Transition metal catalyzed polymerization of olefinic...

Details Transition metal catalyzed polymerization of olefinic... Transition metal catalyzed polymerization of olefinic...

2000-12-05

2003-01-14

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, C526S161000, C526S943000, C526S347000, C526S348600, C526S335000, C526S910000, C526S911000, C502S152000

Reexamination Certificate

active

06506856

ABSTRACT:

The present invention relates to a process for preparing polymers based on monomers having a C—C double bond and/or C—C triple bond by polymerization of these monomers in the presence of a catalyst system comprising as active constituents
A) a transition metal compound of an early transition metal (M-II)
where the substituents and indices have the following meanings:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, or an element of transition group III of the Periodic Table and 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
6
or —NR
6
R
7
, N(CH
2
CH
2
O)
3
,
n is an integer from 1 to 3 corresponding to the valence of M minus 2,
where
R
6
and R
7
are hydrogen, 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 and 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 an —R
15
—A— group, where
R
15
is
═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 may form a ring, and
M
2
is silicon, germanium or tin,
A
where
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 an —R
15
— group, and, if desired, a cation-forming compound B) and, if desired, further components C),
wherein the polymerization mixture contains at least 30% by weight of water.
The present invention also relates to aqueous dispersions or suspensions based on monomers having a C—C double bond and/or C—C triple bond, and polymers obtainable from aqueous dispersions or suspensions by removing the water from these dispersions or suspensions, and also to the use of the aqueous suspensions and/or dispersions.
The polymerization of olefins and vinylaromatic monomers using metallocene catalysts based on early transition metal compounds is known (Angew. Chem. Int. Ed. Engl. 1995, 34, p. 1193).
The polymerizations are customarily carried out with exclusion of water or other protic compounds (compounds having at least one OH group), since these act as poisons toward metallocene catalysts.
Depending on the reaction conditions, it is possible to obtain low molecular weight polymers (dimers, oligomers, waxes) or high molecular weight polymers. Again as a function of the reaction conditions, these are obtained as granular powder or else as very fine powder, which is difficult to handle.
It is an object of the present invention to find a relatively simple polymerization process which gives high molecular weight polymers having a readily handlable particle morphology (for example, free-flowing, high bulk density) or water-containing polymer dispersions.
We have found that this object is achieved by the process defined at the outset, the dispersions or suspensions defined at the outset and the polymers obtainable therefrom.
Particularly well-suited transition metal compounds A) are those containing at least one cyclopentadienyl-type ligand, which are generally referred to as metallocene complexes.
As component A), the catalyst system comprises at least one metallocene complex. Particularly suitable metallocene complexes are those of the formula
where the substituents and indices have the following meanings:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, or an element of transition group III of the Periodic Table and 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
6
or —NR
6
R
7
, N(CH
2
CH
2
O)
3
,
n is an integer from 1 to 3 corresponding to the valence of M minus 2,
where
R
6
and R
7
are hydrogen, 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 and 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 an —R
15
—A— group, where
R
15
is
═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 may form a ring, and
M
2
is silicon, germanium or tin,
A
where
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 an —R
15
— group.
Among the metallocene complexes of the formula M-II, preference is given to
The radicals X may be identical or different, but are preferably identical.
Among the compounds of the formula M-IIa, particular preference is given to those in which
M is titanium, zirconium or hafnium,
X is chlorine, C
1
-C
4
-alkyl, phenyl, OR
6
,
n is 2 and
R
1
to R
5
are hydrogen or C
1
-C
4
-alkyl.
Very particular preference is given to pentamethylcyclopentadienyltitanium compounds having three alkoxide ligands such as methoxy, ethoxy, tert-butoxy or N(CH
2
CH
2
O)
3
, in particular pentamethylcyclopentadienyltitanium trimethoxide.
Among the compounds of the formula M-IIb, preference is given to those in which
M is titanium, zirconium or hafnium,
X is chlorine, C
1
-C
4
-alkyl or phenyl, OR
6

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