WO2000063277A1

WO2000063277A1 - Method of producing carbon monoxide copolymers in an aqueous medium using water-soluble metal complexes and solubilizers

Info

Publication number: WO2000063277A1
Application number: PCT/EP2000/003228
Authority: WO
Inventors: Joachim Queisser; Graham Edmund Mc Kee; Michael GEPRÄGS; Ekkehard Lindner; Markus Schmid; Joachim Wald; Peter Wegner
Original assignee: Basf Aktiengesellschaft
Priority date: 1999-04-20
Filing date: 2000-04-11
Publication date: 2000-10-26
Also published as: CN1347429A; AU3819900A; JP2002542355A; DE19917920A1; EP1171506A1; BR0009386A

Abstract

The invention relates to a method of producing linear, alternating copolymers from carbon monoxide and an olefinically unsaturated compound with three to twenty carbon atoms or from carbon monoxide and at least two different olefinically unsaturated compounds in an aqueous medium. The inventive method is characterized by carrying out the copolymerization in the presence of a1) metal complexes, b) a solubilizer and optionally c) a hydroxy compound.

Description

Process for the production of carbon monoxide copolymers in an aqueous medium using water-soluble metal complexes and solubilizers

description

The present invention relates to a process for the preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having three to twenty carbon atoms or of carbon monoxide and at least two different olefinically unsaturated compounds in an aqueous medium.

Linear, alternating copolymers of carbon monoxide and olefinically unsaturated compounds, also referred to briefly as carbon monoxide copolymers or polyketones, are known. For example, high molecular weight, partially crystalline polyketones with a strictly alternating sequence of monomers in the main chain are generally distinguished by high melting points, good heat resistance, good chemical resistance, good barrier properties against water and air, and advantageous mechanical and rheological properties.

Of particular technical interest are polyketones made from carbon monoxide and two olefins, generally α-olefins, such as, for example, carbon monoxide-ethylene-propylene, carbon monoxide-ethylene-butene-1, carbon monoxide-ethylene-hexene-1, carbon monoxide- Propylene-butene-1 or carbon monoxide-propylene-hexene-1 copolymers.

Transition metal-catalyzed processes for the production of polyketones are known. For example, EP-A 0 121 965 uses a cis-palladium complex chelated with bidentate phosphine ligands, [Pd (Ph ₂ P (CH ₂ ) ₃ PPh)] (OAc) ₂ (Ph = phenyl, Ac = acetyl) . 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 (see also EP-A 0 428 228), and on the other hand non-polar or polar aprotic liquids such as dichloromethane, toluene or tetrahydrofuran (cf. EP-A 0 460 743 and EP-A 0 590 942 ). Complex compounds with bisphosphine chelate ligands whose residues on the phosphorus represent aryl or substituted aryl groups have proven to be particularly suitable for the polymerization processes mentioned. Accordingly, 1,3-bis (diphenylphosphino) propane or 1,3-bis [di- (o-ethoxyphenyl) phosphino)] propane are particularly frequently used as chelating ligands used (see also Drent et al., Chem. Rev., 1996, 96, pp. 663-681). In the cases mentioned, 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 has the disadvantage that the carbon monoxide copolymer which forms has a high absorption capacity for these liquids and up to 80% by volume of e.g. Methanol are bound or taken up by the carbon monoxide copolymer. As a result, a large amount of energy is required to dry and isolate the carbon monoxide copolymers. Another disadvantage is that even after an intensive drying process, residual amounts of alcohol still remain in the carbon monoxide copolymer. Use as a packaging material for food is therefore ruled out from the outset for molding compositions produced in this way. EP-A 0 485 035 proposes the use of additions of water in proportions of 2.5 to 15% by weight to the alcoholic suspending agent in order to eliminate the residual amounts of low molecular weight alcohol in the carbon monoxide copolymer. However, this procedure also 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 poses problems, particularly in handling and disposal.

To circumvent the disadvantages associated with the suspension agents mentioned, Jiang and Sen, Macromolecules, 1994, 27, pp. 7215-7216 describe the preparation of linear, alternating carbon monoxide copolymers in aqueous systems using a catalyst system consisting of [Pd (CHCN) ₄ ] (BF ₄ ) and 1, 3-bis [di- (3-benzenesulfonic acid) phosphino] propane as a water-soluble chelating ligand. However, the catalyst activity achieved is unsatisfactory.

Verspui et al. , Chem. Commun., 1998, pp. 401-402, compared to Jiang and Sen, the catalyst activity in the copolymerization of carbon monoxide and ethene can be increased by using the chelate ligands mentioned in a substantially purer form. Furthermore, the presence of a Bronsted acid is required in order to achieve improved catalyst activities compared to Jiang and Sen. The polyketones described in the publication, produced from carbon monoxide and ethylene, have the disadvantage that their molecular weight is lower than that of comparable polyketones, which are produced in methanol as solvents. The object of the present invention was to provide a process for the preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having three to twenty carbon atoms or of carbon monoxide and at least two different olefinically unsaturated

To provide compounds in an aqueous medium with which, regardless of the olefins used, high catalyst activities and, in the case of several olefins, high copolymer installation rates can also be achieved. Furthermore, the invention was based on the object that the polyketones obtained in this way have high molecular weights and good physical properties, e.g. high bulk densities.

Accordingly, a process for the preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having three to twenty carbon atoms or of carbon monoxide and at least two different olefinically unsaturated compounds in an aqueous medium has been found, which is characterized in that the copolymerization is carried out in Presence of

al) metal complexes of the general formula (I)

in which the substituents and indices have the following meaning:

5-, 6- or 7-atom carbocyclic ring system without or with one or more heteroatoms, - (CR ₂ ) _r -, - (CR ^b ₂ ) _s -Si (R ^a ) ₂ - (CR ^b ₂ ) _t -, -AOB- or -AZ (R ⁵ ) -B- with

5 hydrogen, unsubstituted or with functional groups which contain atoms from groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements, substituted C 1 -C ₈ -alkyl, C ₃ - to C ₄ -cycloalkyl, C ₆ - bis Cι ₅ aryl or alkylaryl having 1 to 20 carbon atoms in the alkyl radical and 6 to 15 carbon atoms Atoms in the aryl radical, -N (R ^b ), -Si (R ^c ) ₃ or a radical of the general formula (II)

in the

q denotes an integer from 0 to 20 and the further substituents in formula (II) have the same meaning as in formula (I).

A, B - (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 component of a ring system or together with Z a (r '+ l) -, (s + 1) - or (t + 1) -atomic component of a heterocycle,

R ^a independently of one another C ~ to C o-alkyl, C ₃ - to

Cio-cycloalkyl, Cς- to Cis-aryl or alkylaryl with 1 to 10 C atoms in the alkyl part and 6 to 15 C atoms in the aryl part, where the radicals mentioned can also be substituted,

R ^b as R ^a , additionally hydrogen or Si (R ^c ) ₃ ,

R ^c Ci to C o ~ alkyl, C - to Cio-cycloalkyl, C ₆ - to cis-aryl or alkylaryl with 1 to 10 C atoms in the alkyl part and 6 to 15 C atoms in the aryl part, the said radicals also can be substituted

r 1, 2, 3 or 4 and

r '1 or 2,

s, t 0, 1 or 2, where 1 <s + t <3,

Z is a non-metallic element from group VA of the periodic table of the elements, M is a metal selected from Groups VIIIB, IB or IIB of the Periodic Table of the Elements,

E ¹ , E ² a non-metallic element from group VA of the periodic table of the elements,

R ¹ to R ^{4 are} linear or branched C ₂ - to C ₂₈ -alkyl, C ₃ - to -C ₄ -cycloalkyl, C _ß- cis-aryl or alkylaryl with 1 to 28 C-atoms in the alkyl part and 6 to 15 C-atoms in the aryl part, where at least one of the radicals R ¹ to R ⁴ has at least one hydroxyl, amino or acid group or contains an ionically functional group,

L ¹ , L ² formally charged or neutral ligands,

X formally mono- or polyvalent anions,

p 0, 1, 2, 3 or 4,

m, n 0, 1, 2, 3 or 4,

where p = m x n,

b) a solubilizer and, if necessary

c) a hydroxy compound

carries out.

According to the invention, water-soluble transition metal complexes and solubilizers were therefore simultaneously used to increase the concentrations of the olefins in solution and to stabilize the water-insoluble polyketones.

The invention also relates to a method in which the metal complex a1) is not presented in the form of a defined compound, but is formed in situ from the individual components during the copolymerization.

The invention further relates to a process for the preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having three to twenty carbon atoms or of carbon monoxide and at least two different olefinically unsaturated compounds in aqueous medium. diu, in which, in addition to the components al) and b) or al.l), al.2) 'and b) mentioned, an acid and, if appropriate, a hydroxy compound is used.

The designations for the groups in the Periodic Table of the Elements are based on the nomenclature used by the Chemical Abstracts Service until 1986 (for example, the VA group contains the elements N, P, As, Sb, Bi; the IB group contains Cu, Ag, Au).

In a preferred process according to the invention, the copolymerization is carried out in the presence of

al) a water-soluble metal complex of the general formula (Ia)

in which the substituents and indices have the following meaning:

G - (CR ^b ₂ ) _r - or - (CR ^b ₂ ) -N (R ⁵ ) - (CR ^b ₂ ) -, wherein

R ^b hydrogen f, Cι ~ to Cio-alkyl or C ₆ - bis

Cio aryl,

r 1, 2, 3 or 4,

R ^{5 is} hydrogen, C 1 to C ₀ alkyl, C ₃ to C ₀ cycloalkyl, 0 to cis aryl, with functional groups which atoms of groups IVA, VA, VIA or VIIA of the periodic table Contain elements, substituted C ~ to Cio-alkyl, C- to Cirj-cycloalkyl or C ₆ - to Cis-aryl,

M palladium or nickel,

E ¹ , E ² phosphorus, R ¹ to R ^{4 are} linear, branched or carbocycle-containing C - to C ₂₈ -alkyl units, C ₃ - to -CC ₄ cycloalkyl units, C _δ- cis-aryl units or alkylaryl - groups with 1 to 20 C atoms in the alkyl part and 6 to 15 carbon atoms in the aryl part, at least one of the radicals R ¹ to R ⁴ having at least one terminal, internal or hydroxy, amino, carboxylic acid, phosphoric acid, ammonium or sulfonic acid group,

L ¹ , L ² acetate, trifluoroacetate, tosylate or halides,

a2) sulfuric acid, p-toluenesulfonic acid, tetrafluoroboric acid, trifluoromethanesulfonic acid, perchloric acid or trifluoroacetic acid as protonic acid or boron trifluoride, antimony pentafluoride or triarylborane as Lewis acid,

b) an anionic, cationic, amphoteric or non-ionic emulsifier and

c) a mono- or polyhydric alcohol or a sugar

carried out .

In a further embodiment, a process is preferred in which the metal complex al) has at least one radical among the substituents R ¹ to R ⁴ which is substituted by at least one free carboxylic acid or sulfonic acid group, C ₂ -C ₂₈ -alkyl, C ₃ -C to -C cycloalkyl, C ₆ -C ₅ aryl or alkylaryl having 1 to 28 carbon atoms in the alkyl part and 6 to 15 carbon atoms in the aryl part, completely dispensing with the presence of external acids a2).

In a further method according to the invention, the metal complex a1) is not prepared beforehand and used in a defined form in the copolymerization, but only by adding the metal component a1) and the chelate ligand a1.2) to the starting materials of the copolymerization. generated in situ.

Basically, bidentate chelate ligands of the general formula (R ¹ ) (R ² ) E ^x -GE ² (R ³ ) (R ⁴ ) (III) are suitable as constituents of the metal complexes al) or as chelate ligand al.2) in the process according to the invention, in which the substituents and indices have the aforementioned meaning. The bridging structural unit G in the metal complexes al) or the chelate ligands al.2) of the process according to the invention generally consists of mono- or polyatomic bridge segments. A bridging structural unit is basically understood to mean a grouping which connects the elements E ¹ and E ^{2 to} one another. Such structural units include, for example, substituted or unsubstituted alkylene chains or those alkylene chains in which an alkylene unit has been replaced by a silylene group, an amino or phosphino group or by an ether oxygen.

The bridging structural unit G can furthermore be a 5-, 6- or 7-atom carbocyclic ring system without or with one or more heteroatoms. The ring system can be aliphatic or aromatic. 5- or 6-atomic ring systems with 0, 1 or 2 heteroatoms selected from N, 0 or S are preferred

The bonds to the atoms E ¹ and E ² can take any position relative to one another. Preferred positions relative to one another are the 1,2, 1,3 and 1,4 positions.

Preferred embodiments for cyclic structural units G are the following (binding sites to E ¹ and E ² are identified):

NH

Among the monatomic bridged structural units are those with a bridging atom from group IVA of the periodic table of the elements such as -C (R ^b ) - or -Si (R ^a ) ₂ -, wherein R ^a independently of one another in particular for linear or branched Cι ~ to Cio-alkyl, for example methyl, ethyl, i-propyl or t-butyl, C ₃ - to Cε-cycloalkyl, such as cyclopropyl or cyclohexyl, Cζ- to Cio-aryl, such as phenyl or naphthyl, with functional groups, which are non-metallic elements of groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements contain substituted Cε- to Cio-aryl, for example tolyl, (trifluoromethyl) phenyl, dirnethylaminophenyl, p-methoxyphenyl or partially or perhalogenated phenyl, aralkyl with 1 to 6 C. -Atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part, for example benzyl, and R ^{b are} in particular hydrogen and also represent the meanings given above for R ^a , preferred. R ^a represents in particular a methyl group, R ^{b represents} in particular hydrogen.

Among the multi-atom bridged systems, the two-, three- and four-atom bridged structural units should be emphasized, with the tri-atomic bridged systems generally being used with preference.

Suitable three-atom bridged structural units are generally based on a chain of carbon atoms, for example propylene (-CH ₂ CHCH-), or on a bridge unit with a heteroatom from group IVA, VA or VIA of the periodic table of the elements, such as silicon, Nitrogen, phosphorus or oxygen in the chain structure.

The bridging carbon atoms can generally with Cι ~ to Cε-alkyl such as methyl, ethyl or t-butyl, C ₆ - to Cio-aryl such as phenyl or by functional groups, which elements of groups IVA, VA, VIA or VIIA of the periodic table of the elements contain, for example, triorganosilyl, dialkylamino, alkoxy, hydroxy or halogen. Suitable substituted propylene bridges are, for example, those with a methyl, phenyl, hydroxy, trifluoromethyl, ω-hydroxyalkyl or methoxy group in the 2-position.

Among the multi-atomic structural units with one

Heteroatoms in the chain structure are advantageously used in which Z is nitrogen or phosphorus, in particular nitrogen (see also formula (I)). The substituent R ⁵ on Z can in particular mean: hydrogen, linear or branched C 1 to C ₂₈ "alkyl, in particular C ₁ to C ₂ o alkyl such as methyl, ethyl, i-propyl, t-butyl, n-hexyl or ή -Dodecyl, C - to C -cycloalkyl, in particular C ₃ to Cs-cycloalkyl such as cyclopropyl or cyclohexyl, C _ß - to cis-aryl, in particular Cς- to Cio-aryl, for example phenyl, or alkylaryl with I to 20 C atoms in the alkyl radical and 6 to 10 C atoms in the aryl radical, for example benzyl.

The alkyl and aryl radicals mentioned can be unsubstituted or substituted. Examples of suitable substituents are functional groups which contain atoms from groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements. Suitable are inter alia triorganosilyl groups such as trimethylsilyl or t-butyldiphenylsilyl, the carboxylic acid group or carboxylic acid derivatives such as esters or amides, primary, secondary or tertiary amino groups such as dimethylamino or methylphenylamino, the nitro and the hydroxyl group, and further alkoxy groups such as methoxy or ethoxy, the sulfon and also halide atoms such as fluorine, chlorine or bromine. For the purposes of the present invention, aryl also means substituted and unsubstituted heteroaryl, for example pyridyl or pyrrolyl. Alkyl radicals R ⁵ also include long-chain alkylene groups with 12 to 22 carbon atoms in the chain, which also have functionalities such as the sulfonic acid, carboxylic acid, phosphoric acid, hydroxy, amino or ammonium group, for example in the terminal position, can dispose of.

Preferred radicals R ^{5 are} also those compounds which represent an electron-withdrawing substituent. Suitable electron-withdrawing substituents are, for example, alkyl groups with one or more electron-withdrawing radicals such as fluorine, chlorine, nitrile or nitro in the α or β position to Z. Aryl groups with the electron-withdrawing radicals mentioned and also as radicals bonded directly to Z are also suitable, too the nitrile, sulfonate and nitro group. Examples of suitable electron-withdrawing alkyl radicals are the trifluoromethyl, trichloroethyl, difluoromethyl, 2, 2, 2-trifluoroethyl, nitromethyl and the cyanomethyl group. Examples of suitable electron-withdrawing aryl radicals are: m-, p-, o-fluorophen or chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2,4,6-trifluorophenyl, 3,5-bis (tri-fluoromethyl) ) phenyl, nitrophenyl, 2-chloro-5-nitrophenyl and 2-bromo-5-nitrophenyl. In this connection, carbonyl units are also suitable as radicals R ⁵ , so that when Z is nitrogen, Z and R ^{5 form} a carboxylic acid amide functionality. The acetyl or trifluoroacetyl group may be mentioned as such a suitable radical.

Among the radicals R ⁵ , t-butyl, phenyl, p-fluorophenyl, trifluoromethyl, 2, 2, 2-trifluoroethyl, pentafluorophenyl, 3, 5-bis (trifluoromethyl) phenyl and ortho-, for example 3,4- , meta, for example 2,4-, or para, for example 2, 5-difluorophenyl. As units A and B according to formulas (I) to (IV) are C 1 -C ₄ -alkylene units in substituted or unsubstituted form, for example methylene, ethylene, propylene or ethylidene, propylidene and benzylidene. Methylene, ethylene, ethylidene or benzylidene are preferably used, particularly preferably methylene.

A and B can also be a one, two, three or four atom component of an aliphatic or aromatic ring system. For example, A and B can be a methylene or ethylene unit of a cyclopropyl, cyclopentyl or cyclohexyl ring. Aliphatic and aromatic heterocycles are also suitable as ring systems.

A and B can furthermore be constituents of a heterocycle which is formed from the components AZ (R ⁵ ) -B, AZR ⁵ and BZR ⁵ , respectively. AZR ⁵ or BZR ⁵ can, for example, form a substituted or unsubstituted pyrrolidine or piperidine ring.

The chelating atoms E ¹ and E ² are, independently of one another, the non-metallic elements of group VA of the Periodic Table of the Elements, preference being given to nitrogen and phosphorus, in particular phosphorus. In a preferred embodiment, E ¹ and E ² in the compounds according to formulas (I) and (III) represent phosphorus.

In the process according to the invention, the radicals R ¹ to R ^{4 represent} substituted C ₂ - to C ₂₈ - »preferably C ₃ - to C ₂ o-alkyl, C ₃ - to Cι ₄ -, preferably C ₃ - to Cs-cycloalkyl, C _β- cis, preferably Cg-Cio-aryl or alkylaryl having 1 to 28, preferably 3 to 20 C atoms in the alkyl part and 6 to 15, preferably 6 to 10 C atoms in the aryl part, at least one, preferably more, particularly preferably all of the radicals R ¹ to R ⁴ have at least one hydroxyl, amino or acid group or contain an ionically functional group. Ionic functional groups are groups based on non-metallic elements from groups IVA to VIA of the periodic table of the elements, for example sulfonate, phosphate, ammonium, carboxylate. R ¹ to R ⁴ are preferably linear, branched or carbocyclic-containing C ₂ to C ₈ ~ A1 alkyl units or C ₃ to C ₄ cycloalkyl units, or C ₆ -C ₅ aryl units or alkylaryl groups having 1 to 28 C- Atoms in the alkyl part and 6 to 15 carbon atoms in the aryl part, at least one, preferably several, particularly preferably all of the radicals containing at least one hydroxyl, carboxylic acid, phosphoric acid, ammonium, amine or sulfonic acid group. The salts of carboxylic, phosphoric, amino or sulfonic acids can also be used. Suitable salts are, for example, ammonium, alkylammonium, arylammonium, alkali or alkaline earth metal salts such as sodium, potassium or magnesium carboxylates or sulfonates.

Counterions for the ammonium radicals mentioned are, in particular, non-nucleophilic anions, as are also used for the metal complexes a1 (see anions X). For example, p-toluenesulfonate, tetrafluoroborate, trifluoroacetate, trichloroacetate, hexafluorophosphate, hexafluoroantimonate or tetraarylborate are particularly suitable.

Particularly suitable aryl radicals R ¹ to R ⁴ are, for example, aryl units with or without one or more, for example 1 to 3, heteroatoms in the ring which are substituted by one or two hydroxyl, carboxylic acid, sulfonic acid or amino groups. The phenyl (en) radical is preferred among the aryl or arylene radicals R ¹ to R ⁴ . Furthermore, the radicals R ¹ to R ^{4 can} also have more than two polar groups and, for example, have four or six hydroxyl, ammonium or carboxylic acid groups. The cyclopentyl and cyclohexyl radicals are preferred as cycloaliphatic radicals R ¹ to R ⁴ . Particularly suitable alkyl radicals R ¹ to R ⁴ are, for example, alkylene units with one or two terminal hydroxyl, carboxylic acid, sulfonic acid or ammonium groups. In these cases too, the radicals R ¹ to R ^{4 can have} more than two polar groups and, for example, have four or six hydroxyl, ammonium or carboxylic acid groups. Accordingly, the radicals R ¹ to R ^{4 can} each also have different functional groups. The radicals R ¹ to R ^{4 can also have} functional groups in different numbers from one another. Suitable functional groups include, for example, the hydroxyl, amine, carboxylic acid, phosphoric acid, ammonium and sulfonic acid groups.

Suitable propylene-bridged chelate ligand compounds can be prepared, for example, from the commercially available 1,3-dibromopropane. A double Arbuzov reaction, for example with triethyl phosphite, leads to 1,3-bisphosphonic acid derivatives which are reductive, as described in "Methods of Organic Chemistry (Houben-Weyl)", 4th edition, Volume XII / 1 , Part 1, Georg Thieme Verlag, 1963, p. 62, can be converted into 1, 3-diphosphinopropane. 1,3-diphosphinopropane opens up flexible access to substituted bisphosphines via a hydrophosphination reaction with functionalized olefins. Hydrophosphination generally proceeds via a radical mechanism and can be carried out thermally, can be initiated chemically or with the help of a radical starter. Temperatures in the range from 20 to 100 ° C. and pressures from 0.1 to 5 bar are generally required for thermal initiation. Suitable radical initiators are, for example, di-t-butyl peroxide or azo-bis- [isobutyronitrile]. For photochemical initiation, UV radiation with a high pressure mercury lamp over a period of 2 to 48 hours is usually sufficient for quantitative hydrophosphination. Anti-Markovnikov products are generally obtained by means of radical-initiated processes in the hydrophosphination.

For the production of chelate ligands with radicals R ¹ to R ⁴ which carry carboxylic acid groups, it has proven to be advantageous to start from olefinically unsaturated compounds which are derivatized with corresponding carboxylic acid ester groups and to use them in the hydrophosphination reaction. The free carboxylic acids can then be obtained by saponification using known methods.

In addition, suitable chelate ligand compounds can also be prepared under acid-catalyzed conditions. The products obtained by this process are often obtained as a mixture under the acidic reaction conditions due to the isomerization of the olefinic double bond. The process step of hydrophosphination is found e.g. in "Methods of Organic Chemistry (Houben-Weyl)", 4th edition, Volume XII / 1, Part 1, Georg Thieme Verlag, 1963, pp. 25 to 28.

In general, all olefins which fall under this class of compounds are suitable for the hydrophosphination reaction mentioned, provided that they have appropriate functional groups, such as, for example, hydroxyl, amino, carboxylic acid, phosphoric acid, ammonium and sulfonic acid groups. For example, propenyl radicals and C ₄ - to C ₂₈ -alkenes with at least one internal or terminal double bond which have at least one hydroxyl, amino, carboxylic acid, phosphoric acid, ammonium or sulfonic acid group. Also suitable are olefinic compounds with aromatic radicals, where the functional group can be present both on the aliphatic and on the aromatic radical, for example 4- (1-pentene) -benzoic acid or 3-phenylpent-5-ene-carboxylic acid . Furthermore, olefinic compounds with aliphatic carbocycles in the alkylene chain are suitable as a substituent. Cyclic olefins such as cyclohexen-3-ol or cycloocten-4-ol can also be used. Naturally carboxylic acid can also olefins with a plurality of functional groups selected from ^'hydroxy, amino, resorted phosphoric acid, ammonium and sulphonic acid groups become. Suitable alkenes with an α-olefinic double bond are preferably used in the hydrophosphination reaction of the α, ω-bisphosphines. As such, for example, heteroatom-containing α-olefins, such as (meth) acrylic acid esters or amides, and homoallyl or allyl alcohols are also suitable.

In the case of aromatic radicals R ¹ to R ⁴ , chelate ligands containing sulfonic acid groups can be prepared by reacting non-sulfonic acid-containing chelate ligands with SO ₃ , chlorosulfonic acid, fuming sulfuric acid or oleum, as described in Jiang et al., Macromolecules 21 (1994 ) 7215-7216 or Verspui et al. , Chem. Commun., 1998, 401-402 or in J. March "Advanced Organic Chemistry", John Wiley & Sons (NY), 1985, ^{3τ &} Edition pp. 473-475.

Further syntheses for chelate ligands with aromatic radicals R ¹ to R ⁴ are described in:

"Phosphorus - An outline of its Chemistry, Biochemistry and Technical Chemistry" D.E.C. Corbridge, Elsevier (Amsterdam,

Tokyo, New York) 1990, 4th. Edition, Chapter 8, and literature cited therein

SO. Grim, R.C. Barth, J. of Organo et. Chem. 94, 1975, p. 327 - W098 / 22482

Particular preference is given to using radicals R ¹ to R ⁴ in which the hydrophilicity induced by functional groups, for example hydroxyl, amino, carboxylic acid, phosphoric acid, ammonium or sulfonic acid groups, is sufficient for the metal complex a1) to be completely water-soluble close. The greater the number of functional groups on the radicals R ¹ to R ⁴ , the greater the lipophilic aliphatic, aromatic or aliphatic-aromatic component. For example, preferred radicals R ¹ to R ⁴ , each having a hydroxyl group, are those having 2 to 15 C atoms in the alkyl unit or 6-15 C atoms in the aryl unit.

In a particularly preferred embodiment of the chelate ligand, the radicals R ¹ to R ^{4 have} aryl substituents with a hydroxyl group having 6 to 12, in particular 6 to 10, carbon atoms, and aryl substituents with a carboxylic acid group have 6 to 15, in particular 6 to 10, carbon atoms , as aryl substituents with a sulfonic acid group over 6 to 15, and as aryl substituents with an ammonium group over 6 to 15 C atoms. Suitable chelating ligands are, for example, 1,3-bis [di- (hydroxyphenyl) phosphino] propane,

1, 3-bis [di- (benzenesulfonic acid) phospino] propane, preferably as a meta-isomer, and its salts, 1, 3-bis [di- (carboxyphenyl) phospino] propane and its salts, 1, 3-bis [di- (o-methoxyhydroxyphenyl) phosphino] propane 1,3-bis [di- (4- (benzenesulfonic acid) butyl) phosphino] propane, Na salt, 1,3-bis [di- (5- (benzenesulfonic acid) pentyl ) phosphino] ropan, sodium salt.

Particularly preferred among the chelate ligand compounds mentioned are those in which the radicals R ¹ to R ^{4 represent} a phenyl radical substituted by one or more, for example 1 to 3, hydroxyl, sulfonic acid or carboxylic acid groups.

In a particularly preferred embodiment of the chelate ligand, the radicals R ¹ to R ^{4 have} alkyl substituents with a hydroxyl group of 4 to 12, in particular 4 to 7, carbon atoms, and alkyl substituents with a carboxylic acid group have 4 to 15, in particular 5 to 12, carbon atoms , as alkyl substituents with a sulfonic acid group over 4 to 18, in particular 5 to 15 C atoms and as alkyl substituents with an ammonium group over 4 to 22, in particular 5 to 20 C atoms.

Examples of suitable chelating ligands are

1, 3-bis (di -4-hydroxybutyl) phosphinopropane,

1,3-bis (di-5-hydroxypentyl) phosphinopropane,

1,3-bis (di-6-hydroxyhexyl) phosphinopropane,

1,3-bis (di-7-hydroxyheptyl) phosphinopropane, 1,3-bis (di-8-hydroxyoctyl) phosphinopropane,

1,3-bis (di (3-hydroxycyclopentyDpropyl) phosphinopropane,

1,3-bis [di-5- (sulfonic acid) pentyl] phosphinopropane,

1,3-bis [di-6- (sulfonic acid) hexyl] phosphinopropane,

1,3-bis [di-7- (sulfonic acid) heptyl] phosphinopropane, 1,3-bis [di-8- (sulfonic acid) octy] phosphinopropane,

1,3-bis [di (3- (sulfonic acid) cyclopentyDpropyl] phosphinopropane,

1,3-bis (di-5-pentanoic acid) phosphinopropane,

1, 3-bis (di-propylmalonic acid) phosphinopropane,

1,3-bis (di-6-hexanoic acid) phosphinopropane, 1,3-bis (di-7-heptanoic acid) phosphinopropane,

1,3-bis (di-8-octanoic acid) phosphinopropane,

Bis [(di -4-hydroxybutyl) phosphinomethyl] phenylamine,

Bis [(di-5-hydroxypentyl) phosphinomethyl] phenylamine,

Bis [(di-6-hydroxyhexyl) phosphinomethyl] phenylamine, bis [(di-7-hydroxyheptyl) phosphinomethyl] phenylamine.

Bis [(di-8-hydroxyoctyl) phosphinomethyl] phenylamine,

Bis [(di (3-hydroxycyclopentyl) propyl] phenylamine, Bis [(di-5- (sulfonic acid) pentodphosphinomethyl] phenylamine, bis [(di-6- (sulfonic acid) hexyDphospinomethyl] phenylamine. Bis [(di-7-sulfonic acid) heptyl) phosphinomethyl] phenylamine, bis [(di-8- sulfonic acid) octyl) phosphinomethyl) phenylamine, bis [(di (3-sulfonic acid) cyclopentyl) propyl) phosphinomethyl] phenylamine.

Bis [(di-5-pentanoic acid) phosphinomethyl] phenylamine bis [(di-δ-hexanoic acid) phosphinomethyl] phenylamine, bis [(di-7-heptanoic acid) phosphinomethyl] phenylamine and bis [(di-8-octanoic acid) phosphinomethyl] phenylamine ,

1,3-bis [di- (4-methylol-5-hydroxyisopentyl)] phosphinopropane.

Particularly preferred among the chelating ligand compounds mentioned are those in which the radicals R ¹ to R ^{4 represent} a hexyl, 4-methylpentyl, octyl, cyclopentyl or cyclohexyl radical substituted by a hydroxyl or carboxylic acid group.

Suitable metals M of the process according to the invention are the metals from groups VIIIB, IB and IIB of the Periodic Table of the Elements, that is, in addition to iron, cobalt and nickel, primarily the platinum metals such as ruthenium, rhodium, osmium, iridium and platinum and very particularly preferably palladium. The metals in the complexes according to formula (I) can be formally uncharged, formally single positively charged or preferably formally double positively charged.

Suitable formally charged anionic ligands L ¹ , L ² are hydride, halides, sulfates, phosphates or nitrates. Carboxylates or salts of organic sulfonic acids such as methyl sulfonate, trifluoromethyl sulfonate or p-toluenesulfonate are also suitable. Among the salts of organic sulfonic acids, p-toluenesulfonate is preferred. The formally charged ligands L ¹ , L ² are carboxylates, preferably Ci to C o ~ carboxylates and in particular C 1 ~ to C ₇ carboxylates, ie, for example, acetate, trifluoroacetate, propionate, oxalate, citrate or benzoate. Acetate is particularly preferred.

Suitable formally charged organic ligands L ¹ , L ² are also -C ~ to Co ~ aliphatic radicals, C ₃ - to C ₃ o-cycloaliphatic radicals, C - to C ₂ o-aralkyl radicals with Cg to -C aryl radicals and Cι ~ bis

Cε-alkyl radicals and C ₆ - to C o-aromatic radicals, for example methyl, ethyl, propyl, i-propyl, t-butyl, n-, i-pentyl, cyclohexyl, benzyl, phenyl and aliphatic or aromatic substituted phenyl radicals. Lewis bases, ie compounds with at least one lone pair of electrons, are generally suitable as formally uncharged ligands L ¹ , L ² . Lewis bases whose free electron pair or whose free electron pairs are located on a nitrogen or oxygen atom, for example nitriles, R-CN, ketones, ethers, alcohols or water, are particularly suitable. Preference is given to using C ~ to Cιo-nitriles such as acetonitrile, propionitrile, benzonitrile or C - to Cio-ketones such as acetone, acetylacetone or C - to Cio-ethers such as methyl ether, diethyl ether, tetrahydrofuran. In particular, acetonitrile, tetrahydrofuran or water are used.

Basically, the ligands L ¹ and L ^{2 can be} in any ligand combination, ie the metal complex (I) can, for example, contain a nitrate and an acetate residue, a p-toluenesulfonate and an acetate residue or a nitrate and a formally charged organic Contain ligands such as methyl. L ¹ and L ² are preferably present as identical ligands in the metal complexes.

Depending on the formal charge of the complex fragment containing the metal M, the metal complexes contain anions X. If the M-containing complex fragment is formally uncharged, the complex according to the invention according to formula (I) does not contain any anion X. Anions X which are as little nucleophilic as possible, ie have as little tendency as possible to interact strongly with the central metal M, whether ionic, coordinative or covalent.

Suitable anions X are, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as, for example, acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids such as, for example, methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate, and furthermore Tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate. Perchlorate, trifluoroacetate, sulfonates such as methyl sulfonate, trifluoromethyl sulfonate, p-toluenesulfonate, tetrafluoroborate or hexafluorophosphate and in particular trifluoromethylsulfonate, trifluoroacetate, perchlorate or p-toluenesulfonate are preferably used.

The following palladium (II) acetate complexes are suitable as defined metal complexes: [1, 3-bis (di-hydroxyphenyl) phosphinopropane] -, [1, 3-bis (di -4-hydroxybutyl) phosphinopropane] -,

[1,3-bis (di-4-methylol - 5-hydroxypentyl) phosphinopropane] -, [1,3-bis (di-5-hydroxypentyl) phosphinopropane] -, [1,3- bis di-6-hydroxyhexyl) phosphinopropane] -,

[1,3- bis di (3-hydroxycyclopentyDpropyl) phosphinopropane] -,

[1,3- bis di-8-hydroxyoctyl) phosphinopropane] -,

[1,3- bis di-3-hydroxycyclohexyl) propyl) phosphinopropane] -,

[1,3- bis bis-sulfonatophenyl) phosphinopropane] -,

[1,3'-bis di-4 -sulfonatobutyl) phosphinopropane] -,

[1,3- bis di -4 -methylol -5 -sulfonatopentyl) phosphinopropane] -,

[1,3- bis di-5-sulfone topentyl) phosphinopropane] -,

[1,3- bis di-6-sulfonatohexyl) phosphinopropane] -,

[1,3- bis di (3-sulfone tocyclopentyDpropyl) phosphinopropane] -

[1,3- bis di-8-sulfonatooctyl) phosphinopropane] -,

[1,3- bis di-3-sulfonatocyclohexyl) propyl) phosphinopropane] -,

[1,3- bis di-carboxyphenyl) phosphinopropane] -,

[1,3'-bis di -4-carboxybutyl) phosphinopropane] -,

[1,3'-bis di-4-methylol -5-carboxypentyl) phosphinopropane] -,

[1,3- bis di-5-carboxypentyl) phosphinopropane] -,

[1,3- bis di-6-carboxyhexyl) phosphino-propane] -,

[1,3- bis di (3-carboxycyclopentyl) propyl) phosphinopropane] -,

[1,3- bis di-8-carboxyoctyl) phosphinopropane] -,

[1,3- bis di-3-carboxycyclohexyl) propyl) phosphinopropane] palladium (II) acetate.

The transition metal complexes described are soluble in water, at least in small parts. As a rule, these metal complexes are readily or very readily soluble in water.

Defined metal complexes according to formula (I) can be produced by the following processes.

The neutral chelate complexes (p = 0) are produced by exchanging weakly coordinating ligands, such as 1, 5-cyclooctadiene, benzonitrile or tetramethylethylenediamine, which are attached to the corresponding transition metal compounds, e.g. transition metal halides, transition metal ( Alkyl) (halides), transition metal diorganyls, are bound against the chelating ligands of the general formula (III) in the meaning described above.

The reaction is generally carried out in a polar solvent, such as, for example, acetonitrile, acetone, ethanol, diethyl ether, dichloromethane or tetrahydrofuran or mixtures thereof, at temperatures in the range from -78 to + 90.degree.

Furthermore, neutral metal complexes of the formula (I) in which L ¹ and L ^{2 are} carboxylate, for example acetate, can be reacted with transition metal salts such as Pd (OAc) with the described chelate ligands (III) in acetonitrile, acetone, ethanol, Diethyl ether, dichloromethane, tetrahydrofuran or water can be prepared at room temperature. Mixtures of solvents can also be used.

A further synthesis method is the reaction of the metal complexes of the general formula (I) with organometallic compounds from groups IA, IIA, IVA and IIB, for example Ci to C _δ alkyls of the metals lithium, aluminum, magnesium, tin, zinc, wherein formally charged inorganic ligands L ¹ , L ^2, as previously defined, are exchanged for formally charged aliphatic, cycloaliphatic or aromatic ligands L ¹ , L ^2, as also previously defined. The reaction is generally carried out in a solvent such as diethyl ether or tetrahydrofuran at temperatures in the range from -78 to 65 ° C.

Monocation complexes of the general formula (I) (p = 1) can be obtained, for example, by reacting (chelate ligand) metal (acetate) (organo) or (chelate ligand) metal (halogeno) (organo) complexes with stoichiometric amounts of a metal salt M'X can be obtained. The reactions are generally carried out in coordinating solvents, for example acetonitrile, benzonitrile, tetrahydrofuran or ether, at temperatures in the range from -78 to 65 ° C.

It is advantageous if the metal salts M'X meet the following criteria. The metal M 'should preferably form poorly soluble metal chlorides, such as silver chloride. The salt anion should preferably be a non-nucleophilic anion X, as previously defined.

Well-suited salts for the formation of cationic complexes are e.g. Silver tetrafluoroborate, silver hexafluorophosphate, silver trifluoromethanesulfonate, silver perchlorate, silver paratoluene sulfonate, silver trifluoroacetate and silver hexafluoroantimonate, sodium tetraphenylborate, sodium tetrakis (pentafluorophenyDborate, silver trifluorodisorbate (3), sodium trifluorodisorbate (also sodium trifluorodisorbate), also sodium trifluoroacetate (3), also sodium trifluorodisorbate (3), also sodium trifluorodisorbate (3), also sodium trifluorodisorbate (3), also sodium trifluoroacetate (5), also sodium trifluorodisorbate (3), also sodium trifluorodisorbate (3).

The dicationic complexes (p = 2) are prepared analogously to the monocationic complexes, except that instead of the (chelate ligand) metal (acetate) (organo) - or the (chelate ligand) metal (halogeno) (organo) complexes, the (chelate ligand) Metal (diacetate) or (Chelate ligand) metal (di-halogeno) complexes can be used as a precursor and two equivalents of the metal salt. A further process for the preparation of the dicationic complexes of the formula (I) is the reaction of [Q ₄ M] X with the chelate ligands of the general formula (III) defined at the outset. Q means the same or different black ligands such as acetonitrile, benzonitrile or 1,5-cyclooctadiene, M and X have the previously defined meaning.

A preferred method for producing the metal complexes of the general formula (I) is the reaction of the dihalometal precursor complexes with silver salts containing non-coordinating anions.

The solubilizers b) used by the process according to the invention are emulsifiers or protective colloids. Of course, a mixture of one or more emulsifiers and one or more protective colloids can also be used.

The emulsifier is preferably anionic, cationic, amphoteric or nonionic, in particular cationic or anionic soaps can be used. These are for example in

"Encyclopedia of Polymer Science and Technology", J. Wiley & Sons (1966), Volume 5, pages 816 to 818, and in "Emulsion Polymerization and Emulsion Polymers", editors P. Lovell and M. El-Asser, Verlag Wiley & Sons (1997), pages 224-226. Examples are alkali salts of organic carboxylic acids with chain lengths of 8-30 C atoms, preferably 12-18 C atoms. These are commonly referred to as soaps. As a rule, they are used as sodium, potassium or ammonium salts. In addition, alkyl sulfates and alkyl or alkylarylsulfonates with 8-30 C atoms, preferably 12-18 C atoms, can be used as anionic emulsifiers. Particularly suitable compounds are alkali dodecyl sulfates, for example sodium dodecyl sulfate or potassium dodecyl sulfate, and alkali metal salts of C ₂ -C ₆ -P raffinsulfonic acids. Sodium dodecylbenzenesulfonate and sodium dioctylsulfonic succinate are also suitable.

Examples of suitable cationic emulsifiers are salts of amines or diamines, quaternary ammonium salts, such as, for example, hexadecyltrimethylammonium bromide, and salts of long-chain substituted cyclic amines, such as pyridine, morpholine, piperidine. In particular, quaternary ammonium salts, such as, for example, hexadecyltrimethylammonium bromide, of trialkylamines are used. The alkyl radicals preferably have 1 to 20 carbon atoms. Suitable nonionic emulsifiers are, for example, polyethylene oxide- or polypropylene oxide-based substances such as Pluronic® or Tetronic® from BASF Aktiengesellschaft.

The ones suitable for stabilizing the reaction mixture

Protective colloids are generally water-soluble polymers which envelop the monomer droplets and the polymer particles formed therefrom and in this way protect them from coagulation. Protective colloids are cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose, poly-N-vinyl pyrrolidone, polyvinyl alcohol and polyethylene oxide, anionic polymers such as polyacrylic acid and cationic polymers such as poly-N-vinyl imidazole. Further suitable protective colloids are described in the above book "Emulsion Polymerization and Emulsion Polymers", pages 226-227.

Suitable hydroxy compounds c) are all substances which have one or more hydroxyl groups. Lower alcohols having 1 to 6 carbon atoms such as methanol, ethanol, n- or iso-propanol, n-butanol, sec-butanol or tert are preferred. Butanol. In addition, aromatic hydroxy compounds, e.g. Phenol. Also suitable are e.g. Sugar such as fructose, glucose, lactose. Also suitable are polyalcohols such as ethylene glycol, glycerin or polyvinyl alcohol. Mixtures of several coactivators can of course also be used.

The copolymerization according to the invention of carbon monoxide and olefinically unsaturated compounds in the presence of the metal complexes or their individual components and the solubilizer is carried out in an aqueous medium. The polymerization mixture is preferably mixed vigorously to achieve reproducibly good productivity. Suitable stirring tools such as anchor or spiral stirrers can be used for this. Suitable stirring speeds are in the range from 100 to 1100 rpm, preferably above 150 rpm.

The carbon monoxide copolymers can in principle be obtained by two different procedures. According to the one manufacturing process, the aforementioned defined metal complexes a1) are used. These complexes are prepared separately and added as such to the reaction mixture or placed in the reaction container. In a further production process, the constituents forming the catalytically active species are added individually to the reaction mixture. In this in-situ generation of the catalyst, the metal M is generally fed to the reaction vessel in salt form or as a complex salt. The chelating ligand compound al.2) is also added. Given Otherwise, an acid a2) and / or a hydroxy compound c) can be added as activator compound in both procedures. The addition of the activator species can be omitted if the chelating ligand al.2) has residues R ¹ to R ⁴ which have at least one free sulfonic or carboxylic acid group.

As a rule, the use of defined metal complexes al) goes hand in hand with higher productivity than with the in-situ process.

Suitable olefinically unsaturated monomer compounds in the processes mentioned for the preparation of the carbon monoxide copolymers are both pure hydrocarbon compounds and heteroatom-containing α-olefins, such as (meth) acrylic acid esters or amides, and homoallyl or allyl alcohols, ethers or halides. Among the pure hydrocarbons, in the case of only one olefin used, C ₃ -C ₂ ol-alkenes are suitable. Among these, the low molecular weight α-olefins, for example α-olefins with 3 to 8 carbon atoms such as propene, 1-butene, 1-pentene, 1-hexene or 1-octene, are to be emphasized. Cyclic olefins, for example cyclopentene, norbornene, aromatic olefin compounds such as styrene or .alpha.-methylstyrene or vinyl esters such as vinyl acetate can of course also be used. Propene is particularly preferred. In the case of at least two different olefins used, C ₁ -C ₂ ol alkenes are suitable. Among these, the low molecular weight α-olefins, for example α-olefins with 2 to 8 carbon atoms such as ethylene, propene, 1-butene, 1-pentene, 1-hexene or 1-octene, are to be emphasized. Cyclic olefins, for example cyclopentene, norbornene, aromatic olefin compounds such as styrene or .alpha.-methylstyrene or vinyl esters such as vinyl acetate can of course also be used. Mixtures of ethene with low molecular weight α-olefins such as propene, 1-butene, 1-hexene, 1-octene or 1-decene are particularly preferably used. Mixtures of ethene and propene, and ethene and hexene are very particularly preferred.

The molar ratio of carbon monoxide to α-olefin or to a mixture of α-olefins is generally in the range from 5: 1 to 1: 5, values in the range from 2: 1 to 1: 2 are usually used.

The amount of metal complex al) or its individual components al.l) and al.2) usually used is in the range from 10 ~ ⁷ to 10 ^{~ 3} mol per mol of olefinically unsaturated monomers, an amount of 10 ^{~ 6} to 10 " ⁴ is preferred If the metal compound al.l) and chelate ligand al.2) are used separately, a stoichiometric composition is advantageous but not necessary. The copolymerization temperature is generally set in a range from 0 to 200.degree. C., preferably at temperatures in the range from 20 to 130.degree. The pressure is generally in the range from 2 to 300 bar and in particular in the range from 20 to 220 bar.

Suitable catalysts a2) can be used as activator compounds for catalyst activation. Both mineral protonic acids and Lewis acids can be used as activator compounds. Suitable protic acids are, for example, sulfuric acid, nitric acid, boric acid, tetrafluoroboric acid, perchloric acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid or methanesulfonic acid. Preferably p-toluenesulfonic acid and tetrafluoroboric acid are used.

Examples of Lewis acids a2) are boron compounds such as triphenylborane, tris (pentafluorophenyl) borane, tris (p-chlorophenyl) borane or tris (3,5-bis (trifluoromethyl) phenyl) borane or aluminum, zinc, antimony - or titanium compounds with a Lewis acidic character in question. Mixtures of

Protonic acids or Lewis acids as well as protonic and Lewis acids are used in a mixture.

The molar ratio of activator to metal complex a1), based on the amount of metal M, is generally in the range from 60: 1 to 1: 1, preferably from 25: 1 to 2: 1 and particularly preferably from 12: 1 to 3: 1 for the cases in which the functional groups of the radicals R ¹ to R ^{4 are} not sulfonic or carboxylic acid functionalities. In the case of metal complexes with chelate ligands which carry the aforementioned functional acid groups, it is of course also possible to add activator compound a2) to the polymerization mixture.

The emulsifier used as solubilizer is advantageously used in an amount of 0.005 to 10% by weight, preferably 0.01 to 5% by weight, in particular 0.1 to 2.5% by weight, based on the total mass of the monomers, used.

The amount of protective colloids additionally or instead used as solubilizers is preferably 0.1 to 5

% By weight, particularly preferably 0.2 to 4% by weight, based on the total mass of the monomers. The molar ratio of hydroxy compound c) to metal complex a1), based on the amount of metal M, is generally in the range from 100,000 to 0, preferably 50,000 to 500 and particularly preferably 10,000 to 1,000. 5

The carbon monoxide copolymerization can be carried out batchwise, e.g. in stirred autoclaves, as well as continuously, e.g. in tubular reactors, loop reactors or cascade stirred tanks.

10

In the polymerization processes according to the invention in the aqueous medium, average catalyst activities are obtained which are generally greater than 0.17 kg polymer per g (metal) per hour, in the case of CO / ethene / olefin copolymerizations greater than 0.5 kg polymer per

15 g (metal) per hour. Reproducible activities greater than 0.7 kg polymer / g (metal) / h can also be achieved.

With the help of the methods according to the invention, the use of organic solvents or even halogenated or aromatic ones

20 hydrocarbons avoided. In addition, elaborate

Separation operations. The method according to the invention consequently opens up an economical, ecological, preparative simple and, in terms of safety, largely harmless access to linear, alternating carbon monoxide copolymers. The invention

The process according to the invention is particularly effective with regard to achievable catalyst activities, polymer bulk densities, molecular weights and their distribution and, in the presence of several different olefins, with regard to the achievable incorporation rates of higher olefins.

30

The present invention is illustrated by the following examples.

Examples 1-6

35

100 ml of distilled water, 3 ml of methanol, 30 ml of hexene-1 (0.24 mol), 0.02 mmol of [1,3-bis (di-6-hydroxyhexyl) phosphinopropane] palladium () were placed in a 300 ml autoclave. II) acetate, 0.2 mmol p-toluenesulfonic acid and the desired amount of

40 solubilizers (hexane-1 and / or solubilizers were omitted for comparative experiments under otherwise identical conditions). The reaction vessel was first evacuated and flooded with nitrogen. The nitrogen atmosphere was displaced by a carbon monoxide / ethene mixture (1: 1) and the polymerization

45 80 bar and 90 ° C over a period of 3 hours at a stirrer speed of 300 rpm. The reaction conditions were kept constant during the polymerization. The reaction was stopped by cooling and relaxing the reaction vessel. The copolymer, separated by filtration, was washed with methanol (500 ml) and acetone (200 ml) and dried at 80 ° C. over a period of 5 h under high vacuum.

Information on the copolymerization parameters and results of experiments 1 to 6 can be found in the table below:

a) determined by NMR spectroscopy (in mol% CO / hexen-1) b) PK = polyketone c) determined in a 0.5% by weight o-dichlorobenzene / phenol

(1: 1) solution using a capillary viscometer. d) Comparison test e) "Emulsifier K30 / 40®" is a sales product of Bayer AG. It is a mixture of the sodium salts of alkanesulfonic acids.

Examples 7-8 Under otherwise identical experimental conditions as in experiments 1 to 6, experiments 7 and 8 instead of [1,3-bis (di-6-hydroxyhexyl) phosphinopropane] palladium (II) acetate 0.02 mmol [bis (p- toluenesulfonato) bis (acetonitrilo) palladium (II)] ([Pd (OTos) ₂ (NCCH ₃ ) ₂ ]) and 0.02 mmol 1,3-bis [di- (sodiumbenzenesulfonate) phosphino] propane ((CH ₂ ) ₃ (P (C ₆ H ₄ S0 ₃ Na))) was used.

Information on the copolymerization parameters and results of experiments 7 to 8 can be found in the table below:

a) determined by NMR spectroscopy b) PK = polyketone c) determined in a 0.5% by weight o-dichlorobenzene / phenol (1: 1) solution using a capillary viscometer. d) Comparison test e) "Emulsifier K30 / 40®" is a sales product of Bayer AG. It is a mixture of the sodium salts of alkanesulfonic acids. f] not determined

Examples 9-10

30 ml of distilled water, 0.1 mmol of fluoroboric acid (HBF), 0.01 mmol were placed in a 70 ml autoclave

[1,3-bis (di-4-methylol-5-hydroxypentyl) phosphinopropane] palladium (II) acetate and the desired amount of solubilizer (for comparative experiments, solubilizers were omitted under otherwise identical conditions). After the autoclave had been closed, the above mixture was saturated with the same by introducing propene into it for 20 minutes. Finally, 21 bar of carbon monoxide are injected up to a total pressure of 30 bar. The polymerization was carried out at 60 ° C. over a period of 4 hours with a stirrer speed of 300 rpm. The reaction conditions were kept constant during the polymerization. The reaction was stopped by cooling and relaxing the reaction vessel. The separated by filtration Copolymer was washed with methanol (100 ml) and acetone (40 ml) and dried at 80 ° C over a period of 5 h under high vacuum.

Information on the copolymerization parameters and results of experiments 9 to 10 can be found in the table below:

b) PK = polyketone d) comparative experiment

Example 11

In a 150 ml autoclave were 30 0.01 ml distilled water, 20 ^m l hexene, 0.1 mmol of fluoboric acid (HBF), mmol

[1, 3-bis (di-6-hydroxyhexyl) phosphinopropane] palladium (II) acetate and 0.3 g of potassium dodecyl sulfate. After the autoclave had been closed, it was flushed with nitrogen and carbon monoxide was injected to a total pressure of 30 bar. The polymerization was carried out at 60 ° C. over a period of 4 hours with a stirrer speed of 300 rpm. The reaction conditions were kept constant during the polymerization. The reaction was stopped by cooling and relaxing the reaction vessel. The copolymer was dried to constant weight by evaporating the solvent at room temperature. The activity was 1.420 kg polyketone / g (Pd) / h.

Example 12

When the test was otherwise the same as in Example 11, instead of [1,3-bis (di-6-hydroxyhexyl) phosphinopropane] palladium (II) acetate, [1,3-bis (di-5-hydroxypentyl) phosphinopropane] palladium (II ) acetate and an additional 2 ml of methanol. Carbon monoxide was injected up to a total pressure of 60 bar. The activity was 2.138 kg polyketone / g (Pd) / h.

Example 13

When the test was otherwise the same as in Example 12, 11.5 g of 5-hexen-l-ol were used instead of 20 ml of hexene. The activity was 2.339 kg polyketone / g (Pd) / h. Example 14

When the test was otherwise the same as in Example 13, 20 ml of 1-decene were used instead of 11.5 g of 5-hexen-l-ol. The activity was 0.794 kg polyketone / g (Pd) / h.

Example 15

When the test was otherwise the same as in Example 14, but without the addition of methanol, the activity was 0.658 kg polyketone / g (Pd) / h.

Claims

claims

Process for the preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having three to twenty carbon atoms or of carbon monoxide and at least two different olefinically unsaturated compounds in an aqueous medium, characterized in that the copolymerization is carried out in the presence of

al) metal complexes of the general formula (I)

in which the substituents and indices have the following meaning:

G 5-, 6- or 7-atomic carbocyclic ring system without or with one or more heteroatoms, - (CR ₂ ) _r -, - (CR ^b ₂ ) _s -Si (R ^a ) ₂ - (CR ^b ₂ ) _t -, -AOB- or -AZ (R ⁵ ) -B- with

R ^{5 is} hydrogen, unsubstituted or with functional groups which contain atoms from groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements, substituted C 1 -C ₂₈ -alkyl, C ₃ - to C ₄ -cycloalkyl, Cg- to Cis- Aryl or alkylaryl with 1 to 20 C atoms in the alkyl radical and 6 to 15 C atoms in the aryl radical, -N (R ^b ), -Si (R ^c ) ₃ or a radical of the general formula (II) \ '/'

E ^l L

(C (R) ₂ ) _g M. (II)

BL ²

R ³ R *

in the

q denotes an integer from 0 to 20 and the further substituents in formula (II) have the same meaning as in formula (I),

A, B - (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 component of a ring system or together with Z a (r '+ l) -, (s + 1) - or (t + 1) -atomic component of a heterocycle,

R ^a independently C ~ ~ to C ₂ o-alkyl, C ₃ - to Cio-cycloalkyl, Cg- to cis-aryl or alkylaryl with 1 to 10 C atoms in the alkyl part and 6 to 15 C atoms in the aryl part, the radicals mentioned can also be substituted,

R as R ^a , additionally hydrogen or Si (R ^c ) ₃ ,

R ^c Ci to C o-alkyl, C ₃ - to Cio-cycloalkyl, Cg to Cis-aryl or alkylaryl with 1 to 10 C-atoms in the alkyl part and 6 to 15 C-atoms in the aryl part, the said radicals also can be substituted

r 1, 2, 3 or 4 and

r '1 or 2,

s, t 0, 1 or 2, where 1 <s + t <3,

Z is a non-metallic element from the group

VA of the Periodic Table of the Elements, M is a metal selected from Groups VIIIB,

IB or I ^' IB of the Periodic Table of the Elements,

E ¹ , E ² a non-metallic element from the group - * VA of the periodic table of the elements,

R ⁱ to R ⁴ linear or branched C - to C ₂ s-alkyl,

C ₃ - to -C ₄ cycloalkyl, Cg-cis-aryl or alkylaryl with 1 to 28 C atoms in the alkyl part and 6 0 to 15 C atoms in the aryl part, at least one of the radicals R ⁱ to R ⁴ having at least one hydroxy -, amino or acid group or contains an ionically functional group, 5

L ^x , L ² formally charged or neutral ligands,

X formally mono- or polyvalent anions,

0 p 0, 1, 2, 3 or 4,

m, n 0, 1, 2, 3 or 4,

5 where p = m x n,

b) a solubilizer and, if necessary

c) a hydroxy compound 0 is carried out.

2. The method according to claim 1, characterized in that the copolymerization in the presence of 5 al) metal complexes of the general formula (I),

a2) an acid,

0 b) a solubilizer and optionally

c) a hydroxy compound

carries out. 5 Process for the preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having three to twenty carbon atoms or of carbon monoxide and at least two different olefinically unsaturated compounds in an aqueous medium, characterized in that the copolymerization is carried out in the presence

al.l) of a metal M, selected from Group VIIIB, IB or IIB of the Periodic Table of the Elements, which is present in salt form or as complex salt,

al.2) a chelating ligand of the general formula (III)

(R) (R ² ) Ei-GE (R3) (R4),

in which the substituents and indices have the following meaning:

G 5-, 6- or 7-atomic carbocyclic ring system without or with one or more heteroatoms, - (CR ^b ) _r -,

- (CR ^b ₂ ) _s -Si (R ^a ) ₂ - (CR ₂ ) _t -, -AOB- or - AZ (R ⁵ ) -B- with

R ^{5 is} hydrogen, unsubstituted or with functional groups which contain atoms from groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements, substituted C ₁ -C 5 -alkyl, C ₃ - to C ₄ -cycloalkyl, Cg- to Cis- Aryl or alkylaryl with 1 to 20 carbon atoms in the alkyl radical and 6 to 15 carbon atoms in the aryl radical, -N (R ^b ) ₂ , -Si (R ^c ) ₃ or a radical of the general formula (IV)

in the

q represents an integer from 0 to 20 and the further substituents in formula (IV) have the same meaning as in formula (III),

A, B - (CR ^b ) _r <- or - (CR ₂ ) _S -Si (R ^a ) ₂ - (CR ^b ) _t - or -N (R) -, an r'-, s- or t- atomic component of a ring system or together with Z a

(r '+ l) -, (s + 1) - or (t + 1) -atomic component of a heterocycle,

R ^a independently of one another is C ~ to C ₂ o ~ alkyl, C ₃ - to Cio-cycloalkyl, Cg- to Cis-aryl or alkylaryl with 1 to 10 C-atoms in the alkyl part and 6 to 15 C-atoms in the aryl part, the radicals mentioned can also be substituted,

R ^b as R ^a , additionally hydrogen or Si (R ^c ) ₃ ,

R ^c C ~ to C ₂ o ~ alkyl, C ₃ - to Cio-cycloalkyl, Cg to Cis aryl or alkylaryl with 1 to 10 C atoms in the alkyl part and 6 to 15 C atoms in

Aryl part, where the radicals mentioned can also be substituted,

r 1, 2,

3 or 4 and

r '1 or 2,

s, t 0, 1 or 2, where 1 <s + t <3,

Z is a non-metallic element from the group

VA of the Periodic Table of the Elements,

E ¹ , E ^{2 is} a non-metallic element from the group

VA of the Periodic Table of the Elements,

R ¹ to R ⁴ linear or branched C - to C ₈ ~ alkyl,

C ₃ - to -C ₄ cycloalkyl, Cg-cis-aryl or alkylaryl with 1 to 28 C atoms in the alkyl part and 6 to 15 C atoms in the aryl part, at least one of the radicals R ¹ to R ⁴ having at least one hydroxy , Amino or acid group or contains an ionically functional group,

a solubilizer and if necessary c) a hydroxy compound

performs.

4. The method according to claim 3, characterized in that the copolymerization in the presence

al.l) of a metal M, selected from Group VIIIB, IB or IIB of the Periodic Table of the Elements, which is in salt form or as a complex salt.

al.2) a chelating ligand of the general formula (III),

a2) an acid,

b) a solubilizer and, if appropriate

c) a hydroxy compound

carries out.

5. Process according to claims 1 to 4, characterized in that the hydroxy compound c) is a mono- or polyhydric alcohol or a sugar.

6. Process according to claims 2 and 4, characterized in that the acid is a Lewis acid selected from the group boron trifluoride, antimony pentafluoride or triarylborane or a protonic acid selected from the group sulfuric acid, p-toluenesulfonic acid, tetrafluoroboric acid, trifluoromethanesulfonic acid, Perchloric acid or trifluoroacetic acid is used.

7. Process according to claims 1 to 6, characterized in that the radicals R ¹ to R ^{4 are} linear, branched or carbocyclic-containing C ₂ - to C ₂₈ -alkyl units, C ₃ - to -C ₄ -cycloalkyl units, Cg -Cis-aryl units or alkylaryl units with 1 to 28 carbon atoms in the alkyl part and 6 to 15 carbon atoms in the aryl part, and at least one of the radicals R ¹ to R ⁴ has at least one hydroxyl, amino, carboxylic acid, Has phosphoric acid, ammonium or sulfonic acid group.

8. The method according to claims 1 or 3, characterized in that the radicals R ¹ to R ⁴ linear, branched or carbocyclic-containing C - to C ₈ -alkyl units, C ₃ - to -C ₄ -cycloalkyl units, Cg- Cis aryl units or alkylaryne units ten with 1 to 28 carbon atoms in the alkyl part and 6 to 15 carbon atoms in the aryl part, and at least one of the radicals R ¹ to R ⁴ is substituted with at least one free carboxylic acid or sulfonic acid group.

9. Process according to claims 1 to 8, characterized in that an anionic, cationic, amphoteric or nonionic emulsifier is used as solubilizer b).

10. Use of a solution mediator for the production of linear, alternating copolymers of carbon monoxide and at least one olefinically unsaturated compound in an aqueous medium.