DE2810794A1 - PROCESS FOR THE MANUFACTURING OF AROMATIC POLYAETHERS - Google Patents

Description

-Ι * η I / / "» Patent attorneys:

IIEDTKE - DÜHLING "IVlNNE " VaRUPE Dipl.-lng. H. Tiedtke

Dipl.-Chem. G. Bühling 9θ1Π70 / ^Di P '- "ng · R-Kinne L OIU / y 4 Dipl.-Ing.P. Grupe

Bavariaring 4, P.O. Box 20 24 8000 Munich 2

Tel .: (0 89) 53 96 53

Telex: 5-24845 tipat

cable: Germaniapatent Munich

March 13, 197 8

B 8781 / ICI case P.29409

Imperial Chemical Industries Limited

London / Great Britain

· Process for the production of aromatic

Polyethers

The invention relates to a process for the manufacture of aromatic polyethers and, more particularly, to their manufacture of certain aromatic polyethers containing sulfone or ketone bonds.

In Canadian patent 847 963 the preparation of polyethers containing sulfone or ketone bonds is described, using a bisphenol and a dihalogen compound with a benzoid structure or a halophenol in which the halogen atoms of the dihalogen compound with a benzoid structure or the halophenol are replaced by -SO ₂ -

or -CO groups in ortho or para position to this acti-. fourth are reacted with an alkali metal carbonate.

In this method, the alkali metal carbonate to be used becomes used in such an amount that little-

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at least two atoms of the alkali metal per phenol group are present or, if the reaction conditions, for example the temperature, are such that the alkali metal carbonate, by reacting the alkali metal carbonate with the phenol group is formed is decomposed, the alkali metal carbonate to be used is in such an amount that there is at least one alkali metal atom per phenol group. In general, a slight excess (up to 20 mol%) alkali metal carbonate is used.

It has now been found that in certain cases the amount of alkali metal carbonate required can be reduced, by the halogen-containing reactants wholly or partially in the form of fluorophenols or difluorocompounds with a benzoid structure can be used.

In British Patent 1,348,630, the preparation of aromatic polyethers is by reacting one Halophenol or a mixture of a dihaloene compound with a benzoid structure and a phenol, with an alkali metal fluoride described. It is shown that the alkali metal fluoride is formed in situ by self-condensation of an alkali metal salt of a fluorophenol or by condensation of an alkali metal salt of a bisphenol with an essentially equimolar amount of a Difluorverbindunq with benzoid structure can be formed.

It is believed that the inventive method takes place via a similar reaction diagram, which can be represented as follows. The polymerization of 4-fluoro-4-hydroxybenzophenone with potassium carbonate as an example taken:

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1 i)

ii)

■ OH + K ₂ CO,

OK

CO-

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• OK + KHCQ _n

+ Theatrical Version

Ui] ivi 2KHCO

2KF

'3 ^ ^K 2 ^C0 3 ^{+ C0} 2 ^{+ H} 2 ° This gives in total:

J ^ y-co - ^^ - oh + K ₂ Co ₃

♦ H ₂ O ♦ CO ₂

KHF.

It has been found that in certain cases this process drives faster reactions, a higher molecular weight
and may give less colored polymers than a polymerization process comprising only reactions iii) and ii), ie using potassium fluoride instead of

Potassium carbonate: 25

iii)

OH ⁺ 2KF

30 ü) F-C ^ VCO-C NM) K d. H. all in all:

vi)

+ Theatrical Version

■ OK + KHF,

* Theatrical Version

+ KHF ₂

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<£ OIU / <3 1 $ It is to be noted that the alkali metal carbonate can be replaced by a suitable amount of alkali metal bicarbonate, where the reaction conditions are such that the alkali metal to form alkali metal carbonate, carbon dioxide and water to decompose. In the example described above, the overall reaction v) would thus proceed as follows:

r \ ~ Z ₇ -V "I

(/ \> - CO- ^ jy-a | + KHF ^ +

₂ + CO ₂ +

It should also be noted that the fluorine-containing reactant, i.e. the fluorophenol or the difluoro compound having a benzoid structure can be used in conjunction with reactants containing other halogen atoms in place contained by fluorine. In such cases, of course, the required amount of alkali metal carbonate (or bicarbonate) greater than if only fluorine-containing reactants are used. '

According to the invention a method for producing a aromatic polyether created in which i) an essentially equimolar mixture of a) at least one Bisphenol of the formula

in which Y is a direct bond, oxygen, sulfur, -SO--, -CO- or a divalent hydrocarbon radical and b) at least one dihalogen compound with a benzoid structure, and / or ii) at least one halophenol, the halogen atoms of the dihalogen compound with benzoid Structure or of the halophenol are activated by -SO ₂ - or -CO groups in the ortho or para position thereto, the halogen of

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2810704 at least part of the halophenol and / or the dihalo compound with a benzoid structure is fluorine, with iii) an alkali metal carbonate or bicarbonate with heating polycondensed to a temperature in the range from 100 to 400 ° C, the amount of the alkali metal carbonate or bicarbonate is such that at least (1 - x / 2) and less than one alkali metal atom is present per phenol group and χ is the fraction of the activated halogen atoms which are fluorine

Particularly preferred bisphenols are:

4,4'-dihydroxybenzophenone
4,4'-dihydroxydiphenyl sulfone
2,2'-bis (4-hydroxyphenyl) propane 4,4'-dihydroxybiphenyl.

The dihalogen compounds with a benzoid structure preferably have the formula:
20th

in which X and X ¹ , which can be the same or different, are halogen atoms and are in the ortho or para position to the groups Q and Q ¹ , Q and Q ¹ , which can be the same or different -CO- or -SO ₃ -, Ar is a divalent aromatic radical and η is 0, 1, 2 or 3.

The aromatic radical Ar is preferably a divalent aromatic radical from the group phenylene, biphenylylene or Terphenylylene and diphenyl ether.

Particularly preferred dihalides are 4,4'-bis (4-halopheny! Sulfonyl) diphenyl ethers, 4,4'-bis (4-halogen-

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281

benzoyl) diphenyl ethers and dihalides with the formula

wherein m is 1, 2 or 3.

Examples of suitable dihalides include?

4,4'-difluorodiphenyl sulfone 4,4'-dichlorodiphenylsulfone 4,4'-difluorobenzophenone 4,4 * -Dichlorobenzophenone 4-chloro-4'-fluorodiphenyl sulfone 4-chloro-4'-fluorobenzophenone 4,4'-bis (4-fluorophenylsulfonyl) biphenyl 4,4 * -bis- (4-chloropheny! Sulfonyl) biphenyl 1,4-bis (4-chlorobenzoyl) benzene 1,4-bis (4-fluorobenzoyl) benzene 4,4'-bis (4-fluorophenylsulfonyl) diphenyl ether 4,4 * -bis- (4-chlorophenylsulfonyl) diphenyl ether Bis (4 '- (4-chlorophenylsulfonyl) biphenyl) sulfone

Mixtures of dihalides can be used so that copolymers are made. For examples of usable Mixtures include 4,4'-difluorodiphenyl sulfone 4,4'-difluorobenzophenone or 4,4'-bis (4-chlorophenylsulfonyl) biphenyl.

Preferred halophenols are those of the formula

Q-Ar-OH

wherein X is halogen that is in the ortho or para position to Q is present, Q is -SO, - or -CO- and Ar is an aromatic radical which is preferably in the para position to the group Q,

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The aromatic radical Ar is preferably a divalent aromatic radical from the group consisting of phenylene, biphenylene and Remnants of the formula:

wherein Q ^{1 is} —CO— or —SO ₂ - and η and m, which can be identical or different, are integers from the group 1, 2 and 3. Particularly preferred halophenols have the formula

where ρ is 0 or 1.
Examples of suitable halophenols are:

A- (4-chlorophenylsulfonyl) phenol
4- (4-fluorophenylsulfonyl) phenol
4- (4-fluorobenzoyl) phenol
4- (4-chlorobenzoyl) phenol

4-hydroxy-4 • - (4-chlorophenylsulfonyl) biphenyl 4-hydroxy-4 '- (4-fluorophenylsulfonyl) biphenyl 4- (4-hydroxyphenylsulfonyl) -4 '- (4-chlorophenylsulfonyl)

biphenyl. 25th

Mixtures of halophenols can be used so that copolymers are formed. For examples of usable Mixtures include 4- (4-FluoroDhenylsulfonyl) phenol with 4- (4-fluorobenzoyl) phenol, 4-hydroxy-4 '- (4-chlorophenylsulfonyl) biphenyl or 4- (4-hydroxyphenylsulfonyl) -4 - (4-chlorophenylsulfonyl) biphenyl.

Likewise, mixtures of one or more halophenols with one or more halophenols may be used equimolar mixture of a dihalide and a

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Bisphenols (having a formula as given above) can be used. As an example there may be mentioned 4- (4-fluorobenzoyl) phenol in admixture with 4,4'-dichloro- (or difluoro-) diphenylsulfone and 4,4'-dihydroxydiphenylsulfone.

It should be noted that at least one of the halogen-containing reactants is a fluorine-containing reactant. Preferably at least 10%, especially at least 50% of the activated halogen atoms in the halogen-containing reactants are fluorine atoms.

The amount of alkali metal carbonate or bicarbonate used is such that less than 1, but at least (1 - x / 2) alkali metal atom per phenol group is present, where χ is the fraction of the activated halogen atoms which Are fluorine. Thus, where all activated halogen atoms are fluorine atoms (x = 1), the alkali metal carbonate or bicarbonate lies in such an amount that at least 1/2 alkali metal atom is present per phenol group. Preferably that is Alkali metal carbonate or bicarbonate in such an amount that between (1 - x / 2) and 1.2 (1 - x / 2) alkali metal atoms per phenol group are present, since larger amounts can lead to cleavage of the polymer, especially at high reaction temperatures (above 300 ° C), with polymers with relatively low molecular weight arise.

Where a bisphenol (with one as listed above Formula) and a dihalogen compound with a benzoid structure are used, they should be in substantially equimolar amounts Quantities are used. A mutual excess leads to the formation of low molecular weight products. However, a slight excess, up to 5 mol.% dihalide, if desired can be applied.

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H 0794 The alkali metal carbonate or bicarbonate is preferred Sodium carbonate, sodium bicarbonate, potassium carbonate, Potassium bicarbonate, rubidium carbonate, or cesium carbonate. Mixtures of these can be used. It is particularly beneficial to use a larger amount of a carbonate or bicarbonate an alkali metal with a low atomic number in admixture with a smaller amount of a carbonate or Use bicarbonate of an alkali metal with a higher atomic number, as this increases the rate of polymerization is enlarged. Particularly effective combinations include sodium carbonate or bicarbonate in admixture with potassium or Cesium carbonates and potassium carbonate in admixture with Cesium carbonate. Potassium carbonate alone or in admixture with cesium carbonate is most preferred.

The reaction can be carried out in the presence or in the absence of a solvent.

The preferred solvent is an aliphatic or aromatic sulfoxide or sulfone of the formula

RS (O) _x -R ¹

used, wherein χ is 1 or 2 and R and R ^{1 are} alkyl or aryl groups, which can be the same or different. R and R ¹ together can form a divalent radical. Preferred solvents are dimethyl sulfoxide, dimethyl sulfone, suIfolane (1,1 dioxothiolane) or aromatic sulfones of the formula

where T is a direct bond, one oxygen atom, or two hydrogen atoms (one hydrogen atom is each with one Benzene ring connected) and Z and Z ', which are the same or different can be, are hydrogen atoms or phenyl groups. to

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Examples of such aromatic sulfones include Diphenylsulfone, Dibenzothiophendioxid, Phenoxathiindioxid and 4-phenylsulphonylbiphenyl. Diphenyl sulfone is the preferred solvent. Other solvents that can be used are N, N-dimethylformamide and N-methyl-2-pyrrolidone »

The polymerization temperature used is in the range from 100 to 400 ° C. and depends on the nature of the reactants and - if present - the solvent used. When using very reactive condensation participants, for example 4,4'-difluorodiphenyl sulfone in admixture with 4,4'-dihydroxydiphenyl sulfide, temperatures of the order of 100 to 140 ° C. can be used. For reactant combinations, for example 4,4'-dichlorodiphenyl sulfone and 2,2-bis (4-hydroxyphenyl) propane ^ temperatures are suitably in the order of 140 to 180 ° C. In systems such as 4,4 * -dihalodiphenylsulfone / 4,4 "-dihydroxydiphenylsulfone and the ketone analogs, however, temperatures above 250 ° C., preferably above 270 ° C., are generally desirable.

For the production of some polymers it may be desirable to to start the polymerization at a temperature, for example between 200 and 25O ° C and to increase the temperature, as soon as the polymerization takes place. This is particularly necessary in the production of polymers that only have one have low solubility in the solvent. A progressive increase in temperature is therefore desirable in order to avoid the Keeping polymers in solution as soon as its molecular weight increases.

Where a solvent is not used, the temperature should be sufficient to remove the halophenol or combination Bisphenol and the dihalo compound having a benzoid structure and the polymer produced therefrom in the molten state keep.

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In order to keep cleavage reactions as small as possible, it is preferred that the maximum polymerization temperature be below 350.degree. In particular, the temperature is as low as possible, provided, however, that a suitable polymerization time results.

Where a bicarbonate is used and is placed in the reaction vessel as such, the heating should be applied to the The polymerization temperature must be carried out carefully so that the adverse effects of carbon dioxide evolution, that occur during the decomposition of the bicarbonate should be kept as small as possible.

The polymerization reaction can be ended by adding a suitable stop reagent or stop agent, for example a mono- or polyfunctional halide such as methyl chloride, tert-butyl chloride or 4,4'-dichlorodiphenyl sulfone mixed with the reaction mixture at the polymerization temperature, although the final stop of the reaction can lead to some reduction in polymer molecular weight.

In the reaction, alkali metal salts are formed as by-products. These can be used together with the if necessary used polymerization solvent can be removed from the reaction product by known methods such as Filtration and leaching.

The polymers produced by the process according to the invention are particularly suitable for applications where the Polymers are easily exposed to high working temperatures.

Examples of such areas of application are moldings for electrical power supply and covers for cooking utensils.

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The invention is illustrated in more detail by the following examples.

Example 1 (comparison)

A 250 ml three-necked flask equipped with a stirrer, nitrogen inlet, and distillation head was attached with 4- (4-fluorobenzoyl) phenol (20.5402 g, 0.095 mol), 4,4'-dihydroxydiphenyl sulfone (0.6257 g, 0.0025 mol), 4,4'-dichlorodiphenyl sulfone (0.8615 g, 0.003 mol), diphenyl sulfone (42 g) and potassium carbonate (7.05 g, 98% by weight K-CO-, as by titration was determined against normal hydrochloric acid, 0.050 mol) charged. (94% of the activated halogen atoms are fluorine atoms, i.e. x = 0.94. The number of potassium atoms per phenol group is 1; the excess of activated halogen atoms over the Phenolic groups is 1 mol%.)

The flask was then placed on a metal bath at 200 C and thereafter the temperature was raised over a period of time

of one hour, increased to 330 ° C. The temperature at 330 ° C was held for 30 minutes. The flask was then removed from the metal bath and cooled to room temperature. That solid reaction product was reduced to a grain size of less ground than 1 mm and then washed under reflux with the following solvents:

Acetone (500 ml, 10 min) - twice water (500 ml, 10 min) 1% by weight aqueous acetic acid
(500 ml, 10 min) water (500 ml, 30 min)

a mixture of 250 ml acetone and 250 ml methanol (10 min)

The resulting solid was placed in an oven

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140 C for 16 hours under a vacuum of 100 mm of mercury dried. The resulting polymer, which is the repeating units

and

in the ratio of 95: 5, had a reduced viscosity (RV) of 1.34 and an absorbance of 0.05 (the reduced Viscosity was at 25 ° C, the extinction at a wave length measured from 550 nm in a 10 mm cell; both measurements were made on a solution of the polymer in concentrated sulfuric acid performed at a density of 1.84 g / cm, wherein the solution contained 1 g of polymer per 100 cm of solution).

Example 2

Example 1 was repeated, but using a smaller amount of the 98% potassium carbonate (6.98 σ, 0.0495 mol) was used. (The number of potassium atoms per phenol group is thus 0.99.) The polycondensation was as in the example 1 carried out, except that the mixture at 330 ° C for 2 h was held for a long time, with small samples being taken after 50 and 80 minutes. The results are shown in Table I.

Example 3

Example 2 was made using a smaller one Repeat the amount of 98% potassium carbonate (6.77 g, 0.048 mol). (The number of potassium atoms per phenol group is thus o, 96.) Samples were taken after 60 and 90 minutes. The results are shown in Table T.

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Example 1 was repeated, but using only 6.55 g, corresponding to 0.0466 mol, of the 98% strength potassium carbonate were, so that the proportion of potassium atoms per phenol group Was 0.932. The mixture was kept at 330 ° C for 3 hours, whereupon a sample was taken. 4,4'-dichlorodiphenyl sulfone (0.5 g) was added to the remainder of the reaction mixture and heating was continued for 10 minutes at 330 ° C to reduce the temperature Complete polymerization before cooling to room temperature. The results are shown in Table I.

Example 5 (comparison)

Comparative Example 1 was repeated, except that only 38 g of diphenyl sulfone were used and potassium fluoride (6.74 g, 0.116 mol) was used instead of potassium carbonate. The reaction mixture was heated at 230 ° C for one hour and then at 275 ° C for one hour. In contrast to the mixtures of Examples 1-4, which formed a thick yellow paste at these temperatures, this mixture remained as a mobile slurry. The temperature was then raised to 33O ⁰ C and maintained for five hours to give a viscous, brown solution was obtained. (In Examples 1-4, the solution was yellow or off-white at the end of the heating.) The results are shown in Table I.

Table I.

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Example K / OH ratio time at

33O ° C (min)

RV

Absorbance

1 (comparison) 1

30th

1.34

0.05

0.99

0.96

0.932

50 1.45 0.05 80 1, 87 0.07 120 2.46 0.11 60 0.90 0.04 90 1.41 0.04 120 1, 67 0.06 180 1.19 0.10 19O ⁺ 1, 08 0.10

(Comparison) 1.16 300

after stopping

KF was 3et instead of K ₂ ^CO 3 ^{USAGE <}

1.5

0.15

It turns out that the use of smaller amounts Potassium carbonate as necessary to achieve one potassium atom per phenol group is the polar condensation reaction slows down, however, the production of high molecular weight polymers (high RV value) is possible with a low absorbance.

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Example 6 (comparison)

Example 1 was repeated using the following reactants: 1-4 (4-fluorobenzoyl) benzene (16.2770 g, 0.505 mol), 4,4'-dihydroxybenzophenone (7.1336 g, 0.0333 mol), 4,4'-dihydroxydiphenyl sulfone (4.1796 g, 0.0167 mol), 98% potassium carbonate (7.05 g, 0.050 mol), diphenyl sulfone (38.3 g). (The proportion of activated halogen atoms which Are fluorine atoms is thus 1; the K / OH ratio is 1; the Fluoride excess compared to the bisphenols is 1 mol%.)

The polycondensation was carried out by keeping the mixture at 230 ° C for 30 minutes, at 280 ° C for 30 minutes and thereafter heated at 320 ° C for 1 hour. A sample was then taken and 4,4'-dichlorodiphenyl sulfone (0.5 g) was then added to added to the rest of the reaction mixture to stop the reaction by heating for a further 5 min at 320 C, be \ the mixture was cooled to room temperature.

The polymer had the repeating units

and
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in a ratio of 2: 1.

The results are shown in Table II. 30th

Example 7

Example 6 was made using a much smaller amount of the 98% potassium carbonate (3.63 g, 0.026 mol) repeated. The ratio of potassium to the phenol group is therefore 0.52.

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The polycondensation was carried out as in Example 6, except that the heating time at 320 ° C. was 2 1/2 hours took (with a sample taken after 1 1/2 hours) before the reaction was stopped. The stopping was carried out, by adding the mixture after adding the 4,4'-dichlorodiphenyl sulfone Heated at 320 ° C for 10 minutes.

The results are shown in Table II.

Table II

Example K / OH ratio time with RV absorbance

0.52

after stopping

(min) 1.81 0, 48 / ⁶⁰ 1.68 0, 48 \ 65 ⁺ 1.17 - Γ 90 2.08 - 150 1.79 0, 31 _L 16O ⁺

These examples show that using smaller amounts of potassium carbonate than those using a K / OH ratio of 1, slows the reaction but enables the creation of high molecular weight polymer with low absorbance. Examples 4, 6 and 7 show that the quenching with 4,4'-dichlorodiphenyl sulfone results in a decrease in reduced viscosity and therefore molecular weight.

Example 8 (comparison)

Example 1 was repeated, but using as a reactant 4- (4-chlorobenzoyl) phenol (20.9403 g, 0.090 mol),

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4- (4-chlorophenylsulfonyl) phenol (2,685Oq, 0.01OmOl) ₁ , 98% potassium carbonate (6.57 g, 0.0466 mol) and diphenyl sulfone (40 g) were used. (The ratio of activated fluorine atoms to chlorine atoms is 0. The K / OH ratio is 0.932.)

The polycondensation was carried out by the The mixture is heated to 320 ° C. within one hour and then maintained at 320 ° C. for 2 hours. The RV value of the resulting polymers, which are the repeating units

and

in the ratio of 90:10 was only 0.45, while the absorbance was 0.13 . This example shows that, in the absence of activated fluorine-containing condensates, only relatively low molecular weight polymers can be obtained if such an amount of potassium carbonate is used that the K / OH ratio is less than 1.
20th

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Claims (10)

Claims _s 1. A process for the preparation of an aromatic polyether, characterized in that i) an essentially equimolar mixture of a) at least one bisphenol of the formula in which Y is a direct bond, oxygen, sulfur, -SO ₂ -, -CO- or a divalent hydrocarbon radical and b) at least one dihalogen compound with a benzoid structure and / or ii) at least one halophenol, the halogen atoms of the dihalogen compound with a benzoid structure or of the halophenol are activated by -SO ₂ - or -CO groups in ortho or para position thereto and the halogen of at least part of the halophenol and / or the dihalo compound with a benzoid structure is fluorine, with iii) an alkali metal carbonate or - bicarbonate is polycondensed by heating to a temperature in the range from 100 to 400 ⁰ C, the alkali metal carbonate or bicarbonate being present in such an amount that at least (1 - x / 2) and less than one alkali metal atom per phenol group is present and χ the fraction of activated halogen atoms, which are fluorine. 2. The method according to claim 1, characterized in that χ is at least 0.1. VIII / 17 «03838 / öd 1i5 Dresdner Bank (Munich) Account 3939844 Postal check (Munich) account 670 43-004 - 2 - B 8781 3. The method according to claim 2, characterized in that χ is at least 0.5. 4. The method according to any one of the preceding claims, characterized in that such an amount of alkali metal carbonate or bicarbonate is used that between (1 - k / 2) and 1.2 (1 - κ / 2) alkali metal atoms per phenol group are present. 5. The method according to any one of the preceding claims, characterized in that at least one dihalo compound having a benzoid structure is used which is derived from Dihalogen compounds having a benzoid structure with the formula is selected in which X and X ¹ , which can be the same or different, are halogen atoms and are in the ortho or para position to the groups Q and Q ¹ ; Q and Q ¹ , which can be the same or different, are -CO- or -SO ₂ -; Ar is a divalent aromatic radical and η is 0, 1, 2 or 3. 6. The method according to claim 5, characterized in that as at least one dihalogen compound with benzoider Structure a "compound from the group of 4,4'-bis (4-halophenylsulfonyl) diphenyl ether, 4,4'-bis (4-halobenzoyl) diphenyl ether and dihalides of the formula wherein m is 1, 2 or 3 is used. «09836/0815 - 3 - B 8781 7. The method according to any one of the preceding claims, characterized in that at least one halophenol compound which is used by halophenols with the formula is selected where X is halogen which is ortho or para to Q, Q is -SO ₂ - or -CO- and Ar is an aromatic radical. 8. The method according to claim 7, characterized in that Ar is a divalent aromatic radical from the group Phenylene, biphenylene and radicals of the formula is where Q'-CO- or SO ₂ - and η and m which are the same or can be different, are 1, 2 or 3. 20th 9. The method according to claim 8, characterized in that the halophenol is halophenols having the formula •OH ~~ L "'" ^J P where ρ is 0 or 1 can be used. 10. Aromatic polyether produced by a process of the preceding claims. 30th