EP0827519A1

EP0827519A1 - Carbon monoxide/olefin-copolymers

Info

Publication number: EP0827519A1
Application number: EP96914190A
Authority: EP
Inventors: Ferdinand Lippert; Arthur Höhn; Peter Hofmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1995-05-22
Filing date: 1996-05-09
Publication date: 1998-03-11
Also published as: WO1996037537A1; JPH11505865A; DE19518737A1; US5891989A

Abstract

The invention concerns copolymers of carbon monoxide with olefinically unsaturated compounds, obtainable by polymerisation of the monomers in the presence of a metal complex of general formula (I) in which the substituents and indices have the following meanings: M is a group VIIIB metal; E1, E2 are a group VA element; Z is a structural unit with a bridging atom selected from among the group IVA, VA or VIA elements; R1-R4 are substituents selected from the group comprising C¿1?-C20 carbon-organic and C3-C30 silicon-organic rests, at least one of the four rests beins a non-aromatic rest; L?1, L2¿ are formally charged or neutral ligands; X stands for formally mono- or polyvalent anions; p is 0, 1 or 2, m and n are 0, 1 or 2, and p = m x n.

Description

Carbon monoxide / olefin copolymers

description

The present invention relates to copolymers of carbon monoxide with olefinically unsaturated compounds, obtainable by polymerizing the monomers in the presence of a metal complex of the general formula (I)

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,

a structural unit with a bridging atom selected from the elements of group IVA, VA or VIA of the periodic table of the elements,

R ¹ to R ⁴ substituents selected from the group consisting of C ₁ to C ₂ o carbon organic and C ₃ to C ₃ o ^organic silicon radicals, at least one of the four radicals being a non-aromatic radical.

l, L ² formally charged or neutral ligands

X formally monovalent or multivalent anions

P 0, 1 or 2

m, n 0, 1 or 2

where p = mxn In addition, the present invention relates to a process for the production of such copolymers, the use of the copolymers for the production of fibers, films and moldings, and the fibers, films and moldings from the copolymers. 5

Carbon monoxide / olefin copolymers, also called polyketones, which are alternately composed of the structural element of an olefin and carbon monoxide, are e.g. from the Journal of Organometallic Chemistry, 417 (1991) 235, and Adv. Polym. Sci., 73/74 (1986) 10 125ff.

The polymers are produced by reacting the monomers in the presence of a catalyst system composed of several components.

15

The components essentially consist of a transition metal compound of subgroup VIII of the Periodic Table of the Elements, phosphine ligands and acids, as described for example in EP-A 121 965.

20th

The constituents of the catalyst system are generally mixed with one another before the polymerization or directly in the polymerization reactor by metering in the individual components, the active catalyst being formed.

25

However, it is expensive to meter the individual components in a reproducible manner and in optimal proportions. The metering process with different metering devices and the stocking of the various catalyst components is furthermore economically disadvantageous.

No. 5,338,825 describes a process for the preparation of carbon monoxide / olefin copolymers using simply positively charged metal complexes which, inter alia, must have a ligand that stabilizes the complex.

The preparative accessibility and the polymerization activity of the catalysts leave something to be desired.

40 US Pat. No. 5,352,767 describes alternating, elastomeric copolymers of carbon monoxide and α-olefins which have been produced using a catalyst system which contains cationic metal complexes from the Villa group of the Periodic Table of the Elements and activators.

45 For the production of such copolymers, however, only α-olefins have been described as comonomers and the polymerization activity of the catalysts is still in need of improvement.

It was therefore an object of the present invention to provide copolymers of carbon monoxide and olefinically unsaturated compounds which do not have the disadvantages mentioned, or only have them to a minor extent. The present invention was also based on the object of providing a process for the preparation of these polymers in which a catalyst is used which consists of as few components as possible and which delivers the copolymers in good yield.

Accordingly, the copolymers defined at the outset were found.

In addition, a process for the production of the copolymers defined at the outset, the use of the defined copolymers for the production of fibers, films and moldings, and also the fibers, films and moldings from the copolymers defined at the outset were 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. The monomers are generally incorporated alternately in the copolymer. In principle, all monomers of this class of compounds can be considered as olefinically unsaturated compounds.

Preference is given to ethylene and C ₃ - to C ~ ~ alkenes such as 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene and mainly propene, butadiene, and also cy - Cloolefins such as cyclopentene, cyclohexene, norbornene and norbornadiene and their derivatives.

Among the olefinically unsaturated aromatic monomers, styrene and α-methylstyrene are primarily mentioned.

Of particular importance are also acrylic and methacrylic acid and derivatives thereof, including in particular, the nitriles, amides and Ci-C _ß alkyl esters, such as ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, methyl methacrylate.

Other suitable monomers are vinyl chloride, vinyl acetate, vinyl propionate, maleic anhydride and N-vinyl pyrrolidone. Mixtures of different monomers can of course also be used, the mixing ratio generally not being critical.

The molar ratio of the olefinically unsaturated compound to carbon monoxide can largely be chosen freely; it is preferably between 0.1: 1 to 10: 1, particularly preferably in the vicinity of 1: 1.

The copolymers according to the invention are notable for a low residual palladium content in the polymer.

The molecular weights Mw (weight average) of the copolymers (measured using the gel permeation chromatography (GPC) method at 25 ° C. using Shodex® HFIP 803 or 805 as the column material and hexafluoroisopropanol as the solvent against the polymethyl methacrylate standard) are generally in the range from 1000 to 1,000,000, preferably 1,000 to 100,000.

The molecular weight distribution Mw / Mn (weight average / number average), measured using the method of gel permeation chromatography (GPC) analogous to the description above, the copolymers according to the invention are generally 2 to 50, preferably 2 to 20.

The K value of the copolymers, measured in accordance with DIN 51562 parts 1 to 3 at 25 ° C. in hexafluoroisopropanol, is 20 to 500, preferably 50 to 400.

The type and number of end groups and also the average molecular weight of the carbon monoxide copolymers was determined using the ¹³ C-NMR spectroscopy method according to J. Orgamometal. Chem. 417 (1991), page 235 ff.

Due to their numerous functional groups, the carbon monoxide copolymers according to the invention can be modified with the usual chemical reactions, such as described for example in EP-A 372 602, or a combination of both methods.

Suitable metals M for the catalyst complexes of the general formula (I) used to prepare the carbon monoxide copolymers according to the invention 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 as well as especially palladium. The metals can be present in the complexes formally uncharged, formally single positively charged, or formally double positively charged.

The elements E ¹ and E ^{2 of} the chelating ligand 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 chelating ligand can contain different elements E ¹ and E ² , for example nitrogen and phosphorus.

The bridging structural unit Z is an atomic grouping that connects the two elements E ¹ and E to one another. An atom from group IVA, VA or VIA of the Periodic Table of the Elements forms the connecting 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, elements from the groups 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.

Particularly suitable bridging structural units are those with only one bridging atom from group IVA of the periodic table of the elements, such as -CR ⁵ R ⁶ - or -SiR ⁵ R ⁶ - in which R ⁵ and R ^{6 are} hydrogen and C 1 ~ until Cio-carbon organic residue is. R ⁵ and R ⁶ can also form a 3- to 10-membered ring together with the bridge atom. Examples of structural units bridging one atom are methylene (-CH ₂ -), ethylidene (CH ₃ (H) C =), 2-propylidene ((CH ₃ ) ₂ C =), diphenylmethylene ((C ₆ H ₅ ) ₂ C = ), Dialkylsilylene, such as dimethylsilylene ((CH ₃ ) ₂ Si =), diphenylsilylene ((C ₆ H ₅ ) ₂ Si =); furthermore as cyclic bridge members cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene.

Preferred bridging structural units are methylene (-CH ₂ -), ethylidene (CH ₃ (H) C =), 2-propylidene ((CH ₃ ) ₂ C =), dimethylsilylene, diphenylsilylene, especially methylene.

Suitable organic carbon radicals R ¹ to R ⁴ are aliphatic and cycloaliphatic and aromatic radicals having 1 to 20 carbon atoms, for example the methyl, ethyl, 1-propyl,

1-butyl, 1-pentyl, 1-hexyl and 1-octyl group. Linear arylalkyl groups each having 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 and aryl radicals such as phenyl, tolyl and other substituted phenyl groups, at least one of the four Re ¬ ste R ¹ to R ^{4 is} a non-aromatic radical. The radicals R ¹ to R ⁴ should preferably be sufficiently space-filling that the central atom, for example the palladium atom, with which the atoms E ¹ and E ^{2 form} the active complex, is largely shielded. Residues which meet this requirement are, for example, cycloaliphatic radicals and branched aliphatic radicals, including in particular those with branching in the α position.

Suitable cycloaliphatic radicals are C ₃ - to Cio-monocyclic radicals such as, for example, the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl groups and menthyl groups, and bicyclic radicals such as the norbornyl, pinanyl, bornyl group and bicyclononyl group in any combination of the ring structure with the atoms E ¹ and E ² into consideration. The cycloaliphatic radicals preferably contain a total of 5 to 20 carbon atoms; cyclohexyl and menthyl are very particularly preferred.

Suitable branched aliphatic radicals are C ₃ - to C ₂₀ - / preferably C ₃ - to C ₂ -alkyl radicals, such as the isopropyl, isobutyl, sec-butyl, neopentyl, and tert-butyl group, furthermore alkylaryl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical.

Particularly suitable branched aliphatic radicals are the tert-butyl group, the iso-propyl group and the see-butyl group.

Alkyl groups with branching located further outside are also suitable as substituents R ¹ to R ⁴ , such as the isobutyl, 3-methyl-but-2-yl and 4-methylpentyl group.

According to the observations made so far, the chemical nature of the radicals R ¹ to R ⁴ is not critical, ie the radicals can also contain atoms from the group IVA, VA, VIA or VIIA of the periodic system of the elements, such as for example halogen, oxygen, sulfur, nitrogen, silicon, here for example the bis (trimethylsilyl) methyl group. Functional groups such as, for example, hydroxy, alkoxy and cyan, which are inert under the polymerization conditions, can also be considered in this context.

Preferred hetero substituents R ¹ to R ⁴ 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 and whose remaining valences are saturated with three carbon-organic radicals, the sum of the carbon atoms of these three silicon-bonded radicals in the range from three to thirty lies. Examples include trimethylsilyl, tert-butyldimethylsi- O 96/37537 PC17EP96 / 01974

7 lyl- or triphenylsilyl group, especially the trimethylsilyl group.

Diphosphines bridged with a methylene group are preferably used as the chelating ligand, such as, for example, [(di-tert.-butylphosphino) (diphenylphosphino)] methane, particularly preferably using C ₃ - to Cio-cycloaliphatic or branched C ₃ - to C ₂₀ ~ aliphatic radicals R ¹ to R ⁴ substituted methylene-bridged diphosphines, such as, for example, bis (di-tert-butyl-phosphino) methane, [(di-tert-butyl-phosphino) (di-cyclohexylphosphino)] methane, bis ( di-cyclohexylphosphino) methane or [(di-tert-butylphosphino) (dimenthylphosphino)] methane whose suitability for the process according to the invention is currently attributed to the methylene linkage of the two phosphorus atoms and the large space-consuming structure of the radicals R ¹ to R ⁴ .

Very particularly preferred compounds as the chelating ligand are bis (di-tert-butylphosphino) methane, [(di-tert-butylphosphino) (di-cyclohexylphosphino)] methane, bis (di-cyclohexylphosphino) methane, [(Di -tert.-butylphosphino) (diphenylphosphine)] methane or [(di-tert-butylphosphino) (dimenthylphosphine)] methane.

Depending on the formal oxidation state of the central metal M, the ligands L ¹ , L ² carry one or two formally negative charges, or if the metal is formally uncharged, the ligands L ¹ , L ^{2 are} also formally uncharged.

The chemical nature of the ligands is not critical. According to the current state of knowledge, they have the function of stabilizing the rest of the metal complex against decomposition, for example deposition of the metal or non-specific reactions, for example aggregation of the complex fragments.

Suitable formally charged inorganic ligands L ¹ , L ² are hydride, halides, sulfates, phosphates or nitrates.

Halides such as chlorides, bromides, iodides and in particular chlorides are preferably used.

Suitable formally charged organic ligands L ¹ , L ² are C ¹ ~ to C ₂ o ^_ aliphatic, C ₃ - to C ₃ o-cycloaliphatic, C ₇ - to C ₂₀ aralkyl radicals with Cξ- to Cirj-aryl radical and Cι ~ to Cio Alkyl radical, Cε to C ₂ aromatic radicals, such as, for example, methyl, ethyl propyl, isopropyl, tert-butyl, neopentyl, cyclohexyl, O 96/37537 PC17EP96 / 01974

8th

Benzyl, neophyl, phenyl and aliphatic or aromatic substituted phenyl radicals.

Also suitable as formally charged organic ligands L ¹ , L ² -C ~ to C ₂ o-carboxylates such as acetate, propionate, oxalate, benzoate, citrate and salts of organic sulfonic acids such as methyl sulfonate, trifluoromethyl sulfonate, p-toluenesulfonate. C 1 -C ₇ -carboxylates, sulfonic acid derivatives and in particular acetate and p-toluenesulfonate are preferably used.

Lewis bases, that is to say compounds with a free 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, ie, for example, nitriles, R-CN, ketones, ethers, alcohols, are particularly suitable. Preference is given to using C ~ to Cirj-nitriles such as acetonitrile, propionitrile, benzonitrile or C ₂ - to Cio-ketones such as acetone, acetylacetone or else C ₂ - to Cirj ethers such as dimethyl ether, diethyl ether, tetrahydrofuran. In particular, acetonitrile or tetrahydrofuran is used.

Depending on the formal charge of the complex fragment containing the metal M, the metal complex (I) contains anions X. If the M-containing complex fragment is formally uncharged, the complex according to the invention does not contain any anion X.

The chemical nature of the anions X is not critical. According to the current state of knowledge, however, it is advantageous if they are as little nucleophilic as possible, i.e. have as little tendency as possible to form a chemical bond with the central metal M.

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 Tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyDborat, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate. Preference is given to using perchlorate, trifluoroacetate, sulfonates such as methylsulfonate, trifluoromethylsulfonate or ponifluorofluoronate, p-toluifluoronate, p-toluifluoronate, p-toluifluoronate, p-toluifluoronate, p-toluifluoronate, p-toluifluoronate, p-toluifluoronate, p-toluifluoronate, p-tolifluorofluoronate, p-toluifluoronate, p-tolifluorofluoronate and p-toluifluoro- Toluenesulfonate.

For the neutral chelate complexes, the metal complexes of the general formula (I) are generally prepared by exchanging weakly coordinating ligands, such as, for example, 1,5-cyclooctadiene, benzonitrile or tetramethylethylenediamine to the corresponding transition metal compounds, for example transition metal halides, transition metal (alkyl) (halides), transition metal diorganyls, against the chelate ligands according to the invention [R ¹ R ² E ¹ ] -Z- [R ³ R ⁴ E ² ] according to claims 1 to 5. The reaction is generally carried out in a solvent such as dichloromethane at temperatures in the range from (-) 78 to 40 ° C.

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

Monocationic complexes of the general formula (I) are converted by reaction of (chelate ligand) metal (halogeno) (organo) complexes of the general formula (I) in which L ¹ halogen and L ² the previously defined formally charged organic ligands (to the exclusion of the anions of organic acids) mean formed with metal salts M'X. The reaction is generally carried out in coordinating solvents such as, for example, acetonitrile or tetrahydrofuran 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. The salt anion should preferably be a non-nucleophilic anion X, as previously defined.

Well-suited salts for the formation of cationic complexes are silver tetrafluoroborate, silver hexafluorophosphate, silver trifluoromethanesulfonate, silver perchlorate, silver paratoluenesulfonate.

The dicationic complexes (II) are prepared analogously to the monocationic complexes, except that now instead of the (chelate ligand) metal (halogeno) (organo) complexes, the (chelate ligand) metal (di-halogeno) complexes of the general Formula (I) (L ¹ and L ² means halogen) can be used as a precursor. A further process for the preparation of the dicationic complexes (I) is the reaction of [Y ₄ M] X ₂ with the initially defined chelate ligands [R ¹ R ² E ¹ ] -Z- [R ³ R ⁴ E ² ] in question. Y means the same or different weak ligands, such as, for example, 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 with non-coordinating anions.

The polymerizations for the production of the carbon monoxide copolymers according to the invention can be carried out either batchwise or continuously.

Pressures from 100 to 500,000 kPa, preferably 200 to 350,000 kPa and in particular 500 to 30,000 kPa, temperatures from (-50) to 400 ° C., preferably 20 to 250 ° C. and in particular 40 to 150 ° C. have proven to be suitable .

Polymerization reactions using the metal complexes (I) defined at the outset can be carried out in the gas phase, in suspension, in liquid and in supercritical monomers and in solvents which are inert under the polymerization conditions.

Suitable inert solvents are alcohols such as methanol, ethanol, propanol, i-propanol, 1-butanol and tert-butanol, sulfoxides and sulfones, for example dimethyl sulfoxide, esters such as ethyl acetate and butyrolactone, ethers such as tetrahydrofuran, dimethyl ethylene glycol and

Diisopropyl ether and aromatic solvents such as benzene, toluene, ethylbenzene or chlorobenzene or mixtures thereof.

The molecular weight of the polymers according to the invention can be influenced by varying the polymerization temperature, by protic compounds such as alcohols, for example methanol, ethanol, tert-butanol, preferably methanol, and by adding hydrogen in a manner known to those skilled in the art. In general, a high concentration of regulating substances and / or a high polymerization temperature results in a relatively low molecular weight and vice versa. 11

The polymers produced using the process according to the invention are generally distinguished by a low palladium content and a narrow molecular weight distribution Mw / Mn.

Examples

Abbreviations bcpm [(di-tert-butylphosphino) (di-cyclohexylphosphino)] methane dtbpm bis- (di-tert-butyl-phosphino) methane tbppm [(di-tert-butylphosphino) (diphenylphosphino)] methane dchpm bis- (di-cyclohexylphosphino) methane MeCN acetonitrile, CH ₃ -CN

General polymerization conditions

100 ml of methanol and the corresponding palladium compound were placed in a 0.3 l autoclave. A mixture of ethylene and carbon monoxide in a molar ratio of 1: 1 to the desired total pressure was then injected at the selected reaction temperature. The polymerization was carried out for 5 hours. The temperature and the partial pressures of the monomers were kept constant throughout the reaction. The polymerization was stopped by reducing the pressure to ambient pressure, the reaction mixture was filtered and the residue was dried. The experimental parameters are shown in Table 1, the polymer properties in Table 2.

Table 1: Test parameters

No. complex, mg, mmol pressure temp. Yield [kPa] [° C] [g]

1 [(dtbpm) Pd (MeCN) ₂ ] (P-Tos) ₂ , 33, 0.05 20,000 80 22.0

2 [(tbppm) Pd (MeCN) ₂ ] (CF ₃ S0 ₃ ) 2, 18, 0.03 20,000 50 50.2

3 [(dchpm) Pd (MeCN) ₂ ] (C10 ₄ ) 2 40, 0.05 20,000 50 41.3

4 [(bcpm) Pd (MeCN) ₂ ] (C10 ₄ ), 19, 0.03 20,000 50 65.3

5 [(tbppm) Pd (CH ₃ ) (MeCN)] (C10 ₄ ), 15, 0.03 20,000 50 2.1

6 [(tbppm) PdCl ₂ ,] 52, 0.1 20,000 50 2.1

7 [(BCPM) Pd (MeCN) _2] (CF ₃ S0 ₃₎ _2, 60, 0.07 6000 85 40.1 Table 2: Polymer properties

No. Melting point [° C] K value

1 236 87

2,258> 300

3,260,300

4,238,198

5 261 182

6 255 57

7 238 76

Claims

claims

Copolymers of carbon monoxide with olefinically unsaturated compounds, obtainable by polymerizing the monomers in the presence of a metal complex of the general formula (I)

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

R ¹ to R ⁴ substituents selected from the group consisting of C ₁ -C ₂ -o-organic carbon and C ₃ - to C ₃ o -silicon organic radicals, at least one of the four radicals being a non-aromatic radical,

L ^l , L ² formally charged or neutral ligands

X formally monovalent or multivalent anions

0, 1 or 2

m, n 0, 1 or 2

where p = mx n.

2. Copolymers according to claim 1, wherein Z is a structural unit with a bridging atom selected from the elements of group IVA of the periodic table of the elements.

3. Copolymers according to claims 1 to 2, wherein Z is -CR ⁵ R ⁶ - or -SiR ⁵ R ⁶ - and R ⁵ and R ^{6 are} hydrogen, Cι ~ to Cio-carbon organic radical.

Copolymers according to claims 1 to 3, wherein E ¹ and E ^{2 are} phosphorus.

5. Copolymers according to claims 1 to 4, wherein R ¹ to R ⁴ Cι ~ o to C ~ ₂ i ^s aliph ^at cher or C ₃ - to C ₂ o ~ means cycloaliphatic radical.

6. Process for the preparation of copolymers from carbon monoxide and olefinically unsaturated monomers by polymerizing the monomers in the presence of a metal complex of the general formula (I)

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

R ¹ to R ⁴ substituents selected from the group consisting of C ₁ to C ₂ o carbon organic and C ₃ to C ₃ ^organic silicon residues, where at least one of the four residues is a non-aromatic residue,

L ¹ , L ² formally charged or neutral ligands

X formally monovalent or multivalent anions

p 0, 1 or 2

m, n 0, 1 or 2

where p = m x n.

7. The method according to claim 6, in which one uses as olefinically unsaturated compounds olefins, diolefins or olefins substituted with functional groups and vinylaromatics.

8. The method according to claims 6 to 7, in which as olefinically unsaturated compounds C ₂ - to C ₂ Q-Alk-l-ene, internal C ₄ - to C ₂ o ~ A. alkenes, C ₄ - to C ₂ o ~ Diolefins or α-ß-unsaturated carboxylic acids or their derivatives are used.

9. Use of the copolymers according to claims 1 to 5 as films, fibers or moldings.

10. Films, fibers and moldings made from the copolymers according to claims 1 to 5.