EP0991696A1 - Functionalised carbon monoxide copolymers - Google Patents

Abstract

The invention relates to functionalised linear alternating carbon monoxide copolymers, consisting of carbon monoxide and at least one 1-alkene (A). The inventive copolymers are characterised in that the compound (A) represents an aryl derivative substituted with at least one terminal allyl and/or homoallyl unit and containing one or several polar groups, excluding 4-allyl anisole.

Description

Functionalized carbon monoxide copolymers

description

The present invention relates to functionalized linear alternating carbon monoxide copolymers of carbon monoxide and at least one 1-alkene (A), the compound (A) being an aryl derivative which contains one or more polar groups and is substituted by at least one terminal allyl and / or homoallylic unit, with the exception of 4 - Allylanisol.

The invention further relates to functionalized linear alternating carbon monoxide copolymers of carbon monoxide, at least one 1-alkene (A) and at least one C ₂ - to C ₁₀ -l alkene (B).

In addition, the invention relates to processes for the production of functional linear alternating carbon monoxide copolymers from carbon monoxide, 1-alkenes (A) and optionally 1-alkenes (B) and the use of the carbon monoxide copolymers for the production of films, films, moldings and coatings.

Now that a large number of processes or process modifications for the production of binary and ternary carbon monoxide copolymers are known (cf. E. Drent, PHM Budzelaar, Chem. Rev. 1996, 96, 663-681), the property profile is now being tried more conventionally To expand or specifically modify carbon monoxide copolymers through process or product modifications. This succeeds, for example, as Rieger et al. (Macromolecules 1996, 29, 4806) were able to show by incorporating long-chain α-olefin units into the carbon monoxide copolymer structure, which makes copolymers with a comparatively low glass transition temperature (T _g value) accessible.

Sen et al. (Macromolecules 1996, 29, 5852 - 5858) describe the preparation of chiral, functionalized polyketones from carbon monoxide and various linear α-olefins which have a hydroxyl or carboxyl group in the ω position. Satisfactory yields and molecular weights M _w could only be achieved with the chiral dicationic complex [Pd ((R, R) - (CH ₃ ⁾ -DUPHOS ^{) (} CH ₃ CN) ₂ ] (BF ₄ ) ₂ ([(R, R) - (CH ₃ ) -DUPHOS] = (-) - 1,2-bis ((2R, 5R) -2,5-dimethylphospholano) benzene). However, this complex cannot be produced in a chemically trivial manner and, from an economic point of view, does not allow access to functionalized carbon monoxide copolymers. They also use the chirals mentioned Complex polymer products obtained, which are characterized by a high

Distinct degree of order and are therefore usually crystalline. The associated poor solubility properties are disadvantageous in particular with regard to large-scale industrial applications when carrying out the reaction, working up and further processing. The success of the method described by Sen et al. The catalyst system described is attributed to the sterically demanding bidentate chelating ligand, which prevents the undesired blocking of the metal coordination sphere by functional groups. For the copolymerization of carbon monoxide with 4-allylanisole e.g. found a product mixture of an alternating 1,4-copolymer and a copolymer which has regularly installed spiroketal units.

According to EP-A 0 463 689, the functional group present in a monomer should not be too close to the terminal double bond, since otherwise no or only a slight copolymerization is observed. However, the production of functionalized carbon monoxide copolymers should already be possible with known catalyst systems, for example based on palladium (II) acetate, 1,3-bis (diphenylphosphino) propane and copper p-tosylate, if the functional group does not directly connect to the terminal double bond system is bound, but at least one alkylene bridge is interposed. Functionalized carbon monoxide copolymers with molecular weights M _w > 1000 and in particular> 5000 g / mol are, however, only obtained by using a special bidentate phosphine bridge ligand which has only aliphatic substituents on the phosphorus atoms, for example 1,3-bis (di-n-butylphosphino) ) - propane.

It would therefore be desirable to be able to produce carbon monoxide copolymers from carbon monoxide and α-olefins, which have one or more functional units adjacent to the terminal double bond, using processes which are also unproblematic to use on an industrial scale and using easily accessible catalyst systems.

The object of the present invention was therefore to provide functionalized carbon monoxide copolymers with high molecular weights by means of easily accessible catalyst systems and preparative, uncomplicated processes in good yields. Accordingly, functionalized linear alternating carbon monoxide copolymers of carbon monoxide and at least one 1-alkene (A) have been found, the compound (A) being an aryl derivative which contains one or more polar groups and is substituted by at least one terminal allyl and / or homoallyl unit, with the exception of 4-allylanisole , represents.

Functionalized linear alternating carbon monoxide copolymers of carbon monoxide, at least one 1 -alkene (A) and at least one C ₂ - to Cιo-1 alkene (B) were also found.

Furthermore, processes for the production of functionalized linear alternating carbon monoxide copolymers and their use for the production of films, films, moldings and coatings have been found.

The copolymers according to the invention are composed of units which are based on the monomers carbon monoxide and one or more olefinically unsaturated compounds.

In the binary copolymers according to the invention, the different monomer units are generally in strict alternation. In the case of the ternary and higher copolymer systems, the sequence of carbon monoxide and olefin component is as a rule also strictly alternating, the functionalized α-olefins being incorporated into the linear copolymer chain essentially in a statistical distribution with respect to the olefin insertion positions in question.

Suitable α-olefinically unsaturated compounds (A) for the binary and higher copolymers according to the invention are, in principle, aryl derivatives containing one or more polar groups and substituted with at least one terminal allyl and / or homoallyne unit, 4-allylanisole being excluded for binary systems.

Preferred functionalized α-olefins or 1-alkenes (A) are compounds of the general formula (Ia) or (Ib)

03518

4 used, in which the substituents and indices have the following meaning:

X OR ¹ , NR ² R ³ , halogen, such as fluorine, chlorine, bromine, iodine, nitro or C0 ₂ R ⁴ , wherein

R ^{1 is} hydrogen, linear and branched Ci- to Cio-alkyl, preferably Cι ~ to Cβ-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, especially methyl, C ₃ - bis Cirj-cycloalkyl, preferably C ₃ - to Cβ-cycloalkyl, such as cyclopropyl or cyclohexyl, C ₆ - to C-aryl, preferably C ₆ - to C ₁₀ -aryl, in particular phenyl, C (0) R ⁵ or Si (R ⁶ ) ₃ with

R ⁵ linear and branched Cι ~ to Cio-alkyl, preferred

Cι ~ to C ₆ alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, especially methyl, or Cς- to Ci ₄ -aryl, preferably C ₆ - to Cio-aryl, especially phenyl,

R ^6, independently of one another, is linear and branched C 1 -C 1 -alkyl, preferably C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, in particular methyl, C ₃ - bis Cι ₀ cycloalkyl, preferably C ₃ - to Cβ cycloalkyl, such as cyclopropyl or cyclohexyl, or C ₆ - to C ₄ ~ aryl, preferably C ₆ - to Cio-aryl, especially phenyl,

R ² , R ^{3 are} hydrogen, linear and branched C ₁ to C 10 alkyl, preferably C ₁ to C ₆ alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, in particular methyl,

C ₃ - to Cio-Cycloalkyl, preferably C ₃ - to C _ß- Cycloalkyl, such as cyclopropyl or cyclohexyl, or C ₆ - to C ₄ -aryl, preferably C ₆ - to Cio-aryl, especially phenyl, or together with N one saturated or unsaturated cycle consisting of 2 to 10 carbon atoms, preferred

4 to 6 carbon atoms, such as pyrrole, pyrrolidine or pyrrolidinone or a cycle consisting of 2 to 10 carbon atoms, preferably 4 to 6 carbon atoms, and at least one further heteroatom such as nitrogen or oxygen in the cycle, for example morpholine,

R ⁴ linear and branched Cι ~ to Cio-alkyl, preferred

Ci to C _δ alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, in particular methyl, or C ₆ to C ₄ aryl, preferably 0 to Cio aryl , in particular phenyl; Y is a compound of the general formula (II)

CH ₂ = C (R ⁷ ) (C (R ^β ) ₂ ) _q ). (II),

wherein

R ^{7 is} hydrogen, linear and branched Cι ~ to Cio-alkyl, preferably Ci- to Cβ-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, especially methyl, C ₃ - bis Cio-cycloalkyl, preferably C ₃ - to C ₆ -cycloalkyl, such as cyclopropyl or cyclohexyl, C ₆ - to Cι-aryl, preferably C ₆ - to Cio-aryl, especially phenyl, and

R ⁸ independently of one another is hydrogen, linear and branched C ₁ -C 1 -alkyl, preferably C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, in particular methyl , C ₃ - to -C ₀ cycloalkyl, preferably C ₃ - to Cβ-cycloalkyl, such as cyclopropyl or cyclohexyl, C ₆ - to Ci ₄ ~ aryl, preferably C ₆ - to Cio-aryl, especially phenyl, or halogen, such as fluorine , Chlorine, bromine, iodine mean and

q 1 or 2,

Q linear or branched Ci * to Cio-alkyl, preferably Ci- to C ₆ -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl or t-butyl, especially methyl or t- butyl, C ₃ - to Cio-cycloalkyl, preferably C ₃ - to C _δ -cycloalkyl such as cyclopropyl or cyclohexyl, C ₆ - to C ₄ -aryl, preferably C ₆ - to Cι ₀ aryl, especially phenyl, aralkyl with 1 to 6, preferably 1 to 3 C atoms in the alkyl part and 6 to 14, preferably 6 to 10 C atoms in the aryl part, for example benzyl or C ₃ - to C ₃ o-organosilyl, for example trimethyl, triethyl, tri isopropyl, triphenyl, t-butyldiphenyl or thexyldimethylsilyl, preferably trimethylsilyl,

where for compounds of formula (Ia)

k, 1 integers from 1 to 5 and

o an integer from 0 to 4 mean with

k + l + o <6

and for compounds of the formula (Ib) m, n integers from 1 to 7 and

p denotes an integer from 0 to 6

m + n + p <8.

Particularly suitable are those compounds (A) which have a terminal allyl unit, i.e. Compounds of the formulas (Ia) and (Ib) in which q = 1. Among these olefinic monomers, preference is again given to those whose terminal allyl unit is in the ortho position to a polar group. For example, Naphthyl compounds with an allyl unit in the 1 position and a polar group in the 2 position or with an allyl unit in the 2 position and a polar group in the 1- and / or 3 position, and in particular allylphenyl compounds with one or two ortho-standing polar groups Ally unit.

In principle, functional groups based on the elements of groups IVA, VA, VIA or VIIA des come as polar groups

Periodic table of elements, e.g. Hydroxy, alkoxy, amino, nitro or ester groups and halogens, preference being given to compounds which have one or more hydroxyl or alkoxy groups, in particular hydroxyl groups, as polar groups. Suitable compounds are e.g. 2-allylphenol, 2-allylmethoxybenzene, 2-allylethoxybenzene and 2-allyl-t-butoxybenzene, in particular 2-allylphenol.

In general, however, it is also possible to use compounds (A) which contain up to a maximum of 5 polar groups on the phenyl ring as an aryl derivative (compounds of the formula (Ia)) and up to a maximum of 7 polar groups on the naphthyl ring as an aryl derivative (compounds of the formula (Ib)) as long as there is a terminal allyl or homoallyne unit in the aryl derivative. Likewise, a plurality of allyl or homoallyne units, preferably allyl units, can also be bound to the aryl derivative at the same time (a maximum of 5 for compounds of the formula (Ia) and a maximum of 7 for compounds (Ib)), provided that the aromatic skeleton still has a polar group.

Terminal allyl or homoallyl units also include those radicals whose hydrogen radicals, apart from the terminal ones, are independently substituted by, for example, alkyl groups such as methyl, ethyl or isopropyl, aryl groups such as phenyl or halogens such as fluorine or chlorine. Examples are isopropylidene or isobutylidene units. However, are preferred 7 unsubstituted allyl and homoallyl units, especially allyl units.

In addition to an allyl or homoallyl group Y and a polar group X, the compounds (A) can have further radicals on the aromatic system. The radicals Q described at the outset can be used as substituents. The residues Q in (A) can be identical or different. Valences in the aromatic systems of formulas (Ia) and (Ib), which are not saturated by functional groups X, Y and Q, are basically hydrogen, i.e. saturated by C-H bonds. Suitable compounds (A) therefore also include l-hydroxy-2,6-dimethyl-4-alkyl-benzene, 1-hydroxy-2-allyl-4-tert-butyl-benzene, 1-hydroxy-2,6- di-tert-butyl-4-allyl-benzene, 1-hydroxy-2-allyl - 4-tert-butyl -6-methyl-benzene or l-hydroxy-2-allyl-4-methyl-benzene.

Suitable monomers (B) for non-binary carbon monoxide copolymers, in particular ternary copolymers, are in principle all compounds of this class of compounds, for example α-olefins or diolefins with at least one terminal double bond. Suitable α-olefins are, for example, C ₂ -C 1 -alkenes, such as propene, ethene, but-1-ene, isobutene, 4-methyl-1-ene, hex-1-ene, oct-1-ene as well as mixtures thereof. Of course, 1-alkenes bearing an aromatic radical can also be used. For example, styrene or α-methylstyrene are suitable; styrene is preferred. In addition, heteroatom-containing compounds, such as (meth) acrylic acid esters or amides or vinyl esters, such as vinyl acetate, are also used as 1-alkenes. Ethene, propene, but-l-ene and styrene, in particular propene, are particularly preferred. These 1-alkenes can of course also be used in a mixture.

Preference is given to carbon monoxide / propene and carbon monoxide / ethene terpolymers with aryl derivatives in which a terminal allyl unit and a hydroxyl group are located ortho to one another, e.g. 2-allylphenol.

The binary carbon monoxide copolymers according to the invention are generally regular poly-1,4-ketones. However, if aryl derivatives (A) are used in which an allyl and a hydroxy unit are ortho-permanent, then the carbon monoxide copolymer obtained can also have semiketal units which can be present both in blocks and in a random distribution along the linear polymer chain. The ratio of ketone to ketal fragments in these cases is usually in the range from 5: 1 to 1: 5, preferably in the range from 3: 1 to 1: 1. The structure of the carbon monoxide copolymers according to the invention can be determined by means of ¹³ C-NMR spectroscopy ( Bruker AMX 500) be determined. These binary copolymer systems, but also terpolymers, are characterized by increased T _g values compared to conventional carbon monoxide copolymers. The resulting higher strength can possibly be attributed to reversible cross-linking by means of semiketal formation.

The average molecular weights M _{w of} the binary carbon monoxide copolymers according to the invention are usually in the range from 1000 to 100000 g / mol, preferably in the range from 3000 to 80,000 g / mol and in particular in the range from 5000 to 50,000 g / mol (measured by the method of gel permeation chromatography (GPC ) at 25 ° C with Microstyragel (Waters) as column material and chloroform as solvent against polystyrene standard).

The binary carbon monoxide copolymers are generally distinguished by narrow molecular weight distributions M _w / M _n (weight average / number average), measured using the gel permeation chromatography (GPC) method analogous to the previous description. The M _w / M _n values are preferably in the range from 1.1 to 3.5 and in particular assume values <2.5. Carbon monoxide copolymers according to the invention having M _w / M _n values in the range from 1.1 to 2.2 are particularly preferred.

The glass transition temperature values (T _g values) of the binary carbon monoxide copolymers according to the invention, if they can be determined, are usually in the range from 0 to 120 ° C., preferably in the range from 20 to 100 ° C. and in particular from 30 to 70 ° C.

The carbon monoxide terpolymers according to the invention generally have an average molecular weight M _w in the range from 5000 to 500000 g / mol, preferably from 20,000 to 300,000 g / mol and in particular from 50,000 to 250,000 g / mol.

The T _g values of the terpolymers according to the invention are usually in the range from 0 to 120 ° C., preferably in the range below 90 ° C.

The proportion attributable to compound (A) in the terpolymers is generally in the range from 0.1 to 60 mol%, based on the carbon monoxide units in the copolymer (determined on the basis of ¹ H-NMR spectra). Suitable terpolymers generally have a proportion of 2 to 50, in particular 3 to 40 mol% of component (A) incorporated. In the terpolymers and in higher copolymers, just like in the binary systems, in addition to pure 1,4-polyketone units, it is also possible to use randomly distributed or block-like, but preferably statistically distributed, semiketal units. Structures. This phenomenon is preferably observed when the polar group in (A) is a hydroxy group.

The binary and ternary carbon monoxide copolymers according to the invention are generally readily soluble in tetrahydro uranium (THF), toluene, dichloromethane or chloroform.

The molar ratio of carbon monoxide to the sum of the structural units attributable to the olefinically unsaturated monomers in the binary or higher carbon monoxide copolymers according to the invention is generally 1: 1.

Due to their polar, thermoplastic properties, the polymer materials according to the invention have a variety of possible uses, e.g. in the field of polymer blend technology.

To produce the functionalized linear alternating carbon monoxide copolymers according to the invention, carbon monoxide can be copolymerized with 1 -alkenes (A) and optionally 1 -alkenes (B) in a virtually alcohol-free or anhydrous polymerization medium in the presence of a catalyst whose active composition is formed from

a) a metal complex of the general formula (purple) or (Illb)

₂ ®

^R

^ E ¹ ^> L ¹ z M [Ts ^Θ ] (purple)

E ^{2 2}

R ^c R ^d

in which the substituents and indices have the following meaning: M is a metal from Group VIIIB of the Periodic Table of the Elements,

E ¹ , E ² an element from group VA of the periodic table of the elements,

Z is a bridging structural unit consisting of one, two, three or four sub-structural units of elements from group IVA, VA, VIA of the periodic table of the elements,

R to R ^d substituents selected from the group consisting of C 1 -C 8 -organo-organic and C ₃ - to C ₃ o-organosilicon radicals, the radicals being one or more elements from group IVA, VA,

VIA and VIIA of the Periodic Table of the Elements can contain

R ^e to R ^h independently of one another, hydrogen, straight-chain or branched Ci to C ₆ alkyl or

R ^f and R9 - together - five- or six-membered carbo- or heterocycle

L ¹ , L ² formally uncharged Lewis base ligands,

T mono- or divalent anions,

r, s 1 or 2,

where r x s = 2, and

an activator component which contains a hydroxyl group in the molecule, which is used in an amount of 0 to 1500 molar equivalents, based on M in (III).

A further method for producing the linear copolymers according to the invention is the copolymerization of carbon monoxide with olefinically unsaturated compounds (A) and optionally (B) in a virtually alcohol-free or water-free polymerization medium in the presence of a catalyst whose active composition is formed out

i) a salt of a metal M from group VIIIB of the periodic table of the elements, ii) one or more compounds selected from the group of protonic acids and Lewis acids,

iii) a chelate compound of the general formula (IVa) or (IVb)

_R a _R b _E l- _Z _ _E 2 _R c _R d ( _IVa ),

in which the substituents and indices have the following meaning:

E ¹ , E ² an element from group VA of the periodic table of the elements,

Z is a bridging structural unit consisting of one, two, three or four substructural units from elements of group IVA, VA, VIA of the periodic table of the

Elements,

R ^a to R ^d substituents selected from the group of

Ci- to Co ~ organic carbon and C ₃ - to C ₃ o-organosilicon radicals, where the radicals can contain one or more elements from groups IVA, VA, VIA and VIIA of the Periodic Table of the Elements,

R ^e to R ^h independently of one another, hydrogen, straight-chain or branched Ci to C _δ alkyl or

R ^f and R9 - together - five- or six-membered carbo- or heterocycle

iv) an activator component which contains a hydroxyl group in the molecule which, based on the metal M in i), is used in an amount of 0 to 1500 molar equivalents. In a preferred embodiment, the addition of an activator component b) or iv) in the preparation of the binary or higher carbon monoxide copolymers according to the invention can be dispensed with if a compound is used as the 1-alkene (A) which has a hydroxy function as the polar group. An example is 2-allylphenol.

The polymerizations for the preparation of the carbon monoxide copolymers according to the invention can be carried out either batchwise or continuously in the presence of a polymerization catalyst from a) or i), ii), iii) and optionally b) or iv).

Possible polymerization catalysts are metal compounds of the eighth subgroup of the Periodic Table of the Elements (VIIIB), which exist as defined metal complexes (purple) or (Illb) or in situ from a metal salt i) of the metals of Group VIIIB of the Periodic Table of the Elements, protons and / or Lewis acids ii) and a chelate compound iii) of the formula (IVa) or (IVb) can be formed. If necessary, activators b) or iv) can be added to the metal compounds.

Suitable metals M are the metals from group VIIIB 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 palladium. The metals cobalt, nickel, palladium and platinum are generally formally charged twice positively, the metals rhodium and iridium generally formally singly positively charged and the metals iron, ruthenium and osmium generally formally uncharged in the

Complexes. In addition, iron and ruthenium can also be formally charged twice or three times positively, and rhodium can also appear formally three times positively.

The elements E ¹ and E ^{2 of} the chelate ligand, hereinafter also referred to as chelate compound (IVa), are the elements of the 5th main group of the Periodic Table of the Elements (group VA), that is to say nitrogen, phosphorus, arsenic, antimony or bismuth. Nitrogen or phosphorus, in particular phosphorus, are particularly suitable. The chelate compound (IVa) can contain different elements E ¹ and E ² , for example nitrogen and phosphorus, but preferably it contains the same elements E ¹ and E ² and in particular E ¹ and E ^{2 are} phosphorus,

The bridging structural unit Z is an atomic grouping that connects the two elements E ¹ and E ^{2 to} one another. Substructure units made up of one atom or several interconnected Atoms from group IVA, VA or VIA of the periodic table of the elements usually form the bridge between E ¹ and E ² . Possible free valences of these bridge atoms can be saturated in a variety of ways, for example by substitution with hydrogen or with elements from group IVA, VA, VIA or VIIA of the periodic table of the elements. These substituents can form ring structures with one another or with the bridge atom.

Suitable bridging structural units Z are those with one, two, three or four elements from group IVA of the Periodic Table of the Elements, such as methylene (-CH ₂ -), 1,2-ethylene (-CH ₂ -CH ₂ -), 1, 3-propylene (-CH ₂ -CH ₂ -CH ₂ -), 1,4-butylene, 1,3-disilapropylene (-R ⁵ R ⁶ Si-CH ₂ -SiR ⁵ R ⁶ -, in which R ⁵ , R ⁶ Cι ~ to Cio-alkyl, C ₆ - to Cio-aryl), ethylidene (CH ₃ (H) C =), 2-propylidene ((CH ₃ ) ₂ C =), diphenylmethylene ((C ₆ H ₅ ) ₂ C =) or ortho-phenylene.

Ortho-phenylene, 1,3-propylene and 1,4-butylene may be mentioned as particularly suitable bridging structural units.

Suitable carbon-organic radicals R ^a to R ^d are, independently of one another, aliphatic and cycloaliphatic and aromatic radicals having 1 to 20 carbon atoms, for example the methyl, ethyl, isopropyl, 1-butyl, 1-pentyl , 1-hexyl and 1-octyl group and their structural analogs. Linear arylalkyl groups with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical are also suitable, such as benzyl. Aryl radicals may be mentioned as further radicals R ^a to R ^d , for example tolyl, anisyl, preferably ortho-anisyl, xylyl and other substituted phenyl groups, in particular phenyl.

Suitable cycloaliphatic radicals are C ₃ - to Cio-monocyclic systems such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclohexyl is particularly preferred.

As branched aliphatic radicals are C ₃ - to Co ~, preferably C ₃ - to -C ₂ alkyl, such as the i-propyl, i-butyl, s-butyl, neopentyl and t-butyl group.

Particularly suitable branched aliphatic radicals are the t-butyl group, the i-propyl group and the s-butyl group.

Alkyl groups with branching further out are also suitable as substituents R ^a to R ^d , such as the i-butyl, the 3-methyl-but-2-yl and 4-methylpentyl group. The substituents R ^a to R ^d can also, independently of one another,

Contain atoms from group IVA, VA, VIA or VIIA of the periodic table of the elements, for example halogen, oxygen,

Sulfur, nitrogen, silicon, here, for example, the bis (trimethylsilyl-methyl group. Functional groups which are inert under the polymerization conditions can also be considered in this connection.

Preferred hetero substituents R to R ^d are C ₃ - to C ₃ o-organosilicon radicals, that is to say tetravalent silicon atoms which are bonded to E ¹ or E ² on the one hand and their remaining valences with three carbon-organic radicals such as alkyl and / or aryl radicals are saturated, the sum of the carbon atoms of these three silicon-bonded groups being in the range from three to thirty. Examples include the triethylsilyl, t-butyldimethylsilyl or triphenylsilyl group, in particular the trimethylsilyl group.

The preferred chelate ligands or chelate compound (IVa) used are 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane or 1,4-bis (diphenylphosphino) butane.

Very particularly preferred compounds as the chelating ligand or chelating compound (IVa) are 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane.

The radicals R ^e to R ^h in formula (Illb) or (IVb) independently of one another are hydrogen, straight-chain or branched C ₁ -C ₆ -alkyl, such as methyl, ethyl or i-propyl. Furthermore, the radicals R ^f and R9 together can form a five- or six-membered carbocycle or heterocycle. Chelate ligands (IVb) such as 1, 10-phenanthroline, 2, 2 '-bipyridine or 4, 4' -dimethyl-bipyridine and their substituted derivatives can be traced back to diatomically bridged structural units.

Lewis bases, ie compounds, preferably organic compounds with at least one lone pair of electrons or water, 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, ie amines, nitriles (R-CN), ketones, ethers or preferably water, are particularly suitable.

Suitable Lewis bases are C 1 ~ to Cio-nitriles such as

Acetonitrile, propionitrile, benzonitrile or C ₃ - to Cio-ketones such as acetone, acetylacetone or C ₂ - to Cio-ether, such as dimethyl ether, Diethyl ether or tetrahydrofuran, or A ine such as ethylenediamine or diethylamine.

In particular for catalysts which do not require an activator b) or iv), ligands L ¹ , L ² in (III) are those of the formula (V)

G-OH (V)

suitable. Herein, G means hydrogen or a Ci to Cis carbon organic provided with a Lewis base group

. Residue Highly suitable Ci- to C-organic radicals G are for example, linear or cyclic - (H ₂ -) - _n ^"E i units wherein n is 1 to 10, ie, methylene, 1,2-ethylene, 1, ⁿ 3-propylene, 1,4-butylene, 1, 5-pentylene, 1,6-hexylene, 1, 7-heptylene, 1,8-octylene, 1, 9 -nonylene or 1, 10-decylene.

Possible Lewis base groups are ether, ester, ketone, amine, phosphine and in particular nitrile (-C = N) or tertiary amine.

Well-suited compounds G-OH are, for example, water or α-ω-hydroxynitriles such as NC CH -) - _h OH with h = 1 to 10 or (2-hydroxymethyl) tetrahydrof ran, and (2-hydroxymethyl) (N-organo) pyrrolidine (Va) or (2-hydroxymethyl) (N-organo) - piperidine (Vb)

^R ' ^R '

(Va) (Vb)

wherein R 'is Ci to Cio-alkyl or C ₃ - to Cio-cycloalkyl, for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclopentyl, Cyclohexyl. Furthermore, R 'can also be C ₆ -C ₁ -aryl, such as phenyl or naphthyl.

In general, apart from water, the ligands G-OH are bound to the metal M in (III) via the Lewis base group already defined.

The choice of the anions T is generally not critical. Suitable anions T in (III) are, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as, for example, acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate,

Benzoate, as well as conjugated anions of organosulfonic acids, for example methyl sulfonate, trifluoromethyl sulfonate and p-toluene sulfonate, furthermore tetrafluoroborate, tetrakis (bis (trifluoromethyl) phenyl) borate, tetraphenylborate, tetrakis (pentafluorophenyDborat, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate). sulfonate, tetrafluoroborate or hexafluorophosphate and especially trifluoroacetate, perchlorate or p-toluenesulfonate as anion T.

Particularly suitable metal complexes (purple) include (bis-1,3 (diphenylphosphino) propane-palladium-di-acetonitrile) bis - (tetrafluoroborate) (& tPd (dppp) (NCCH ₃ ) ₂ ] (BF ₄ ) ₂ , dppp = 1.3 (diphenylphosphino) propane), (bis-1,3 (diphenylphosphino) propane-palladium-di-aquo) bis (tetrafluoroborate), bis-1, 3 (diphenyl-phosphino) propane-palladium-bis (3rd -hydroxypropionitrile) bis (tetrafluoroborate), (bis -1,4 (diphenylphosphino) butane-palladium-di-acetonitriDbis (tetrafluoroborate) and (bis-1,4- (diphenylphosphino) butane-palladium-di-aquo) bis ( tetrafluoroborate).

The metal complexes (Illb) or catalyst systems containing compound (IVb) are preferably used when a vinyl aromatic compound, e.g. Styrene is a component of the copolymerization mixture.

The metal complexes of the general formula (III) are generally prepared by processes known from the literature, such as in Makromol. Chem. 1993, 194, p. 2579. Tetrakis-ligand-metal complexes, such as tetrakis-acetonitrile-palladium-bistrafluoroborate, can usually be reacted with the chelate compounds (IV) and the ligands L ¹ , L ² or G-OH to give the metal complexes (III). A preferred process for the preparation of aquo complexes (III) is the reaction of the chelate phosphane-acetonitrile metal complexes with water. The reaction is generally carried out in a solvent, for example dichloromethane, acetonitrile, water, at temperatures in the range from 0 ° C. to 40 ° C.

In the in-situ generation of the polymerization catalysts, the metals M are usually used in the form of their salts and brought into contact with the chelate compound iii) of the general formula (IV) and the acids ii). This can be done before the catalytically active composition thus obtainable comes into contact with the monomer and optionally further activator iv), generally outside the polymerization reactor. The reaction of the individual components metal salt i), chelate compound iii) of the general formula (IV), acid ii) and optionally activator Component iv) can also be carried out in the polymerization reactor in the presence of the monomers.

Suitable salts of the metals M are generally halides, sulfates, phosphates, nitrates and carboxylates, such as acetates, propionates, oxalates, citrates, benzoates, and sulfonic acid salts such as, for example, methyl sulfonates, trifluoromethyl sulfonate and p-toluenesulfonate. Carboxylates, sulfonic acid derivatives and in particular acetates are preferably used.

Particularly suitable catalyst components i) are palladium dicarboxylates, preferably palladium diacetate, palladium di-propionate, palladium bis (trifluoroacetate) and palladium oxalate, and also palladium sulfonates, preferably palladium bis (trifluoromethanesulfonate), palladium bis (methanesulfonate), especially palladium bis (p- toluene) to palladium diacetate.

Lewis and protonic acids and mixtures thereof can be used as catalyst components ii).

Suitable protonic acids ii) are strong mineral acids, such as sulfuric acid and perchloric acid, and also strong organic acids, for example trichloro and trifluoroacetic acid, and also the sulfonic acids methanesulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid, that is to say those acids which are preferably smaller than pK _a have as 3.

Furthermore, the acidic salts of strong acids with weak bases, such as ammonium salts of the aforementioned acids, are suitable.

Examples of suitable Lewis acids are halides of elements of group IIIA of the periodic table of the elements, for example boron trifluoride, boron trichloride, aluminum trifluoride, aluminum trichloride, halides of elements of group VA of the periodic table of elements, such as phosphorus pentafluoride, antimony pentafluoride, and halides of metals Subgroup IVB of the Periodic Table of the Elements, such as titanium tetrachloride or zirconium tetrachloride. Other suitable Lewis acids are organically substituted Lewis acids, for example tris (pentafluoropheny1) borane.

Preference is given to using boron trifluoride, antimony pentafluoride or tris (pentafluorophenyl) borane as Lewis acids. 18th

Particularly preferred components ii) are those which have a weakly coordinating conjugated anion, i.e. an anion which forms only a weak bond to the central metal of the complex, such as tetrafluoroborate, hexafluorophosphate, perchlorate, tri luoroacetate, trifluoromethylsulfonate, p-tosylate and borates, such as pyrocatecholate borate and tetraaryl borate, with 2, 2, 5-dimethylphenyl in particular as the aryl group -Bistrifluoromethylphenyl- or pentafluorophenyl- come into question.

For the rest, suitable catalyst components i) and ii) are those as are generally known for systems with bisphosphines from EP-A 501 576 and 516 238.

As component iii), the catalyst systems contain a chelate compound R ¹ R ² E ¹ -ZE ² R ³ R ⁴ (IVa) or a bipyridyl compound (IVb), which were already described in the discussion of the metal complexes (III).

The ratio of the catalyst components i), ii) and iii) to one another is generally chosen so that the molar

Ratio of metal compound i) to acid ii) 0.01: 1 to 100: 1, preferably 0.1: 1 to 1: 1 and the molar ratio of metal compound i) to component iii) 0.01: 1 to 10: 1 , preferably 0.1: 1 to 2: 1.

The activator component b) or iv) is generally a chemical compound which contains at least one hydroxyl group in the molecule. These include above all Ci- to Cι ₀ alcohols, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, t-butanol, n-hexanol, n-octanol, n -Decanol, cyclohexanol, phenol or water. Methanol and / or water is preferably used as activator component b) or iv).

The molar ratio of activator component b) or iv) to metal M is in the range from 0 to 1500, preferably in the range from 0 to 1300. It has proven advantageous not to exceed the maximum ratio in the polymerization reaction, since otherwise the middle one Molecular weights Mw of the carbon monoxide copolymers formed may be too low.

The addition of the activator b) or iv) is superfluous when the catalyst contains as Lewis base ligands L ¹ , L ² those which have a hydroxyl group in the molecule and which have previously been represented by the general formula G-OH (V ) have been defined more precisely. 19

In addition, it was found that in order to achieve high productivity and yields, the addition of an activator component can be dispensed with if the 1-alkene compounds used are those whose polar groups represent hydroxyl groups. The carbon monoxide copolymers according to the invention obtainable in this way are generally distinguished by comparatively high molecular weights M _w .

Suitable reaction parameters for producing the functionalized copolymers from carbon monoxide and olefinically unsaturated compounds (A) and optionally (B) are pressures from 100 to 500,000 kPa, preferably 500 to 350,000 kPa and in particular 1000 to 10,000 kPa and temperatures from -50 to 400 ° C, preferably 10 to 250 ° C and in particular 20 to 100 ° C have been found to be particularly suitable.

The polymerization reactions can be carried out in the gas phase in a fluidized bed or stirred, in suspension, in solution, in liquid and in supercritical monomers and in solvents which are inert under the polymerization conditions.

The polymerization reactions can be carried out in a virtually alcohol-free or water-free polymerization medium. This means that no further amount of alcohol or water was or will be added to the reaction mixture of monomers, catalyst and, if appropriate, inert solvent or suspending agent, apart from, where appropriate, the activator component b) or iv).

Suitable inert solvents and suspending agents are those which do not contain any hydroxyl group in the molecule, i.e. ethers such as diethyl ether, tetrahydrofuran, aromatic solvents such as benzene, toluene, ethylbenzene, chlorobenzene, aliphatic hydrocarbons such as i-butane or chlorinated aliphatic hydrocarbons such as dichloromethane, 1.1 , 1-trichloromethane or mixtures of the compounds mentioned.

A particularly suitable polymerization process has been the introduction of the catalyst in the inert solvent, optionally subsequent addition of activator component b) or iv) and the subsequent addition of the monomers and polymerization at a temperature in the range from 20 to 100 ° C. and a pressure in the range from 1000 to 10000 kPa.

The carbon monoxide copolymers according to the invention can be processed by means of injection molding, blow molding, spinning, rotary molding, extrusion or spin coating. It also succeeds Coating of metallic, ceramic and other surfaces, such as those made of plastic materials.

The carbon monoxide copolymers according to the invention are suitable for the production of fibers, films, moldings and coatings.

The invention is described in more detail with reference to the following examples.

Examples

I. Measurement methods and devices

Molecular weights M _w and molecular weight distributions M _w / M _n were determined by GPC in CHCI ₃ using a Waters 590 HPLC pump, Waters microstyragel columns with pore sizes of 10 ⁵ , 10 ⁴ and 10 ³ Å, a Waters 410 differential refractometer and a Waters 486 UV detector.

^ -H-NMR and ¹³ C-NMR measurements were carried out using the Bruker AC 200 or AMX 500 spectrometer.

The DSC data were determined using the Perkin Elmer DSC 7 device equipped with a Perkin Elmer TAC 7 / DX thermal controller. Cyclohexane, indium and gallium were used for the calibration.

Melting points were determined with a Mettler FP82HT heating plate and a Mettler FP90 processor using a Zeiss Axioskop Pol microscope.

IR spectra were recorded on a Bruker IFS 66V spectrometer. The measurement samples were produced from a dichloromethane solution by pulling a thin film onto KBr plates.

The catalyst used was [Pd.dppp] (NCCH ₃ ) ₂ ] (BF) ₂ , produced from [Pd [NCCH ₃ ) ₄ ] (BF ₄ ) ₂ (from Aldrich) and 1,3-bis (diphenylphosphino) propane (= dppp) (from Strem Chemicals) according to FY Xu, AX Zhao, JCW Chien, Makromol. Chem. 1993, 194, 2597.

Toluene, dichloromethane and triethylamine were distilled over sodium, benzophenone or calcium hydride or KOH before use. Methanol was purified by distillation over magnesium wires. 2-Allylphenol (Ml), 4-Allylmethoxybenzol (M3) (both Fluka products) and 4-Allyl-2-methoxyphenol (M4) (Merck) were used in the form in which they are commercially available. 2 -Allylmethoxybenzol (M2), was analogous to a procedure in F. Ullmann, Liebigs Ann. Chem. 1995, 327, p. 114.

General copolymerization regulations

a) Production of binary carbon monoxide copolymers

To a solution of the catalyst complex

[Pdtdppp] (NCCH ₃ ) ₂ ] (BF) ₂ (0.049 mol) in dichloromethane

(25 ml) in a 100 ml steel autoclave were added methanol (0.25 ml) and the monomer compound (A) (Ml, M2, M3 or

M4; 38 mmol) (Examples 1 to 4) and stirred under a carbon monoxide pressure of 60.8 × 10 ⁵ Pa for 24 h at room temperature. The polymerization was terminated by degassing and by dilution with dichloromethane, the reaction mixture was freed from catalyst residues by filtration over a short silica column and the majority of the solvent was distilled off before the polymer product was precipitated by adding methanol. After filtration and drying in vacuo, pure copolymer material could be obtained. Was instead of methanol for

To give reaction mixture, the solvent was slowly evaporated, an almost colorless polymer film was obtained. Further information regarding initial quantities and product parameters can be found in Table 1. Table 2 shows the results of a copolymerization of carbon monoxide and 2-allylphenol according to a) with the difference that the activator concentration was varied (Examples 5 to 8).

b) To a solution of the catalyst complex

[Pdtdppp] (NCCH ₃ )] (BF) ₂ (0.049 mmol) in dichloromethane (40 ml) in a 100 ml steel autoclave were added methanol (0.25 ml) and the monomer component (A) (Ml or M3). The copolymerization was carried out at a propene pressure of 9.1 × 10 ⁵ Pa and a carbon monoxide pressure of 51.7 × 10 ⁵ Pa over a period of 16 h at room temperature with stirring. The polymerization was stopped by degassing the autoclave and diluting with dichloromethane. The reaction mixture was freed from catalyst residues by filtration through a short silica gel column, the majority of the solvent was removed by distillation and the polymer product was added by adding methanol failed. After filtration and vacuum drying, the desired terpolymer was obtained. If, instead of precipitating the polymer product by adding methanol, the solvent was evaporated slowly, an almost colorless polymer film was obtained. Further information on the amount of component (A) used and the product parameters can be found in Table 3 (Examples 9 to 12).

III. Spectroscopic data

Copolymer of carbon monoxide and 2-allylphenol (Ml): IR: 3421 cm ' ¹ (OH); 1700 cm " ¹ (C = 0). IH-NMR (CDC1 ₃ ): δ = 7.2 - 6.4; 3.4 - 1.0; integration ratio 1: 1.2. 1C-NMR (CDCI ₃ ): δ = 209.1; 153.8; 151.6; 130.6; 127.4; 125.8; 120.4; 116.4; 108.2; 42.4; 33.8; 28 , 7th

Copolymer of carbon monoxide and 2-allylmethoxybenzene (M2): IR: 1707 cm " ¹ (C = 0). IH-NMR (CDCI ₃ ): δ = 7.10 (m, 2H, Ar); 6.83 (m, 2H, Ar); 3.80

(m, 3H, CH ₃ ); 3.4 - 1.5 (m, 5H, CH ₂ and CH).

"C NMR (CDCI ₃ ): δ = 212.0; 157.3; 131.0; 129.8; 127.4; 120.6;

110.4; 55.4; 45.9; 34.3; 32.1.

Copolymer of carbon monoxide and 4-allylmethoxybenzene (M3):

IR: 1707 cm " ¹ (C = 0).

^ H NMR (CDCI ₃ ): δ = 6.97 (m, 2H, Ar); 6.78 (m, 2H, Ar); 3.74

(s, 3H, CH _3); 3.11 (m, 1H, CH); 2.71 (m, 2H, α-CH ₂ ); 2.19 (m, 2H, CH _2).

1 ³ C-NMR (CDCI _3): δ = 211.6; 211.0; 208.6; 157.8; 131.8; 129.7;

113.6; 56.7; 47.5; 43.5; 33.9.

Copolymer of carbon monoxide and 4-allyl-2-hydroxymethoxybenzene (M4):

IR: 3436 cm " ¹ (OH); 1705 cm" ¹ (C = 0). ⁱ H-NMR (CDCI ₃ ): δ = 6.85 (m, 2H, Ar); 6.65 (m, 2H, Ar); 6.00

(m, 1H, -OH); 3.82 (s, 3H, CH _3); 3.10 (m, 1H, -CH); 2.65

(m, 2H, CH ₂ ); 2.12 (m, 2H, CH _2).

¹³ C NMR (CDCI ₃ ): δ = 213.2; 211.3; 209.2; 146.5; 144.1; 131.7;

212.5; 115.2; 111.4; 55.4.

Terpolymer of carbon monoxide, 2-allylphenol and propene: ⁱ H-NMR (CDCI3): δ = 7.2 - 6.5 (m, Ar); 3.3 - 1.5 (m, CH, CH ₂ , α-CH ₂ ); 1.4 to 0.5 (CH _3). Terpolymer of carbon monoxide, 2-allylmethoxybenzene and propene: ⁱ H-NMR (CDC1 ₃ ): δ = 7.2 - 6.6 (m, Ar); 4.1 ^■ 3.7 (OCH ₃ ); 3.3 - 1.5 (m, CH, CH ₂ , α-CH ₂ ); 1.4 to 0.6 (CH _3).

Table 1

^a) determined by means of GPC against a polystyrene standard ^b) no glass transition was observed ^c) not determined

Table 2

^a) determined by means of GPC against a polystyrene standard

Table 3

^a) determined by means of GPC against a polystyrene standard ^b) proportion of incorporated component (A), based on the CO units in the polymer chain (determined by means of Η-NMR spectroscopy)

Claims

claims

1. Functionalized linear alternating carbon monoxide copolymers of carbon monoxide and at least one 1-alkene (A), characterized in that the compound (A) contains an aryl derivative containing one or more polar groups and substituted with at least one terminal allyl and / or homoallyl unit, except 4-allylanisole.

2. Functionalized linear alternating carbon monoxide copolymers of carbon monoxide, at least one 1-alkene (A) and at least one C ₂ - to Cχo-1-alkene (B), characterized in that the compound (A) is an allyl with at least one terminal - and / or homoallyl unit substituted aryl derivative containing polar groups.

3. Carbon monoxide copolymers according to claims 1 or 2, wherein (A) is a compound of the general formula (Ia) or (Ib)

in which the substituents and indices have the following meaning:

X OR ¹ , NR ² R ³ , halogen, nitro or C0 ₂ R ⁴ , wherein

R ^{1 is} hydrogen, C ¹ to C ₀ alkyl, C ₃ to Cio-cycloalkyl, C ₆ to C ₁₄ aryl, C (0) R ⁵ or Si (R ⁶ ) ₃ ,

R ^2, R ³ is hydrogen, Ci- to Cι ₀ alkyl, C ₃ - to Cio-cycloalkyl, Cg to Cι ₄ aryl or together with N a ring consisting of 2 to 10 carbon atoms or a ring composed of 2 to 10 carbon atoms and at least one further heteroatom in the cycle,

R ⁴ Ci to Cio-alkyl or C ₆ - to -C aryl; R ⁵ Ci to Cio alkyl or C ₆ to C ₁₄ aryl,

R ⁶ independently of one another are ci- to cio-alkyl, C ₃ - to cio-cycloalkyl or C ₆ - to Ci ₄ -aryl,

Y is a compound of the general formula (II)

CH ₂ = C (R ⁷ ) (C (R ⁸ ) ₂ ) _q ) - (II),

wherein

R ⁷ Wasserstof f, Ci- to Cio-alkyl, C ₃ - to Cι ₀ cycloalkyl or C ₆ - to Cι ₀ aryl, and

R ⁸ independently of one another hydrogen, Ci, bis

Cio-alkyl, C ₃ - to Cio-cycloalkyl, C ₆ - to Cio-aryl or halogen and

1 or 2 ,

Ci- to Cio-alkyl, Ce ~ to -C-aryl, C ₃ - to Cio-cycloalkyl, aralkyl with 1 to 6 carbon atoms in the alkyl and with 6 to 14 carbon atoms in the aryl part or C ₃ - to C ₃ o-organosilyl,

where for (Ia)

k, 1 integers from 1 to 5 and

o an integer from 0 to 4 mean with

k + l + o <6

and for (Ib)

m, n integers from 1 to 7 and

p denotes an integer from 0 to 6

m + n + p <8.

4. Carbon monoxide copolymers according to claims 1 to 3, characterized in that the terminal allyl unit in (A) is in the ortho position to a polar group.

5. Carbon monoxide copolymers according to claims 1 to 4, characterized in that at least one polar group in (A) means hydroxy.

6. Carbon monoxide copolymers according to claims 2 to 5, characterized in that ethene, propene, but-1-ene or styrene or mixtures of the above-mentioned 1-alkenes are used as 1-alkene (B).

7. A process for the preparation of functionalized linear alternating carbon monoxide copolymers according to claims 1 to 6, characterized in that the copolymerization of carbon monoxide with at least one 1-alkene (A) and optionally at least one 1-alkene (B) in a practically alcoholic or water-free polymerization medium in the presence of a catalyst, the active mass of which is formed from

a) a metal complex of the general formula (purple) or (Illb)

2®

R * R ^b

El

Ll

Z M [s®] (purple)

E ² L ²

R ^c R

in which the substituents and indices have the following meaning:

M is a metal from Group VIIIB of the Periodic Table of the Elements, E ¹ , E ² an element from group VA of the periodic table of the elements,

Z is a bridging structural unit made up of one, two, three or four substructural units from elements of group IVA, VA, VIA of the periodic table of the elements,

R ^a to R ^d substituents selected from the group consisting of -C ~ to C ₂₀ organic carbon and C ₃ - to C ₃ o ^_ organosilicon radicals, the radicals being one or more elements from group IVA, VA, VIA and VIIA des Periodic table of the elements can contain

R ^e to R ^h independently of one another, hydrogen, straight-chain or branched Ci to C ₆ alkyl or

R ^f and R ^ - together - five or six members

Carbo- or heterocycle,

L ¹ , L ² formally uncharged Lewis base ligands,

T mono- or divalent anions,

r, s 1 or 2,

where r x s = 2, and

b) an activator component which contains a hydroxyl group in the molecule which, based on M in (III), is used in an amount of 0 to 1500 molar equivalents.

8. A process for the preparation of functionalized linear alternating carbon monoxide copolymers according to claims 1 to 6, characterized in that the copolymerization of carbon monoxide with at least one 1-alkene (A) and optionally at least one 1-alkene (B) in a practically alcoholic or carries out anhydrous polymerization medium in the presence of a catalyst, the active mass of which is formed from

i) a salt of a metal M from group VIIIB of the periodic table of the elements, ii) one or more compounds selected from the group of protonic acids and Lewis acids,

iii) a chelate compound of the general formula (IVa) or (IVb)

_R a _R b _E l_ _Z _ _E 2 _RCR d (IVa),

in which the substituents and indices have the following meaning:

E ¹ , E ² an element from group VA of the periodic table of the elements,

Z is a bridging structural unit consisting of one, two, three or four substructural units from elements of group IVA, VA, VIA des

Periodic table of the elements,

R ^a to R ^d substituents selected from the group of -C ~ to C o-carbon organic and C ₃ - to C ₃ o-organosilicon radicals, the

Radicals can contain one or more elements from groups IVA, VA, VIA and VIIA of the Periodic Table of the Elements,

R ^e to R ^h independently of one another, hydrogen, straight-chain or branched Ci to C ₆ alkyl or

R ^f and R9 - together - five- or six-membered carbo- or heterocycle

iv) an activator component which contains a hydroxyl group in the molecule which, based on the metal M in i), is used in an amount of 0 to 1500 molar equivalents.

9. The method according to claims 7 or 8 for the production of carbon monoxide copolymers according to claim 5, wherein the addition of an activator component is dispensed with.

10. Use of the carbon monoxide copolymers according to claims 1 to 6 for the production of films, films, moldings and coatings.