WO2000049060A1 - Method for producing functionalised alternating carbon monoxide copolymers - Google Patents

Abstract

The invention relates to a method for producing alternating carbon monoxide copolymers containing covalently bonded organic substituents. According to the inventive method, organic compounds (B) are provided with a C-C double or triple bond or a tertiary or bencyclic hydrogen atom. Said organic compounds (B) and linear alternating carbon monoxide copolymers (A) are made to react together in the carbon monoxide copolymer melt at temperatures ranging from 180 to 290 DEG C.

Description

Process for the production of functionalized alternating carbon monoxide copolymers

description

The present invention relates to a process for producing alternating carbon monoxide copolymers containing covalently bonded organic substituents, hereinafter also referred to as functionalized alternating carbon monoxide copolymers. The invention further relates to the functionalized carbon monoxide copolymers obtainable by this process and their use in the production of fibers, films and moldings and as a phase mediator in the production of polymer mixtures. In addition, the invention relates to polymer mixtures containing unfunctionalized and functionalized carbon monoxide copolymers.

Carbon monoxide copolymers and among them linear, alternating carbon monoxide copolymers and processes for their preparation are well known to the person skilled in the art (see also EP-A 0 121 965 and E. Drent, P.H. N. Budzelaar, Chem. Rev., 1996, 96, pages 663-681). In this class of substances, in particular, high molecular weight, partially crystalline carbon monoxide copolymers with a strictly alternating sequence of carbon monoxide and olefinically unsaturated monomer in the main chain have application potential as engineering plastics due to high melting points, good chemical resistance and advantageous mechanical and rheological properties. A disadvantage of the partially crystalline carbon monoxide copolymers, particularly with regard to further processing and subsequent chemistry, is their poor solubility in all conventional solvents. For example, carbon monoxide / ethene and carbon monoxide / ethene / propene copolymers with low proportions of propene are only reasonably readily soluble in solvents such as hexafluoro-i-propanol or cresol. Subsequent implementations or further processing steps are either not possible as a result of the poor solubility or are associated with a high level of preparative effort, which usually makes technical applications impossible from the outset. Accordingly, attempts have been made to improve the solubility of carbon monoxide copolymers.

This can be done on the one hand by using suitably functionalized comonomers in the production of the carbon monoxide copolymers.

For example, Liaw et al. , J. Polym. Be., Part A,

1988, 36, pages 1785-1790, in the transition-metal-catalyzed production of carbon monoxide copolymers with functional groups Pen provided norbornene derivatives as exclusive vinyl monomers. In this case, however, only norbornene substituted with acetate groups could be incorporated into the copolymer chain, but not norborne substituted with hydroxy, amino or carboxylic acid groups. In addition, since only functionalized carbon monoxide copolymers with maximum average molecular weights M _n of 5470 g / mol were obtained, which in dimethyl sulfoxide, dimethylformamide, pyridine, N, N-dimethylacetamide and acetone, but not in common aromatic or halogenated hydrocarbons such as benzene, toluene or chloroform are soluble, the range of uses of the Liaw et al. Functionalized carbon monoxide copolymers described as very low. Against a wide application, the complex production of the vinyl monomers used and the very poor productivity of the process described also speak against.

Sen et al. , Macromolecules, 1996, 29, pages 5852-5858, use ω-alkenols or ω-alkenecarboxylic acids as comonomers in the production of linear carbon monoxide copolymers. Adequate yields are, however, only obtained with an optically active catalyst complex whose bidentate bisphosphine chelate ligand is only accessible in a complex manner. In the rest of the described carbon monoxide / alkenol copolymers, the structural element of the 1,4-dione unit typical of carbon monoxide copolymers is partially or completely removed by intra- and intermolecular ketal formation. In addition, the abovementioned copolymers are obtained only in molecular weights of less than 50,000 g / mol and are therefore not suitable for applications in the field of engineering plastics. In the production of linear carbon monoxide / alkenecarboxylic acid copolymers, Sen et al. the formation of inconsistent products was also observed. Basically, the Sen et al. achieved productivity as too low for a technical application. Accordingly, it is fundamentally not trivial to include suitable long-chain termonomers in addition to ethene and carbon monoxide in carbon monoxide copolymers.

Alternatively, functional groups were inserted into the carbon monoxide copolymer chain via polymer-analogous reactions. Liaw et al. , Eur. Polym. J., 1996, 32 (11), pages 1285-1288, describe the reaction of carbon monoxide / ethene copolymers with hydroxylamine to polyketoximes, which are soluble in dimethyl sulfoxide and dimethylformamide. The described method is very expensive to prepare and only leads to functional groups with low reactivity, which are not very suitable for subsequent or grafting reactions. In addition, Liaw et al. the characteristics - see 1, 4-dione unit of the linear, alternating carbon monoxide copolymer chain lost.

In addition to the reactivity of the carbonyl group, the reactivity of the hydrogen atoms in the α-position to the ketone units can also be used to functionalize the copolymer chain.

The patent US Pat. No. 4,616,072 shows the reaction of statistical carbon monoxide copolymers with chlorine, in which chlorine substituents are installed in the polymer chain in position to the carbonyl group. The product obtained is soluble in carbon tetrachloride, dioxane, tetrahydrofuran, dichloromethane and styrene. A disadvantage, however, is that the chlorine substituent as such does not represent a reactive group that could be used directly for subsequent 5 or grafting reactions. In addition, the range of applications for halogen-containing polymers is inevitably rather limited.

In WO 98/28354 the suitability of low molecular weight carbon monoxide / olefin copolymer compositions as binders or adhesives for wood applications is improved by grafting vinyl monomers such as styrene or methyl methacrylate onto the carbon monoxide copolymer chain. The grafting reaction is carried out in an oil-in-water dispersion, to which the grafting monomer and a radical initiator are added. The molar masses of the carbon monoxide copolymers used are in the range from 200 to 20,000 g / mol and preferably assume values less than 4000 g / mol. The graft copolymers obtained have a reduced viscosity and very good adhesion properties. Amines should be added regularly to harden the binder obtained.

US Pat. No. 5,079,316 shows that carbon monoxide copolymers with a carbon monoxide content of less than 40% by weight with vinyl and vinylidene monomers at temperatures in the range from

35 25 to 100 ° C can be grafted radically. It is possible both to graft the graft monomers directly onto the copolymer chain and to attach a previously prepared polymer chain from the graft monomers to the polymer backbone in order to arrive at the desired graft copolymer. According to this

The described grafting reactions take place under the radical polymerization conditions of the production of statistical carbon monoxide copolymers. These statistical copolymers generally have only a small proportion of carbon monoxide built into the polymer chain. However

45 graft copolymers obtained only with such carbon monoxide copolymers polymers are suitable as compatibilizers for polycarbonate / ABS or polyethylene terephthalate / polycarbonate blends.

It would be desirable to also be able to functionalize linear, alternating carbon monoxide copolymers in a preparatively simple manner while maintaining the characteristic structural units of this substance class with suitable substituents.

The present invention was therefore based on the object of finding a process for the production of functionalized alternating carbon monoxide copolymers which is preparatively simple to implement, tolerates carbon monoxide copolymers with a high carbon monoxide content, the thermoplastic material properties of the carbon monoxide copolymers used not or not significantly changed and leads to copolymers with good processing properties.

Accordingly, a process for the production of alternating carbon monoxide copolymers containing covalently bonded organic

20 niche substituents were found, in which organic compounds (B) which have a C-C double or triple bond or a tertiary or benzylic hydrogen atom, and linear, alternating carbon monoxide copolymers (A) in the carbon monoxide copolymer melt at temperatures in the range from 180 to

25 290 ° C to react with each other.

Furthermore, the functionalized alternating carbon monoxide copolymers obtained by the process according to the invention and their use for the production of fibers, fibers,

30 lines and moldings found. Their use as a phase mediator in the production of polymer mixtures has also been found. Finally, polymer mixtures containing unfunctionalized and functionalized carbon monoxide copolymers were found.

35

In the process according to the invention, linear, alternating carbon monoxide copolymers (A) are used, which preferably have a thermoplastic property profile. These carbon monoxide copolymers generally have a molecular weight M _w

40 greater than 30,000, preferably greater than 50,000 and in particular greater than 80,000 g / mol. Carbon monoxide copolymers with lower molecular weights are generally not suitable as engineering plastics and are therefore generally out of the question as a polymer material to be functionalized. The thermoplastic used

45 carbon monoxide copolymers are usually semi-crystalline. Linear, alternating carbon monoxide copolymers are preferably used which are based on carbon monoxide and olefinically unsaturated compounds having 2 to 18, preferably 2 to 12 and in particular 2 to 8 carbon atoms. Among the unsaturated vinyl aromatic compounds, those of 8 to 18 and in particular of 8 to 12 carbon atoms are preferred. The melting point of this class of substances is usually in the range from 100 to 260 ° C., preferably from 180 to 240 ° C., the glass transition temperature T _g in the range from -60 to 80, preferably from -20 to 10 40 ° C.

Preferred olefins for the preparation of binary linear, alternating carbon monoxide copolymers (A) are C ₂ - to Cχo-alk-1-enes such as ethene, propene, but-1-ene, pent-1-ene, hex-1-ene, vinyl norbornene ,

15 norbornene, hept-1-ene, oct-1-ene or styrene, particularly preferably ethene or propene and in particular ethene. Any mixture of the aforementioned olefinic monomers can be used for the production of ternary or higher carbon monoxide copolymers, ethene as the main comonomer component

20 is preferred. Suitable terpolymers are, for example, carbon monoxide / ethene / propene or carbon monoxide / ethene / but-1-ene copolymers with an ethene content of 60 to 99.9, preferably 70 to 99 and particularly preferably 80 to 98 mol. %, based on the olefinic components in the carbon monoxide copolymer. NATURALLY

25 loans can e.g. ternary copolymers of carbon monoxide, but-1-ene and styrene or of carbon monoxide, propene and oct-1-ene can also be used.

The linear, alternating carbon monoxide copolymers (A) are obtained from transition metal-catalyzed carbon monoxide and the olefins mentioned. It can be found in DE-A 19 610 385 and in the unpublished German patent application Az. 19 649 072.3 described methods can be used. These manufacturing methods are hereby expressly included in the present disclosure. Other processes for the production of linear, strictly alternating carbon monoxide copolymers, as disclosed in EP-A 0 485 035 or EP-A 0 702 045, can of course also be used.

40 For the production of carbon monoxide copolymers (A) containing vinyl aromatic monomer units, transition metal complexes with nitrogen ligands such as 2, 2'-bipyridines or bisoxazolines, or with phosphino (dihydrooxazole) ligands are generally used. Such manufacturing processes can be found in Sperle et

45 al., Helv. Chim. Act., 1996, 79, p. 1387, by Brookhart et al., J. Am. Chem. Soc, 1994, 116, p. 3641 and in EP-A 0 345 847.

The transition metal-catalyzed preparation of the carbon monoxide copolymers is suitably carried out in the presence of defined palladium (II) complexes which are chelated with at least one bidentate ligand system which contains phosphorus or nitrogen as coordinating atoms and which act as counterions over non-coordinating or poorly coordinating Anions.

As defined transition metal complexes, i.e. as metal complexes, which are prepared separately before being added to the polymerization mixture and are present in purified form, are particularly suitable [1,3-bis (diphenyl) phosphinopropane] palladium (II) acetate, [1,3-bis (di- (2- methoxyphenyl)) phosphinopropane] palladium (II) acetate, [bis (diphenylphosphinomethyl) henylamine] palladium (II) acetate and [bis (diphenylphosphinomethyl) -2, 4-difluorophenylamine] palladium (II) acetate.

The carbon monoxide copolymerization generally takes place at pressures in the range from 20 to 200, preferably from 50 to 150, bar and at temperatures in the range from 0 to 150, preferably from 20 to 120 ° C. The copolymerization can be carried out in suspension, solution or in the gas phase. Carbon monoxide terpolymers can be used particularly advantageously in a low molecular weight solvent, e.g. Methanol, acetone, tetrahydrofuran, dichloromethane or any mixtures of the compounds mentioned in the presence of Broensted acids with pKa values less than 6, e.g. para-toluenesulfonic acid or trifluoroacetic acid.

According to the invention, organic compounds (B) are used for the functionalization of the thermoplastic linear, alternating carbon monoxide copolymers (A) which have a C-C double or triple bond or a tertiary or benzylic hydrogen atom. The double or triple bond can be in the terminal position of linear or branched aliphatic or substituted aromatic compounds. Connections with an internal double or triple bond are also suitable. Connections with conjugated or non-conjugated multiple bonds can also be used. Suitable alk-1-enes are, for example, those which are liquid or solid at room temperature under normal pressure, such as 2-methyl-pent-1-ene, 4-methylpent-1-ene, oct-1-ene, non-1-ene en, undec-1-en, do-dec-l-en, tetradec-1-en, hexadec-1-en, octadec-1-en, styrene or vinyl naphthalene. Examples of alkynes are hept-1-in,

Oct-l-in, non-l-in, dodec-1-in or phenylacetylene. Suitable compounds with internal or conjugated double or triple bonds are, for example, but-2-ene, pent-2-ene, hex-2-ene, hex-3-ene, 2-methylpent-2-ene, 4-methylpent-2-ene, butadiene, cyclohexene, cyclooctadiene, 2,4-hexadiene or 1,3-pentadiene. In addition, organic compounds which have a tertiary or benzylic hydrogen atom in the molecule can also be used for the reaction in the carbon monoxide copolymer melt. For example, such compounds (B) are 2-methylhexane, 2-methylheptene, 2-methyldodecane, 2-methylhexadecane or 2, 7-dimethyloctane and isopropylbenzene, 4-isopropyl-1-methylbenzene or 7-isopropyl-1-methylphenanthrene Question. Any mixtures of the compounds (B) mentioned can of course also be used.

Compounds (B) which have at least one functional group, preferably a reactive functional group, are particularly suitable. Preferred functionalized carbon monoxide copolymers according to the invention can be obtained, for example, by reacting the aforementioned carbon monoxide copolymers (A) in the melt with compounds which, in addition to a CC double or triple bond, have one or more carbonyl, carboxylic acid, carboxylate, carboxylic anhydride, carboxamide, , Carboximide, carboxylic acid ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups can be obtained. When reacting in the melt, the C-C double or triple bonds react with the carbon monoxide copolymer chain to form covalent bonds. Under the conditions mentioned, the functional groups of the compounds containing C-C double or triple bonds described usually do not undergo any reaction with the copolymer structure.

Typical suitable unsaturated compounds (B) provided with reactive groups are, for example, maleic acid, methylmaleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, vinyloxazoline, isopropenyloxazoline, fumaric acid, the mono- and diesters of these acids, for example Cχ-Ci ₈ -alkanols, the mono- or diamides of these acids such as N-phenylmaleinimide or maleic acid hydrazide as well as acrylic acid, methacrylic acid, glycidyl (meth) acrylate, C 1 ~ to C ₁₈ - (meth) acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate or stearyl (meth) acrylate, furthermore terminal C ₆ - to C ₂₀ -alk-linines with reactive groups such as hydroxyl,

Carboxylic acid, oxazoline or epoxy, for example oct-7-in-1-ol or dodec-11-in-1-carboxylic acid. (Meth) acrylic acid, glycidyl (meth) acrylate, in particular glycidyl acrylate, α, β-unsaturated dicarboxylic acids or their anhydrides and mono- or diesters of the general structures I and II below are preferably used:

in which

R ¹ , R ² , R ³ and R ^{4 are} independently hydrogen and

C 1 -C ₈ alkyl groups such as methyl, ethyl, propyl, butyl, pentyl or octyl can be in linear or branched-chain form.

Particularly suitable compounds are acrylic acid, maleic anhydride, fumaric acid and itaconic acid.

Carbon monoxide copolymers (A) or functionalized carbon monoxide copolymers for the purposes of the present invention are also to be understood as those copolymers which are protected against thermal, oxidative or light-induced degradation or crosslinking reactions by adding one or more stabilizers.

Examples of antioxidants which are substituted with sterically demanding alkyl groups are phenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4 -isobutyl - phenol or 2, 6-di-nonyl-4-methylphenol or mixtures thereof. Also suitable are hydroquinone and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, ascorbic acid or tocopherol. The esters or amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, β- (3,5-dicyclohexyl-4-hydroxyphenyl) -pro- can also be used as suitable antioxidants. pionic acid, 3, 5-di-tert-butyl-4-hydroxyphenylacetic acid or ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with for example methanol, ethanol, octadecanol, ethylene glycol or 1, 9- Nonanediol or hexamethylene diamine or trimethylene diamine can be used. Examples include (octadecyl-3 - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox ^® 1076, Ciba specialty chemistry) and pentaerythrityl tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox ^® 1010 (Ciba specialty chemicals)). In addition, piperidine or pyrrolidine derivatives such as N, N-bis- (2, 2, 6, 6-tetramethyl-piperidin-4-yl) substituted with sterically demanding vicinal 2,6- or 2,5-alkyl groups are also -hexamethylene diamine. Bis (2,2,6,6) tetramethylpiperidin-4-yl) sebacate, 2, 2, 6, 6-tetramethylpiperidin-4-one or 2,2,6, 6-tetramethylpiperidin-4 -ol suitable.

Chelating metal deactivators are also suitable. In addition to organic compounds with a 1,3-diketone unit such as stearoylbenzoylmethane or dibenzoylmethane and compounds of hydrazine, for example N-salicylal-N '-salicyloylhydrazine, N, N'-bis (salicyloyl) -hydrazine or in particular N, N'-bis - (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, these include hydrazide compounds such as isophthalic acid dihydrazide, sebacic acid bisphenyl hydrazide, N, N '-diacetyl-adipic acid dihydrazide, N, N'-bis-salicyloyl-oxalic acid dihydrazide and N, N'-bis-salicycloyl-thiopropionic acid dihydrazide, as well as bisphosphane, hydrazone and bishydrazone derivatives. Furthermore come as stabilizer compounds carboxamides such as oxalic acid amides, for example 4,4'-di-octyloxy-oxanilide, 2,2'-diethoxy-oxanilide, 2,2'-di-octyloxy-5, 5'-di-tert-butyl- oxanilide, 2,2'-di-dodecyloxy-5, 5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N 'bis (3-dimethylaminopropyl) oxalamide , 2-ethoxy-5-tert-butyl-2 '-ethyloxanilide and its mixture with 2-ethoxy-2-ethyl- 5, 4-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy- and of o- and p-ethoxy-di-substituted oxanilides and N, N'-diphenyloxalic acid diamide or triazole derivatives such as 3-salicyloylamino-1, 2, 4-triazole. Among the metal deactivators mentioned, the hydrazine, oxalic acid diamide and 1,3-diketone derivatives are preferred. N, N'-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine and 2,2'-oxalyldiami - dodi- (ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate The compounds mentioned above can also be used in the form of any mixtures. The preparation of the metal deactivators mentioned is generally known to the person skilled in the art and in most cases represents textbook knowledge these compounds can be purchased commercially, for example, N, N '-Bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine and 2, 2' -oxalyldiamidodi- (ethyl -3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate available under the names Irganox ^® 1024 MD (Ciba Specialty Chemicals) or Naugard ^® XL-1 (Uniroyal). As a UV absorber or light stabilizer, 2-hydroxybenzophenones, such as 2-hydroxy-4-methoxybenzophenone, 2- (2 '-hydroxyphenyDbenzotriazoles, such as 2- (2' -hydroxy-5 '-methylphenyl) -benzotria- zol, or sterically hindered amines, such as 4-morpholino-2, 6-di-chloro-1, 3, 5-triazine, and 2- (2 '-hydroxyphenyl) -1, 3, 5-triazines Suitable sunscreen.

Furthermore, to stabilize against degradation and crosslinking reactions, lactone compounds of the benzofuran-2-one type, e.g. those according to the following formulas III to V are used:

H ₃ CC CH ₃ H ₃ C-CH ₃

CH ₃ CH ₃

(III) (IV)

(V)

Benzofuran-2-one compounds are preferably used in the form of a mixture of the compounds III and IV as stabilizer additive. Basically, suitable lactone compounds are those which come under the formula VI

in which the substituents have the following meaning:

R ⁵ unsubstituted or with C 1 -C to alkyl, in particular C 1 to C ₆ alkyl, C 1 to C 10 alkoxy, in particular C ₁ to C ₆ alkoxy, C ₆ to C ₄ aryl, with functional groups the base of the elements of groups IVA, VA, viA or VIIA of the periodic table of the elements substituted C ₆ - to C ₄ aryl, hydroxy, halogen, amino, Ci- to Cio-alkylamino, in particular C 1 -C ₄ -alkylamino, phenylamino or di- (Cχ ~ to Cio-alkyl) amino, especially di- (Cχ ~ to C ₄ -alkyl) amino, substituted phenyl, naphthyl, phenanthryl, anthryl, 5, 6, 7, 8-tetrahy- dro- 2-naphthyl, 5, 6, 7, 8-tetrahydro-l-naphthyl, thienyl, benzo [b] thienyl, naphthol [2, 3-b] thienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, Pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridine yl, carbozolyl, b-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, bisphenyl, terphenyl, fluorenyl or phenoxazinyl,

R ⁶ to R ⁹ independently of one another are hydrogen, chlorine, hydroxyl,

C 1 -C ₂₅ alkyl, C ₇ -C ₉ phenylalkyl, phenyl which is unsubstituted or substituted by C 1 -C ₄ -alkyl, in particular C 1 -C ₄ -alkyl, unsubstituted or substituted by C ₁ -C 8 -alkyl, in particular Cχ ~ to C ₄ -alkyl, substituted C ₅ -C ₆ -cycloalkyl, -C-C ₁₈ -alkoxy, Cχ-C ₁₈ -alkylt- hio, -C-C ₄ -alkylamino, di- (-C-C ₄ -alkyl) amino, Cχ-C ₂₅ -Al- kanoyloxy, Cι-C ₂ 5-alkanoylamino, C ₃ -C ₅ -alkenoyloxy, by oxygen, sulfur or> NR "(R" = Cι ~ to C ₆ alkyl or C ₆ - to Cι _0- aryl) interrupted C ₃ -C ₂ 5 ^_ alkanoyloxy, C ₆ -C ₉ cycloalkylcarbonyloxy, benzoyloxy or benzoyloxy substituted by -C ~ C ₁₂ alkyl, or furthermore the radicals R ⁶ and R ⁷ or the radicals R. ⁷ and R ⁸ and R ⁹ together with the carbon atom to which they are attached form a benzene ring, R ⁸ additionally represents (CH ₂ ) _p -COR 'or - (CH ₂ ) _q OH,

Rio hydrogen or unsubstituted or with functional groups based on the elements of groups IVA, VA,

VIA or VIIA of the periodic table of the elements substituted Cχ ~ to Cχ ₀ alkyl, C - to Cχo-cycloalkyl, C ₆ - to Cχ ₄ -aryl.

Compounds (VI) in which the radical R ^{5 is} phenyl or naphthyl, in particular phenyl, or phenyl or naphthyl, in particular phenyl which is mono- or polysubstituted by C ₆ -C ₆ -alkyl groups, are preferred. Particularly preferred as radical R ⁵ is phenyl substituted in the ortho and meta or in the meta and para position with methyl, ethyl, i-propyl or tert-butyl, preferably methyl. In preferred compounds (VI) the radicals R ⁶ and R ⁸ furthermore mean i-propyl, tert-butyl or cyclohexyl, in particular tert-butyl, and the radicals R ⁷ , R ⁹ and R ^{10 are} hydrogen or methyl, in particular hydrogen. 3- [4- (2-Aceto-xyethoxy) phenyl] -5, 7-di-tert-butyl-benzofuran-2-one is also preferred. Any mixtures of the lactone compounds described can also be used. Mixtures of compounds of the formula (VI) in which R ^{5 is} 3, 4-dimethylphenyl, R ⁶ and R ^{8 are} tert-butyl and R ⁷ , R ⁹ , R ^{10 are} hydrogen, and compounds of the formula are particularly preferred (VI) in which R ^{5 is} 2, 3-dimethylphenyl, R ⁶ and R ^{8 are} tert-butyl and R ⁷ , R ⁹ , R ^{10 are} hydrogen.

Compounds of the benzofuran-2-one type, as described above, are known to the person skilled in the art and can be obtained, for example, according to the regulations according to US 4,325,863, US 5,175,312, US 5,488,117 or US 5,516,920. An isomer mixture of 3 - (2, 3-di-methyl-phenyl) - and 3 - (3, 4-di-methyl-phenyl) -5, 7-di-tert-butyl-benzofuran-2 -one ( IV or III) is, for example commercially available under the name HP 136 (Ciba Specialty Chemicals).

Furthermore, inorganic compounds such as phosphates, carbonates or sulfates of in particular alkali or alkaline earth metals, preferably alkaline earth metals, can also be added for stabilization, in particular for melt stabilization of the carbon monoxide copolymers. Alkaline earth phosphates and hydroxyphosphates are particularly suitable among the inorganic additives. Calcium phosphate (Ca ₃ (P0 ₄ ) ₂ ) and natural or synthetic hydroxyapatite (Ca ₁₀ (P0 ₄ ) ₆ (OH) ₂ ) are preferably used. Calcium phosphate is particularly preferred. Any mixtures of the stabilizer compounds mentioned can of course also be used.

Calcium phosphate preferably are added in combination with phenolic antioxidants see as Irganox ^® 1076 or Irganox ^® 1010 or benzofuran-2-onen- to Kohlenmonoxidcopolymer. Stabilizer systems based on calcium phosphate, benzofuran-2-ones and metal deactivators, for example N, N'-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, or are particularly preferred, or based on calcium phosphate, metal deactivator and phenolic antioxidant.

The stabilizer compounds are suitably made before the carbon monoxide copolymer is melted. mixed with this.

In general, total amounts of stabilizer in the range from 0.0005 to 10.0, preferably from 0.0005 to 5.0 and particularly preferably from 0.001 to 3.0% by weight, based on the amount of carbon monoxide copolymer used, have proven to be sufficient . The individual stabilizer components are generally present in the carbon monoxide copolymers in amounts of 0.0001 to 2.0% by weight.

According to the process on which the invention is based, the linear, alternating carbon monoxide copolymers (A) and the organic compounds (B) are reacted with one another in the carbon monoxide copolymer melt. Depending on the carbon monoxide copolymer, the reactions are usually carried out at temperatures in the range from 180 to 290 ° C. A common radical starter is often added.

The compounds described in the specialist literature can be used as radical initiators (e.g. J.K. Kochi, "Free Radicals", J. Wiley, New York, 1973).

The following are particularly cheap radical starters:

Di- (2,4-dichlorobenzoyl) peroxide, tert-butyl peroxide, di- (3,5,5-tri-methylhexanol) peroxide, dilauroyl peroxide, didecanoyl peroxide, di-propionyl peroxide, dibenzoyl peroxide, tert-butylperoxy-2-ethylhexoate, tert-Butylperoxydiethylacetat, tert-Butylperoxyisobutyrat, 1, l-Di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, tert-Butylperoxyisopropyl carbonate, tert-Butylperoxy-3, 3, 5-trimethylhexoate, tert-Butylperacetat, tert- Butyl perbenzoate, 4, 4-di-tert-butylperoxyvaleric acid butyl ester, 2, 2-di-tert-butylperoxybutane, dicumyl peroxide, tert-butylcumyl peroxide, 1, 3-di (tert-butylperoxyisopropyl) benzene and di- tert-butyl peroxide. Mention may also be organic hydroperoxides such as di-isopropyl pylbenzolmonohydroperoxid, cumene hydroperoxide, tert-Butylhydrope- hydroxide, p-menthyl hydroperoxide and pinane hydroperoxide, organic _D iazoverbindungen such as azoisobutyronitrile or 2, 2-azobis [N- (isopropyl) -2-methylpropionamide] and highly branched alkanes. Examples of the latter are 2, 3-dimethyl-2, 3-diphenylbutane, 3, 4-dimethyl-3, 4-diphenylhexane and 2, 2, 3, 3-tetraphenylbutane; Because of their decay properties, they are particularly suitable for modification in the melt.

The proportion of radical initiators is generally in the range from 0.1 to 4, preferably below 2.0% by weight, based on the amount of carbon monoxide copolymer and reactive compound used.

Functionalized carbon monoxide copolymers are preferred which, by reacting from 60 to 99.99, preferably 70 to 99.9 and particularly preferably from 80 to 99.5% by weight of the unmodified, optionally stabilized carbon monoxide copolymer (A) with 0.01 to 40 preferably 0.1 to 30 and particularly preferably from 0.5 to 20% by weight of said organic compound (B), which preferably also has at least one reactive functional group.

The proportion of residues covalently attached to the linear, alternating carbon monoxide copolymer by the method according to the invention can be determined by known methods of organic analysis such as titration, IR, UV, NMR and electron spectroscopy. This proportion is usually in the range from 0.01 to 20, preferably from 0.01 to 10% by weight and in particular in the range from 0.05 to 5.0% by weight.

All units suitable for the preparation of polymer melts can be used to melt the unfunctionalized linear, alternating starting copolymer. The carbon monoxide copolymer is preferably melted in a kneader or an extruder. The reactants can be reacted in the melt in a continuously or batch-wise mixing unit, for example a single- or twin-screw extruder. Organic compounds (B) which are liquid under normal pressure at room temperature, even if their boiling point is below the melt temperature of the carbon monoxide copolymer used, can be fed into the mixing units mentioned in a manner known to those skilled in the art. If the process according to the invention is carried out in an extruder, the functionalized carbon monoxide copolymer can be obtained directly in the form of granules which generally only have to be subjected to one drying step. Further processing or purification steps are usually not necessary.

The reaction components carbon monoxide copolymer (A), optionally stabilized, organic compound (B) and, if appropriate, free radical initiators can be converted into the

Melt to be mixed together. It is also possible to add the organic compound (B) and, if appropriate, the radical initiator to the melted carbon monoxide copolymer (A), the order in which the components mentioned are generally not critical.

The reaction times for the functionalization usually range from 0.1 to 180 minutes. In general, however, adequate functionalization can be achieved with reaction times of 0.1 to 60 min.

The functionalized carbon monoxide copolymer obtainable by the process according to the invention can be processed into fibers, films or moldings by known processes. In addition, these carbon monoxide copolymers are suitable as phase mediators in polymer blends, particularly in those in which the polymer components are not or only moderately compatible or miscible with one another. Mixtures of functionalized and unfunctionalized carbon monoxide copolymers are also available.

The method according to the invention opens up access to carbon monoxide copolymers functionalized in many ways with reactive groups in a preparatively simple manner, without being dependent on solvents or suspending agents. In addition, when using organic compounds (B) which have no functional groups, it is possible to obtain carbon monoxide copolymers with a far higher proportion of aliphatic residues, optionally longer-chain covalently bonded to the copolymer backbone, than this by means of transition-metal-catalyzed copolymerization long-chain alkenes or alkynes is possible. Accordingly, functionalized carbon monoxide copolymers, which are characterized by an amorphous structure and, from a mechanical point of view, by good impact strength values, are also accessible with the method according to the invention. b

The present invention is illustrated by the following examples.

Examples

I. Carbon monoxide / ethene / propene terpolymer (A)

To methanol (4.0 l) and propene (440 g), para-toluenesulfonic acid (0.7 mmol) and [1,3-bis (diphenylphosphino) propane] palladium (II) acetate (0.04 mmol) and stirred the polymerization mixture at a total CO / ethene (1: 1) pressure of 100 bar for 6 h at 90 ° C. After the pressure vessel had cooled and relaxed, the polymer suspension was filtered and the white polymer powder obtained was washed with methanol (5 1), water (10 1) and acetone (5 1) and last at 80 ° C. in a vacuum drying cabinet at 1 bar Removes solvent residues. Yield: 584 g. The terpolymer obtained had a melting point of 225 ° C. and a viscosity number VZ, measured in a 0.5% by weight solution in ortho-dichlorobenzene / phenol (1: 1), of 104 ml / g.

To stabilize the melt, the terpolymer powder was calcium phosphate (0.5% by weight), Irganox ^® MD 1024 (Ciba specialty chemicals) (0.2% by weight) and Irganox ^® 1010 (Ciba specialty chemicals) (0.2% by weight). %), each based on the amount of terpolymer used, dry mixed at room temperature.

II. Functionalization reactions

1. The stabilized terpolymer according to I. (3 kg) was melted with maleic anhydride (60 g) at 240 ° C. in a twin-screw extruder ZSK 25 from Werner and Pfleiderer at a speed of 250 min ^-1 and a throughput of 5 kg / h mixed. The product obtained was granulated and dried in a conventional manner. The viscosity number VZ of the functionalized carbon monoxide copolymer was 106 ml / g. Part of the material obtained was dissolved in hexafluoroisopropanol and precipitated in ethanol. After drying in a high vacuum at 80 ° C. for 8 h, the proportion of anhydride groups was determined to be 0.42% by weight by means of IR spectroscopy.

The stabilized terpolymer according to I. (3 kg) was melted with acrylic acid (40 g) at 240 ° C in a twin-screw extruder ZSK 25 from Werner and Pfleiderer at a speed of 250 min ^-1 and a throughput of 5 kg / h mixed. The product obtained was granulated and dried in a conventional manner. The viscosity number VZ of the functionalized carbon monoxide copolymer was 108 ml / g. Part of the material obtained was dissolved in hexafluoroisopropanol and precipitated in ethanol. After drying in a high vacuum at 80 ° C. for 8 h, the proportion of acrylic acid groups was determined to be 0.21% by weight by means of IR spectroscopy.

Claims

claims 1. A process for the preparation of alternating carbon monoxide copolymers containing covalently bonded organic substituents, characterized in that linear, alternating carbon monoxide copolymers (A) and organic compounds (B) which have a CC double or triple bond or a tertiary or benzylic hydrogen atom have, at temperatures in the range of 180 to 290 ° C with each other in the carbon monoxide copolymer melt. 2. The method according to claim 1, characterized in that the C- 5 C double or triple bonds or compounds containing tertiary or benzylic hydrogen atoms (B) have at least one functional group. Method according to claims 1 or 2, characterized gekennzeich¬ 20 net that one carries out the reaction in the presence of a radical initiator. 4. Process according to claims 1 to 3, characterized in that the compounds (B) via at least one carbonyl, ²⁵ carboxylic acid, carboxylate, carboxylic anhydride, carboxamide, carboximide, carboxylic ester, amino, hydroxyl -, Epoxy, oxazoline, urethane, urea, lactam or halobenzyl group. ^• 3 fl ^{J j} 5. Carbon monoxide copolymers obtainable according to claims 1 to 4. 6. Carbon monoxide copolymers according to claim 5, containing as stabilizers antioxidants, metal deactivators, UV absorbers 35 ber, benzofuran 2 -one or inorganic phosphates, carbonates or sulfates or mixtures of the compounds mentioned. 7. Use of the carbon monoxide copolymers according to claims 5 or 6 in the production of fibers, films and molded articles 40 pern. 8. Use of the carbon monoxide copolymers according to claims 5 or 6 as phase mediators in the production of polymer mixtures. 45 Polymer mixtures containing unfunctionalized carbon monoxide copolymers and functionalized carbon monoxide copolymers according to claims 5 or 6.