Catalyst for the (co)polymerization of alk-1-enes

Details Catalyst for the (co)polymerization of alk-1-enes Catalyst for the (co)polymerization of alk-1-enes

2000-02-17

2002-10-01

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...

C526S127000, C526S134000, C526S160000, C526S943000, C502S104000, C502S108000, C502S117000, C502S118000

Reexamination Certificate

active

06458904

ABSTRACT:

The present invention relates to a catalyst composition suitable for the (co)polymerization of alk-1-enes, obtainable by
a) mixing a metallocene complex of the formula (I)
 where the substituents have the following meanings:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
X is hydrogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, —OR
6
or —NR
6
R
7
,
 where
R
6
and R
7
are C
1
-C
10
-alkyl, C
6
-C
15
-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical,
R
1
to R
5
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C
1
-C
10
-alkyl group as substituent, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals may also together form a saturated or unsaturated cyclic group having from 4 to 15 carbon atoms, or Si(R
8
)
3
where
R
8
is C
1
-C
10
-alkyl, C
3
-C
10
-cycloalkyl or C
6
-C
15
-aryl,
Z is X or
 where the radicals
R
9
to R
13
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C
1
-C
10
-alkyl group as substituent, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals may also together form a saturated or unsaturated cyclic group having from 4 to 15 carbon atoms, or Si(R
14
)
3
where
R
14
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
or the radicals R
4
and Z together form a —R
15
—A— group, where
═BR
16
, ═AlR
16
, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO
2
, ═NR
16
, ═CO, ═PR
16
or ═P(O)R
16
,
 where
R
16
, R
17
and R
18
are identical or different and are each a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl group, a C
1
-C
10
-fluoroalkyl group, a C
6
-C
10
-fluoroaryl group, a C
6
-C
10
-aryl group, a C
1
-C
10
-alkoxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
8
-C
40
-arylalkenyl group or a C
7
-C
40
-alkylaryl group, or two adjacent radicals together with the atoms connecting them form a ring, and
M
2
is silicon, germanium or tin,
R
19
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl, C
3
-C
10
-cycloalkyl, alkylaryl or Si(R
20
)
3
,
R
20
is hydrogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl which may in turn bear C
1
-C
4
-alkyl groups as substituents, or C
3
-C
10
-cycloalkyl
or the radicals R
4
and R
12
together form a —R
15
— group, with a C
3
-C
20
-alk-1-ene in an inert solvent, where the molar ratio of metallocene complex to alk-1-ene is in the range from 1:0.1 to 1:100,
b) reacting the mixture obtained in a) in a controlled manner with a compound (II) capable of forming metallocenium ions and
c) diluting the mixture obtained in b) with an inert nonpolar, essentially aliphatic solvent and, if desired,
d) applying the catalyst composition obtained in c) to a particulate support material.
Furthermore, the present invention relates to a process for preparing this catalyst composition, a process for preparing alk-1-ene (co)polymers in the presence of this catalyst composition and also the use of this catalyst composition for the polymerization of alk-1-enes.
Cationically activated metallocene catalyst systems for olefin (co)polymerization are sufficiently well known. These systems which are generally derived from a plurality of components can be prepared using a number of different process variants. For example, JP 0 5320240 describes the separate addition of the individual components, viz. alkylated metallocene complex, non-coordinating anion and metal alkyl compound, to the polymerization vessel. If the polymerization-active cationic complex is prepared physically separately from the polymerization system, it is generally necessary to take account of the polarity of the catalyst species when selecting the solvent system to be used. This is because the structure of many metal complexes, but particularly the structure of the activating reagents and also the ion pairs of cationic metallocene complex and anionic non-coordinating counterion formed during the course of the activation, generally make it necessary to employ moderately polar solvents, for example aromatic or halogenated hydrocarbons, for this reaction. Thus, EP-A-709 393 describes the cationic activation of metallocene complexes using substituted fluorophenyl ligands in toluene as solvent. WO-93/25590 likewise describes the cationic activation of metallocene complexes, with preference being given to using aromatic solvents, in particular toluene (see examples), for these reactions. The straight-chain, branched or alicyclic hydrocarbons which are likewise mentioned have generally been found to be unsuitable for this purpose, since they are not able to dissolve, in particular, the cationic metallocene complexes and the activating reagents to a sufficient extent. The document cited describes a binuclear transition metal complex as precursor of the cationically activated catalyst species. Bochmann et al. (J. Chem. Soc., Dalton Trans., 1996, pp. 255-270) were likewise able to detect binuclear systems as intermediates or by-products in cationic metallocene activation. These complexes have only a very low catalyst activity, if any, and make no contribution to increasing the catalyst productivity. In addition, in aliphatic solvents they form an insoluble precipitate which can have a long-term hindering effect in the production process for preparing the polymer.
The cationically activated metallocene complexes can also be advantageously used in unsupported form in slurry or solution polymerization processes. Solvents which have been found to be suitable for these polymerization processes, in particular for polymerization processes at high temperature and high pressure, are, in particular, aliphatic solvents, particularly saturated hydrocarbons. In contrast, aromatic and halogenated hydrocarbons have disadvantages which are presumably attributable to their reactivity and to destruction or blocking of the catalyst by these compounds. As a result, a lower catalyst productivity, a greater need for alkyl compounds to eliminate impurities and an increased proportion of wax-like by-products in the polymers are observed in polymerizations in these solvents.
The unsatisfactory solubility and thus also the low productivity of cationically activated metallocene catalysts in aliphatic solvents has hitherto usually made it necessary to use aromatic solvents in such solution polymerization processes.
It would therefore be desirable to be able to employ cationically activated metallocene catalysts which are readily soluble even in aliphatic solvents and, in particular, are stable under the conditions of high pressure polymerization and give good productivities. Furthermore, it would be desirable to be able to monitor the concentration of reactive catalyst species during the entire polymerization process in order, even in large-scale applications, to achieve uniform product compositions and avoid process malfunctions in the polymerization.
It is an object of the present invention to provide cationically activated metallocene catalyst compositions which are soluble in aliphatic solvents and display good productivities in the (co)polymerization of alk-1-enes.
We have found that this object is achieved by the catalyst composition described at the outset, a process for preparing this catalyst composition, a process for the (co)polymerization of alk-1-enes in the presence of this catalyst composition and also the use of this catalyst composition for the polymerization of alk-1-enes.
Among the metallocene complexes of the formula (I), preference is given to
Particular preference is given to transition metal complexes which have two aromatic ring systems bridged to one another as ligands, ie. in particular the transition metal complexes of the formula Ic.
The radicals X can be identical or different; they are preferable identical.
Among the compounds of the formula Ia, particular preference is given to those in which
M is titanium,

Affiliated with

Also associated with

Rating

Catalyst for the (co)polymerization of alk-1-enes does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Catalyst for the (co)polymerization of alk-1-enes, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Catalyst for the (co)polymerization of alk-1-enes will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2987933