0 129 368, EP-A-0 561 479, EP-A-0 545 304 and EP-A-0 576 970, monocyclopentadienyl complexes such as bridged amidocyclopentadienyl complexes as described, for example, in EP-A-0 416 815, multinuclear cyclopentadienyl complexes as described in EP-A-0 632 063, &pgr;-ligand-substituted tetrahydropentalenes as described in EP-A-0 659 758 or &pgr;-ligand-substituted tetrahydroindenes as described in EP-A-0 661 300. In addition, it is possible to use organometallic compounds in which the complexing ligand contains no cyclopentadienyl ligand. Examples of such complexes are diamine complexes of transition groups III and IV of the Periodic Table of the Elements, as described, for example, in D. H. McConville et al., Macromolecules, 1996, 29, 5241 and D. H. McConville et al., J. Am. Chem. Soc., 1996, 118, 10008. It is also possible to use diimine complexes of transition group VIII of the Period Table of the Elements (e.g. Ni
2+
or Pd
2+
complexes), as described in Brookhart et al., J. Am. Chem. Soc. 1995, 117, 6414 and Brookhart et al., J. Am. Chem. Soc., 1996, 118, 267. Furthermore, it is possible to use 2,6-bis(imino)pyridyl complexes of transition group VIII of the Periodic Table of the Elements (e.g. Co
2+
or Fe
2+
complexes), as described in Brookhart et al., J. Am. Chem. Soc. 1998, 120, 4049 and Gibson et al., Chem. Commun. 1998, 849.
Preferred metallocene compounds are unbridged or bridged compounds of the formula (V),
where
M is a metal of transition group III, IV, V or VI of the Periodic Table of the Elements, in particular Ti, Zr or Hf,
R
10
are identical or different and are each a hydrogen atom or SiR
3
12
, where R
12
are identical or different and are each a hydrogen atom or a C
1
-C
40
group, preferably C
1
-C
20
-alkyl, C
1
-C
10
-fluoroalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
10
-fluoroaryl, C
6
-C
10
-aryloxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalky
Bohnen Hans
Fritze Cornelia
Kueber Frank
Basell Polypropylen GmbH
Keil & Weinkauf
Lu Caixia
Wu David W.
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