Dispersion polymerization in the presence of metallocene...

Details Dispersion polymerization in the presence of metallocene... Dispersion polymerization in the presence of metallocene...

1998-05-07

2001-04-24

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...

C526S160000, C526S169200, C526S201000, C526S347000

Reexamination Certificate

active

06221983

ABSTRACT:

The present invention relates to a process for preparing copolymers of vinylaromatic and olefinic compounds.
The present invention further relates to the use of the copolymers obtainable in this way for producing fibers, films and moldings and also to the fibers, films and moldings produced therefrom.
Owing to their property profile, copolymers of vinylaromatic and olefinic compounds can be used in many areas, for example as electrical components.
EP-A 416 815 discloses a process for preparing copolymers of vinylaromatic and olefinic compounds, in which the polymerization is carried out in solution. A disadvantage here is that the resulting copolymer can only be isolated by costly removal of the solvent. In addition, the increasing viscosity of the polymerization solution often presents problems.
It is an object of the present invention to provide a novel process for preparing copolymers of vinylaromatic and olefinic compounds, which process does not have the disadvantages mentioned, can, in particular, be carried out simply in process terms, makes it possible for the resulting copolymer to be separated off easily and gives copolymers having a low residual monomer content.
We have found that this object is achieved by a process for preparing copolymers of vinylaromatic and olefinic compounds, wherein the polymerization is carried out in dispersion in the presence of metallocene catalyst systems.
Furthermore, we have found the use of the copolymers obtainable in this way for producing fibers, films and moldings and also the fibers, films and moldings obtainable therefrom.
In the process of the present invention, suitable vinylaromatic compounds are, for example, those of the formula IV
where the substituents have the following meanings:
R
16
is hydrogen or C
1
-C
4
-alkyl,
R
17
to R
21
are, independently of one another, hydrogen, C
1
-C
12
-alkyl, C
6
-C
18
-aryl, halogen or two adjacent radicals together form a cyclic group having from 4 to 15 carbon atoms.
Preference is given to using vinylaromatic compounds of the formula IV in which
R
16
is hydrogen and
R
17
to R
21
are hydrogen, C
l
-C
4
-alkyl, chlorine or phenyl or two adjacent radicals together form a cyclic group having from 4 to 12 carbon atoms, so that the compounds of the formula IV are, for example, naphthalene derivatives or anthracene derivatives.
Examples of such preferred compounds are:
styrene, p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene, 1,4-divinylbenzene, 4-vinylbiphenyl, 2-vinylnaphthalene or 9-vinylanthracene.
It is also possible to use mixtures of various vinylaromatic compounds, but preference is given to using only one vinylaromatic compound.
Particularly preferred vinylaromatic compounds are styrene and p-methylstyrene.
The preparation of vinylaromatic compounds of the formula IV is known per se and is described, for example, in Beilstein 5, 367, 474, 485.
Olefinic compounds which can be used in the process of the present invention are, for example, ethylene or C
3
-C
10
-alkenes, in particular C
3
-C
10
-alk-1-enes. Preference is given to ethylene, propylene, 1-butene, isobutene, 4-methylpent-1-ene, 1-hexene, 1-octene and mixtures thereof. Particular preference is given to ethylene.
As metallocene catalyst systems, preference is given to those comprising as active constituents
A) metallocene complexes of the formula I
where the substituents have the following meanings:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
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
6
or -NR
6
R
7
,
where
R
6
, 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 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 the radicals RS and Z together form a —R
9
—A— group, where
 ═BR
10
, ═AlR
10
, —Ge—, —Sn—, —O—, —S—, ═SO,
 ═SO
2
, ═NR
10
, ═CO, ═PR
10
or ═P(O)R
10
,
where
R
10
, R
11
and R
12
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 R
10
and R
11
or R
10
and R
12
, in each case together with the atoms connecting them, form a ring, and
M
1
is silicon, germanium or tin,
A is —O—,—S—,
where
R
13
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl, C
3
-C
10
-cycloalkyl, alkylaryl, Si(R
14
4
)
3
,
&Parenopenst;CH
2
&Parenclosest;
n
O—R
14
, &Parenopenst;CH
2
—CH
2
O&Parenclosest;
n
R
14
or &Parenopenst;CH
2
—O&Parenclosest;
n
R
14
where
R
14
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 and
n is 1, 2 or 3 and
B) a compound capable of forming metallocenium ions.
Particularly preferred metallocene complexes of the formula I are those in which
M is titanium, zirconium or hafnium, in particular titanium,
X is chlorine, C
1
-C
4
-alkyl or —OR
6
, where
R
6
is C
1
-C
6
-alkyl, in particular methyl, ethyl, propyl or n-butyl,
R
1
to R
5
are hydrogen, C
1
-C
6
-alkyl, in particular methyl, ethyl, propyl, n-butyl or tert-butyl, phenyl or two adjacent radicals together form a cyclic group having from 4 to 15 carbon atoms,
z is X
or the radicals R
5
and Z together form a —R
9
—A— group, where
 where
R
10
and R
11
are hydrogen or C
1
-C
6
-alkyl and
M
1
is silicon,
A is
where
R
13
is C
1
-C
6
-alkyl, in particular methyl, ethyl, propyl, n-butyl or tert-butyl, phenyl or
&Parenopenst;CH
2
&Parenclosest;
n
O—R
14
R
14
is C
1
-C
4
-alkyl, in particular methyl, and
n is 2.
Particularly suitable metallocene complexes of the formula I are:
pentamethylcyclopentadienyltitanium trichloride,
pentamethylcyclopentadienyltrimethyltitanium,
pentamethylcyclopentadienyltitanium trimethoxide,
[(methoxyethylamido)dimethylsilyl(tetramethylcyclopentadienyl)]dichlorotitanium,
[(methoxyethylamido)dimethylsilyl(tetramethylcyclopentadienyl)]dimethyltitanium,
[(methoxyethylamido)dimethylsilyl(3-tert-butylcyclopenta-dienyl)dichlorotitanium,
[methoxyethylamido)dimethylsilyl(3-tert-butylcyclopentadienyl)]dimethyltitanium,
[(methoxyethylamido)dimethylsilyl(cyclopentadienyl)]dichlorotitanium,
[(methoxyethylamido)dimethylsilyl(cyclopentadienyl)]dimethyltitanium,
[(tert-butylamido)dimethylsilyl(tetramethylcyclopentadienyl)]dichlorotitanium.
Mixtures of various metallocene complexes can also be used.
The complexes of the formula I and processes for their preparation are known per se and are described, for example, in Organometallics 1995, Vol. 14, No. 7, pages 3129 to 3131 and in Journal of Organometallic Chemistry, 369 (1989), 359-370.
As compound B) capable of forming metallocenium ions, the catalyst systems can comprise open-chain or cyclic aluminoxane compounds.
Examples of suitable aluminoxane compounds are open-chain or cyclic aluminoxane compounds of the formula II or III
where
R
15
is a C
1
-C
4
-alkyl group, preferably methyl or ethyl, and m is an integer from 5 to 30, preferably from 10 to 25.
The preparation of these oligomeric aluminoxane compounds is usually carried out by reacting a solution of trialkylaluminum with water and is described, for example, in EP-A 284 708 and U.S. Pat. No. 4,794,096.
In general, the oligomeric aluminoxane compounds obtained in this way are in the form of mixtures of both li

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