JPH0476022A - New aromatic polyether and its production - Google Patents

Abstract

PURPOSE:To obtain a new aromatic polyether which is free from the problem of a decrease in the degree of polymerization during molding and phase separation, and excellent in heat resistance and chemical resistance by selecting a specified aromatic polyether. CONSTITUTION:The title polyether is one prepared by substituting at least part of the Ar groups of an aromatic polyether comprising formulas I, II and/or III [wherein Ar and Ar' are each a bivalent aromatic group; X is C(O) or SO2; Z is an electron-withdrawing group; and (n) is 0-2] by groups of formula IV (wherein X1 is a hydrocarbon group having 2-3 ring aliphatic carbon atoms which form the iminoether ring; and Ar'' is a trivalent aromatic group) and substituting part of the Z groups of the polyether by groups of formula V, e.g. a resin obtained by reacting 4,4-dichlorodiphenyl sulfone with bisphenol A and 2-(3,5-dihydroxyphenyl)-2-oxazoline.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel polyether. More specifically, the present invention relates to a novel polyether that is free from the problems of reduced degree of polymerization and phase separation during molding.

<Prior Art> In recent years, with the advancement of technology, there has been a demand for resins that have excellent heat resistance, excellent mechanical properties, and excellent moldability. Among these resins, reaction-molding resins using reactive monomers or oligomers, that is, resins in which molding and polymerization are simultaneously performed using raw materials with relatively low viscosity, have attracted particular attention. Such resins include polyurethane resin and polyurea resin.

Nylon resins, epoxy resins, unsaturated polyester resins, etc. are known, and some have been commercialized.

However, each of these resins has its advantages and disadvantages.
For example, polyurethane resins have low heat resistance, and unsaturated polyester resins have drawbacks such as the fact that reaction, that is, molding, takes time, and they cannot necessarily be said to have sufficient performance and moldability.

To overcome these problems, a resin has been proposed in which a composition comprising a thermoplastic resin and an oxazoline derivative is heated and reacted in the presence of a catalyst (Japanese Patent Laid-Open No. 63-248852). However, when polycarbonate or polyester, for example, is used as a thermoplastic resin, the degree of polymerization of these polymers tends to decrease during molding, and it is difficult to say that the toughness of the thermoplastic polymer is fully utilized. Furthermore, when polystyrene or the like is used as the thermoplastic polymer, there is a problem that the polysulfone and the oxazoline derivative tend to undergo phase separation during the heating reaction, and the properties of the resulting resin are still insufficient.

<Purpose of the Invention> As a result of intensive studies aimed at solving these problems, the present inventors found that a polyether in which an oxazoline ring was introduced into the polymer side chain did not cause a decrease in the degree of polymerization during molding and did not cause phase separation. There were no problems, and by heating and reacting with a specific catalyst, we were able to make full use of the toughness of thermoplastic polymers and create thermosetting polymers with excellent heat resistance, chemical resistance, etc. Heading, Don't Get to the Invention.

<Structure of the invention> Zunawaji, the present invention provides the following formulas (I), (II) and 7.
or (1) in an aromatic polyether composed of
At least a part of Z is represented by the following formula (IV) Ar'-Ar...(I>) or at least a part of Z is represented by the above formula (V)c'. An aromatic polyneedle characterized in that it is substituted with

The present invention will be explained in detail below.

In the above formulas (I) and (n), Ar and Ar' may be aromatic groups or fS divalent groups bonded to a plurality of aromatic groups, and these may have a substituent. Ar.

Specifically, Ar' is -1 ko) to, -rQ low, 1-) ding■
Examples of these compounds include aliphatic substitutes such as methyl, ethyl, and propyl, alicyclic substitutes such as cyclohexyl, and aryl substitutes such as phenyl, naphthyl, and tolyl.

For Ar, (x)()- is particularly preferred among these, and for <, Ar', this is preferred. Further, in formula (II), X is C- or -5O2-, n is an integer from ○ to 2, and n=o is preferably n-1. In other words, a particularly preferred structure of (II) is (,) where Z is an electron-withdrawing group. Specifically, R as Z is CN, NO2, C=O, SO2 [where R is aliphatic, alicyclic, or aromatic. ] etc. Among them, C
N is preferred.

In the above formula (IV), Ar' may be an aromatic group or a trivalent group to which a plurality of aromatic groups are not bonded, and these may have a substituent.

Specifically, Ar'' includes () 1.1-1.2, and further includes aliphatic substituted products of these compounds such as methyl, ethyl, and propyl, alicyclic substituted products such as cyclohexyl, phenyl, naphthyl, and tolyl. It is also possible to exemplify aryl substituted products such as U.Among these, U is particularly preferred.

In formulas (IV) and (V), Xl is a divalent hydrocarbon group having two or three ring-membered aliphatic carbon atoms forming an iminoether ring. Such hydrocarbon groups include:
For example, ethylene, unsubstituted alkylene such as trimethylene, 1-methylethylene, 1,1-dimethylethylene,
1.2-dimethylethylene, 1-ethylethylene, 1,
2-diethylethylene, 1-propylethylene, 1.2
-dipropylethylene, 1-methyltrimethylene, 1.
Examples include alkylene substituted with a lower alkyl group having 1 to 6 carbon atoms, such as 2-dimethyltrimethylene. Among these, ethylene or trimethylene is preferred, and ethylene is particularly preferred.

The polyether may contain at least a part of the structural units of formulas (IV) and (V), but in reality, polymer 1
0.0 structural unit of formula (IV) or formula (V) per kg
It is preferable to contain 1 equivalent or more, more preferably 0.05 equivalent or more, and most preferably 0.1 equivalent or more. That is, the cyclic imino ether content represented by formula (V) is preferably 10 equivalents/106 g polymer or more,
More preferably it is 50 equivalents/106 g of polymer or more, most preferably 100 equivalents/106 g or more.

A method for quantifying the content of cyclic imino needle groups represented by the above formula <V) in a polymer is to dissolve the polyether in a solvent, add an excess amount of p-toluenesulfonic acid therein, and dissolve the cyclic imino needle group in the polymer. A salt of p-toluenesulfonic acid is prepared, and the amount of excess p-toluenesulfonic acid is determined by titration with an alkali such as sodium hydroxide.
-) Calculating the content of cyclic imino ether groups from the amount of decrease in luenesulfonic acid6 The polyether of the present invention has a reduced viscosity (concentration 1, 0 g/'
dl) is 0.25 or more, F, preferably 0.3 or more. When the reduced viscosity is less than 0.25, the mechanical properties of the polymer are unsatisfactory, which is not preferable.

There are no particular limitations on the properties of the polyneedle of the present invention, but if the softening point of the polymer is too high, it will be difficult to turn the polyether into a crosslinked resin through post-treatment. It is preferable that there be 3
The temperature is more preferably 20°C or less, most preferably 280° (D or less). Also, in order to obtain sufficient heat resistance when binding the crosslinked resin by post-treatment, the Tg is 80°C or less.
The temperature is preferably 110°C or higher, more preferably 110°C or higher, and most preferably 130°C or higher.

Next, a method for producing the polyether will be described. The method for producing the polyether is not particularly limited, and examples include methods (a), (b) and fc) below.

(a) The aromatic dihydroxy compound contained in the following formula (VI) HO0T-T \ / Ar' C゛ and the aromatic dihydroxy compound and the halogen in substantially the same molar amount as the aromatic dihydroxy compound are activated. Shiba IT7gen compound and
A method of reacting a halogenophenol with an activated halogen as necessary in the presence of an alkali, (b) A method of reacting the following formula (■) with a halogenophenol with an activated halogen as necessary. , a method of reacting in the presence of an alkali, (C) 'l'' enlargement (■) Halogen containing at least in part an aromatic dihalogeno compound in which the halogen represented by Hal Ha \ / Ar' ρ is activated an aromatic dihalogeno compound in which is activated, and a halogenophenol in which a halogen is activated and contains at least a part of a compound represented by an aromatic dihydroxy compound in a substantially equimolar amount to the aromatic dihalogeno compound; , a method of reacting an aromatic dihydroxy compound and a dihalogen compound activated with substantially equimolar halogen to the aromatic dihydroxy compound in the presence of an alkali, if necessary.

Among these, the aromatic dihydroxy compound represented by formula (Vl) used in methods (a) and (b) or preferred method (a) is specifically 2-
(3,5-dihydroxyphenyl)-2oxazoline,
2-[4=(3,5-dihydroxyphenyl)-phenyl 1-2-oxacillin.

2-[1-<3. ．． 5-dihydroxybenzoyl)-
phenyl]-2-oxazoline, 2-[4-<3゜5
-dihydroxybenzenesulfonyl)-phenyl]-2
-Oxazoline, 2-(3,5-dihydroxyphenyl)-5,6-dihydro 4H-1,3oxazine, 2-
[4-<3.5-dihydroxybenzoyl)-phenyl]-5,6-dihydro 4H1,3-oxazine,
2- [4'-(3,5-dihydroxybenzenesulfonyl)-phenyl]-5,6 dihydro 48-1.3-
Examples include oxazine. Among these, 2-(3,5=dihydroxyphenyl)-oxazoline is particularly preferred.

There are no particular restrictions on aromatic dihydro monooxy compounds other than those represented by formula (Vl), but specific examples include hydroquinone, resorcinol, 1,4-naphthalenediol, 1,5-naphthalenediol, 2,6 Naphthalene diol, 2,7-naphthalene diol.

4.4'-dihydroxydiphenyl, bisphenol A
, bisphenol S, 4.4'-dihydroxydiphenyl ether, 4.4'-dihydroxybenzophenone,
Examples include phenolphthalein.

In the present invention, the compound represented by formula (Vl) may be used as a part of the aromatic dihydroxy compound, and its proportion is preferably 0.01 mol or more, more preferably 0.01 mol or more per 1 kg of produced polymer. The amount should be at least .05 mole, most preferably at least 0.1 mole.

Next, the halogen-activated dihalogen compound used in method (a) is not particularly limited as long as it has sufficient activity to react with the dihydroxy compound to form a polyether, but is preferred. Specific examples include 4.4'-dichlorodiphenylsulfone, 4.4'
-dichlorobenzophenone, 4-chloro-4'-(4-
chlorobenzoyl)benzophenone, 4-chloro-3'
-(4-Chlorobenzoyl)benzophenone, 4-chloro-4'(4-di-tetrabenzenesulfonyl)diphenylsulfone, 4-chloro-3''(4-di-tetrabenzenesulfonyl)diphenylsulfone, 2,6-dichloro Benzonitrile, 2,4-dichlorobenzonitrile, 2.6-
Bis(p-chlorobenzoyl)naphthalene, 1,5-bis(p-chlorobenzoyl)naphthalene, 2,6-bis(p-chlorobenzenesulfonyl)naphthalene, 1,5
Examples include -bis(p-chlorobenzenesulfonyl)naphthalene and compounds in which the chlorine atom of these dichloro compounds is replaced with a fluorine atom or a bromine atom.

The proportion of the dihalogen compound to be used is substantially equimolar to the aromatic dihydroxy compound, for example, 0.95 to 1.0 to 1 mole of the aromatic dihydroxy compound.
It is about 5 moles.

Further, the halogen-activated herogenophenol is not particularly limited as long as it has sufficient activity to produce the polyether, but a preferred specific example is 4-fluoro-4'-hydroxybenzophenone. , 4-
Fluoro-4'-hydroxydiphenylsulfone, 4-
Fluoro-4'(4-hydroxyphenyl)benzophenone, 4fluoro-4'-<4-hydroxyphenyl>
Diphenylsulfone, 2-hydroxy-6-<pfluorobenzoyl)naphthalene, 1-hydroxy-5-(p
-fluorobenzoyl) naphthalene.

Examples include 2-hydroxy-6-(p-fluorobenzenesulfonyl)naphthalene, 1-hydroxy-5(p-fluorobenzenesulfonyl)naphthalene, and these fluorophenols in which the fluorine atom is replaced with a chlorine atom.

In method (a), it is not necessary to use such halogenophenol, but it is possible to use it in combination depending on the properties of the desired polymer.

The polymer of the present invention is produced by reacting the above-mentioned compound in the presence of an alkali, and the alkali includes hydroxides 1 to 1.
Alkali metal hydroxides such as RIUNO＼, potash hydroxide, etc., alkali metal bicarbonates such as helium hydrogen carbonate, potassium hydrogen carbonate, and alkali metal carbonates such as potassium carbonate and RIUNO＼. Examples include salt and the like. Among these, carbonates such as potassium carbonate and sodium carbonate are preferably used. The amount of alkali present during the reaction varies depending on the reactants and reaction conditions, but
95 in terms of alkali equivalent based on all human l-coxy groups in the raw material.
% or more, and it is better to make it 98% or more and 250% or more.

In addition, in method (b), in addition to the method in which an alkali is present simultaneously with the raw materials during polyneedle polymerization, an alkali metal salt of the above-mentioned hydroxy compound is prepared in advance, and the above-mentioned dihalogeno compound in which the halogen is activated is used. If a method of reaction is used, it is also possible to produce the polyneedle without the presence of an alkali during one reaction.

The reaction temperature varies depending on the type of dihalogen compound and dihydroxy compound, but is preferably about 80 to 400°C.

This reaction temperature represents the maximum reaction temperature, and it is also preferable (and possible) to start the reaction at a lower temperature and increase the reaction temperature continuously or stepwise.

The reaction temperature is more preferably about 100 to 370°C, particularly preferably about 120 to 350°C. If the reaction temperature is too low, the polymerization rate will be too slow to be of practical use.

In addition, if the reaction temperature is too high, side reactions are likely to occur, and in some cases, even decomposition may occur.

The reaction can be carried out at normal pressure, increased pressure or reduced pressure. Nitrogen when performing at normal pressure■ or pressurized 10゛.

It is preferable to use an atmosphere of an inert gas such as argon.

When carrying out the reaction, only the above raw materials may be heated and reacted without a solvent, but in order to keep the reaction system uniform and obtain a polymer with a high degree of polymerization at a lower temperature, a solvent may be used. is also preferable. As such a solvent, any compound can be used as long as it is stable by itself at the reaction temperature, is non-reactive with the raw material compound, reaction product, or polymer, and is compatible with the solvent, the solvent, and the produced polymer at the reaction temperature. Suitable solvents that can be used include sulfone compounds, amide compounds, etc. Specific examples of sulfone compounds include diphenyl sulfone, dimethyl sulfoxide, sulfolane, and ditolylsulfolane. -cyclohexyl-2-pyrrolido>.N,N--dimethylacetamide, etc. can be exemplified. Among these, diphenyl sulfone, sulporan, and dimethyl sulfoxide are preferred.

The amount of the solvent to be used is not particularly limited, but it is preferably about 20-95% by weight based on the total amount of the polymer to be produced and the solvent.

The heating reaction time is not particularly limited, and may be any time that is sufficient to sufficiently increase the degree of polymerization of the polymer, and this will vary depending on the type of raw materials used, the amount of solvent, and the reaction temperature, but approximately] - - ~ 10 It takes about an hour.

After completion of the reaction, the desired polyether can be obtained by treating and removing the salt produced by the reaction and, if necessary, the solvent, respectively, with water and an organic solvent that dissolves the solvent but does not dissolve the polymer.

The aromatic dihalogeno compound 1 represented by formula (VIA) used in method (b) is specifically 2-
(2,6-difluorophenyl)-2-ohethol>
',2<2',4-difluorophenyl)2-oxazoline,2-[(2,6-difluoro4-phenyl)
phenyl]-2-oxazoline 2-[(2,6-difluoro-4-benzenesulfonyl)phenyl] = 2-oxazoline, 2-(26-difluorophenyl)-5,6
-Sihydro 48-1,3-oxazine, 2-(2,4
-difluorophenyl)-5,6-dihydro41-■
-1,3-oxazine, 2-[(2,6-difluoro-
4-phenyl) phenyl-]-5,6-dishidraw 48
-1j oxazine, 2-[(2,6-fluoro-4-
benzenesulfonyl)phenyl]-5,6-dihydro4
Examples include H-1,3-oxazine and the above compounds in which the fluorine atom is replaced with a chlorine atom. Among these, especially 212.6 difluorophenyl)
-2-oxazoline is preferred.

Further, the aromatic dihalogeno compound in which a halogen other than that represented by formula (VI[) is activated is not particularly limited, but specifically, 44'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone , 4.4'
-dichlorobenzophenone, 4,4' difluorobenzophenone, 1,5-bis(p-fluorobenzoyl)naphthalene, 2,6-bis(p-fluorobenzoyl)naphthalene, 1,5-bis(p-chlorobenzoyl)naphthalene , 2,6-bis(p-chlorobenzoyl)naphthalene, 1.5bis(p-di-tetralobenzenesulfonyl)naphthalene, 2,6-bis(p-chlorobenzenesulfonyl)naphthalene, 2,6-cyclobenzonitrile etc. can be exemplified.

In the present invention, the compound represented by -Noshiro (■) may be used as a part of the aromatic dihalogeno compound, and the proportion thereof is preferably 0.001 kg per 1 kg of produced polymer.
0.01 mole or more, more preferably 0.05 mole or more, and most preferably 0.1 mole or more.

The aromatic dihydroxy compound used in method (b) is not particularly limited, but specifically includes hydroquinone, resorcinol, 1,4-naphthalenediol, 1,
5-naphthalene diol, 2,6 naphthalene diol,
2,7-naphthalene diol.

Examples include 4,4' dihydroxydiphenyl, bisphenol A, bisphenol S, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, and phenolphthalein.

The proportion of the dihydroxy compound used is substantially equimolar to the aromatic dihalogeno compound, for example, the aromatic dihalogeno compound! The amount is about 0.95 to 1.05 mol per 1 mol.

Further, the halogenophenol in which the halogen is activated is not particularly limited as long as it has sufficient activity to produce the polyether, but a preferred specific example is 4-fluoro-4perhydroxybenzophenone. , 4-
Fluoro-4'-citroxydiphenylsulfone, 4-
Fluoro-4'(4-hydroxyphenyl)benzophenone, 4fluoro-4'-(4-hydroxyphenyl)
Diphenylsulfone, 2-hydroxy-6, -(pfluorobenzoyl)naphthalene, 1-hydroxy-5-(
p-fluorobenzoyl) naphthalene.

Examples include 2-hydroxy-6-(p-fluorobenzenesulfonyl)naphthalene, 1-hydroxy-5(p-fluorobenzenesulfonyl)naphthalene, and these fluorophenols in which the fluorine atom is replaced with a chlorine atom. .

In method (b), it is not necessary to use such halogenophenol, but it is possible to use it in combination depending on the properties of the desired polymer.

Reaction conditions such as alkali to be present, reaction temperature, etc. 7. Reaction solvent, post-treatment, etc. when producing a polymer by reacting the above compounds are the same as in method (a).

The polyether is mixed with a specific catalyst and heated.

By reacting, it becomes a tough crosslinked resin.

There are no particular restrictions on the method of mixing the catalyst with the polyether, but specific examples include a method of melt-mixing, a method of uniformly dissolving in a solution, and a method of removing the solvent.

Catalysts used here include protonic acids with pKa of 2.5 or less, pKa of 1. It is a compound selected from proton acid esters of θ or less, Lewis acids and their complexes, alkyl halides, and iodine.

Here, pKa is the value in an aqueous solution, and when there are two or more dissociable protons, it represents the value for the first proton.

Examples of the above-mentioned catalyst include sulfonic acids, inorganic protonic acids, etc. as protonic acids having a pKa of 2.5 or less.
Examples of the sulfonic acids include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p,-)luenesulfonic acid, and inorganic tetratonic acids such as sulfuric acid,
Phosphoric acid, phosphorous acid.

Examples include phosphinic acid, phosphonic acid, and perchloric acid.

Examples of protonic acid esters having a pKa of 1.0 include methyl benzenesulfonate, ethyl benzenesulfonate, p-)methyl luenesulfonate, p-)rue〉・
Examples include sulfonic acid esters such as ethyl sulfonate, inorganic proton acid Nisdels such as dimethyl sulfate, and the like. Examples of Lewis acids and their complexes include titanium tetrachloride, tin tetrachloride, zinc chloride, and aluminum chloride.
Examples include lifluoroborane, trifluoroborane ether complex, and the like. Examples of alkyl halides include methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pencil iodide, and benzyl bromide. These catalysts can be used alone or in combination of two or more. There is no particular restriction on the amount of catalyst used, but it is usually 0.01-20% by weight, preferably 0.01-20% by weight based on the polyether.
．． The amount is about 1 to 5% by weight.

In order to produce a crosslinked resin by reacting the polyether of the present invention, it is sufficient to mix the polyether and the above-mentioned catalyst and heat the mixture to react. The heating reaction temperature at this time is preferably 7 g or more of the polyether, more preferably Tg+20°C, particularly preferably Tg+40°C or more. If the temperature is too high, the polyether may deteriorate, so it is preferable to carry out the reaction at a temperature of 350° C. or lower.

The reaction time may be sufficient as long as it is sufficient to harden the target resin, and this time varies depending on the type of polyether used, the amount of catalyst added, etc., but is preferably 10 seconds to 60 seconds. minutes, more preferably 20 seconds to 45
minutes, particularly preferably about 1 minute to 30 minutes. The reaction can be carried out under normal pressure to increased pressure.

<Effects of the Invention> The crosslinked polymer thus obtained retains the mechanical properties of polyether, which is a thermoplastic resin, and has excellent heat resistance and
A resin with chemical resistance.

The resin thus obtained can be preferably used not only as a resin medium but also, for example, as a matrix resin for composite materials. When used for this purpose, the fibers may be impregnated by a solution method, or the composition before being heated and cured may be melt-molded into fibers or sheets, and this and reinforcing fibers may be impregnated into so-called F 7 "F. Methods such as forming a composite I~, laminating and bending are also preferred (and can be implemented).

<Examples> The present invention will be described below in detail with reference to Examples, but the Examples are merely illustrative, and the present invention is not limited thereto.

In the examples, "1 part" means [part by weight - 1].

In addition, the reduced viscosity (ηsp/c) of the polymer is 3 at a concentration of Ig/di using N-methyl-2-pyrrolidone as a solvent.
Measured at 0°C. Secondary transition point (Tg) of the polymer,
The melting point (Tm) is measured using SDC at a heating rate of 10°C/min.

Example code 57.43 parts of 4,4'-dichlorodiphenyl sulfone.

Bisphenol A 43.36 parts, 2-<3.5-dihydro-4diphenyl)-2-oxazoline 1.79 parts,
60.81 parts of anhydrous potassium carbonate, 176 parts of dimethyl sulfoxide, and 50 parts of toluene were added to a stirrer and a Dean-
The reaction mixture was placed in a reactor equipped with 3 tarks of crap, and nitrogen was bubbled into the system, heated to an internal temperature of 150"C, and reacted for 6 hours while water was distilled off.The resulting reaction product Pour it into methanol and solidify it, then crush it to a particle size of 5.
Dimethyl sulfoxide and inorganic salts were removed by extracting the chips three times under refluxing methanol and three times under flowing water. Then dry at 100'C for 4 hours. The obtained polymer has ηsp/c=o,
7L Tg=189°C, and Tm cannot be observed. Thereafter, 10 parts of this polymer and 0.1 part of methyl p-toluenesulfonate were thoroughly mixed, and the mixture was heated at 230°C for 30 minutes.
When heated for 1 minute, a pale yellow transparent tough resin was obtained. Moreover, this resin was completely insoluble in various solvents.

Example 2 The amount of bisphenol A in Example 1 was changed to 41.07 parts 2-(
The reaction and post-treatment were carried out in the same manner as in Example 1, except that the amount of 3,5-dihydroxyphenyl)-2-oxacillin was changed to 3.58 parts. The obtained polymer is r) sp/c
= 0.58. Tg=189°C, and Tm could not be observed.

Next, 10 parts of the polymer and 0.1 parts of benzenesulfonic acid
1 part was dissolved in 40 parts of chloroform and a film was prepared by a casting method. The film was then heated at 230°C for 3
After heating for 0 minutes, a pale yellow transparent tough resin was obtained. Manako's resin was completely insoluble in various solvents.

Example 3 4-fluoro-3'-(p-fluorobenzoyl)benzophenone 4.83 parts, hydroquinone 1.32 parts.

0.54 parts of 2-(3,5-dihydroxyphenyl)-2-oxazoline, 2.07 parts of anhydrous potassium carbonate, and 12.2 parts of sulfolane were placed in a reactor equipped with a stirring device and a distillation system, and the system was heated with nitrogen. After replacing, 20 minutes in a nitrogen atmosphere under normal pressure.
The reaction was carried out at 0°C for 60 minutes. After that, the temperature was raised to 230℃ and 9
0 minutes, heated to 250℃ for 60 minutes, heated to 270℃ for 60 minutes
It was allowed to react for a minute. Next, the reaction product was cooled and poured into methanol, and the precipitate was crushed into chips, which were extracted and dried in the same manner as in Example 1. The obtained polymer was 77
s'p/c''=0196. Tg=154°C, and Tm was not detected.

Next, 10 parts of the polymer and 0.08 part of benzyl iodide were thoroughly mixed and heated at 220°C for 40 minutes to obtain a pale yellow transparent tough resin. Manako's resin was completely insoluble in various solvents.

Example 4 4.4'-dichlorodiphenylsulfone 5'1.69g
.

2.6-cyclopenzonitrile 3.44 g, 2-(
35-dihydroxyphenyl)-2-oxazoline1.
79 parts, 6 parts of bisphenol A43j, 60.81 parts of anhydrous potassium carbonate, 176' parts of dimethyl sulfoxide.

Add 50 parts of toluene to a stirrer and Dean-8tark.
) The mixture was placed in a reactor equipped with a wrap, heated to an internal temperature of 150° C. while blowing nitrogen into the system, and reacted for 5 hours while water was distilled off. Next, the obtained reaction product was poured into methanol, solidified, and then pulverized to a particle size of 500 μm.
The following chips were obtained, and the chips were extracted three times under refluxing methanol and three times under fast water flow to remove dimethyl sulfoxide and inorganic salts.

Then dry at 100°C for 4 hours. The obtained polymer had a 77 sp'/c=0.60. 'Tg=184℃
Therefore, Tm could not be observed. Thereafter, 10 parts of this polymer and 0.1 part of benzenesulfonic acid were thoroughly mixed and heated at 2'50°C for 10 minutes to obtain a pale yellow transparent tough resin. Moreover, this resin was completely insoluble in various solvents.

Example 5 6.46 parts of 44'-dichlordiphenylsulfone, 2(
2,6-difluorophenyl)-2-oxazoline 0.
46 parts of 4.4'-dihydroxydiphenyl, 3.46 parts of anhydrous potassium carbonate, and 11 parts of dimethyl sulfoxide were placed in a reactor equipped with a stirring device and a distillation system.
After purging the system with nitrogen, it was heated at 220°C under normal pressure in a nitrogen atmosphere.
It was allowed to react for 0 minutes. Thereafter, the mixture was reacted at 250°C for 120 minutes. Next, after cooling the reaction product, it was poured into methanol, and the precipitate was crushed into chips, and then extracted in the same manner as in Example 1.
Do not dry. The resulting polymer has a 77 sp/c=
0.52. Tg = 212°C, and T'm cannot be detected. Thereafter, 10 parts of this polymer and 1 part of p-toluene sulfonic acid ether were thoroughly mixed, and 250 parts of
After heating at ℃ for 10 minutes, a pale yellow transparent tough resin was obtained. Moreover, this resin was completely insoluble in various solvents.

Claims (3)

[Claims] (1) The following formula (I) (II) and/or (III) ▲ formula,
There are chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) [However, Ar and Ar' are divalent It is an aromatic group. X is ▲There is a mathematical formula, chemical formula, table, etc.▼ or -SO_
It is 2-. Z is an electron-withdrawing group. n is an integer from 0 to 2. ] In the aromatic polyether composed of
At least a part of is the following formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) [Here, X_1 is 2 or 3 ring member aliphatic carbon atoms forming an iminoether ring It is a hydrocarbon group with Ar″ is a trivalent aromatic group.] Or at least a part of Z is the following formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼…(V) [Here, X_1 is the above formula (IV) The same as the definition of. ] An aromatic polyether characterized by being substituted with. (2) Aromatic dihydroxy represented by the following formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(VI) [Here, X_1 and Ar'' are the same as the definitions of the above formula (IV).] an aromatic dihydroxy compound containing at least a part of the compound, a dihalogen compound in which substantially equimolar halogen is activated with respect to the aromatic dihydroxy compound, and a halogen compound in which halogen is activated as necessary. Claim 1 characterized in that the reaction with phenol is carried out in the presence of an alkali.
A method for producing the aromatic polyether described. (3) The following formula (VII) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (VII) [Here, X_1 and Ar'' are the same as the definitions of the above formula (IV).Hal is a halogen atom. A halogen-activated aromatic dihalogeno compound containing at least a part of the halogen-activated aromatic dihalogeno compound represented by ] and an aromatic compound in a substantially equimolar amount to the aromatic dihalogeno compound 2. The method for producing an aromatic polyether according to claim 1, wherein the dihydroxy compound and a halogenophenol whose halogen is activated as required are reacted in the presence of an alkali.