Water-soluble transition metal complexes

Details Water-soluble transition metal complexes Water-soluble transition metal complexes

2000-12-18

2003-12-23

Wu, David W. (Department: 1713)

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

Synthetic resins

Polymer of an ethylenically unsaturated reactant with a...

C526S142000, C526S126000, C526S172000

Reexamination Certificate

active

06667386

ABSTRACT:

The present invention relates to water-soluble transition metal complexes of the formula (I)
where
G is —(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′—,
R
5
is hydrogen or is C
1
- to C
28
-alkyl, C
3
- to C
14
-cycloalkyl, C
6
- to C
15
-aryl, alkylaryl where the alkyl radical is of 1 to 20 carbon atoms and the aryl radical is of 6 to 15 carbon atoms, each of which is unsubstituted or substituted by functional groups based on elements 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 (II) have the same meanings as in (I),
A′ and B′ are each —(CR
b
2
)
r′
,— or —(CR
b
2
)
s
—Si(R
a
)
2
—(CR
b
2
)
t
— or —N(R
b
)—, an r′-, s- or t-atom component of a ring system or, together with Z, an (r′+1)-, (s+1)- or (t+1)-atom component of a heterocyclic structure,
R
a
, independently of one another, are each C
1
- to C
20
-alkyl, C
3
- to C
10
-cycloalkyl, C
6
- to C
15
-aryl or alkylaryl where the alkyl moiety is of 1 to 10 carbon atoms and the aryl moiety is of 6 to 15 carbon atoms,
R
b
is the same as R
a
, or hydrogen or Si(R
c
)
3
,
R
c
is C
1
- to C
20
-alkyl, C
3
- to C
10
-cycloalkyl, C
6
- to C
15
-aryl or alkylaryl where the alkyl moiety is of 1 to 10 carbon atoms and the aryl moiety is of 6 to 15 carbon atoms,
r is 1, 2, 3 or 4,
r is 1 or 2,
s and t are each 0, 1 or 2, where 1≦s+t≦3,
z is a nonmetallic element from group VA of the Periodic Table of Elements,
M is a metal selected from the groups VIIIB, IB or IIB of the Periodic Table of Elements,
E
1
and E
2
are each a nonmetallic element from group VA of the Periodic Table of Elements,
R
1
to R
4
are each linear or branched C
2
- to C
28
-alkyl, C
3
- to C
14
-cycloalkyl or alkylaryl where the alkyl moiety is of 1 to 28 carbon atoms and the aryl moiety is of 6 to 15 carbon atoms, each of which is substituted by at least one polar protic or ionic functional group based on nonmetallic elements of groups IVA to VIA of the Periodic Table of Elements,
L
1
and L
2
are formally charged or neutral ligands,
X are formally monovalent or polyvalent anions,
p is 0, 1, 2, 3 or 4,
m and n are each 0, 1, 2, 3 or 4
and p =m×n.
The present invention furthermore relates to the use of these metal complexes for the preparation of linear, alternating copolymers of carbon monoxide and &agr;-olefinically unsaturated compounds. The present invention also relates to water-soluble chelate ligands, a process for the preparation of these chelate ligands and their use for the preparation of water-soluble transition metal complexes.
Transition metal-catalyzed processes for the preparation of linear, alternating copolymers of carbon monoxide and &agr;-olefinically unsaturated compounds, also referred to as carbon monoxide copolymers or polyketones for short, are known. For example, in EP-A 0 121 965 a cis-palladium complex chelated with bidentate phosphine ligands, [Pd(Ph
2
P(CH
2
)
3
PPh
2
)] (OAc)
2
(Ph=phenyl, Ac=acetyl), is used. The carbon monoxide copolymerization can be carried out in suspension, as described in EP-A 0 305 011, or in the gas phase, for example according to EP-A 0 702 045. Frequently used suspension media are on the one hand low molecular weight alcohols, in particular methanol (cf. also EP-A 0 428 228), and on the other hand nonpolar or polar aprotic liquids such as dichloromethane, toluene or tetrahydrofuran (cf. EP-A 0 460 743 and EP-A 0 590 942). Complex compounds having bisphosphine chelate ligands whose radicals on the phosphorus atom are aryl or substituted aryl groups have proven particularly suitable for said polymerization process. Accordingly, 1,3-bis(diphenylphosphino)propane or 1,3-bis[di-(o-methoxyphenyl)phosphino]propane is particularly frequently used as a chelate ligand (cf. also Drent et al., Chem. Rev. 96 (1996), 663-681). Usually, the carbon monoxide copolymerization is carried out in the presence of acids.
The carbon monoxide copolymerization in low molecular weight alcohols, such as methanol, has the disadvantage that the resulting carbon monoxide copolymer absorbs up to 80% by volume of, for example, methanol. Accordingly, a large amount of energy is required to dry the resulting carbon monoxide copolymer and to isolate it in pure form. Another disadvantage is that, even after an intensive drying process, residual amounts of alcohol still remain in the carbon monoxide copolymer. Molding materials prepared in this manner are thus from the outset unsuitable for use as packaging materials for food. EP-A 0 485 035 proposes the use of additions of water in amounts of from 2.5 to 15% by weight to the alcoholic suspending medium in order to eliminate the residual amounts of low molecular alcohol in the carbon monoxide copolymer. However, this procedure, too, does not lead to methanol-free copolymers. On the other hand, the use of halogenated hydrocarbons or aromatics, such as dichloromethane or chlorobenzene or toluene, gives rise to problems particularly in disposal.
To overcome the disadvantages associated with said suspending media, Jiang and Sen, Macromolecules 27 (1994), 7215-7216, describe the preparation of linear, alternating carbon monoxide copolymers in aqueous systems using a catalyst system consisting of [Pd(CH
3
CN
4
) ] (BF
4
)
2
and 1,3-bis[di(3-sulfophenyl)phosphino]propane as water-soluble chelate ligands. However, the catalyst activity achieved is very low and therefore unsuitable for a large-scale industrial preparation.
Compared with Jiang and Sen, Verspui et al., Chem. Commun. (1998), 401-402, achieve an increase in the catalyst activity in the copolymerization of carbon monoxide and ethene by using said chelate ligands in substantially purer form as a result of an improved synthesis method (cf. also Hermann et al., Angew. Chem. Int. Ed. Engl. 34 (1995) 811 et seq.). Furthermore, the presence of a Brönsted acid is required in order to obtain catalyst activities improved in comparison with Jiang and Sen. Although it is actually possible to prepare the chelate ligand 1,3-bis[di(3-sulfophenyl)phosphino]propane in purer form with the aid of an improved synthesis method, this does not provide a route to suitable chelate ligands having other substitution patterns. Thus, the water-soluble transition metal complexes described are limited exclusively to sulfonated aromatic substituents on phosphorus. Preparation of these chelate ligands furthermore requires the handling of very aggressive substances, such as boric acid, concentrated sulfuric acid and oleum. Owing to the given structure, an extension to other systems is in principle not possible.
It is therefore desirable, for the copolymerization of carbon monoxide and &agr;-olefinically unsaturated compounds in aqueous systems, to be able to rely on metal complexes which should from the outset permit a large number of different substituents on chelate ligands and at the same time enable constantly good reproducibility in combination with high efficiency.
It is an object of the present invention to provide water-soluble transition metal complexes which are suitable as the active component of a catalyst system for the preparation of linear, alternating carbon monoxide copolymers in aqueous media.
We have found that this object is achieved by the water-soluble transition metal complexes defined at the outset. We have also found a process for the preparation of these transition metal complexes and their use for the preparation of linear, alternating carbon monoxide copolymers.
We have furthermore found water-soluble chelate ligands, a process for the preparation of these chelate ligands and their use for the preparation of water-soluble transition metal complexes.
Preferred novel water-soluble transition metal complexes are based on compounds of the formula (Ia)
where
G is —(CR
b
2
)
r
— or —(CR
b
2
)—N(R

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