Preparation of copolymers of carbon monoxide and an...

Details Preparation of copolymers of carbon monoxide and an... Preparation of copolymers of carbon monoxide and an...

2002-04-23

2003-04-01

Acquah, Samuel A. (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

At least one aryl ring which is part of a fused or bridged...

C528S392000, C527S300000, C527S313000, C527S600000, C524S403000, C524S404000, C524S413000, C524S414000, C524S417000, C524S432000, C524S709000, C524S732000, C524S734000, C524S798000

Reexamination Certificate

active

06541564

ABSTRACT:

The present invention relates to a process for preparing copolymers of carbon monoxide and an olefinically unsaturated compound having from 2 to 20 carbon atoms in an aqueous medium, to the aqueous copolymer system and to its use.
Copolymers of carbon monoxide and olefinically unsaturated compounds, also known as carbon monoxide copolymers or polyketones for short, are known. For example, high molecular weight partially crystalline polyketones having a strictly alternating sequence of the monomers in the main chain generally display high melting points, good heat distortion resistance, good resistance to chemicals, good barrier properties toward water and air and advantageous mechanical and rheological properties.
Polyketones derived from carbon monoxide and olefins, generally &agr;-olefins, are of industrial interest. Examples are carbon monoxide-ethene, carbon monoxide-propene, carbon monoxide-ethene-propene, carbon monoxide-ethene-1-butene, carbon monoxide-ethene-1-hexene, carbon monoxide-propene-1-butene and carbon monoxide-propene-1-hexene copolymers.
The preparation of polyketones by processes catalyzed by transition metals is known. For example, a cis-palladium complex chelated with bidentate phosphine ligands, viz. [Pd(Ph
2
P(CH
2
)
3
PPh
2
)](OAc)
2
(Ph=phenyl, Ac=acetyl), is used in EP-A 0 121 965. The copolymerization of carbon monoxide can be carried out in suspension, as described in EP-A 0 305 011, or in the gas phase, for example as described in EP-A 0 702 045. Frequently used suspension media are low molecular weight alcohols, in particular methanol (cf. EP-A 0 428 228), and nonpolar or polar aprotic liquids such as dichloromethane, toluene or tetrahydrofuran (cf. EP-A 0 460 743 and EP-A 0 590 942). Complexes containing chelating bisphosphine ligands whose radicals on the phosphorus are aryl or substituted aryl groups have been found to be particularly useful for the copolymerization processes mentioned. Accordingly, particularly frequently used chelating ligands are 1,3-bis(diphenylphosphino)propane and 1,3-bis[di(o-methoxyphenyl)phosphino)]propane (cf. Drent et al., Chem. Rev., 1996, 96, pp. 663 to 681). In the abovementioned cases, the carbon monoxide copolymerization is usually carried out in the presence of acids.
The carbon monoxide copolymerization in low molecular weight alcohols such as methanol suffers from the disadvantage that the carbon monoxide copolymer which is formed has a high absorption capacity for these liquids and up to 80% by volume of, for example, methanol are bound or absorbed by the carbon monoxide copolymer. As a result, a high energy input is necessary to dry the carbon monoxide copolymers and isolate them in pure form. A further disadvantage is that even after intensive drying, residual alcohol always still remains in the carbon monoxide copolymer. For this reason, molding compositions produced in this way are ruled out from the start as packaging material for food. EP-A 0 485 035 proposes the addition of water in amounts of from 2.5 to 15% by weight to the alcoholic suspension medium in order to eliminate residual low molecular weight alcohol in the carbon monoxide copolymer. However, this procedure does not lead to methanol-free copolymers either. The use of halogenated hydrocarbons or aromatics such as dichloromethane or chlorobenzene or toluene also causes problems, particularly in handling and disposal.
To circumvent the disadvantages associated with the abovementioned suspension media, Jiang and Sen, Macromolecules, 1994, 27, pp. 7215 to 7216, describe the preparation of carbon monoxide copolymers in aqueous systems using a catalyst system comprising [Pd(CH
3
CN)
4
] (BF
4
)
2
and 1,3-bis[di(3-benzenesulfonic acid)phosphino]propane as water-soluble chelating ligand. However, the catalyst activity achieved is unsatisfactory.
Verspui et al., Chem. Commun., 1998, pp. 401 to 402, were able to increase, compared to the results of Jiang and Sen, the catalyst activity in the copolymerization of carbon monoxide and ethene by using the abovementioned chelating ligand in significantly purer form. Furthermore, the presence of a Bronsted acid is necessary to achieve the improved, compared to the results of Jiang and Sen, catalyst activities. The polyketones described in the publication, which are prepared from carbon monoxide and ethylene, have the disadvantage that their molecular weight is less than that of the comparable polyketones which have been prepared in methanol as solvent.
The patent application filed by the present applicant at the German patent and trademarks office under the application number 19917920 relates to a process for the metal-catalyzed preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having from three to twenty carbon atoms in an aqueous medium using a specific metal catalyst system.
In the patent application likewise filed by the present applicant at the German patent and trademarks office under the application number 10061877, stable aqueous polymer dispersions are obtained using the metal catalyst system described in the abovementioned application when the polymerization of carbon monoxide and an olefinically unsaturated compound is carried out in an aqueous medium using specific comonomers.
It is an object of the present invention to improve the catalytic preparation of copolymers of carbon monoxide and an olefinically unsaturated compound having from 2 to 20 carbon atoms in an aqueous medium using the metal catalyst system described in the two abovementioned applications.
We have found that this object is achieved by a process for preparing copolymers of carbon monoxide and an olefinically unsaturated compound having from 2 to 20 carbon atoms in an aqueous medium, in which the copolymerization of carbon monoxide and the olefinically unsaturated compound is carried out in an aqueous medium in the presence of
a1) metal complexes of the formula (I)
 where the substituents and indices have the following meanings:
G is a 5-, 6- or 7-membered carbocyclic ring system without heteroatoms or containing one or more heteroatoms, —(CR
b
2
)r—, —(CR
b
2
)
s
—Si(R
a
)
2
—(CR
b
2
)
t
—, —A—O—B— or —A—Z(R
5
)—B—, where
R
5
is hydrogen, C
1
-C
20
-alkyl, C
3
-C
14
-cycloalkyl, C
6
-C
14
-aryl or alkylaryl having from 1 to 20 carbon atoms in the alkyl part and from 6 to 14 carbon atoms in the aryl part, each of which may be unsubstituted or substituted by functional groups containing atoms of groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements, or is —N(R
b
)
2
, —Si(R
c
)
3
or a radical of the formula (II)
 where
q is an integer from 0 to 20 and the further substituents in formula (II) are as defined for formula (I),
A, B are each —(CR
b
2
)
r′
, —(CR
b
2
)
s
—Si(R
a)
2
—(CR
b
2
)
t
—, —N(R
b
)—, an r′—, s- or t-atomic constituent of a ring system or together with Z form an (r′+1)-, (s+1)- or (t+1)-atomic constituent of a heterocycle,
R
a
are each, independently of one another, linear or branched C
1
-C
20
-alkyl, C
3
-C
14
-cycloalkyl, C
6
-C
14
-aryl or alkylaryl having from 1 to 20 carbon atoms in the alkyl part and from 6 to 14 carbon atoms in the aryl part, where the specified radicals may also be substituted,
R
b
is as defined for R
a
, and may also be hydrogen or —Si (R
c
)
3
,
R
c
are each, independently of one another, linear or branched C
1
-C
20
-alkyl, C
3
-C
14
-cycloalkyl, C
6
-C
14
-aryl or alkylaryl having from 1 to 20 carbon atoms in the alkyl part and from 6 to 14 carbon atoms in the aryl part, where the specified radicals may also be substituted,
r is 1, 2, 3 or 4 and
r′ is 1 or 2,
s, t are each 0, 1 or 2, where 1≦s+t≦3,
Z is a nonmetallic element of group VA of the Periodic Table of the Elements,
M is a metal selected from groups VIIIB, IB and IIB of the Periodic Table of the Elements,
E
1
, E
2
are each a nonmetallic element from group VA of the Periodic Table of the Elements,
R
1
to R
4
are each, independentl

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