Supported catalyst system for polymerizing alk-1-enes

Details Supported catalyst system for polymerizing alk-1-enes Supported catalyst system for polymerizing alk-1-enes

1999-09-08

2002-09-03

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...

C526S133000, C526S126000, C526S160000, C526S943000, C502S103000, C502S152000, C502S202000

Reexamination Certificate

active

06444764

ABSTRACT:

The present invention relates to a catalyst system for polymerizing C
2
-C
12
-alk-1-enes which comprises
A) an organic or inorganic support,
B) at least one metallocene complex,
C) oligomeric aluminum oxide compounds and
D) at least one boron compound of the formula I
 or a cyclic boron compound of the formula II
 or mixtures of boron compounds I and II,
where, in the formulae I and II, the substituents have the following meanings:
R
1
to R
4
are each
a C
1
-C
20
-alkyl group which may bear halogen atoms, C
6
-C
15
-aryl groups and/or C
1
-C
10
-alkoxy groups as substituents,
a C
4
-C
7
-cycloalkyl group which may bear halogen atoms, C
1
-C
10
-alkyl groups and/or C
1
-C
10
-alkoxy groups as substituents,
a C
1
-C
10
-alkoxy or alkyl sulfide group which may bear halogen atoms, C
1
-C
10
-alkyl groups and/or C
6
-C
15
-aryl groups as substituents,
a C
6
-C
15
-aryl group which may bear halogen atoms, C
1
-C
10
-alkyl groups, C
1
-C
10
-haloalkyl groups, C
4
-C
10
-cycloalkyl groups, C
6
-C
15
-aryl groups, C
1
-C
10
-alkenyl groups, amino groups, monoalkylamino or dialkylamino groups, nitro groups, formyl groups, acetamido groups and/or C
1
-C
10
-alkoxy groups as substituents or
a C
3
-C
15
-heterocycle which contains from one to three oxygen, sulfur and/or nitrogen atoms in the ring system and may bear halogen atoms, C
1
-C
10
-alkyl groups and/or C
6
-C
15
-aryl groups as substituents,
furthermore, R
1
to R
4
are as defined above and additionally bear from one to three further B(OR′)(OR″) groups or, if R
1
to R
4
contain an aromatic ring, this is part of a metallocene system,
R′ and R″ are identical or different and are each hydrogen or a C
1
-C
10
-alkyl group.
The present invention further relates to a process for preparing such catalyst systems, the use of such catalyst systems for preparing polymers of C
2
-C
12
-alk-1-enes, a process for preparing the polymers with the aid of these catalyst systems, the polymers obtainable in this way and their use for producing films, fibers and moldings.
To be able to use metallocene catalysts for the polymerization of alk-1-enes in suspension or gas-phase processes, they have to be in supported form. Methods of applying metallocenes which are activated with oligomeric aluminum oxide compounds such as methylaluminoxane (MAO) to supports are described, for example, in EP-A 206 794, EP-A 250 600 and WO 95/07939.
Supported catalyst systems which are obtained in this way can be used in suspension (DE-A 43 44 672) or gas-phase processes (EP-A 323 716). However, in order to ensure high productivities, these catalyst systems have a very high content of expensive methylaluminoxane. Apart from this economic disadvantage, high methylaluminoxane contents lead to high contents of aluminum residues in the polymer products, which can have an adverse effect during processing or necessitate complicated steps to purify the polymer.
WO 93/16116 describes the use of cyclic boron-oxygen compounds as an additive in the solution polymerization of propylene. The addition of these compounds enables the activity of the metallocene/MAO catalyst system to be tripled.
The preparation of a solid cocatalyst by reacting an aluminoxane compound and a boroxane is described in EP-A 612 753 and U.S. Pat. No. 5,411,925. U.S. Pat. No. 5,480,848 teaches the preparation of a similar solid cocatalyst by reacting an aluminoxane with an organoboron compound which has no acidic H atom. Boroxane-containing cocatalysts are also described in EP-A 683 179. Furthermore, boronic acids can also be used for preparing analogous cocatalysts (U.S. Pat. Nos. 5,414,180 and 5,449,650).
However, these documents provide no information about polymerization using catalyst systems which are supported on an inert material. The properties of supported catalyst systems nevertheless very frequently deviate from those of systems in solution, as is known to those skilled in the art. It is precisely this behavior which enables the morphology of the polymer produced to be set exactly by selection of a suitable support material, which represents a great advantage when using these catalyst systems in particle forming processes such as suspension and gas-phase processes.
It is an object of the present invention to develop a catalyst system supported on an inert material for polymerizing alk-1-enes which has a high productivity, causes no reactor fouling, i.e. no deposits on stirrer and reactor walls, and gives polymers having a good morphology.
We have found that this object is achieved by the catalyst system defined in the introduction for preparing polymers of C
2
-C
12
-alk-1-enes. We have also found a process for its preparation, the use of such catalyst systems for preparing polymers of C
2
-C
12
-alk-1-enes, a process for preparing polymers with the aid of these catalyst systems, the polymers obtainable in this way and their use for producing films, fibers and moldings.
The catalyst system of the present invention comprises an organic or inorganic support as component A). Support materials used are preferably finely divided supports which have a particle diameter in the range from 0.1 to 1000 &mgr;m, preferably from 10 to 300 &mgr;m, in particular from 30 to 70 &mgr;m. Suitable organic supports are, for example, finely divided polymers, e.g. finely divided polyethylene or finely divided polypropylene. Suitable inorganic supports are, for example, aluminum oxide, silicon dioxide, titanium dioxide or their mixed oxides, aluminum phosphate or magnesium chloride. Preference is given to using silica gels of the formula SiO
2
.a Al
2
O
3
where a is from 0 to 2, preferably from 0 to 0.5. The support particles can be used in granulated form or spray-dried in microscopic form. Such products are commercially available, e.g. silica gel 332 from Grace or ES 70 X from Crosfield.
The amount of support, i.e. of component A), is preferably from 50 to 99.9% by weight based on metallocene complex, i.e. on component B).
As component B), the catalyst system of the present invention comprises one or more metallocene complexes. Particularly useful metallocene complexes are those of the formula III
where the substituents have the following meanings:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, or an element of transition group III of the Periodic Table or the lanthanides,
X is fluorine, chlorine, bromine, iodine, 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
10
or —NR
10
R
11
,
n is 1, 2 or 3, where n corresponds to the valence of M minus 2,
where
R
10
and R
11
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
5
to R
9
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which in turn may bear C
1
-C
10
-alkyl as substituents, 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
12
)
3
where
R
12
can be C
1
-C
10
-alkyl, C
3
-C
10
-cycloalkyl or C
6
-C
15
-aryl and
 where the radicals
R
13
to R
17
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which in turn may bear C
1
-C
10
-alkyls as substituents, C
6
-C
15
-aryl or arylalkyl and two adjacent radicals may together form a saturated or unsaturated cyclic group having from 4 to 15 carbon atoms, or Si(R
18
)
3
where
R
18
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
or the radicals R
8
and Z together form a group —R
19
—A— where
 ═BR
20
, ═AlR
20
, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO
2
, ═NR
20
, ═CO, ═PR
20
or ═P(O)R
20
,
where
R
20
, R
21
and R
22
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
-fluoralkyl group, a C
6
-C
10
-fluoraryl group, a C
6
-C
10
-aryl group, a C
1
-C
1

Affiliated with

Also associated with

Rating

Supported catalyst system for polymerizing 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 Supported catalyst system for polymerizing alk-1-enes, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Supported catalyst system for polymerizing alk-1-enes will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2855631