DE4128147A1 - Modified aromatic polyether for moulded prod. - prepd. by reacting aromatic di:halide with bisphenol for hydroxyl terminated polyether and reacting with aromatic di:acid and bisphenol, for high mol. wt. - Google Patents

Abstract

Polyethers (I) contain units of formula (IIA), (IIB) and (IIC) with mol. ratio (IIA+IIC):(IIB) = (0.8;1-(1.2:1) and mol. ratio (IIA):(IIC) = (0.1:1)-(1.0.1); R1-R6 = Hal, H, 1-4C alkyl, 6-12C aryl or 7-12C aralkyl; A = SO2, CO, SO or a gp. of formula (IV); B = direct bond, CO, O, S, S2 or a gp. of formula -CR7R8- or (V) (with R7, R8 = Hal, H, 1-4C alkyl or 5-12C cycloalkyl, opt. with alkyl substits)., eg., (methyl)cyclopentyl or (methyl)cylohexyl; p = 4-7; R9, R10 = H or 1-6C alkyl, pref. Me (may be different for each Z, and with both = alkyl on Z(s) Z = carbon)); n = 0 or 1-4; m = 0 or 1-3; and x = 1-100. Prodn. comprises reaction of dihalides of formula Hal-Ar-A-Ar-Hal with bis-phenols HO-Ar-(B-Ar)m-OH in the presence of 1-1.5 equivs. basic catalyst (w.r.t bisphenol) and dipolar aprotic solvents of formula (III) and/or R12-Q-R13, to give OH-terminated polyethers of formula HO-Ar-(B-Ar)m- (O-Ar-A-Ar-O-Ar-(B-Ar)m)y-OH, followed by reaction with monomers of formula D-Ar-D and E-Ar-E; Ar = variously substd. phenylene, as in (I); Hal = F, Cl or Br; R11-R13 = 1-20C alkyl 5-7C cycloalkyl or 6-20C aryl, pref. Ph; Q = SO or SO2; s = 3, 4 or 5, (3 or 5); and D = COCl, COOH, COOMe, COOEt, COOPr or COOBu. E = OH or OCOMe. USE/ADVANTAGE - High-mol. wt. modified aromatic polyethers have high Tg and high heat distortion temp.; and the modified polymers have increased solvent resistance and are still soluble in specific common solvents.

Description

The invention relates to modified aromatic polyethers, a process for Production of the modified aromatic polyether and the use of modified aromatic polyether for the production of moldings.

Aromatic polyethers, e.g. B. polyphenylene oxide, polysulfones, polyether ketones and Polyetheramides are highly heat-resistant polymers and not very sensitive to oxidation, flame retardant and have an excellent mechanical Property level. Semi-crystalline polyarylene ethers, e.g. B. polyether ether ketones, are also resistant to chemicals and solvents.

Polysulfones, e.g. B. the commercial products Ultrason® (BASF) or Udel® (Amoco) have high glass temperatures and are amorphous. An essential one The disadvantage of these materials is their solubility in conventional organic solvents.

They are also block copolymers of aromatic polyethers and liquid crystalline ones Polyesters have been prepared and described, e.g. B. in EP-A-2 14 612 or DE-A-36 23 319. The coproducts were obtained in a melt condensation and are practically insoluble.

It has now been found that the modification of polyethers with certain Polyester building blocks also changed the solubility behavior. The modified Materials have improved solvent resistance, but are selected and common solvents are still soluble.  

The invention relates to modified aromatic polyethers which Structural elements of the formula (Ia) to (Ic) are constructed

wherein
R¹ to R⁶ are the same or different and represent halogen, preferably fluorine, chlorine and bromine, and hydrogen, C₁-C₄-alkyl, preferably methyl and ethyl, C₆-C₁₂-aryl, preferably phenyl and biphenyl, or C₇-C₁₂-aralkyl, preferably methylphenyl and ethylphenyl,
A for SO₂, CO, SO or a radical of the formula (II)

preferably represents CO and SO₂,
B is a chemical bond, CO, O, S, SO₂,

means what
R⁷ and R⁸ are the same or different and are halogen, preferably fluorine, chlorine and bromine, and hydrogen, C₁-C₄-alkyl, preferably methyl and ethyl, or C₅-C₁₂-cycloalkyl, optionally with one or more alkyl substituents such as cyclopentyl, cyclohexyl, methylcyclopentyl , and methylcyclohexyl,
p is an integer from 4 to 7, preferably 4 or 5,
R⁹ and R¹⁰ are individually selectable for each Z and independently of one another are hydrogen or C₁-C₆-alkyl, preferably H or methyl, and
Z means carbon
with the proviso that the radicals R⁹ and R¹⁰ are at the same time alkyl on at least one atom Z,
n is 0 or an integer from 1 to 4, preferably 0, 1 or 2,
m is 0 or an integer from 1 to 3, preferably 0, 1 or 2, particularly preferably 0 or 1,
x is an integer from 1 to 100, preferably from 2 to 50,
wherein the molar amounts of the sum of (Ia + Ic) are in the ratio 0.8: 1 to 1.2: 1 to the molar amount of (Ib) and (Ia) and (Ic) in the molar ratio of 0.1: 1 to 1: 0.1.

The preferred modified aromatic polyethers are in the form of their containing Structural elements called formulas, wherein R⁵ = H or phenyl and R⁶ = phenyl mean:

Of particular note are the new structural groups containing the following structural elements aromatic polyethers containing:

Another object of the invention is a method for producing the modified aromatic polyether constructed from structural elements of the formulas (Ia) to (Ic)  

wherein
R¹ to R⁶ are the same or different and represent halogen, preferably fluorine, chlorine and bromine, and hydrogen, C₁-C₄-alkyl, preferably methyl and ethyl, C₆-C₁₂-aryl, preferably phenyl and biphenyl, or C₇-C₁₂-aralkyl, preferably methylphenyl and ethylphenyl,
A for SO₂, CO, SO or a radical of the formula (II)

preferably represents CO and SO₂,
B is a chemical bond, CO, O, S, SO₂,

means what
R⁷ and R⁸ are the same or different and are halogen, preferably fluorine, chlorine and bromine, and hydrogen, C₁-C₄-alkyl, preferably methyl and ethyl, or C₅-C₁₂-cycloalkyl, optionally with one or more alkyl substituents, such as cyclopentyl, cyclohexyl, Methylcyclopentyl and methylcyclohexyl,
p is an integer from 4 to 7, preferably 4 or 5,
R⁹ and R¹⁰ are individually selectable for each Z and independently of one another are hydrogen or C₁-C₆-alkyl, preferably H or methyl, and
Z means carbon
with the proviso that the radicals R⁹ and R¹⁰ are at the same time alkyl on at least one atom Z,
n is 0 or an integer from 1 to 4, preferably 0, 1 or 2,
m is 0 or an integer from 1 to 3, preferably 0, 1 or 2, particularly preferably 0 or 1, and
x is an integer from 1 to 100, preferably from 2 to 50,
wherein the molar amounts of the sum of (Ia + Ic) are in the ratio 0.8: 1 to 1.2: 1 to the molar amount of (Ib) and (Ia) and (Ic) in the molar ratio of 0.1: 1 to 1: 0.1,
which is characterized in that aromatic dihalides of the formula (V)

wherein
R¹, R², A and n have the meaning given above and
Hal represents fluorine, chlorine or bromine, preferably fluorine or chlorine,
with aromatic bisphenols of the general formula (VI)

wherein
R³, R⁴, B, m and n have the meaning given above,
in the presence of 1 to 1.5 equivalents of basic catalysts, based on dihydroxy compounds of the general formulas (VI) and (VII), and in the presence of dipolar, aprotic solvents of the formulas (VIII) and / or (IX)

R¹²-Q-R¹³ (IX)

in which
R¹¹, R¹² and R¹³ are the same or different and are C₁-C₂₀-alkyl, C₅-C₇-cycloalkyl, preferably methyl, ethyl and propyl, and C₆-C₂₀-aryl, preferably phenyl,
Q represents a sulfoxide or sulfone group and
s represents the numbers 3, 4 or 5, preferably 3 or 5,
by appropriate choice of the ratio of dihalo compound (V)

and aromatic bisphenols of the formula (VI)

be implemented in such a way that hydroxyl-terminated aromatic Polyether of formula (X)  

arise.

These functionalized polyethers are used in a second reaction Monomers of the general formula (XI) and (XII)

wherein
D for COCl, COOH, COOCH₃, COOC₂H₅, COOC₃H₇, COOC₄H₉, preferably COCl, COOH, particularly preferably COCl and
E represents OH or OOC-CH₃, and
R⁵ and R⁶ have the meaning given above,
to high molecular weight compounds, built up from structural elements of the formulas Ia to Ic.

Examples of aromatic dihalogen compounds of the formula (V) to be used are

4,4′-dichlorodiphenyl sulfone,
4,4′-difluorodiphenyl sulfone,
4,4'-difluorobenzophenone and / or
4,4'-dichlorobenzophenone.

Suitable diphenols of the formula (VI) are e.g. B .:

Hydroquinone,
Methylhydroquinone,
Phenylhydroquinone,
Resorcinol,
Dihydroxydiphenyls,
Bis (hydroxyphenyl) alkanes,
Bis (hydroxyphenyl) cycloalkanes,
Bis (hydroxyphenyl) sulfides,
Bis (hydroxyphenyl) ether,
Bis (hydroxyphenyl) ketones,
Bis (hydroxyphenyl) sulfones,
Bis (hydroxyphenyl) sulfoxides,
α, α′-bis (hydroxyphenyl) diisopropylbenzenes

and their nuclear alkylated and nuclear halogenated compounds.

These and other suitable other diphenols (III) are e.g. Tie US-PS 30 28 365, 29 99 835, 31 48 172, 20 69 560, 32 75 601, 29 91 273, 32 71 367, 30 62 781, 29 70 131, 20 69 573 and 29 99 846, in the German Publications 15 70 703, 20 63 050, 20 63 052, 22 11 095 and the German patent application P 38 32 396.6, the French patent specification 15 61 518, JP-OS 62 093/86, 62 040/86 and 1 05 550/86 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 ".

Preferred other diphenols are, for example:

4,4'-dihydroxydiphenyl,
2,2-bis (4-hydroxyphenyl) propane,
2,4-bis (4-hydroxyphenyl) -2-methylbutane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl) propane,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone,
2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane,
α, α′-bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl propane
1,1-bis (4-hydroxyphenyl) cyclohexane,
4,4'-dihydroxydiphenyl sulfone,
1,6-, 1,7-, 2,6-, 2,7-naphthalenediol,
4,4'-dihydroxydiphenyl sulfone and
4,4'-dihydroxybenzophenone.

As further bisphenol components in the production of the ester groups Aromatic polyethers containing:

3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane,
3,3,5-trimethyl-1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane,
3,3,5,5-tetramethyl-1,1-bis (4-hydroxyphenyl) cyclohexane,
3,3,5,5-tetramethyl-1,1-bis (4-hydroxy-2,5-dimethylphenyl) cyclohexane,
3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclopentane and
3,3,5-trimethyl-1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclopentane

suitable.

Examples of dipolar, aprotic solvents of the formula (VIII) N-methylpyrrolidone and / or N-methylcaprolactam can be used.

Dimethyl sulfoxide, Diphenyl sulfone and / or sulfolane.  

Suitable (basic) catalysts are the (earth) alkali metal salts, such as Sodium hydroxide, potassium hydroxide, sodium methoxide, potassium carbonate and / or Potassium hydrogen carbonate.

Before the reaction (condensation) according to the invention, the reaction mixture be dewatered azeotropically. This procedure has several advantages. For Drainage becomes a common entrainer, such as toluene, mesitylene, chlorobenzene, Dichlorobenzene and / or other known entrainer, the reaction mixture added. The reaction is preferably carried out under an inert gas atmosphere, for example in the presence of nitrogen and / or argon. As it progresses Condensation, the reaction temperature is gradually increased, preferably to Temperatures in the range of 145 to 280 ° C. The water and the added Entrainer removed from the reaction mixture. A gradual one An increase in viscosity can be observed.

The polymer is then removed from the reaction mixture by a conventional one Precipitation reaction, e.g. B. by adding alcohols or alcohol / water mixtures, e.g. B. by adding methanol, ethanol or isopropanol.

If necessary, the reaction mixture, especially if it is very highly viscous Solutions are present, for example with the polar reaction solvent or diluted with another solvent for the polyether and then filtered. The polymer is then isolated in the usual way.

Applicable synthetic methods for generating the hydroxyl-terminated aromatic polyethers are e.g. B. described in DE-36 23 319 and EP-02 14 612. The molecular weights can be determined by the ratio of dihalogen compound (V) to bisphenol (VI) can be set on a wide scale.

The implementation of the hydroxyl-terminated aromatic polyethers Formula (X) with bifunctional compounds of formula (XI) and (XII)  according to methods known from the literature such. B. A. Bilibin et al., Makromol. Chem., Rapid Communications 10, p. 249, A. Bilibin et al., Makromol. Chem., Vol. 186, 1985, 1575 and US-44 40 945, respectively.

It can be carried out in bulk or in solution. As a suitable solvent can e.g. B. diphenyl ether or 1-chloronaphthalene can be used. In cases in which solvents are used, the modified ones are isolated aromatic polyether e.g. B. by filling in suitable solvents such as alcohols or ketones.

The aromatic polyethers according to the invention have average molecular weights M _w (weight average determined by gel permeation chromatography (GPC) with polystyrene as the standard) from 600 to 300,000, in particular from 1,000 to 200,000 and especially from 2,000 to 100,000.

The modified polyethers according to the invention are distinguished by high glass transition temperatures and heat resistance.

They can be used for the production of moldings. Such moldings can be produced for example by extrusion, injection molding, sintering or pressing in a known manner. The modified aromatic polyethers are can be used wherever high dimensional stability is required, for example on the field of electrical engineering and electronics, vehicle construction, in the air and Sports equipment as well as for functional parts and dishes for microwave ovens. Furthermore for the production of sterilizable medical devices, Coffee machine parts, egg cookers, hot water containers, hot water pipes and pumps and hair dryers.

The modified polyethers according to the invention can also contain conventional additives, such as plasticizers, mold release agents, stabilizers, such as UV absorbers or Antioxidants, intumescent agents (flame retardants), reinforcing fibers, such as glass fibers, carbon fibers or aramid fibers, fillers, inorganic and organic pigments, ceramic raw materials and carbon black are added. The  Amounts of additives to be added can easily be determined by preliminary tests become and hang u. a. depending on the intended use of the molded body. Amounts of up to 80, preferably up to 60, particularly preferably up to, are customary 50 wt .-%, based on the total polymer. It is advisable to add the additives to add the processing to the polyethers according to the invention.

example 1

23.7800 g bisphenol A (0.1042 mol) 22.2600 g (0.0775.) In a countercurrent in a heated and nitrogen-coated three-necked flask with KPG stirrer (KPG stirring sleeve with nitrogen connection), reflux condenser, bubble counter, water separator and inert gas connection mol) 4,4'-dichlorodiphenyl sulfone, 21.59 g K₂CO₃ p. A. (0.1562 mol), 150 ml DMSO and 50 ml toluene at 160 ° C oil bath temperature, azeotropically distilled for 6 h. The toluene was distilled off completely and the reaction mixture was then stirred at 190 ° C. for 8 h. The product was precipitated with 2.5 l of methanol, to which 2.5 g of oxalic acid had been added, and purified three times by reprecipitation with CHCl₃ / methanol. 91.7% of a colorless product with M _n = 2600 (vapor pressure osmometry and NMR) were obtained.

Example 2

17.120 g of bisphenol A (0.0753 mol) and 20.275 g (0.0706 mol) of 4,4′-dichlorodiphenylsulfone, 13, were in a nitrogen countercurrent in a heated three-necked flask charged with dry nitrogen with reflux condenser, bubble counter, water separator, magnetic stirrer and inert gas connection 5 g K₂CO₃ p. A. (0.0977 mol), 200 ml of NMP and 50 ml of toluene. The mixture was azeotropically distilled at 160 ° C. oil bath temperature for 6 hours. The toluene was then distilled off while increasing the temperature to 180 ° C. and then condensed at this temperature for 16 h. After filtration, the product was precipitated in 3 l of HCl acidic methanol. The cleaning is done by dissolving in CHCl₃ and renewed precipitation. The polymer was washed neutral, pre-dried in a desiccator over Sicapent ^™ at room temperature for 2 days and then freed from solvent residues over a further 2 days at 10 ^-2 torr and 108 ° C. in a drying gun over Sicapent ^™ . The yield was 70.2% and the molecular weight was 4650.

Example 3

In a heated, three-necked flask filled with argon with a reflux condenser, Bubble counter, water separator, magnetic stirrer and inert gas connection  be 12.556 (0.055 mol) bisphenol A and 14.35 g in the argon countercurrent (0.050 mol) 4,4'-dichlorodiphenyl sulfone, 10.36 g (0.075 mol) K₂CO₃ p. A., 50 ml Submitted NMP and 50 ml of toluene. The mixture was oil bath temperature at 180 ° C for 4.5 h Distilled azeotropically. The toluene was then within 30 min. distilled off. After a reaction time of 4 h at 180 ° C in chloroform the dissolved batch is shaken out with dilute HCl and washed neutral with water. After concentration of the chloroform solution to about 100 ml, the product precipitated in methanol. The polymer was dried at 12 torr and 80 ° C in 24 h. The yield was 22.2 g (90%).

Example 4

30.0000 g (0.0805 mol) of disilylated bisphenol A, 22.124 g (0.0770 mol) of 4,4′-dichlorodiphenyl sulfone and 11 were in a countercurrent in a heated and dry nitrogen-charged three-necked flask with reflux condenser, base counter, magnetic stirrer and inert gas connection , 26 g (0.08129 mol) of K₂CO₃ p. A. reacted in 250 ml of NMP at 190 ° C with constant nitrogen supply for 48 h. The inorganic salts were then separated off and the product was precipitated in 5 l of hydrochloric acid methanol. The yield lab at 90.7% and M _n = 9700.

Found: C 73.8; H 5.1; O 14.6; S 7.1;
calc .: C 73.5; H 5.1; O 14.6; S 7.1.

Example 5 Preparation of a hydroxyl-terminated polyether ketone

349.1 g (1.6 mol) 4,4'-difluorobenzophenone, 456.0 g (2.0 mol) bisphenol A and 360 g (2.6 mol) K₂CO₃ are placed in 2000 ml of NMP and 1000 ml of toluene. The reaction mixture is heated overnight at a water separator at 145 to 155 ° C and the resulting Water of reaction circled.  

The internal temperature is then gradually increased by decreasing the toluene increased to 185 ° C. At this temperature, stirring is continued for 6 h and then the Temperature increased to 195 ° C for one hour. The reaction mixture is 8 liters of H₂O / CH₃OH (1: 1) precipitated, suction filtered, taken up in 2 liters of CH₂Cl₂, with dilute HCl acidified, washed neutral with H₂O, about concentrated and in Methanol precipitated and isolated.

The product has a glass transition temperature of 104 ° C (determined by DSC, second Warm up).

Example 6

1.397 g (0.0075 mol) of phenylhydroquinone and 1.584 g (0.0078 mol) of terephthalic acid dichloride were added to 3.158 g (0.0003 mol) under a gentle stream of nitrogen of a telechelic polyethersulfone with a molecular weight of 10,000 in 50 ml Given diphenyl ether. The reaction vessel, consisting of a heated one 100 ml of nitrogen flask with reflux condenser, stirring fish and bubble counter was then sealed, the reaction mixture devitrified three times and then under Inert gas atmosphere set. Then condensed at 160 ° C for 8 h, at 200 ° C for 36 h and 8 h at 250 ° C with constant passage of dry nitrogen to the resulting Expel HCl gas. After the reaction, the viscous product was with additional diphenyl ether partially dissolved in the heat and then in 1 l of methanol like. The polymer was extracted with methanol for 3 days and dried. The Yield was 92.3%.

Example 7

A modified polyether was produced in an analogous manner

with a molecular weight of 10,000 g / mol and terephthalic acid dichloride and phenylhydroquinone, wherein the polysulfone block is 90% by weight. The product has a glass transition temperature Tg of 190 ° C (determined by DSC).

Example 8

As example 7 but replacement of the terephthalic acid dichloride by Isophthalic acid dichloride. The product has a glass transition temperature Tg of 188 ° C (determined by DSC).

Example 9

As example 7 but replacement of the terephthalic acid dichloride by Phenyl terephthalic acid. The product has a glass transition temperature Tg of 166 ° C (determined by DSC).

Example 10

Like example 7, but the polyether block has only a molecular weight of 7000 g / mol. The product has a glass transition temperature Tg of 183 ° C (determined by DSC).

Example 11

As example 10 but substitution of terephthalic acid by phenyl terephthalic acid. The The product has a glass transition temperature Tg of 166 ° C (determined by DSC).

The modification increases the solvent resistance of the polyethers. So are the modified polyethers from Examples 7, 8 and 10 only at 50 ° C in chlorobenzene soluble while the corresponding unmodified products at room temperature are soluble in methylene chloride.

Claims (3)

1. Aromatic polyethers composed of structural elements of the formulas (Ia) to (Ic) wherein
R¹ to R⁶ are the same or different and represent halogen, and also hydrogen, C₁-C₄-alkyl, C₆-C₁₂-aryl or C₇-C₁₂-aralkyl,
A for SO₂, CO, SO or a radical of the formula (II) stands,
B is a chemical bond, CO, O, S, SO₂, means what
R⁷ and R⁸ are the same or different and represent halogen, and also hydrogen, C₁-C Alkyl-alkyl or C₅-C₁₂-cycloalkyl, optionally with one or more alkyl substituents such as cyclopentyl, cyclohexyl, methylcyclopentyl and methylcyclohexyl,
p is an integer from 4 to 7,
R⁹ and R¹⁰ are individually selectable for each Z and are independently hydrogen or C₁-C₆-alkyl and
Z means carbon
with the proviso that the radicals R⁹ and R¹⁰ are at the same time alkyl on at least one atom Z,
n is 0 or an integer from 1 to 4,
m 0 or an integer from 1 to 3,
x is an integer from 1 to 100,
wherein the molar amounts of the sum of (Ia + Ic) are in the ratio 0.8: 1 to 1.2: 1 to the molar amount of (Ib) and (Ia) and (Ic) in the molar ratio of 0.1: 1 to 1: 0.1. 2. Process for the preparation of the modified aromatic polyethers composed of the structural elements (Ia) to (Ic) wherein
R¹ to R⁶ are the same or different and represent halogen, and also hydrogen, C₁-C₄-alkyl, C₆-C₁₂-aryl or C₇-C₁₂-aralkyl,
A for SO₂, CO, SO or a radical of the formula (II) stands,
B is a chemical bond, CO, O, S, SO₂, means what
R⁷ and R⁸ are the same or different and represent halogen, and also hydrogen, C₁-C Alkyl-alkyl or C₅-C₁₂-cycloalkyl, optionally with one or more alkyl substituents such as cyclopentyl, cyclohexyl, methylcyclopentyl and methylcyclohexyl,
p is an integer from 4 to 7,
R⁹ and R¹⁰ are individually selectable for each Z and independently of one another are hydrogen or C₁-C₆-alkyl, preferably H or methyl, and
Z means carbon
with the proviso that the radicals R⁹ and R¹⁰ are at the same time alkyl on at least one atom Z,
n is 0 or an integer from 1 to 4,
m 0 or an integer from 1 to 3,
x is an integer from 1 to 100,
wherein the molar amounts of the sum of (Ia + Ic) are in the ratio 0.8: 1 to 1.2: 1 to the molar amount of (Ib) and (Ia) and (Ic) in the molar ratio of 0.1: 1 to 1: 0.1;
which is characterized in that aromatic dihalides of the formula (V) wherein
R¹, R², A and n have the meaning given above and
Hal represents fluorine, chlorine or bromine,
with aromatic bisphenols of the formula (VI) wherein
R³, R⁴, B, m and n have the meaning given above,
in the presence of 1 to 1.5 equivalents of basic catalysts, based on dihydroxy compounds of the general formulas (VI) and (VII), and in the presence of dipolar, aprotic solvents of the formulas (VIII) and / or (IX) R¹²-Q-R¹³ (IX) in which
R¹¹, R¹² and R¹³ are the same or different and are C₁-C₂₀-alkyl, C₅-C₇-cycloalkyl, and C₆-C₂₀-aryl, preferably phenyl,
Q represents a sulfoxide or sulfone group and
s represents the numbers 3, 4 or 5, preferably 3 or 5,
by appropriate choice of the ratio of dihalo compound (V) and aromatic bisphenols of the formula (VI) are implemented in such a way that hydroxyl-terminated aromatic polyethers of the formula (X) arise, which then with monomers of the general formula (XI) and (XII) wherein
D for COCl, COOH, COOCH₃, COOC₂H₅, COOC₃H₇, COOC₄H₉, and
E stands for OH and OOC-CH₃, and
R⁵ and R⁶ have the meaning given above,
to high molecular weight compounds that contain the structural elements (Ia) to (Ic). 3. Use of the aromatic polyether according to claim 1 for the preparation of moldings.