Process for preparing polymers of C2-C10 alkenes in the...

Details Process for preparing polymers of C2-C10 alkenes in the... Process for preparing polymers of C2-C10 alkenes in the...

1998-07-15

2001-01-30

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, C526S160000, C526S352000, C526S943000, C502S152000, C502S155000, C502S103000

Reexamination Certificate

active

06180737

ABSTRACT:

Preparation of polymers of C
2
-C
10
-alkenes in the presence of metallocene complexes having cationically functionalized cyclopentadienyl ligands
The present invention relates to a process for preparing polymers of C
2
-C
10
-alkenes in the presence of catalyst systems.
The present invention further provides for the use of the polymers obtainable in this way for producing fibers, films or moldings as well as the fibers, films and moldings obtainable therefrom.
The metallocenes used for the polymerization of alkenes are generally very sensitive to air and moisture, which makes the use of these metallocenes difficult since they have to be handled under an inert gas atmosphere.
EP-A 608 054 describes catalyst systems for preparing polyolefins, in which the metallocene complexes are functionalized with Lewis bases. These complexes are very sensitive to air and moisture.
The same disadvantage is exhibited by the catalyst systems described in Organometallics 1994, 13, 4140-4142 for preparing polyethylene and polypropylene, these likewise comprising metallocene complexes functionalized with Lewis bases.
It is an object of the present invention to provide metallocene catalyst systems for polymerizing alkenes, which catalyst systems are insensitive to air and moisture and thus are simpler to handle.
We have found that this object is achieved by a process for preparing polymers of C
2
-C
10
-alkenes in the presence of catalyst systems comprising as active constituents
A) a metallocene complex of the general formula I
 where the substituents and indices have the following meanings:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
R
1
to R
4
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which in turn can bear a C
1
-C
10
-alkyl as substituent, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals may also together be cyclic groups having from 4 to 15 carbon atoms, Si(R
6
)
3
,
 where
R
6
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
R
7
and R
8
are hydrogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
R
9
and R
10
are C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
Y is nitrogen, phosphorus, arsenic, antimony, or bismuth,
Z is oxygen, sulfur, selenium or tellurium,
n is an integer in the range from 0 to 10,
 where
R
11
and R
12
are hydrogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
R
13
and R
14
are C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
n
1
is an integer in the range from 0 to 10,
X
1
to X
4
are 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
15
, —NR
15
R
16
or
 where
R
15
and R
16
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
17
to R
21
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which in turn can bear a C
1
-C
10
-alkyl as substituent, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals may also together be cyclic groups having from 4 to 15 carbon atoms, Si(R
22
)
3
,
 where
R
22
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
R
23
and R
24
are hydrogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
R
25
and R
26
are C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
n
2
is an integer in the range from 0 to 10 and
o, p, q, r are integers in the range from 0 to 4, where the sum o+p+q+r+1 corresponds to the valence of M and
B) a compound forming metallocenium ions.
Furthermore, the present invention provides for the use of the polymers obtainable in this way for producing fibers, films or moldings and provides the fibers, films and moldings obtainable therefrom.
Among the metallocene complexes of the general formula I which are used in the process of the present invention, preference is given to those in which
M is titanium, zirconium or hafnium, in particular titanium,
R
1
to R
4
are hydrogen, C
1
-C
6
-alkyl, C
6
-C
15
-aryl or where two adjacent radicals may be cyclic groups having from 8 to 12 carbon atoms, in particular hydrogen,
 where
R
11
and R
12
are hydrogen or C
1
-C
4
-alkyl, in particular hydrogen, methyl or ethyl,
R
13
and R
14
are C
1
-C
6
-alkyl, in particular methyl, ethyl, n-propyl, iso-propyl, n-butyl or tert.-butyl or phenyl,
n
1
is an integer in the range from 1 to 4,
Y is nitrogen or phosphorus,
Z is oxygen or sulfur,
X
1
to X
4
are chlorine, C
1
-C
4
-alkyl or
 where
R
17
to R
21
are hydrogen, C
1
-C
6
-alkyl, C
6
-C
15
-aryl or where two adjacent radicals may be cyclic groups having from 8 to 12 carbon atoms or
R
23
and R
24
are hydrogen or C
1
-C
4
-alkyl, in particular hydrogen, methyl or ethyl,
R
25
and R
26
are C
1
-C
6
-alkyl, in particular methyl, ethyl, n-propyl, iso-propyl, n-butyl or tert.-butyl or phenyl and
n
2
is an integer in the range from 1 to 4.
Particular preference is given to metallocene complexes of the general formula I in which R
5
is
in particular
and R
1
to R
4
are hydrogen. It is also preferred, particularly when M is titanium, that X
1
, X
2
and X
3
are chlorine and o is 1, p is 1, q is 1 and r is 0 or that X
1
and X
2
are chlorine and X
3
is
and o is 1, p is 1, q is 1 and r is 0, so that symmetrical complexes result.
Examples of particularly preferred metallocene complexes of the general formula I are:
trichloro-&eegr;
5
-[2-(N,N-diisopropylammonium)ethylcyclopentadienyl]titanium(IV) chloride
dichlorodi-{&eegr;
5
-[2-(N,N-diisopropylammonium)ethylcyclopentadienyl]}titanium(IV) dichloride
trichloro-&eegr;
5
-[2-(N,N-diisopropylammonium)ethylcyclopentadienyl]zirconium(IV) chloride
dichlorodi-{&eegr;
5
-[2-(N,N-diisopropylammonium)ethylcyclopentadienyl]}zirconium(IV) dichloride
trichloro-&eegr;
5
-[2-(N,N-dimethylammonium)ethylcyclopentadienyl]titanium(IV) chloride
dichlorodi-{&eegr;
5
-[2-(N,N-dimethylammonium)ethylcyclopentadienyl]}titanium(IV) dichloride
trichloro-&eegr;
5
-[2-(N,N-dimethylammonium)ethylcyclopentadienyl]zirconium(IV) chloride
dichlorodi-{&eegr;
5
-[2-N,N-dimethylammonium)ethylcyclopentadienyl]}zirconium(IV) dichloride
dichloro-&eegr;
5
-[2-(N,N-diisopropylammonium)ethylcyclopentadienyl](trimethylsilylcyclopentadienyl)titanium(IV) chloride
dichloro-&eegr;
5
-[2-(N,N-diisopropylammonium)ethylcyclopentadienyl](trimethylsilylcyclopentadienyl)zirconium(IV) chloride
dichloro-cyclopentadienyl-&eegr;
5
-[2-(N,N-diisopropylammonium)ethylcyclopentadienyl]titanium(IV) chloride
dichloro-cyclopentadienyl-&eegr;
5
-[2-(N,N-diisopropylammonium)ethylcyclopentadienyl]zirconium(IV) chloride.
It is also possible to use mixtures of various metallocene complexes I.
The metallocene complexes I can be prepared by first preparing the cyclopentadienyl systems functionalized with the hetero atom by reacting cyclopentadienyllithium or cyclopentadienylsodium with a hetero atom-functionalized chloroalkane, as described in Journal of Organometallic Chemistry, 1992, 423, 31-38 and Journal of Organometallic Chemistry, 1994, 480, C18-C19. The hetero atom-functionalized cyclopentadienyl systems can subsequently be reacted with alkyllithium, for example n-butyllithium to give the corresponding hetero atom-functionalized cyclopentadienyllithium systems, as described, for example, in Journal of Organometallic Chemistry, 1995, 486, 287-289. These can now, preferably using MCl
4
, be converted into the corresponding metallocene complexes as described in Journal of Organometallic Chemistry, 1995, 486, 287-289, but with the metallocene complexes not yet bearing cationically functionalized cyclopentadienylligands. The conversion to the metallocene complexes of the general formula I can be carried out by additio

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