EP2209833A2

EP2209833A2 - Method for producing polyaryl ethers

Info

Publication number: EP2209833A2
Application number: EP08849095A
Authority: EP
Inventors: Martin Weber; Volker Warzelhan; Faissal-Ali El-Toufaili; Andreas Greiner; Heiner Stange; Seema Agrarwal
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2007-11-13
Filing date: 2008-11-11
Publication date: 2010-07-28
Also published as: JP5490011B2; WO2009062923A3; US20100286303A1; MY150563A; US8378054B2; JP2011503310A; KR20100100863A; CN101855271A; IN2010CN02651A; WO2009062923A2; CN101855271B

Abstract

The invention relates to a method for producing polyaryl ethers. The invention is characterized by a polycondensation of the monomer units as the starting materials and a concurrent irradiation with microwaves. The invention allows the production of thermoplastic molding masses having improved color properties.

Description

Process for the preparation of polyaryl ethers

description

The present invention relates to a process for the preparation of polyaryl ethers and molding compositions based on polyaryl ethers. The polyaryl ethers prepared using radiation in the microwave range, in particular polysulfones (PES), polyether sulfones (PES) and polyphenylsulfones (PPSU), have improved mechanical and optical properties in molding compositions. In particular, the thermoplastic molding compositions have an improved inherent color.

Moreover, the present invention relates to the use of such molding compositions for the production of moldings, films, membranes and foams.

Polyaryl ethers belong to the group of high-performance thermoplastics and are distinguished by high heat resistance, good mechanical properties and inherent flame retardancy (see EM Koch, H. M. Walter, Kunststoffe 80 (1990) 1146, E. Döring, Kunststoffe 80 (1990) ) 1149). Because of their good biocompatibility, polyaryl ethers are also used as material for the preparation of medical materials, such as dialysis membranes (S. Savariar et al., Desalination 144 (2002) 15).

The polyaryl ethers are usually prepared by thermal polycondensation of suitable monomer units in dipolar aprotic solvents at elevated temperature (see RN Johnson et al., J. Polym., Vol al., Polymer 25 (1984) 1827).

Molding compounds of various polyaryl ethers have been known from the literature for years. In EP-A 215 580, for example, miscible, d. H. single-phase blends of two or more polyarylene ether sulfones having repeating units of the following building blocks:

From DE-A 2 917 903 the person skilled in compositions for the preparation of z. B. semipermeable membranes obtained by mixing powdered polyarylene ether, wherein the one polymer consists essentially of the structural units (I) and the other polymer consists essentially of structural units (II):

EP-A 127 852 discloses a polyaryl ether comprising a mixture of polyarylene ether sulfones with the following recurring units (III):

and those containing the above-mentioned structural units (I) and (II) are known.

EP-A 663 426 also discloses polymer blends based on a copolyaryl ether, consisting of 91 to 97 mol% of structural units (I) and 3 to 9% by weight of structural units (II) having a disperse phase consisting of one a further copolyaryl ether which has 91 to 97 mol% of structural units (II) and 3 to 9 mol% of structural units (I). These blends are characterized by improved flowability, reduced bleed tendency and improved chemical resistance.

Various processes for the thermal preparation of polyarylene ether sulfones from aromatic bishalogen compounds and aromatic bisphenols or their salts in the presence of at least one alkali metal or ammonium carbonate or ammonium bicarbonate in an aprotic solvent are known to the person skilled in the art.

In US 4,870,153, for example, polyaryl ethers are produced under the action of heat energy containing naphthalene and terphenylene structures. For example, naphthalenediphenol salts are reacted with a phenyl ether dibromide in a condensation reaction.

EP-A 1 13 1 12 describes thermoplastic polymers which are obtained from three different monomer building blocks by thermal condensation reaction. For this purpose, a polymerization at temperatures of 120 ° to 180 ° under a set equimolar amounts of the corresponding hydroxy compounds and the halogen compounds in the presence of an alkali metal carbonate.

EP-A 297 363 describes high-temperature-resistant molding compositions which are composed of polyarylethersulfone building blocks and polyarylether units and can be obtained by thermal polycondensation using potassium carbonate and having a temperature of 190 °.

EP-A 135 130 describes a process for the preparation of linear polyarylene polyethers in which alkali metal double salts of dihydric phenols are reacted in equimolar amounts with a dihalobenzene compound. The reaction is carried out in N-methylpyrrolidone with heating and it is added anhydrous potassium carbonate.

The cited documents of the prior art can be taken both from the suitable starting materials, catalysts and solvents and suitable proportions of the substances involved and suitable reaction times and reaction parameters, such as reaction temperatures and reaction pressures, as well as suitable work-up methods.

However, all said processes have in common that to achieve suitable molecular weights, the condensation at high temperature, ie usually above 160 ⁰ C (and usually above 140 ⁰ C) must be carried out for several hours. Therefore, the polyaryl ethers obtained have a yellowish inherent color, which can be characterized, for example, on the basis of the so-called yellowness index.

The object of the present invention is to provide an improved process for the preparation of polyarylethers. The process should be cost-effective and lead to products with improved color properties.

It has long been known from the literature that reactions can also be accelerated under the action of radiation in the microwave range (see Gedye, R. et al., Tetrahedron Letters 1986, 27, 279, Chatti, S. et al., European Polymer Journal 2002, 38, 1851).

In the context of the present invention, the term microwaves summarizes the decibel, centimeter and millimeter waves. Microwaves are electromagnetic waves whose wavelength is between 1 m and 1 mm, which corresponds to a frequency range of about 300 MHz to about 300 GHz. Microwaves are used, for example, in radar technology, in the microwave oven as well as in many technical applications such as plasma systems, wireless communication systems or sensor systems.

Due to their wavelength, microwaves are particularly suitable for exciting dipole and multipole oscillations of molecules. They can therefore accelerate chemical reactions. This effect is particularly clear in the case of the vibration excitation of water molecules in the microwave oven. The heating of water is not based on a specific resonant frequency, but the water molecules as dipoles constantly try to align themselves with the electromagnetic alternating field, whereby heat is generated as a dielectric loss.

For example, microwaves of different frequency and power can be produced by runtime tubes (klystrons or magnetrons). In microwave ovens, magnetrons are commonly used to produce microwaves in the range of up to 500W.

In principle, microwave reactors can also be used for the preparation of polymers (see S. Mallakpour et al., Journal of Applied Polymer Science, 2005, 96, 435, SA Scrinivasan et al., Journal of Applied Polymer Science 1997, 64, 179), however, problems also arise with the use of microwaves for the polymerization. For example, polymerization may be incomplete or lead to unfavorable molecular weight distribution.

Surprisingly, however, it has been found that the use of electromagnetic radiation in the microwave range, the production of polyaryl ethers can be significantly accelerated by nucleophilic substitution. The invention thus relates to a process for the preparation of polyaryl ethers, characterized in that, starting from the monomer building blocks, a polycondensation is carried out using microwave irradiation.

The resulting products also have a significantly improved intrinsic color. Compared to the products polycondensed by thermal reaction, the products of the same viscosity number produced by microwave-assisted reaction have improved processing stability and reduced oligomer content.

The molding compositions which can be prepared by the novel process comprise the polyaryl ether or ethers (component A) in a proportion of from 5 to 100, in particular from 5 to 99.8, usually from 5 to 98, preferably from about 20 to 96,% by weight. Polyaryl ethers (component A) which can be prepared according to the invention are preferably composed of recurring units of the general formula (I)

wherein

x is 0.5 or 1, t and q independently of one another are 0, 1, 2 or 3,

Q, T, Y and Z are each independently a chemical bond or a group selected from -O-, -S-, -SO ₂ -, S = O, C = O, -N = N-,

-R ^a C = CR ^b - and -CR ^c R ^d -, where

R ^a and R ^b independently of one another each represent a hydrogen atom or a C 1 -C ₂ -alkyl group, and

R ^c and R ^d are each independently a hydrogen atom or a _d-Ci2 alkyl, _Ci-Ci2 alkoxy or C ₆ -C ₈ - are aryl group wherein R ^c and R ^d optionally substituted independently with fluorine and / or chlorine atoms are substituted or optionally together with the

C-atom to which they are attached, a C ₃ -C ₂ - form cycloalkyl group which is optionally substituted with one or more C ₆ alkyl groups,

with the proviso that at least one of T, Q, Y and Z is -SO ₂ - or C = O and, when t and q are 0, Z is -SO ₂ - or C = O,

Ar, Ar ¹ is C ₆ -C ₈ arylene groups are independently of one another, which is optionally substituted with CrCl ₂ -AIkIy-, C ₆ -C ₈ -aryl, CrCl ₂ - alkoxy groups or halogen atoms are substituted.

It is also possible for different units of the formula (I) to be present randomly or in blocks distributed in the polyaryl ether.

Preference is furthermore given to polyaryl ethers which can be prepared according to the invention and which are synthesized from recurring units of the general formula (I): wherein

x is 0.5 or 1, t and q are independently 0, 1, 2 or 3, Q, T and Z are each independently a chemical bond or a

Group selected from -O-, -SO ₂ -, C = O,

with the proviso that at least one of the groups T, Q and Z is -SO ₂ - or C = O and, when t and q are 0, Z is -SO ₂ - or C = O,

Ar, Ar ¹ is C ₆ -C ₂ are independently arylene groups, which is optionally substituted with CrCl ₂ -AIkIy-, C ₆ -C ₂ aryl, CrCl ₂ - alkoxy groups or halogen atoms are substituted.

Preference is given to polyaryl ethers which can be prepared according to the invention and which are built up from recurring units of the general formula (I) where Q, T and Z independently of one another each represent a chemical bond or a group -O-, -SO ₂ - or C = O and Ar and Ar ^{1 are} each 1, 4-phenylene groups.

The preparation of polyaryl ether A based thereon by thermal reaction is described, for example, in GB-A 1 152 035 and US Pat. No. 4,870,153. The classical thermal process conditions for the synthesis of polyaryl ethers are described, for example, in EP-A 0 113 112 and EP-A 0 135 130. For example, the reaction of the monomers in aprotic polar solvents in the presence of anhydrous alkali carbonate is described.

A preferred combination is N-methylpyrrolidone as solvent and potassium carbonate as catalyst. The reaction in the melt is also known.

Examples of suitable polyaryl ethers A are those having at least one of the following recurring structural units I ₁ to I ₂₉ :

for x = 0.5 in formula (I):

Particularly preferred units of the formula (I) are units of the formulas (I ₁ ), (I ₂ ) and (I ₈ ) which may be present individually or in a mixture.

Also preferred are polyaryl ethers which can be prepared according to the invention and consist of recurring units having at least one of the structures I ₁ , I ₂ and I ₈ .

The polyaryl ethers A can also be copolymers or block copolymers in which polyarylene ether segments and segments of other thermoplastic polymers, such as polyamides, polyesters, aromatic polycarbonates, polyester carbonates, polysiloxanes, polyimides or polyetherimides are present.

The molecular weights (number average) of the block or the graft arms in the copolymers are generally in the range from 1,000 to 30,000 g / mol. The blocks of different structure may be arranged alternately or statistically. The overall winhtcαntoii n _e r polyaryl ethers in the copolymers or block copolymers is Allgemeine at least 10% by weight. The proportion by weight of the polyaryl ethers can be up to 99.8, in particular 97 wt .-%. Preference is given to copolymers or block copolymers having a weight fraction of polyaryl ether of up to 90% by weight. Particular preference is given to copolymers or block copolymers containing from 20 to 80% by weight of polyaryl ether.

In general, the polyarylether have average molecular weights M _n (number average) in the range of 5,000 to 60,000g / mol and relative viscosities of 0.20 to 0.95 dl / g. Depending on the solubility of the polyaryl ethers, the relative viscosities are measured either in 1% strength by weight N-methylpyrrolidone solution, in mixtures of phenol and dichlorobenzene or in 96% strength sulfuric acid at 20 ^° C. or 25 ^° C.

As further component D, the thermoplastic molding compositions according to the invention contain 0 to 50, preferably 0 to 45 and in particular 0 to 40 wt .-% of additives, such as fillers and reinforcing agents or impact-modifying rubbers.

The molding compositions of the polyarylethers prepared according to the invention may also contain other components, in particular auxiliaries, such as, for example, processing aids, pigments, stabilizers or mixtures of various additives.

In the molding compositions, for example, 0 to 45, in particular 0 to 40 wt .-%, fibrous or particulate fillers or reinforcing materials or mixtures thereof may be included. The quantities are in each case based on the total mass of the components.

Preferred fibrous fillers or reinforcing materials are carbon fibers, potassium tantanate whiskers, aramid fibers and particularly preferably glass fibers. When glass fibers are used, they can be provided with a size, preferably a polyurethane size, and a primer for better compatibility with the matrix material. In general, the carbon and glass fibers used have a diameter in the range of 6 to 20 microns.

The incorporation of the glass fibers can take place both in the form of short glass fibers and in the form of endless strands (rovings). In the finished injection molded part, the average length of the glass fibers is preferably in the range of 0.08 to 0.5 mm. Carbon or glass fibers can also be used in the form of woven fabrics, mats or glass silk rovings.

Suitable particulate fillers are amorphous silicic acid, carbonates, such as magnesium carbonate (chalk), powdered quartz, mica, various silicates, such as clays, muscovite, biotite, suzoite, tin malite, talc, chlorite, phlogophite, feldspar, calcium carbonate. silicates, such as wollastonite or aluminum silicates, such as kaolin, especially calcined kaolin.

According to a further embodiment, particulate fillers are used, of which at least 95% by weight, preferably at least 98% by weight, of the particles have a diameter (largest dimension) determined on the finished product of less than 45 μm, preferably less than 40 μm, and whose so-called aspect ratio is in the range from 1 to 25, preferably in the range from 2 to 20, determined on the finished product.

The particle diameter can be determined, for example, by taking electron micrographs of thin sections of the polymer mixture and using at least 25, preferably at least 50 filler particles for the evaluation. The particle diameters can also be determined by sedimentation analysis, for example according to "Transactions of ASAE", page 491 (1983) .The proportion by weight of the fillers which is less than 40 μm can also be measured by sieve analysis from particle diameter to thickness (largest dimension to smallest dimension).

Particularly preferred particulate fillers are talc, kaolin, such as calcined kaolin or wollastonite or mixtures of two or all of these fillers. Of these, talc with a proportion of at least 95 wt .-% of particles having a diameter of less than 40 microns and an aspect ratio of 1, 5 to 25, each determined on the finished product, particularly preferred. Kaolin preferably has a content of at least 95% by weight of particles with a diameter of less than 20 μm and an aspect ratio of 1.2 to 20, in each case determined on the finished product.

The molding compositions according to the invention may also contain, as further component E, auxiliaries or additives, such as processing aids, pigments, stabilizers, flame retardants or mixtures of different additives.

Conventional additives are, for example, also oxidation inhibitors, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes and plasticizers.

Their proportion is according to the invention from 0 to 30, preferably 0.2 to 30, preferably from 0 to 20 wt .-%, in particular 0 to 15 wt .-%, based on the total weight of the components. In the case of component E being stabilizers, the proportion of these stabilizers is usually up to 2% by weight. %, preferably 0.01 to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the total weight of A to E.

Pigments and dyes are generally present in amounts of up to 6, preferably 0.05 to 5 and in particular 0.1 to 3 wt .-%, based on the sum of all components.

The pigments for coloring thermoplastics are generally known, see, for example, R. Gächter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pages 494 to 510. As the first preferred group of pigments are white pigments, such as zinc oxide , Zinc sulfide, lead white [2 PbCOs-Pb (OH) ₂ ], lithlone, antimony white and titanium dioxide. Of the two most common crystal modifications (rutile and anatase-type) of titanium dioxide, in particular the rutile form is used for the whitening of the molding compositions according to the invention. Black color pigments which can be used in the present invention are iron oxide black (Fe ₃ O ₄ ), spinel black [Cu (Cr, Fe) ₂ O ₄ ], manganese black (mixture of manganese dioxide, silica and iron oxide), cobalt black and antimony black, and particularly preferable Carbon black, which is usually used in the form of furnace or gas black [see G. Benzing, pigments for paints, Expert-Verlag (1988), pages 78 ff.].

To adjust certain shades, inorganic colored pigments, such as chromium oxide green or organic colored pigments, such as azo pigments or phthalocyanines, can be used according to the invention. Such pigments are generally commercially available.

Oxidation inhibitors and heat stabilizers which can be added to the thermoplastic compositions according to the invention are, for example, halides of Group I metals of the periodic table, for example sodium, potassium, lithium halides, for example chlorides, bromides or iodides. Furthermore, zinc fluoride and zinc chloride can be used.

Further, sterically hindered phenols, hydroquinones, substituted members of this group, secondary aromatic amines, optionally in combination with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations up to 1 wt .-%, by weight of the entire composition.

Examples of UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benophenones, which are generally used in amounts of up to 2 wt .-%. Lubricants and mold release agents, which are generally added in amounts of up to 1% by weight of the thermoplastic composition, are stearyl alcohol, stearic acid alkyl esters and amides, and also esters of pentaerythritol with long-chain fatty acids. It is also possible to use dialkyl ketones, for example distearyl ketone.

Other additives include so-called nucleating agents, such as talc, into consideration.

A further embodiment of the invention relates to a process, characterized in that the reaction mixture containing the monomer units in the polycondensation reaction by irradiation of microwaves with frequencies in the range of 0.1 to 100 GHz to a temperature of 120 ⁰ C to 280 ⁰ C, preferably to a temperature of 120 ⁰ C to 250 ⁰ C, is brought.

One embodiment of the invention relates to a process in which a solvent and optionally a component collecting the resulting water are used in the polycondensation.

A further embodiment of the invention relates to a process, wherein in the polycondensation at least two different monomer units are used, wherein at least one dihalo-diarylsulphone and at least one dihydroxy-diarylsulphone and / or bisphenol A are used.

The subject matter also provides polyaryl ethers, which can be prepared by a process as described above. A further embodiment of the invention relates to a thermoplastic molding composition comprising, based on the total weight of the molding composition, the following components:

a) 5 to 99.8 wt .-% of at least one polyaryl ether, which was prepared starting from the monomer units using microwave irradiation

b) 0% to about 60% by weight of fibrous or particulate fillers or reinforcing materials, and

c) 0.2 to about 30 wt .-% of other additives.

A further embodiment of the invention relates to a thermoplastic molding composition comprising, based on the total weight of the molding composition, the following components: a) 20 to 96 wt .-% of at least one polyaryl ether, prepared according to a method according to any one of claims 1 to 9,

b) 1 to about 50% by weight of fibrous or particulate fillers or reinforcing agents and

c) 3 to about 30 wt .-% of other additives.

The invention further relates to the use of thermoplastic molding compositions described above for the production of fibers, films and moldings. It also relates to the fibers, films, molded articles produced using a molding composition as described above.

Another embodiment of the invention relates to a shaped body, in particular selected from household articles, electronic components, laboratory equipment, medical devices or parts thereof.

The molding compositions according to the invention can be prepared by processes known per se, for example by means of extrusion. The molding compositions can be prepared, for example, by mixing the starting components A, and optionally D and E in conventional mixing devices, such as screw extruders, preferably twin-screw extruders, Brabender mills or Banbury mills and kneaders and then extruded. Usually, the extrudate is cooled and comminuted after extrusion.

The molding compositions according to the invention can preferably also be prepared by precipitating the components from a solution containing the components A in a solvent (L) (such as N-methylpyrollidone) and then extracting them if necessary, and then adding the components if appropriate D and E mixed in conventional mixing devices and then extruded.

The order of mixing of the components can be varied, so two or possibly three components can be premixed, but it can also be mixed all components together.

Components A can also be premixed in the solution. The addition of components D and E optionally takes place via the state of the melt. In order to obtain the most homogeneous molding compound, intensive mixing is advantageous. For this purpose, average mixing times of 0.2 to 30 minutes, in particular 1 to 20 minutes at temperatures of 280 ° to 420 °, preferably 290 ° to 380 ⁰ C, are generally required.

The molding compositions according to the invention are characterized by good mechanical properties, good flowability, improved toughness, especially elongation at break and notched impact strength and by an improved intrinsic color. The molding compositions according to the invention are therefore suitable for the production of moldings for household articles, electrical or electronic components and moldings for the vehicle sector.

The invention is illustrated by the following examples.

Examples

The properties of the molding compounds

The viscosity number of the polyarylethersulfones is determined in 1% solution of N-methylpyrrolidone at 25 ⁰ C.

The heat resistance of the samples is determined according to ISO 306 (Vicat B) (load 50 N, temperature increase of 50 K per hour, on ISO rods).

The notched impact strength of the products is determined in accordance with ISO 179 1 eB.

The elongation at break of the materials is determined according to ISO 527. The flowability of the products is determined by measurement in a capillary rheometer at 370 ⁰ C.

The melt stability of the products is determined by measuring the melt viscosity in a plate-plate rheometer at 400 ^° C. The change in the viscosity determined at 55 Hz over a period of 5 or 60 minutes is considered.

η ₆₀ ,: viscosity after 60 min η ₅ , viscosity after 5 min Measurement Methods:

To evaluate the optical properties of the products are injection molded test specimens (circular disks, diameter 60 mm, thickness 2 mm) at a melt temperature of 310 ⁰ C ((for polysulphones PSU)) and 350 ⁰ C (for polyethersulfone (PES)) and a tool temperature of 140 ⁰ C produced. The measurement of the transmission and haze was carried out according to the standard ASTM D 1003.

The surface quality is determined visually on plates and classified according to the school grading system between 1 (very good) and 6 (insufficient).

The intrinsic color of the products was determined on the basis of the yellowness index (YI) according to the standard DIN 6167.

Example 1 (comparative experiments on thermal polycondensation)

The dried monomers, (for experiment 1.1) dichlorodiphenylsulfone (DCDPS) and bisphenol A, or (for experiment 1.2) DCDPS and dihydroxydiphenylsulfone (DHDPS) were placed in a 4 l reactor with internal thermometer, gas inlet tube, reflux condenser with water separator. so combined that a 1, 5 mol% iger

Excess of DCDPS and a 5 mol% excess of dried potassium carbonate under nitrogen atmosphere, with stirring in N-methylpyrrolidone (NMP) (monomer concentration 1, 9 mol / l) and heated to 190 ⁰ C.

The reaction time, the residence time at 190 ⁰ C is considered. The water of reaction is distilled off and the level is kept constant by adding NMP during the reaction.

The reaction is stopped by dilution with cold NMP, then methyl chloride (10 l / h) is introduced into the batch at 140 ^° C. for 45 minutes (45 minutes). Thereafter, nitrogen is introduced (20 l / h) and cooled the approach. The resulting potassium chloride is filtered off and the polymer solution is precipitated in water. The product is then extracted with 80 ⁰ C hot water for 24 h, then dried at 120 ⁰ C in a vacuum. The resulting powder is then granulated on a twin-screw extruder. The polymer viscosity is evaluated by the viscosity number (VZ / ml / g).

Example 2 Preparation of the Polyaryl Ether of the Invention in the Microwave Reactor

A 50 ml flask equipped with a KPG stirrer and water removal was charged in Example 2.2 of anhydrous potash with 20 ml of NMP, 11, 483 g DCDPS, 9.857 g DHDPS and 5,804 g (potassium carbonate) and in a single mode microwave oven with Powemax ^® - Technology introduced. By irradiation of microwaves (70 W), the reaction mixture was brought to 190 ⁰ C. After 3 hours, the reaction was stopped. The polymers obtained were isolated by precipitation in water, extraction of the resulting powder with hot water and subsequent drying. Several attempts were made.

Corresponding experiments were carried out as Example 2.1 for the preparation of polysulfone. The starting materials used were: 20 ml of NMP, 1 l, 483 g of DCDPS, 8.991 g of bisphenol A and 5.804 g of anhydrous potash.

The results of the tests for the thermal treatment or microwave irradiation polymers are shown in Tables 1 and 2.

Table 1: Test results for polysulfone

Table 2: Test results for polyethersulfone

From these results it can be seen that the syntheses carried out under the influence of microwaves lead with shorter reaction time to products with higher molecular weights. Furthermore, the polymers of the invention show better melt stability.

Claims

claims

1. A process for the preparation of polyaryl ethers, characterized in that starting from the monomer building a polycondensation is carried out using microwave irradiation.

2. The method according to claim 1, characterized in that polyaryl ethers are prepared, which are composed of recurring units of the general formula (I):

wherein

x is 0.5 or 1, t and q independently of one another are 0, 1, 2 or 3,

Q, T and Z are each independently a chemical bond or a group selected from -O-, -S-, -SO ₂ -, S = O, C = O, - N = N-, -R ^a C = CR ^b - and -CR ^c R ^d -, where

R ^c and R ^d are each independently a hydrogen atom or a _d-Ci2 alkyl, _Ci-Ci2 alkoxy or C ₆ -C ₈ - are aryl group wherein R ^c and R ^d optionally substituted independently with fluorine and / or chlorine atoms are substituted or optionally together with the C atom to which they are attached, a _{_C3-Ci2} - form cycloalkyl group is optionally substituted with one or more C Cβ alkyl groups,

Ar, Ar ¹ is C ₆ -C ₈ are independently arylene groups, said optionally substituted with CrCl ₂ -AIkIy-, C ₆ -C ₈ -aryl, CrCl ₂ - alkoxy groups or halogen atoms are substituted,

A / auc

3. The method according to any one of the claims 1 or 2, characterized in that polyaryl ethers are prepared, which are composed of recurring units of the general formula (I):

wherein

x is 0.5 or 1, t and q independently of one another are 0, 1, 2 or 3,

Q, T and Z independently of one another each represent a chemical bond or a group selected from -O-, -SO ₂ -, C = O,

A process according to any one of claims 1 to 3, characterized in that polyaryl ethers are prepared which are made up of recurring units of the general formula (I) in which Q, T and Z are each independently of one another a chemical bond or a group -O-, - SO ₂ - or C = O and Ar and Ar ^{1 are} each 1, 4-phenylene groups.

Process according to one of claims 1 to 4, characterized in that polyaryl ethers are prepared which consist of repeating units having at least one of the following structures I ₁ to I ₂ g:

6. The method according to any one of claims 1 to 5, characterized in that polyaryl ethers are prepared, which consist of recurring units having at least one of the following structures I ₁ , 1 ₂ and Is:

7. The method according to any one of the claims 1 to 6, characterized in that the monomer mixture containing the reaction mixture at the PoIy condensation reaction is brought by irradiation of microwaves with frequencies in the range of 0.1 to 100 GHz to a temperature of 120 ⁰ C to 250 °.

8. The method according to any one of claims 1 to 7, characterized in that in the polycondensation, a solvent and optionally a water-absorbing component are used.

9. The method according to any one of claims 1 to 8, characterized in that in the polycondensation at least two different monomer units are used, wherein at least one dihalo-diarylsulphone and at least one dihydroxy-diarylsulfone and / or bisphenol A are used.

10. Polyarylether, preparable by a method according to any one of patent claims 1 to 9.

1 1. Thermoplastic molding composition containing, based on the total weight of the molding composition, the following components:

b) 0 to about 60% by weight of fibrous or particulate fillers or reinforcing agents, and

c) 0.2 to about 30 wt .-% of other additives.

12. Thermoplastic molding composition according to claim 11, comprising, based on the total weight of the molding composition, the following components:

a) 20 to 96 wt .-% of at least one polyaryl ether, prepared according to a method according to any one of claims 1 to 9,

b) 1 to about 50 wt .-% of fibrous or particulate fillers or reinforcing agents and

c) 3 to about 30 wt .-% of other additives.

13. Use of thermoplastic molding compositions according to any one of claims 11 or 12 for the production of fibers, films and moldings.

14. Fibers, films, moldings, produced using a molding composition according to any one of claims 1 1 or 12th

15. Shaped body according to claim 14, selected from household articles, electronic components, laboratory equipment, medical devices or parts thereof.