DE4332964B4 - Process for the preparation of aromatic polyether ketones - Google Patents

Abstract

Process for the preparation of polyether ketones by reacting an aromatic dihydroxy compound of general formula I. HO-Ar-OH (I) in which Ar is phenylene or a condensed aromatic radical having 10 to 30 C atoms or Ar consists of two to five phenylene rings which are bonded by single bonds, ether bridges, thioether bridges, carbonyl groups, sulfone groups or methylene groups whose H atoms are represented by C 1 -C 5 -alkyl groups can be replaced, connected to each other,
wherein the hydrogen atoms bound to aromatic rings may be wholly or partially replaced by C 1 -C 4 -alkyl, nitro, chlorine and / or bromine, with the proviso that an aromatic ring is not simultaneously substituted by halogen and nitro,
with an aromatic dihalogen compound of the general formula II Hal-Ar ² -CO-Ar ³ -Hal (II) in which Hal is chlorine and / or fluorine, Ar ² and Ar ^{3 are} aromatic radicals each having 6-24 carbon atoms, the radical Ar ^{3 may} also consist of several phenylene rings, which may be replaced by at least one carbonyl group or sulfonyl group and optionally Ether groups or thioether groups are interconnected, and the two radicals Hal ...

Description

The The present invention relates to a process for producing aromatic Polyether ketones by polycondensation of aromatic hydroxy compounds with chlorine or fluoroaryl ketones using phase transfer catalysts.

Aromatic polyethers whose aromatic moieties are linked via polar functional groups (eg, keto or sulfone groups) have gained increasing importance in numerous fields in recent years because of their outstanding properties. They can be produced mainly by two methods:
In the so-called electrophilic process, aromatic acyl halides and aromatic ethers are polymerized by the mechanism of Friedel-Crafts acylation in the presence of Lewis acids such as AlCl ₃ or BF ₃ as catalysts and dichloromethane / DMF or HF as solvent. A disadvantage of this method is that the inclusion of metal salts in the polymer can not be excluded and defects occur in the polymer by ortho substitution.

in dieser Gleichung bedeutet M ein Alkalimetallkation, X ein Halogenatom, Ar einen aromatischen Rest und Ar' einen bisaromatischen Rest, der mindestens eine elektronenziehende Brücke enthält.The synthesis of aromatic polyether ketones can also be effected by nucleophilic substitution. In this case, aromatic dihydroxy compounds are reacted with aromatic dihalogen compounds in the presence of acid-binding agents, in particular alkali metal carbonates, according to the following reaction equation:

in this equation, M represents an alkali metal cation, X represents a halogen atom, Ar represents an aromatic radical and Ar 'represents a bis-aromatic radical containing at least one electron-withdrawing bridge.

Semi-crystalline Aromatic polyether ketones are known. R.N. Johnson, R.A. Clendinning, A.G. Farnham, W.F. Hall, C.N. Merriam, J. Polym. Sci., Part A-1, Vol. 5, 2375 (1967) investigated the reactivity of many activated aromatic Dihalides in the reaction with an alkali metal salt of bisphenol A with dimethyl sulfoxide as solvent. They realized that activated Difluoride compared to the corresponding dichlorides essential are more reactive and about it higher Molecular weights can be achieved.

In US 4010147 For example, the reaction of the di-alkali salt of an aromatic dihydroxy compound, which may optionally contain a keto group, with an activated aromatic dichloro compound in the presence of an aromatic sulfone as a solvent at 250 - 400 ° C described. The implementation is slow. The analog difluorocompounds react faster. Another method is based on the reaction of a hydroxy-halogen derivative of benzophenone or diphenylsulfone with alkali metal carbonate or alkali bicarbonate in the presence of N-methylpyrrolidinone or an aromatic or aliphatic sulfone at 200 ° C to 400 ° C (eg US-PS 4113699 ).

Out EP-B-182 648 is known that the alkaline polycondensation of halophenols, such as 4-chloro-4'-hydroxybenzophenone, favored by copper compounds becomes. In the absence of copper or in the production of the same Polymers of 4,4'-dichloro-benzophenone and 4,4'-bihydroxybenzophenone Products with significantly lower inherent viscosity (lower Molecular weight).

In these processes for the preparation of semicrystalline polyether ketones via the method of nucleophilic aromatic substitution so far mostly Difluorarylketone such. B. 4,4'-difluorobenzophenone used (see, EP-A 1 879, US 40101471 , The analogous and easily accessible chlorine monomers have not yet been used with satisfactory results for the economical production of polyether ketones.

According to PM Hergenrother, BJ Jensen, SJ Havens, Polymer, 29, 358 (1988) amorphous and thus soluble and partially crystalline polyaryletherketones can be prepared using bischloro- and bisfluoroaromatics. The reaction time was 16 hours at 155 ° C. The polymer obtained in the reaction of bisphenol A with 1,4-bis (chlorobenzoyl) benzene in the presence of K ₂ CO ₃ in dimethylacetamide had only an inherent viscosity (chloroform, 0.1%, 20 ° C.) of 0, 68 dl / g. The glass transition temperature was 166 ° C. Bisfluoroaromatics have resulted in polymers that have a significantly higher inherent viscosity than polymers derived from the analogous bischloroaromatics.

It The task was to provide a method that was economical Preparation of aromatic polyether ketones with high space-time yields using easily accessible Bischlorarylketonen allowed. In particular, polymers should be used become accessible with high molecular weight.

A process has now been found for the preparation of aromatic polyether ketones, in which an aromatic dihydroxy compound of the general formula I HO-Ar-OH I in which Ar is phenylene or a condensed aromatic radical having 10 to 30 C atoms or Ar consists of two to five phenylene rings which are bonded by single bonds, ether bridges, thioether bridges, carbonyl groups, sulfone groups or methylene groups whose H atoms are represented by C ₁ -C ₅ Alkyl groups can be replaced, are connected to each other,
wherein the hydrogen atoms bound to aromatic rings may be wholly or partly replaced by C ₁ -C ₄ -alkyl, nitro, chlorine and / or bromine, with the proviso that an aromatic ring is not simultaneously substituted by halogen and nitro-substituted,
at elevated temperature in an aprotic-polar solvent in the presence of alkali metal carbonate, an aromatic dihalogen compound of general formula II Hal-Ar ² -CO-Ar ³ -Hal II in which Hal is chlorine and / or fluorine, Ar ² and Ar ^{3 are} aromatic radicals each having 6-24 carbon atoms, the radical Ar ^{3 may} also consist of several phenylene rings, which may be replaced by at least one carbonyl group or sulfonyl group and optionally Ether groups or thioether groups are interconnected, and the two radicals Hal are each arranged in the para position or ortho position to a CO and / or SO ₂ group.

This Process is characterized in that the reaction in the presence a phase transfer catalyst performs.

Preferably you work with a molar ratio I: II from 0.9: 1 to 1: 0.9.

With the method according to the invention it is possible to produce amorphous and partially crystalline polyether ketones. The products obtained have high molecular weight, high stability against Chemicals, high temperature stability and good mechanical properties on.

you has already observed that on In the field of low molecular chemistry, the use of a phase transfer catalyst is advantageous.

D. J. Brunelle, D.A. Singleton; Tetrahedron Letters, 25, 3383 (1984) concerned in the field of low-molecular chemistry with etherification reactions of phenols and thiophenols with little activated haloaromatics such as 4-chloro-nitrobenzene or bis-4-chlorophenyl-benzophenone and -benzosulfone. They could show that at Addition of N-alkyl-4-N ', N'-dialkylamino-pyridinium salts the yields of ether products are almost quantitative. It will indicated that the used catalysts to a temperature of 300 ° C thermally are stable and the catalyst is slow from sodium phenoxide and also attacked by sodium hydroxide.

It is completely surprising that these Phase transfer catalyst systems the nucleophilic reaction bivalent Phenols with activated bis-haloaromatics for the production of Accelerate polymers and above In addition, allow the use of bischloro derivatives.

The amount of added alkali metal carbonate is not critical. Preference is given to 1 to 2 moles of alkali metal carbonate per mole of the aromatic dihydroxy compound of the general formula (I). The alkali metal carbonates of lithium, sodium, potassium, cesium and rubidium are suitable. Particularly preferred are sodium or potassium carbonate. In addition, base combinations consisting of at least one alkali metal carbonate (eg Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ ) and at least one further alkali compound (eg Li salt, Na salt, K Salt) from the group of alkali metal hydroxides and hydrogencarbonates.

In the process according to the invention, the preferred solvents are dimethylacetamide, dime thylsulfoxide, N-methyl-2-pyrrolidone and diphenylsulfone used, and particularly preferably dimethylacetamide and diphenylsulfone.

The Amount of added phase transfer catalyst is not critical. Preferably, per mole of the aromatic dichloro compound of general formula (II) 0.01 to 0.1 mol of the phase transfer catalyst added.

The Dichloroaryl ketones are easier and cheaper to produce than the otherwise used Difluoranaloga and prove to be under the reaction conditions of the invention as sufficiently reactive. The corresponding bisfluoro compounds of the general formula (II) are more reactive but harder to make than the corresponding one Dichloro compound of general formula (II). It is possible, however, aromatic Dichloro compounds of general formula (II) at elevated temperature in the presence of a dipolar organic solvent in the presence of finely divided alkali fluoride and phase transfer catalyst at least partially to convert to fluorinated compounds under halogen exchange. In a variant of the method according to the invention is therefore the aromatic dichloro compound of general formula (II) in the presence of alkali metal fluoride (and phase transfer catalyst) with the Dihydroxy compound (I) reacted. In this variant, fluoride acts as a catalyst. The addition of alkali metal fluoride can therefore be very be low. Preferably he 0.01 to 0.1 mole per mole of dichloro compound of general formula II.

To In a further embodiment of the method according to the invention, first the aromatic dichloro compound of general formula II with the at least equivalent Amount of an alkali metal fluoride at elevated temperature for at least 5 hours in the presence of a phase transfer catalyst in an aprotic polar solvents react and only then sets the aromatic dihydroxy compound of general formula (I) and the alkali metal carbonate. Preferably gives the aromatic dihydroxy compound of the general formula (I) successively added and heated the approach until a viscous solution is, d. H. the wished Polymers is formed. The phase transfer catalyst favors here the reaction of the dichloro compound with alkali metal fluoride such as also the later one Reaction of the dihydroxy compound.

For the process according to the invention, the following dihydroxy compounds of the general formula I may preferably be used as dihydroxy compounds:
Mononuclear compounds such as hydroquinone, polynuclear dihydroxy compounds such as 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 2,2-bis-4- (hydroxyphenyl) -propane, 2,2-bis-4- (hydroxyphenyl) -methane, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone, 1,4-bis (4-hydroxybenzoyl) benzene, 1,3-bis (4-hydroxybenzoyl) benzene, and each their nuclear-substituted derivatives in which H atoms of the nucleus are replaced by C ₁ -C ₄ -alkyl groups, chlorine and / or bromine atoms or nitro groups. Simultaneous substitution of a nucleus by nitro and halo groups, which could lead to activation of the halogen group, is not desired.

Prefers are 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) pentane and hydroquinone used.

When examples for Dihydroxy compounds having a fused aromatic radical be 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene and 1,5-Dihydroxyanthracen listed.

wobei
Z Wasserstoff, R³, R³R⁴N oder R⁵R⁶N
R³ und R⁴ unabhängig voneinander C₁-C₆-Alkyl oder
R³ und R⁴ zusammen eine Alkylengruppe mit 4 bis 10 C-Atomen, die mit dem N-Atom einen gesättigten 5- oder 6-Ring bildet,
R⁵ und R⁶ Phenylringe, die unabhängig voneinander durch C₁-C₄-Alkyl, Halogen oder Nitrogruppen substituiert sein können,
R C₁-C₅-Alkyl oder einen Phenylring der durch C₁-C₄-Alkyl, Halogen oder Nitrogruppen substituiert sein kann,
X und Y unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder R⁷R⁸N
R⁷ und R⁸ Phenylringe, die unabhängig voneinander durch C₁-C₄-Alkyl, Halogen oder Nitrogruppen substituiert sein können, und
A ein vorzugsweise einwertiges Anion, z. B. Chlorid, Jodid oder Methylsulfonat, bedeuten.As a phase transfer catalyst, a pyridinium salt of the general formula IV is used

in which
Z is hydrogen, R ³ , R ³ R ⁴ N or R ⁵ R ⁶ N
R ³ and R ^{4 are} independently C ₁ -C ₆ alkyl or
R ³ and R ⁴ together form an alkylene group having 4 to 10 C atoms, which forms a saturated 5- or 6-membered ring with the N atom,
R ⁵ and R ^{6 are} phenyl rings which may be substituted independently of one another by C ₁ -C ₄ -alkyl, halogen or nitro groups,
R is C ₁ -C ₅ -alkyl or a phenyl ring which may be substituted by C ₁ -C ₄ -alkyl, halogen or nitro groups,
X and Y independently of one another are hydrogen, C ₁ -C ₄ -alkyl or R ⁷ R ⁸ N
R ⁷ and R ^{8 are} phenyl rings which may be independently substituted by C ₁ -C ₄ alkyl, halogen or nitro groups, and
A is a monovalent anion, e.g. As chloride, iodide or methyl sulfonate mean.

All especially suitable as phase transfer catalysts are the compounds N-Neopentyl-4- (dibutylamino) -pyridinium chloride, N-neopentyl-4- (dihexylamino) -pyridinium chloride and N-Neopentyl-4- (4'-methylpiperidinyl) -pyridinium chloride.

in welchen Hal Chlor und/oder Fluor bedeutet
Z für eine Ethergruppe, ein Thioether, eine Carbonylgruppe oder eine Sulfonylgruppe steht, und
m und n unabhängig voneinander für die Zahlen 1, 2 oder 3 steht.Preferred dihalo compounds are represented by the formulas (V), (VI), (VII)

in which Hal is chlorine and / or fluorine
Z is an ether group, a thioether, a carbonyl group or a sulfonyl group, and
m and n independently of one another represent the numbers 1, 2 or 3.

suitable aromatic dihalo-keto compounds are, for. B. 4'-dichlorobenzophenone, 2,4'-dichlorobenzophenone, 1,4-bis (4-chlorobenzoyl) benzene, 1,3-bis (4-chlorobenzoyl) benzene, 4,4'-bis (4-chlorobenzoyl) biphenyl and 4,4'-bis (4-chlorobenzoyl) diphenyl ether.

Dichlorarylketone of the formula (II) have the chlorine substituents preferably in the para position at the respective terminal aromatic nucleus.

Especially preferred dihaloaryl ketones are 4,4'-dichlorobenzophenone and 1,4-bis (4-chlorobenzoyl) benzene.

The reaction of bis (chlorobenzoyl) benzene with bis (4-hydroxyphenyl) pentane gives, in the absence of a phase transfer catalyst, a product of molecular weight M _w = 124200. However, the reaction requires a reaction time of 17 h. With an addition of 5 mol% (based on the chlorine compound) of a phase transfer catalyst (PTC I), the molecular weight increases to 179200 and it takes only 7 h. Increasing the addition of phase transfer catalyst to 10 mol%, the required reaction time decreases to 4.5 h and the molecular weight of the resulting polymer continues to rise to 195300th When the chlorine compound by replacing the analogous bis-fluorine compound, catalysis is no longer required (but possible): After only 2 h, a polymer with a molecular weight of 222450 is present.

The inventive method will be first preferably at 155-230 ° C performed. The end The reaction water formed the alkali carbonate can be by an entraining agent distill. After completion of dehydration, the reaction mixture another 1 - 24 Hours, preferably 2 - 10 Hours, kept at 155-350 ° C. To achieve high molecular weights, the aromatic dihydroxy compounds with the Dihalogenarylketonen in approximately equimolar amounts with each other implemented.

When azeotropic entrainer can Compounds are used which form an azeotrope with water and a lower boiling point than the solvent used, for example, benzene, toluene, xylene, etc., preferably toluene.

The obtained amorphous polymers are soluble in THF, chloroform and Methylene chloride.

The Invention is explained in more detail by the examples.

In Examples 1 to 4 is carried out without fluoride addition.

example 1

0.05 mol of 1,4-bis (chlorobenzoyl) benzene, 0.05 mol of 2,2-bis (4-hydroxyphenyl) pentane, 0.12 mol of K ₂ CO ₃ and 2.5 mmol of N-neopentyl -4- (dibutylamino) -pyridinium chloride (= PTC I) are placed in a 250 ml reaction vessel with mechanical stirrer and gas inlet and outlet device in 100 ml of dimethylacetamide and 35 ml of toluene. The reaction mixture is then heated to the reaction temperature of 155 ° C. in an argon stream, whereupon the toluene-water azeotrope is distilled off. After 7 h reaction time, the mixture is highly viscous. The polymer is precipitated by pouring the still hot mixture into methanol and the polymer is purified by reprecipitation from chloroform solutions. The polymer thus obtained has an inherent viscosity of 0.94 dl / g (chloroform, 0.1% solution, 25 ° C) and has a glass transition temperature of 158 ° C.

Example 2:

It the procedure is as in Example 1, but 0.05 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.1 mol of potassium carbonate and 2.5 mol of N-neopentyl-4- (dihexylamino) -pyridinium chloride (= PTC II). After 7.2 hours, the mixture becomes highly viscous. You pour without cooling in an acetic acid / water mixture and then wash the Polymers in methanol. The polymer thus obtained has a glass transition temperature from 166 ° C.

The inherent Viscosity, in chloroform (0.1% solution) was determined 0.88 dl / g.

Example 3:

It The procedure is analogous to Example 1, but 0.05 mol of 2,2-bis (4-hydroxyphenyl) heptane and 5 mmol of N-neopentyl-4- (4'-methylpiperidinyl) -pyridinium chloride (= PTC III) used. The inherent viscosity was 1.23 dl / g (chloroform, 0.1% solution, 25 ° C), the reaction time 4.5 hours.

Example 4:

0.05 mol of 1,4-bis (chlorobenzoyl) benzene, 0.05 mol of 4,4'-bishydroxydiphenyl ether, 0.06 mol of sodium carbonate, 2.5 mmol of PTC I and 40 g of diphenyl sulfone as a solvent are presented in a 250 ml reaction vessel. After multiple Evacuate and ventilate the apparatus is heated with argon, the reaction mixture to 200 ° C. and held at this temperature for three to eight hours. Then heated one to 270 ° C up to 300 ° C. After about 60 to 180 minutes, the mixture becomes very viscous. You give as a termination reagent to 4-fluorobenzophenone and allowed to cool. The solidified mixture is ground and then washed alternately with acetone and water and finally at Dried 100 ° C. The inherent viscosity of 0.80 dl / g was determined on 0.1% sulfuric acid solution. The so produced Polymer is partially crystalline with a glass transition temperature of 156 ° C and a Melting temperature of 347 ° C.

In Examples 5 to 9, the reaction is carried out in the presence of alkali fluoride

Example 5:

The Polycondensation is similar to Example 1, but with a Catalyst mixture of 2.5 mmol PTC I and 0.125 mmol KF performed. To a reaction time of 5 hours, the reaction was complete. The Measurement of the inherent viscosity in chloroform (0.1% solution) gave a value of 0.97 dl / g. The glass transition temperature Tg was 160 ° C.

Example 6:

Becomes proceed analogously to Example 2, but a catalyst mixture 2.5 mmol of PTC II and 0.15 mmol of KF used, we obtain after a reaction time of 5.2 hours a polymer having an inherent viscosity of 0.88 dl / g (chloroform, 0.1% solution, 25 ° C). Tg = 165 ° C.

Example 7:

Becomes proceed according to Example 3, but a catalyst mixture from 2.5 mmol PTC I and 0.125 mmol KF, so after 5 hours reaction time a polymer of the inherent viscosity of 0.92 dl / g (0.1% chloroform solution).

Example 8:

0.05 mol of 1,4-bis (4-chlorobenzoyl) benzene, 0.06 mol of potassium carbonate, 5 mmol PTC I, 4 mmol KF and 40 g diphenyl sulfone are in a 250 ml Surface grinding reaction vessel with mechanical stirrer, Gas inlet and outlet device and heated dropping funnel presented. The apparatus is evacuated and ventilated with argon. The reaction mixture is heated to 200 ° C in argon stream. Then 0.049 mol of hydroquinone dissolved in 20 g of diphenylsulfone, dropwise. The reaction temperature is then on 250 ° C increased. To 2 - 4 Hours the temperature is increased to 280 ° C - 320 ° C. The viscous solution is allowed to cool, ground the solidified mixture in an analytical mill and washed alternately with acetone and water. The inherent viscosity of the thus purified polymer measured in sulfuric acid is 0.9 dl / g. The polymer has a glass transition temperature of 160 ° C and a Melting temperature of 358 ° C.

In Examples 9 and 10 were followed by a two-step reaction

Example 9:

Level A:

0.05 mol of 1,4-bis (chlorobenzoyl) benzene, 0.05 mol of KF and 2.5 mmol of PTC I are presented in 100 ml of dimethylacetamide and about 10 hours at 165 ° C touched.

Of the Halogen exchange of chlorine for fluorine, which by NMR spectroscopy was detected provides fluorinated substitution products of 1,4-bis (chlorobenzoyl) benzene. In the 1,4-bis (chlorobenzoyl) benzene used, 30% of the chlorobenzoyl groups replaced by fluorobenzoyl groups.

Level B:

To a reaction product prepared according to step A is 0.05 mol 2,2-bis- (4-hydroxyphenyl) -heptane, which was dissolved in 30 ml of toluene, dropwise. The reaction mixture is heated to 155 ° C. in an argon stream. After 4 hours reaction time, a polymer with an inherent viscosity of 0.83 dl / g (determined from 0.1% chloroform solution at 25 ° C).

Example 10:

Level A:

Becomes as in Example 9 (step A), but 0.05 mol of 4,4'-dichlorobenzophenone used, so is the content of fluorinated substitution products by the halogen exchange reaction about 35%.

Level B:

The after step A of this example the reaction mixture is as in Example 10 (step B), but using 0.05 mol 2,2-bis (4-hydroxyphenyl) propane reacted. It will be a polymer with an inherent viscosity of 0.95 dl / g. The reaction time is 4 hours. The glass transition temperature is 155 ° C.

Comparative Examples 1-3: One-stage reactions

Comparative Example 1

Becomes analogously to Example 1, but without the presence of PTC I, proceed, thus, a polymer having the inherent viscosity of 0.72 dl / g (chloroform, 25 ° C) after a reaction time of over 17 hours received.

Comparative Example 2:

It The procedure is analogous to Example 2, but without the addition of PTC II. A Polymer with an inherent viscosity of 0.62 dl / g (measured in chloroform at 25 ° C) forms only after 18 Hours of reaction time.

Comparative Example 3

The analogue implementation as in Example 3, but without PTC III, provides polymeric material the inherent viscosity of 0.94 dl / g (measured in chloroform) only after 19 hours of reaction time.

Comparative Example 4 (halogen exchanger in the starting product):

Becomes proceed as in Example 9 step A, but no added PTC I, so is no halogen exchange reaction on 1,4-bis (chlorobenzoyl) benzene demonstrated.

Example 11 (Preparation a starting product)

2,2-bis (4-hydroxyphenyl) pentane (= BPP)

A mixture of 0.05 mol of 2-pentanone, 2 mol of phenol and 0.005 mol of mercaptoacetic acid was saturated with HCl gas. The red mixture was stirred for 24 h at room temperature in argon atmosphere. Then, the reaction mixture was poured into hot water and the unused starting components were removed by steam distillation. Recrystallization from toluene gave in 90% yield a colorless solid product with mp. 147 ° C.
¹ H-NMR (200 MHz, DMSO-d _6, δ / ppm): 9.11 (s, 2H, -OH), 6.82 (AB system, 8H), 1.92 (m, 2H methylene,) , 1.45 (s, 3H, methyl), 1.05 (m, 2H, methylene), 0.85 (t, 3H, methyl)

Example 12 (Preparation a starting product)

2,2-bis (4-hydroxyphenyll-heptan (= BPH)

The synthesis is carried out analogously to Example 11 (BPP). The yield of colorless purified product was 85%. The mp was at 136 ° C.
¹ H-NMR (200 MHz, DMSO-d6, δ / ppm): 9.08 (s, 2H, -OH), 6.81 (AB system, 8H), 1.92 (m, 2H, methylene), 1.45 (s, 3H, methyl), 1.25 (m, 2H, methylene), 1.05 (m, 2H, methylene), 0.84 (t, 3H, methyl).

Claims (7)

Process for the preparation of polyether ketones by reacting an aromatic dihydroxy compound of general formula I. HO-Ar-OH (I) in which Ar is phenylene or a condensed aromatic radical having 10 to 30 C atoms or Ar consists of two to five phenylene rings which are bonded by single bonds, ether bridges, thioether bridges, carbonyl groups, sulfone groups or methylene groups whose H atoms are represented by C 1 -C 5 -alkyl groups be replaced wherein the hydrogen atoms bound to aromatic rings may be wholly or partially replaced by C 1 -C 4 -alkyl, nitro, chloro and / or bromo, with the proviso that an aromatic ring is not simultaneously substituted by halogen and nitro, with an aromatic dihalogen compound of general formula II Hal-Ar ² -CO-Ar ³ -Hal (II) in which Hal is chlorine and / or fluorine, Ar ² and Ar ^{3 are} aromatic radicals each having 6-24 carbon atoms, the radical Ar ^{3 may} also consist of several phenylene rings, which may be replaced by at least one carbonyl group or sulfonyl group and optionally Ether groups or thioether groups are interconnected, and the two radicals Hal are each arranged in the para position or ortho position to a CO and / or SO2 group, at elevated temperature in an aprotic-polar solvent in the presence of alkali metal carbonate and in the presence a phase transfer catalyst, characterized in that the phase transfer catalyst is a pyridinium salt of the general formula IV

where Z is hydrogen, R ³ , R ³ R ⁴ N or R ⁵ R ⁶ NR ³ and R ⁴ independently of one another are C ₁ -C ₆ -alkyl or R ³ and R ⁴ together form an alkylene group having 4 to 10 C atoms, which is substituted with N atom forms a saturated 5- or 6-membered ring, R ⁵ and R ⁶ phenyl rings, which may be substituted independently of each other by C ₁ -C ₄ alkyl, halogen or nitro groups, RC ₁ -C ₅ alkyl or a phenyl ring of may be substituted by C ₁ -C ₄ -alkyl, halogen or nitro groups, X and Y independently of one another are hydrogen, C ₁ -C ₄ -alkyl or R ⁷ R ⁸ NR ⁷ and R ^{8 are} phenyl rings which are independently of one another C ₁ -C ₄ alkyl, halogen or nitro groups may be substituted, and A is an anion. Method according to claim 1, characterized in that that he as a phase transfer catalyst, a pyridinium salt of the general Formula IV, in which X and Y are hydrogen and R is the neopentyl radical mean. Method according to claim 1 or 2, characterized that he as a phase transfer catalyst, a pyridinium salt of the general Formula IV uses, in which Z is a dialkylamino radical. Method according to claim 1 or 2, characterized that he uses a compound in which Z represents the 4'Methylpiperidinyl residue. Method according to one or more of claims 1 to 4, characterized in that in the presence of an alkali metal fluoride works. Method according to claim 5, characterized in that that he in the presence of 0.1 to 1 mole of alkali metal fluoride per mole of dihalo compound the formula II works. A method according to claim 1, characterized in that at least one aromatic dihalogeno compound of the general formula II in which Hal is chlorine, in the absence of an aromatic dihydroxy compound of the general formula I with the equivalent amount of an alkali metal fluoride in the presence of a phase transfer catalyst of the general formula IV at least Heated for 5 hours and then to the reaction mixture, the aromatic dihydroxy compound of general formula I and the alkali metal carbonate adds.