EP1064317A1

EP1064317A1 - Derivatized carbon monoxide copolymers

Info

Publication number: EP1064317A1
Application number: EP99907594A
Authority: EP
Inventors: Joachim Queisser; Michael GEPRÄGS; Bernhard Rieger; Roland Wursche
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1998-03-16
Filing date: 1999-03-04
Publication date: 2001-01-03
Also published as: JP2002506899A; WO1999047583A1; US6306979B1; AU2727999A; DE19811123A1

Abstract

The invention relates to a method for producing derivatized carbon monoxide copolymers. According to this method, functionalised, linear, strictly alternating carbon monoxide copolymers consisting of carbon monoxide, at least one 1-alkene (A), (A) representing an aryl compound substituted with at least one terminal allyl- or homoallyl unit and at least one hydroxy- or amino group or an alpha -olefinically unsaturated aliphatic alcohol, and at optionally, at least one C2- to C20-1-alkene (B) are reacted with an organic compound (C) which has at least one electrophilic group, in an aprotic organic solvent.

Description

Derivatized carbon monoxide copolymers

description

The present invention relates to derivatized carbon monoxide copolymers. The invention further relates to a process for the preparation of these carbon monoxide copolymers and their use for the production of graft copolymers. In addition, the invention relates to graft copolymers, a process for the preparation of these copolymers and their use for the production of moldings, fibers, films and coatings and their use as phase mediators in polymer mixtures or as a coating component. Finally, the invention relates to the use of functionalized carbon monoxide copolymers for the production of derivatized carbon monoxide copolymers.

Carbon monoxide copolymers can now be produced from carbon monoxide and α-olefins such as ethene or propene in the form of strictly alternating linear copolymers catalyzed by transition metals. Suitable catalyst systems are based on palladium complexes chelated with bidentate phosphine ligands (cf. EP-A-0 121,965 and J. Organomet. Chem., 1991, 417, p. 235). Conventional carbon monoxide / ethene or carbon monoxide / ethene / propene copolymers can generally be understood as polymeric materials with a range of thermoplastic properties. They are characterized by good mechanical properties e.g. in impact resistance and abrasion as well as good chemical resistance.

In addition to attempts to vary the polymer properties of carbon monoxide copolymers, such as the glass transition temperature, via the choice of the olefin component (cf. Jiang et al., J. Am. Chem. Soc. 1995, 117, p. 4455), approaches are also known , novel polymers via a functionalization of the carbonyl group in the chain structure, ie accessible by means of polymer-analogous reactions.

Japanese patent applications JP-A 22 32 338 and JP-A 62 26 925, for example, describe the catalytic reduction of alternating carbon monoxide copolymers to 1,4-polyalcohols. The reaction with nitrogen-containing nucleophiles to carbon monoxide / ethene / propene terpolymers with 2,5-pyrrole units is known from the publication US 1346-H. The Mannich reaction can also be carried out on carbon monoxide copolymers 2 as the halogenation of the methylene unit (cf. US 4,424,317 and US 4,616,072).

If the carbon monoxide / ethene copolymer, which is relatively easy to produce in large quantities under the known carbon monoxide copolymers, is used as the substrate for the polymer-analogous reactions mentioned, its insolubility in all conventional solvents constitutes a considerable limitation for the practical application of subsequent reactions.

Secondary reactions also stand in the way of an effective derivatization of carbon monoxide copolymers. These include, for example, subsequent radical reactions of the Norrish I and II types. In the same way, the addition of N-nucleophiles to the carbonyl group can also lead to cleavage of the polymer backbone and thus to a reduction in the molecular weight of the copolymer.

It would therefore be desirable to be able to carry out polymer-analogous reactions on carbon monoxide copolymers without having to put up with side reactions and chain degradation.

The object of the present invention was therefore to find carbon monoxide copolymers which can be derivatized without problems, without side reactions and molecular weight degradation occurring. The invention was also based on the object of developing derivatized carbon monoxide copolymers which are also suitable for further subsequent reactions.

Accordingly, derivatized carbon monoxide copolymers, obtainable by reacting functionalized linear strictly alternating carbon monoxide copolymers from carbon monoxide, have at least one 1-alkene (A), where (A) is an aryl compound substituted with at least one terminal allyl or homoallyne unit and at least one hydroxyl or amino group, or an α represents olefinically unsaturated aliphatic alcohol, and optionally at least one C 1 -C 4 -alkene (B) with an organic compound (C) which has at least one reactive electrophilic group, found in an aprotic organic solvent.

Furthermore, a process for the production of derivatized carbon monoxide copolymers and their use for the production of graft copolymers were found.

Furthermore, graft copolymers, a process for the preparation of these copolymers and their use for the production of moldings, fibers, films and coatings and their 3

Found as a phase mediator in polymer mixtures or as a coating component.

Finally, the use of functionalized linear alternating carbon monoxide copolymers of carbon monoxide, at least one 1-alkene (A), where (A) is an aryl compound substituted with at least one terminal allyl or homoallyl unit and at least one hydroxyl or amino group, or an α-olefinically unsaturated aliphatic alcohol represents, and optionally found at least one C - to C o ~ l alkene (B) for the production of derivatized carbon monoxide copolymers.

Suitable functionalized carbon monoxide copolymers, which are available here for derivatization reactions, are based on linear alternating carbon monoxide copolymers made of carbon monoxide, at least one 1-alkene (A), one with at least one terminal allyl and / or homoallyne unit and with at least one hydroxy and / or amino group substituted aryl compound or an α-olefinically unsaturated aliphatic alcohol, and optionally at least one C ₂ - to C ₂₀ -1-alkene (B).

Compounds of the general formulas (Ia) or (Ib) are preferably used as 1-alkenes (A)

(Yn

in which the substituents and indices have the following meaning:

X OH or NH ₂ ,

Y is a compound of the general formula (II)

CH ₂ = C (R ^l ) (C (R ² ) ₂ ) _q ) - (II)

wherein 4

R ^{1 is} 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 ₆ cycloalkyl, such as cyclopropyl or cyclohexyl, C ₆ to Cio-aryl, preferably C ₆ to Cio-aryl, in particular phenyl, and

R ² independently of one another hydrogen, linear and branched C 1 -C ₁₀ -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 Cio-cycloalkyl, preferably C ₃ - to C _ö -cycloalkyl, such as cyclopropyl or cyclohexyl, C $ - to Ci ₄ -aryl, preferably C ₆ - to Cio-aryl, especially phenyl, or halogen, such as fluorine, Chlorine, bromine, iodine mean and

1 or 2,

Q is independently linear or branched Cχ ~ bis

Cio-alkyl, preferably C 1 ~ to Cε-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl or t-butyl, in particular methyl, i-propyl or t-butyl, C ₃ - to Cio-cycloalkyl, preferably C ₃ - to C ₆ cycloalkyl, such as cyclopropyl or cyclohexyl, C ₆ ~ C to ₄ ~ aryl, preferably C ₆ - to Cι ₀ aryl, especially phenyl, aralkyl having from 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 + 1 + 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. 5

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 located in the ortho position to a hydroxyl or amino group. For example, Naphthyl compounds with an allyl unit in the 1-position and one of the polar groups mentioned 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 orthostane polar groups to the allyl unit.

The polar groups X are the hydroxyl and the primary amino group. Suitable compounds are e.g. 2-allylphenol, 2-allyl-p-hydroquinone, 3-allyl-o-hydroquinone, 2-allylaniline, 2-allyl-4-aminophenol or 3-allyl-4-aminophenol, in particular 2-allylphenol.

In general, it is also possible to use compounds (A) which have more than two or three polar groups X on the phenyl ring (compounds of the formula (Ia)) and more than three or four polar groups on the naphthyl ring (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 X.

Terminal allyl or homoallyne units also include those radicals whose hydrogen radicals, apart from the terminal ones, are independent of one another, for example by Alkyl groups such as methyl, ethyl or isopropyl, aryl groups such as phenyl, aralkyl groups such as benzyl or halogens such as fluorine or chlorine are substituted. Examples include isopropylidene or isobutylidene units. However, unsubstituted allyl and homoallyne units, in particular allyl units, are preferred.

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. If the valences on the aromatic ring systems of the formulas (Ia) and (Ib) are not already saturated by the radicals X, Y or Q, they are saturated by hydrogen atoms (CH bonds). Suitable compounds (A) therefore also include 2-allyl-4-methylphenol, 2-allyl-4-t- 6 butylphenol, 2-allyl-6-methylphenol, 2-allyl-4-phenylphenol, 2-allyl-4, 6-dimethylphenol, 2, 6-dimethyl-4-allylphenol, 2-allyl-4-t -butyl-6-methyl-phenol, 2,6-di-t-butyl-4-allyl-phenol, 2-allyl-6-methylaniline, 2-allyl-4-methylaniline or 2-allyl-4-t-5 butylaniline.

Other suitable 1-alkenes (A) are α-olefinically unsaturated aliphatic alcohols. These are, in particular, terminal alcohols with a substituted or unsubstituted one

10 C ₂ - to Co ~ alkylene chain, for example allyl alcohol, 3-butene-l-ol, 4-pentene-l-ol, 5-hexen-l-ol, 6-heptene-l-ol, 10-undecene-l -ol or 15-hexadecen-l-ol. Particularly suitable are α-olefinically unsaturated alcohols with a C to Cis alkylene chain, in particular with a C to Cio alkylene chain such as allyl alcohol or

15 10-Undecen-l-ol. In the alkylene chain, single alkylene, e.g. Methylene units can also be replaced by ether bridges. It is of course also possible to use any desired monomer mixtures consisting of one having at least one terminal allyl or homoallyne unit and at least one hydroxyl or amino group.

20 tuned aryl compound and an α-olefinically unsaturated aliphatic alcohol can be used.

In principle, all monomers (B) for non-binary carbon monoxide copolymers, in particular ternary copolymers, are

25 bonds of this class of compounds, for example α-olefins or diolefins with at least one terminal double bond in question. Suitable α-olefins are, for example, C ₂ - to C ₂ ol-alkenes, such as ethene, propene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene and mixtures thereof. Of course, 1-alkenes,

30 which carry an aromatic residue. Suitable are e.g. Styrene, α-methylstyrene, p-methylstyrene or 2-methylstyrene, 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. Especially

Ethene, propene, 1-butene and styrene, in particular propene, are preferred. The aforementioned 1-alkenes can of course also be used in a mixture.

As functionalized carbon monoxide terpolymers 40, preference is given to using those composed of carbon monoxide, propene and component (A) and of carbon monoxide, ethene and component (A), in which a terminal allyl unit and a hydroxyl or amino group are present in ortho position in (A).

45 The binary functionalized carbon monoxide copolymers are generally regular poly-1, ketones. Especially when using arylderi- 7 vaten (A), in which the allyl and hydroxy units are ortho, the carbon monoxide copolymers obtained can also have semiketal units. These, in turn, can occur both in blocks and statistically distributed along the linear polymer chain. The ratio of ketone to ketal fragments in these cases is usually in the range from 10: 1 to 1: 5, preferably in the range 4: 1 to 1: 1.

The structure of the functionalized carbon monoxide copolymers can be determined by means of ¹ H-NMR and ¹³ C-NMR spectroscopy.

The average molecular weights M _{w of} the binary carbon monoxide copolymers are usually in the range from 1000 to 3500000 g / mol, preferably in the range from 3000 to 250000 g / mol and in particular in the range from 5000 to 200000 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 with 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, 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 85 ° C.

In the functionalized carbon monoxide terpolymers, the average molecular weights M _{w are} generally 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 are usually in the range from 0 to 150 ° 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 as well as in higher copolymers as well as in the binary systems 8 In addition to pure 1,4-polyketone units, statistically distributed or block-like, but preferably statistically distributed semiketal structures can also be present. This phenomenon is preferably observed when the polar group in (A) is a hydroxy group.

The binary and ternary carbon monoxide copolymers described are generally readily soluble in tetrahydrofuran (THF), toluene, dichloromethane or chloroform.

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

With regard to the production of the functionalized linear binary and higher carbon monoxide copolymers, reference is expressly made here to the German patent application 19727271.1. If α-olefinically unsaturated aliphatic alcohols are used as monomers (A), the functionalized carbon monoxide copolymers can also be prepared according to the methods described in EP-A 0 463 689 and in Sen et al. , Macromolecules, 1996, 29, pp. 5852 -5858. The manufacturing processes described in the cited documents are hereby expressly included in the present disclosure.

Suitable organic compounds (C) which have one or more reactive electrophilic groups are, for example, aliphatic or aromatic carboxylic acid chlorides or anhydrides. Among the anhydrides, both symmetrical such as hexane or heptanoic anhydride, and also mixed anhydrides such as benzoic acid anhydride or propionic acetic anhydride or cyclic carboxylic acid anhydrides such as glutaric anhydride, succinic anhydride, maleic anhydride, succinic anhydride or amine hydroxylated amide or phthalic anhydride, To derivatize carbon monoxide copolymer. Possible reactants for the amide or ester formation include acidic chlorides such as aromatic acid chlorides such as benzoyl chloride and saturated or unsaturated, linear or branched aliphatic acid chlorides such as acetyl, hexanoyl or (meth) acroyl chloride. Long-chain saturated or double bond-containing compounds having a Cβ ~ to C ₂₄ alkylene unit, the end group of which represents an electrophilic group, can also be used. Examples include decenoyl, undecenoyl and octadecenoyl chloride. Acid chlorides of di- or polycarboxylic acids such as oxalyl chloride or hexanedicarboxylic acid dichloride can also be used. Of course, the carboxylic acid group itself can also be used as an electrophilic group 9 occur, especially if suitable coupling reagents or reaction mediators are also used.

The amide or ester formation between the functionalized carbon monoxide copolymer and the organic compound (C) can be carried out in a weakly acidic or in a weakly basic medium. Basic compounds include Triethylamine, tributylamine, pyridine, quinoline or ammonium hydroxide in question. In the case of acylation with carboxylic acid chlorides, anhydrides or carboxylic acids, reaction mediators such as 4-dimethylaminopyridines, imidazolides such as carbonyldimidazole, dicyclyclohexylcarbodimides, 2, 2'-dipyridyldisulfide / triphenylphosphine or 2-pyrididylthiochlorine can also be added.

Isocyanates (R-N = C = 0) are also suitable as organic compounds (C) with a reactive electrophilic group. Aromatic as well as aliphatic or cycloaliphatic isocyanates are suitable. Examples include phenyl, cyclohexyl, isopropyl and 1-phenylethyl isocyanate. The reaction with isocyanates is suitably carried out in the presence of Lewis acids or Lewis bases, which are preferably present in catalytic amounts. In general, all compounds which come under this class can be used as Lewis acids, for example weak and also strong Lewis acids. Preferably, organometallic compounds of the 4th and 5th main group of the Periodic Table of the Elements are described as Lewis acids, e.g. Compounds of tin, antimony or bismuth are used. Tin dioctoate, di-butyltin-bis-dodecyl mercaptide, bis (tri-n-butyltin) oxide, dibutyltin oxide, tri-n-butyl-antimony oxide and bismuth oxide, in particular dibutyltin dilaurate, are suitable, for example. Tertiary amines such as diazabicyclooctane (DABCO) are suitable as Lewis bases. The inventive implementation of the functionalized carbon monoxide copolymers with isocyanates in the manner described above provides carbon monoxide copolymers derivatized with urethane units.

Suitable organic solvents for the derivatization reactions according to the invention are polar aprotic solvents, for example halogenated hydrocarbons such as dichloromethane, 1, 2-dichloroethane or chloroform, furthermore ethers such as diethyl ether or tetrahydrofuran as well as dimethylformamide, dimethyl sulfoxide, hexamethyl phosphoric acid triamide or mixtures of the aforementioned solvents. 10

The implementation about with eg. Acid chlorides or isocyanates obtainable derivatized carbon monoxide copolymers according to the invention can generally be obtained with degrees of derivatization greater than 10%, preferably greater than 15% and in particular greater than 20%, the degree of derivatization also depending on the amount of organic compound (C) used. The degree of derivatization, based on the free hydroxyl or amino groups in the starting copolymer, reflects the proportion of coupled electrophilic reagent. The degree of derivatization can be determined by means of ^X H NMR spectroscopy.

The molecular weights M _{w of} the derivatized carbon monoxide copolymers according to the invention are generally above 1000 g / mol, preferably above 10000 g / mol and particularly preferably above 25000 g / mol.

The derivatized carbon monoxide copolymers differ from the starting compounds, i.e. the functionalized carbon monoxide copolymers over one and possibly also several glass transition temperatures. These are generally above 20, preferably above 30 and particularly preferably above 40 ° C.

In a further preferred embodiment, there are carbon monoxide copolymers which are derivatized with organic compounds (C) which have two or more electrophilic groups. These compounds include, for example, acid chlorides or anhydrides of dicarboxylic acids such as adipic, glutaric or fumaric acid. In particular, this also includes diisocyanate compounds. As diisocyanates e.g. 2,4- or 2,6-tolylene diisocyanate, isophorone diisocyanate, 4,4'-diisocyanate diphenylmethane, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate or 1,5-naphthyl diisocyanate in question, 2, 4-tolylene diisocyanate and 1 , 6-hexamethylene diisocyanate are preferred. The carbon monoxide copolymers derivatized with the bifunctional or polyfunctional compounds mentioned thus have at least one free electrophilic group.

It has been found that this free functionality is suitable for coupling reactions with nucleophilic organic compounds. In addition to aliphatic or aromatic mono- or polyhydroxy compounds or amino compounds such as methanol, ethanol, i-propanol, n-butanol, t-butanol, 1,4-butanediol, cyclohexanol, phenol, methylamine, dimethylamine, ethylamine, ethylenediamine, di- i-propylamine or cyclohexylamine are in particular also macromers with at least one nucleophilic end group. In the present case, the term macromers should be understood to mean oligomers 11 which have an average molar mass M _w greater than 100 g / mol and preferably less than 10,000 g / mol. In a special embodiment, amino- or hydroxy-functionalized macromers are used. Examples of suitable macromers are the polyethers derived from polyethylene glycol or poly-1,4-butanediol, such as polyethylene glycol monobutyl ether or poly (1,4-butanediol) bis (4-aminobenzoate).

Polymers with functional end or side groups, for example polyamides, polybutylene terephthalate, polyphenylene ethers, polyether sulfones or polycarbonates, each with at least one hydroxyl or amino end group, are also suitable for coupling. In addition to the polymers mentioned, which as a rule already have functional end groups or side groups in conventional form, in particular also modified polymers into which hydroxy- or amino-functional groups have been incorporated in a targeted manner. Exemplified as suitable conventional polymers commercially available polyamide, such as Ultramid ^® or Ultramid T, polybutylene terephthalate as Ultradur, polyethersulfone as Ultra- son ^® E are (the aforementioned brands from BASF AG Products), polyphenylene ether as Noryl ^® (GE Plastics) or polycarbonate such as Lexan ^ (GE Plastics). Preferred among the aforementioned compounds are the polyamides and polybutylene terephthalate. Polyphenylene ethers with hydroxy end groups can be found, for example, in JE McGrath et al., Poly. Closely. Be. 1977, 17, p. 647.

As solvents for the grafting reaction according to the invention and for the derivatization of the functionalized carbon monoxide copolymers, polar aprotic solvents, for example halogenated hydrocarbons such as dichloromethane, 1, 2-dichloroethane or chloroform, are also ethers such as diethyl ether or tetrahydrofuran and dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide or mixtures of the abovementioned solvents.

Reaction times for the derivatization and for the grafting reactions are usually in the range from 1 to 2 hours to several days. The reaction temperatures in the processes according to the invention mentioned are generally in the range from -10 to 100, preferably in the range from 0 to 80 and particularly preferably from 10 to 60 ° C.

The acidic or basic systems described in the derivatization reaction can be used for the grafting reaction. Basic compounds include triethylamine, tributylamine, pyridine, quinoline or ammonium hydroxide 12 the formation of an ester or amide bond in question. Likewise, reaction mediators such as 4-dimethylaminopyridines, imidazolides such as carbonyldiidazole, dicyclyclohexylcarbodiimides, 2, 2'-dipyridyldisulfide / triphenylphosphine or 2-pyrididylthiochloroform can also be used in the acylation with carboxylic acid chlorides, anhydrides or carboxylic acids. If the group available for the grafting is an isocyanate unit, the Lewis acids and Lewis bases, in particular dibutyltin dilaurate, used for the derivatization of the functionalized carbon monoxide copolymers can also be used to mediate the reaction.

For the grafting reaction, the derivatized carbon monoxide copolymer advantageously, without isolating or purifying it, sets it directly with the nucleophilic organic one

Connections around. The reaction components can generally be mixed with one another in any order, but the reaction solution of the derivatized carbon monoxide copolymer is preferred to give a solution of, for example, a macromer bearing a hydroxyl or amino group.

The derivatized carbon monoxide copolymers according to the invention can also be carried out with macromers or polymers bearing hydroxyl or amino groups under the conditions of reaction extrusion, as described in the monograph "Reactive Exrusion, Principles and Practice" by M. Xanthos, Carl Hanser Verlag, Munich, 1992 become.

The with e.g. Carbon monoxide copolymers derivatized with isocyanates or carboxylic acid chlorides can be obtained by precipitation in, for example, petroleum ether or methanol. Isolation and purification are achieved using conventional techniques by redissolving and re-controlled precipitation of the derivatized product. In the same way, the graft copolymers according to the invention can be precipitated in e.g. Win methanol or diethyl ether. If appropriate, the grafted products can be taken up again, for example in dichloromethane, in order then to be obtained in a highly pure form by precipitation, free of impurities.

In the graft copolymers according to the invention, the degree of grafting, ie the proportion of coupled nucleophile, for example macromer, based on, for example, the free isocyanate groups in the starting compound, is generally above 10%, preferably above 15%. The molecular weights of the graft copolymers depend both on the molecular weights of the derivatized carbon monoxide copolymers and on the coupling component, for example the macro 13 he, as well as the degree of derivatization. As a rule, the graft copolymers according to the invention have molecular weights greater than 10,000 g / mol.

The graft copolymers according to the invention are suitable for the production of moldings, fibers, films or coatings and as phase mediators in polymer mixtures. They can also include coating components, e.g. can be used in multilayer film systems.

The processes according to the invention for producing the derivatized carbon monoxide copolymers and also the graft copolymers are distinguished, inter alia, by: characterized in that side reactions do not occur and thus chain cleavage or molecular weight reduction are not observed.

The present invention is illustrated by the following examples.

Examples

The acid chlorides and isocyanates and dibutyltin dilaurate (Bu ₂ SnLau ₂ ) used in the derivatization reactions were obtained from Fluka, poly (ethylene glycol) monobutyl ether and poly (1,4-butanediol) bis (4-aminobenzoate) from Aldrich based. These products were used without further purification.

Dichloromethane was dried over CaH and then distilled. All implementations were carried out under standard Schlenk conditions.

The ¹ H and ¹³ C NMR spectra were recorded using a Bruker AMX 500 spectrometer. A Perkin-Elmer DSC-7 (heating rate 20 ° / minute) was used for the DSC measurement. The glass transition temperature was determined from the second run after cooling to -50 ° C. The GPC measurements were carried out relative to a standard of linear polystyrene in chloroform or tetrahydrofuran (THF), using a Waters device equipped with Microstyragel columns and an RI detector.

The alternating copolymer of CO and 2-allylphenol (APCO) was produced in accordance with the specification of the German patent application 19727271.1. It had an average molecular weight M _w of 22,700 g / mol and a polydispersity of 2.2, measured in chloroform. 14

General instructions for the reaction of functionalized carbon monoxide copolymers of carbon monoxide and 2-allylphenol (APCO) with carboxylic acid chlorides

Pyridine (3 ml) and the carboxylic acid chloride (30 mmol) were added to APCO (0.45 g) in dichloromethane (20 ml) at 0 ° C. The mixture was stirred at room temperature for 48 h, the reaction product was precipitated by pouring the reaction mixture into methanol (500 ml), filtered and dried under high vacuum. The results are summarized in Table 1.

Table 1

5 carboxylic acid chloride M _w ^a '- ^b ' (g / mol) derivative. -grad (%) ^c »

1 benzoyl chloride 35,000 24 2 undecenoyl chloride 42 700 23

Molecular weight of the derivatized carbon monoxide copolymer 0 b) Determined by means of gel permeation chromatography in chloroform against a polystyrene standard c) Determined by means of 1 H-NMR spectroscopy

5 II. General instructions for the reaction of APCO with isocyanates

APCO (0.45 g) in dichloromethane (20 ml) was treated with isocyanate (RN = C = 0) (30 mmol) and Bu ₂ SnLau ₂ (0.5 ml). In the case of _Q aromatic isocyanates, the mixture was stirred for 24 hours at room temperature, and for aliphatic isocyanates for 24 hours at 40 ° C. The reaction product was precipitated by adding the reaction solution to petroleum ether 40/60 (500 ml) and filtered off. The crude product obtained was dissolved in dichloromethane, separated from sparingly soluble fractions and precipitated from methanol, then filtered and dried under high vacuum. The results are summarized in Table 2.

Table 2 0

RM _w ^b >< ^c > Deriv. -grad T _g (° C) (g / mol) (%) ^d >

3 phenyl- 36 900 25 53.7

4 cyclohexyl- 30 800 27 nb 5 5 isopropyl- 29 300 28 nb 6 R (+) -1-phenylethyl ^a »28 300 5 nb 15 ^a) The amount of R (+) -1-phenylethyl isocyanate used was 3 mmol

^b) Molecular weight of the derivatized carbon monoxide copolymer 5 ^c) Determined by means of gel permeation chromatography in chloroform against a polystyrene standard

^d) Determined by 1 H NMR spectroscopy 10

III. General instructions for the reaction of APCO with diisocyanates

APCO (0.45 g) in dichloromethane (10 ml) was treated with 2,4-tolylene ^ diisocyanate (5.6 mmol) and Bu ₂ SnLau (0.5 ml) and stirred for 24 h at room temperature. The reaction solution obtained was used as such, or else filtered, for subsequent derivatizations.

20th

IV. Manufacture of graft copolymers

a) Reaction with poly (ethylene glycol) monobutyl ether

25 Poly (ethylene glycol) monobutyl ether (11.7 ml; M _n = 206 g / mol) in dichloromethane (20 ml) was added dropwise with stirring at room temperature as described in III. reaction solution obtained. A further 0.5 ml of Bu ₂ SnLau _{2 were} added and the mixture was stirred at room temperature for 24 h. The reaction solution was added to methanol (500 ml), the

30 precipitated product was filtered off and the last solvent residues were removed in a high vacuum (yield: 0.3 g; molecular weight M _w = 54 600 g / mol; degree of derivatization: 21%).

b) reaction with poly (1,4-butanediol) bis (4-aminobenzoate)

35

Poly (1, 4-butanediol) bis (4-aminobenzoate) (3 mmol; M _n = 1200 g / mol) in dichloromethane (20 ml) was added dropwise with stirring at room temperature as described in III. reaction solution obtained and stirred for 24 h. The reaction was terminated by adding n-butylamine 0 (2 ml), the reaction mixture was precipitated in diethyl ether, separated and, if necessary, taken up again in dichloromethane for further purification and precipitated in diethyl ether. The filtered product was freed of any residual solvent in a high vacuum (yield: 1 g; molecular weight M _w =

45 14 800 g / mol).

Claims

16 patent claims

1. A process for the preparation of derivatized carbon monoxide copolymers, characterized in that functionalized linear, strictly alternating carbon monoxide copolymers of carbon monoxide, at least one 1-alkene (A), where (A) one with at least one terminal allyl or homoallyl Unit and at least one hydroxyl or amino group substituted aryl compound or an α-olefinically unsaturated aliphatic alcohol, and optionally at least one C - to C ₂ ol alkene (B) with an organic compound (C) which has at least one electrophilic group , in an aprotic organic solvent.

2. A process for the preparation of derivatized carbon monoxide copolymers according to claim 1, characterized in that compounds of the general formulas (Ia) or (Ib) are used as 1-alkenes (A)

(X) k

in which the substituents and indices have the following meaning:

X OH or NH ₂ ,

Y is a compound of the general formula (II)

CH ^ CtR ¹ ) ⁽ C (R ²⁾ ₂ ) σ ⁾ (II)

wherein

R ¹ hydrogen f, linear and branched Cι ~ to Cio-alkyl, C ₃ - to Cio-cycloalkyl, Cς- to Cio-aryl, and 17

R ² independently of one another are hydrogen, linear and branched Ci to Cio alkyl, C ₃ - to -C ₀ cycloalkyl, C ₆ - to C ₄ aryl or halogen and

q 1 or 2,

Q independently of one another linear or branched C 1 ~ to C 10 alkyl, C ₃ - to Cio cycloalkyl, C 6 to C ₄ aryl, aralkyl with 1 to 6 C atoms in the alkyl part and 6 to 14 C atoms in the aryl part or C ₃ - to C o-organosilyl,

where for compounds of formula (Ia)

k, 1 integers from 1 to 5 and

o an integer from 0 to 4 mean with

k + 1 + 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.

3. A process for the preparation of derivatized carbon monoxide copolymers according to claims 1 or 2, characterized in that organic compounds (C) are used which have two or more electrophilic groups.

4. Derivatized carbon monoxide copolymers, obtainable by the process according to claims 1 or 2.

5. Derivatized carbon monoxide copolymers, obtainable by the process according to claim 3.

6. Use of the derivatized carbon monoxide copolymers according to claim 5 for the production of graft copolymers.

7. A process for the preparation of graft copolymers, characterized in that derivatized carbon monoxide copolymers according to claim 5 are reacted with a nucleophilic organic compound in an aprotic organic solvent. 18th

8. A process for the preparation of graft copolymers according to claim 7, characterized in that amino- or hydroxy-functionalized macromers or polymers are used as nucleophilic organic compounds.

5

9. A process for the preparation of graft copolymers according to claim 8, characterized in that amino or hydroxy-functionalized polyamides, polybutylene terephthalates, polycarbonates or poly- are used as nucleophilic organic compounds.

10 uses sulfones.

10. Graft copolymers obtainable by the process according to claims 7 to 9.

15 11. Use of functionalized linear, alternating

Carbon monoxide copolymers of carbon monoxide, at least one 1-alkene (A), where (A) is an aryl compound substituted by at least one terminal allyl or homoallyne unit and at least one hydroxyl or amino group, or one

20 α-olefinically unsaturated aliphatic alcohol, and optionally at least one C ₂ - to C ₂₀ -1-alkene (B) for the production of derivatized carbon monoxide copolymers.

25 12. Use of the graft copolymers according to claim 10 for the production of moldings, fibers, films and coatings.

13. Use of the graft copolymers according to claim 10 as 30 phase mediators in polymer mixtures or as a coating component.

35

40

45