JP2515421B2 - Novel aromatic polyether and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a novel polyether.
More specifically, the present invention relates to a novel polyether which does not have a problem of deterioration of polymerization degree and phase separation during molding.

<Prior Art> In recent years, with the progress of technology, a resin having excellent heat resistance and mechanical properties and excellent moldability has been demanded. Among these resins, a reaction-molding type resin using a reactive monomer or oligomer, that is, a resin in which molding and polymerization are simultaneously performed by using a relatively low-viscosity raw material has attracted attention. As such resins, polyurethane resins, polyurea resins, nylon resins, epoxy resins, unsaturated polyester resins and the like are known, and some of them are commercialized.

However, each of these resins has advantages and disadvantages, for example, polyurethane resins have low heat resistance, and unsaturated polyester resins have drawbacks such as reaction, that is, molding takes time, and thus they do not always have sufficient performance and moldability. It cannot be said that

Therefore, as a solution to these problems, there has been proposed a resin or the like obtained by heating and reacting a composition comprising a thermoplastic resin and an oxazoline derivative in the presence of a catalyst (JP-A-63-248852). However, for example, when using polycarbonate or polyester as the thermoplastic resin, it is difficult to say that the toughness of the thermoplastic polymer is sufficiently utilized because the degree of polymerization of these polymers tends to decrease during molding. When polystyrene or the like is used as the thermoplastic polymer, there is a problem that the polysulfone and the oxazoline derivative are likely to undergo phase separation during the heating reaction, and therefore the properties of the obtained resin are still insufficient.

<Purpose of the Invention> As a result of intensive studies to solve these problems, the present inventors have found that a polyether having an oxazoline ring introduced into the polymer side chain does not cause a decrease in the degree of polymerization during molding and causes phase separation. It has been found that there is no problem, and the toughness of the thermoplastic polymer can be fully utilized by heating and reacting in the presence of a specific catalyst, and a thermosetting polymer excellent in heat resistance, chemical resistance, etc. can be obtained, and the present invention can be obtained. Arrived

<Structure of Invention> That is, the present invention provides the following formulas (I), (II) and / or
Or (III) and -O-Ar -... (I) In an aromatic polyether composed of at least a part of the above Ar, Or at least a part of Z is the following formula (V) The reduced viscosity (concentration 1.0 g / dl) measured at 30 ° C. in N-methyl-2-pyrrolidone is 0.25.
The aromatic polyether and the method for producing the same are as described above.

 The present invention will be described in detail below.

In the above formulas (I) and (II), Ar and Ar ′ may be an aromatic group or a divalent group in which a plurality of aromatic groups are bonded,
These may have a substituent. Specifically as Ar, Ar ′ And methyl, ethyl, and
Examples thereof include aliphatic substituted products such as propyl, alicyclic substituted products such as cyclohexyl, and aral substituted products such as phenyl, naphthyl and tolyl.

Of these, especially for Ar Is preferred, especially for Ar ′, among these It is preferred that X in formula (II) is Or —SO ₂ —, n is an integer of 0 to 2, and n =
It is preferred that 0 or n = 1. That is, as a particularly preferable structure of (II), Etc. can be illustrated.

Z is an electron-withdrawing group. Specifically as Z [Here, R is aliphatic, alicyclic, or aromatic. ], Etc. Is preferred.

In the above formula (IV), Ar ″ may be an aromatic group or a trivalent group in which a plurality of aromatic groups are bonded, and these may have a substituent.

Specifically as Ar ″ And the like, and examples thereof include aliphatic substitution products such as methyl, ethyl and propyl, alicyclic substitution products such as cyclohexyl, and aryl substitution products such as phenyl, naphthyl and tolyl. Especially of these Is preferred.

In the formulas (IV) and (V), X ₁ has 2 or 3 ring-membered aliphatic carbon atoms forming an imino ether ring.
It is a valent monovalent hydrogen group. Examples of such a hydrocarbon group include unsubstituted alkylene such as ethylene and trimethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-
C1-C6 such as dimethylethylene, 1-ethylethylene, 1,2-diethylethylone, 1-propylethylene, 1,2-dipropylethylene, 1-methyltrimethylene, 1,2-dimethylrythmethylene Examples thereof include alkylene substituted with a lower alkyl group. Of these, ethylene or trimethylene is preferable, and ethylene is particularly preferable.

The polyether may include the structural units represented by the above formulas (IV) and (V) in at least a part thereof.
It is preferable that 0.01 g or more of the structural unit of formula (IV) or formula (V) is contained in g, more preferably 0.05 equivalent or more, and most preferably 0.1 equivalent or more. That is, the content of the cyclic imino ether represented by the formula (V) is preferably 10 equivalent / 10 ⁶ g or more, more preferably 50 equivalent / 10.
^{It is 6} g polymer or more, most preferably 100 equivalent / 10 ⁶ g or more.

As a method for quantifying the content of the cyclic iminoether group represented by the above formula (V) in the polymer, the polyether is dissolved in a solvent, and an excess amount of p-toluenesulfonic acid is added to the solution to form a cyclic iminoether. And p-toluenesulfonic acid salt are prepared, the amount of excess p-toluenesulfonic acid is titrated with an alkali such as sodium hydroxide, and the content of cyclic iminoether group is calculated from the reduced amount of p-toluenesulfonic acid. There is a method of doing.

Further, the polyether of the present invention has a reduced viscosity (concentration 1.0 g / dl) of 0.2 measured at 30 ° C. in N-methyl-2-pyrrolidone.
It is 5 or more, preferably 0.3 or more. When the reduced viscosity is less than 0.25, the mechanical properties of the polymer are insufficient, which is not preferable.

The properties of the polyether of the present invention are not particularly limited, but if the softening point of the polymer is too high, it becomes difficult to make the polyether into a crosslinked resin by post-treatment, so that the softening point is 350 ° C or lower. Preferably at 320 ° C
The temperature is more preferably below, and most preferably 280 ° C or below. Further, in order to obtain sufficient heat resistance when the crosslinked resin is post-treated, Tg is preferably 80 ° C. or higher, more preferably 110 ° C. or higher, and 130
Most preferably, the temperature is not lower than ° C.

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

(A) The following formula (VI) The aromatic dihydroxy compound containing at least a part of the aromatic dihydroxy compound represented by, a dihalogen compound in which substantially equimolar halogen is activated with respect to the aromatic dihydroxy compound, and a halogen if necessary A method of reacting an activated halogenophenol in the presence of an alkali, (b) the following formula (VII) And a halogen-activated aromatic dihalogeno compound containing at least a portion of the halogen-activated aromatic dihalgeno compound, and a substantially equimolar amount of aromatic dihydroxy with respect to the aromatic dihalogeno compound. A method of reacting a compound with a halogenophenol in which halogen is activated, if necessary, (c) the following formula (VIII) A halogenophenol containing at least a part of the compound represented by and activated halogen, and optionally an aromatic dihydroxy compound and substantially the same mole of halogen activated with respect to the aromatic dihydroxy compound. And a dihalogen compound in the presence of an alkali. Of these, the methods (a) and (b) are preferable.

Specific examples of the aromatic dihydroxy compound represented by the formula (VI) used in the method (a) include 2-
(3,5-dihydroxyphenyl) -2-oxazoline, 2
-[4- (3,5-dihydroxyphenyl) -phenyl]
2-oxazoline, 2- [4- (3,5-dihydroxybenzoyl) -phenyl] -2-oxazoline, 2- [4-
(3,5-Dihydroxybenzenesulfonyl) -phenyl] -2-oxazoline, 2- (3,5-dihydroxyphenyl) -5,6-dihydro-4H-1,3-oxazine, 2- [4
-(3,5-Dihydroxybenzoyl) -phenyl] -5,6
-Dihydro-4H-1,3-oxazine, 2- [4- (3,5-dihydroxybenzenesulfonyl) -phenyl] -5,6-
Examples thereof include dihydro-4H-1,3-oxazine. Of these, 2-3,5-dihydroxyphenyl) -oxazoline is particularly preferable.

The aromatic dihydroxy compound other than that represented by the formula (VI) is not particularly limited, but specifically, it is hydroquinone, resorcin, 1,4-naphthalene diol, 1,5-naphthalene diol, 2,6-naphthalene diol. , 2,7-naphthalene diol, 4,4'-dihydroxydiphenyl, bisphenol A, bisphenol S, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone,
Examples thereof include phenolphthalein.

In the present invention, the compound represented by the formula (VI) may be used as a part of the aromatic dihydroxy compound, and the ratio thereof is preferably 1 kg of the produced polymer,
The amount is 0.01 mol or more, more preferably 0.05 mol or more, and most preferably 0.1 mol or more.

Next, the halogen-activated dihalogen compound used in the 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 preferable. Specific examples include 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorobenzophenone, 4-chloro-4 '-(4-chlorobenzoyl) benzophenone, 4-chloro-3'-(4-
Chlorobenzoyl) benzophenone, 4-chloro-4'-
(4-chlorobenzenesulfonyl) diphenyl sulfone, 4-chloro-3 '-(4-chlorobenzenesulfonyl) diphenyl sulfone, 2,6-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, 2,6-bis (p-chloro) Chlorine atom of benzoyl) naphthalene, 1,5-bis (p-chlorobenzoyl) naphthalene, 2,6-bis (p-chlorobenzenesulfonyl) naphthalene, 1,5-bis (p-chlorobenzenesulfonyl) naphthalene and these dichloro compounds Examples thereof include compounds in which is replaced by a fluorine atom or a bromine atom.

The usage ratio of the dihalogen compound is substantially equimolar to the aromatic dihydroxy compound, and is, for example, about 0.95 to 1.05 mol with respect to 1 mol of the aromatic dihydroxy compound.

The halogen-activated halogenophenol is not particularly limited as long as it has sufficient activity for producing the polyether, but a preferred specific example is 4-fluoro-4'-hydroxybenzophenone. , 4-
Fluoro-4'-hydroxydiphenyl sulfone, 4-fluoro-4 '-(4-hydroxyphenyl) benzophenone, 4-fluoro-4'-(4-hydroxyphenyl)
Diphenyl sulfone, 2-hydroxy-6- (p-fluorobenzoyl) naphthalene, 1-hydroxy-5- (p-
Fluorobenzoyl) naphthalene, 2-hydroxy-6-
Examples thereof include (p-fluorobenzenesulfonyl) naphthalene, 1-hydroxy-5- (p-fluorobenzenesulfonyl) naphthalene, and those fluorophenols in which the fluorine atom is changed to a chlorine atom.

In the method (a), such a halogenophenol does not necessarily have to be used, but it can be used in combination because of the characteristics of the target polymer.

The polymer of the present invention is obtained by reacting the above compound in the presence of an alkali. Examples of the alkali include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide,
Examples thereof include alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, and alkali metal carbonates such as potassium carbonate and sodium carbonate. Of these, it is preferable to use a carbonate such as potassium carbonate or sodium carbonate. The amount of alkalinity present during the reaction varies depending on the substance to be reacted and the reaction conditions, but it is preferably 95% or more, and 98% or more and 250% or less in terms of alkali equivalent, based on all hydroxy groups of the raw material. More preferable.

Further, in the method (b), in addition to the method in which an alkali is present at the same time as a raw material at the time of polyether polymerization, an alkali metal salt of the above-mentioned hydroxy compound is produced in advance, and the above-mentioned halogen-activated dihalogeno compound is produced. It is also possible to produce the polyether without the presence of alkali during the reaction.

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

Further, this reaction temperature represents the maximum reaction temperature, and it is also preferable to start the reaction from a lower temperature and raise the reaction temperature continuously or stepwise.

The reaction temperature is more preferably about 100 to 370 ° C, and particularly preferably about 120 to 350 ° C. If the reaction temperature is too low, the polymerization rate will be too slow for practical use. On the other hand, if the reaction temperature is too high, a side reaction is likely to occur, and in some cases, the monomer may be decomposed.

The reaction can be carried out under normal pressure, increased pressure or reduced pressure. When it is carried out under normal pressure or under pressure, it is preferable to be in an atmosphere of an inert gas such as nitrogen or argon.

In carrying out the reaction, only the above raw materials may be heated and reacted without a solvent, but it is also preferable to use a solvent in order to keep the reaction system uniform and obtain a polymer having a high degree of polymerization at a lower temperature. . As such a solvent, any compound may be used as long as it is a compound which is stable at the reaction temperature, is non-reactive with the raw material compound, the reaction product or the polymer, and is compatible with the monomer and the produced polymer at the reaction temperature. Suitable solvents include sulfone compounds and amide compounds. Specific examples of the sulfone-based compound include diphenyl sulfone, dimethyl sulfoxide, sulfolane, and ditolylsulfolane, and specific examples of the amide-based compound include N 2
-Methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide and the like can be exemplified. These diphenyl sulfone, sulfolane,
Dimethyl sulfoxide is preferred.

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

The heating reaction time is not particularly limited, as long as the polymerization degree of the polymer is sufficiently increased, and this depends on the type of raw material used, the amount of solvent, and the reaction temperature,
It is about 1 to 10 hours.

After the completion of the reaction, the desired polyether can be obtained by treating the salt formed by the reaction and the solvent in some cases with an organic solvent that dissolves water and the solvent but does not dissolve the polymer.

Specific examples of the aromatic dihalogeno compound represented by the formula (VII) used in the method (b) include 2-
(2,6-Difluorophenyl) -2-oxazoline, 2-
(2,4-Difluorophenyl) -2-oxazoline, 2-
[(2,6-Difluoro-4-phenyl) phenyl] -2
-Oxazoline, 2-[(2,6-difluoro-4-benzenesulfonyl) phenyl] -2-oxazoline, 2-
[(2,6-Difluorophenyl) -5,6-dihydro-4H-
1,3-oxazine, 2- (2,4-difluorophenyl) -5,
6-dihydro-4H-1,3-oxazine, 2-[(2,6-difluoro-4-phenyl) phenyl] -5,6-dihydro-4
H-1,3-oxazine, 2-[(2,6-difluoro-4-benzenesulfonyl) phenyl] -5,6-dihydro-4H-
Examples thereof include 1,3-oxazine and the above compounds in which a fluorine atom is replaced with a chlorine atom. Among these, especially 2- (2,6-difluorophenyl) -2
-Oxazoline is preferred.

The halogen-activated aromatic dihalogeno compound other than that represented by the formula (VII) is not particularly limited, but specifically, 4,4′-dichlorodiphenyl sulfone,
4,4'-difluorodiphenyl sulfone, 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
Examples thereof include -chlorobenzoyl) naphthalene, 1,5-bis (p-chlorobenzenesulfonyl) naphthalene, 2,6-bis (p-chlorobenzenesulfonyl) naphthalene and 2,6-dichlorobenzonitrile.

In the present invention, the compound represented by the general formula (VII) may be used as a part of the aromatic dihalogeno compound, and the ratio thereof is preferably 0.01 per 1 kg of the produced polymer.
It should be at least mol, more preferably at least 0.05 mol, and most preferably at least 0.1 mol.

The aromatic dihydroxy compound used in the method (b) is not particularly limited, but specifically, hydroquinone, resorcin, 1,4-naphthalene diol, 1,5-naphthalene diol, 2,6-naphthalene diol, Examples include 2,7-naphthalene diol, 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, about 0.95 to 1.05 mol per 1 mol of the aromatic dihalogeno compound.

The halogen-activated halogenophenol is not particularly limited as long as it has sufficient activity for producing the polyether, but a preferred specific example is 4-fluoro-4'-hydroxybenzophenone. , 4-
Fluoro-4'-hydroxyphenyl sulfone, 4-fluoro-4 '-(4-hydroxyphenyl) benzophenone, 4-fluoro-4'-(4-hydroxyphenyl) diphenyl sulfone, 2-hydroxy-6- (p-fluoro Benzoyl) naphthalene, 1-hydroxy-5- (p-fluorobenzoyl) naphthalene, 2-hydroxy-6-
Examples thereof include (p-fluorobenzenesulfonyl) naphthalene, 1-hydroxy-5- (p-fluorobenzenesulfonyl) naphthalene, and those fluorophenols in which the fluorine atom is changed to a chlorine atom.

In the method (b), such a halogenophenol does not necessarily have to be used, but can be used in combination because of the characteristics of the target polymer.

The alkali, the reaction conditions such as reaction temperature, the reaction solvent, the post-treatment and the like which are present when the above compounds are reacted to produce a polymer are the same as in the method (a).

The polyether becomes a tough crosslinked resin by mixing a specific catalyst, heating and reacting.

The method of mixing the catalyst with the polyether is not particularly limited, and specific examples thereof include a melt mixing method and a method of uniformly dissolving the catalyst in a solution and removing the solvent.

The catalyst used here is a compound selected from a protonic acid having a pKa of 2.5 or less, a protonic acid ester having a pKa of 1.0 or less, a Lewis acid and its complex, an alkyl halide 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 catalyst include proton acids having a pKa of 2.5 or less, such as sulfonic acids and inorganic proton acids, and examples of the sulfonic acids include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like. However, as the inorganic protonic acid, for example, sulfuric acid, phosphoric acid,
Examples thereof include phosphorous acid, phosphinic acid, phosphonic acid, perchloric acid and the like. Examples of the protonic acid ester having pKa of 1.0-position include sulfonic acid esters such as methyl benzenesulfonate, ethyl benzenesulfonate, methyl p-toluenesulfonate and ethyl p-toluenesulfonate, and inorganic protonic acid such as dimethyl sulfate. And the like. Examples of the Lewis acid and its complex include titanium tetrachloride, tin tetrachloride, zinc chloride, aluminum chloride, trifluoroborane, trifluoroborane ether complex and the like. Examples of the alkyl halide include methyl iodide, ethyl iodide, propyl iodide, butyl iodide, benzyl iodide, benzyl bromide and the like. These catalysts can be used alone or in combination of two or more.
The amount of these catalysts used is not particularly limited, but is usually 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the polyether.

To produce a crosslinked resin by reacting the polyether of the present invention, the polyether and the above catalyst may be mixed and heated and reacted. The heating reaction temperature at this time is preferably Tg of the polyether or more, more preferably Tg + 20 ° C., and particularly preferably Tg + 40 ° C. or more. If the temperature is too high, the polyether may be deteriorated, so that the reaction is preferably carried out at 350 ° C. or lower.

The reaction time may be a time sufficient for the target resin to be sufficiently cured, and this time varies depending on the type of polyether used, the amount of catalyst added, the reaction temperature, etc.
It is preferably 10 seconds to 60 minutes, more preferably 20 seconds to 45 minutes, and particularly preferably 1 minute to 30 minutes. The reaction can be performed under normal pressure to under pressure.

<Effects of the Invention> The crosslinked polymer thus obtained is a resin having excellent heat resistance and chemical resistance while retaining the mechanical properties of the thermoplastic resin polyether.

The resin thus obtained can be preferably used not only as a resin alone but also as a matrix resin for a composite material, for example. When used as the application, the fiber may be impregnated by a solution method, or the composition before heat curing may be melt-molded into a fiber or a sheet, and this and a reinforcing fiber may be so-called F / F composite. A method of forming or laminating can also be preferably carried out.

<Examples> Hereinafter, the present invention will be described in detail with reference to Examples, but the Examples are for the purpose of illustration, and the present invention is not limited thereto.

 In the examples, "part" means "part by weight".

The reduced viscosity (ηsp / c) of the polymer was measured at a concentration of 1 g / dl at 30 ° C. using N-methyl-2-pyrrolidone as a solvent. The second-order transition point (Tg) and melting point (Tm) of the polymer are
It measured using SDC at the temperature rising rate of 10 degree-C / min.

Example 1 57.43 parts of 4,4'-dichlorodiphenyl sulfone, 43.36 parts of bisphenol A, 2- (3,5-dihydroxyphenyl)
-2-oxazoline 1.79 parts, anhydrous potassium carbonate 60.81
Parts, 176 parts of dimethyl sulfoxide, and 50 parts of toluene were placed in a reactor equipped with a stirrer and a Dean-Stark trap, and the system was heated to an internal temperature of 150 ° C while blowing nitrogen into the system, and water was distilled off. While reacting for 6 hours. The obtained reaction product was poured into methanol to be solidified and then pulverized to obtain chips having a particle size of 500 μm or less. The chips were subjected to extraction treatment under methanol reflux three times and water reflux three times to obtain dimethyl sulfoxide and an inorganic substance. The salt was removed. Then, it was dried at 100 ° C. for 4 hours. The obtained polymer has ηsp / c = 0.71, Tg
= 189 ° C, Tm could not be observed. Then, 10 parts of this polymer and 0.1 part of methyl p-toluenesulfonate were thoroughly mixed and heated at 230 ° C. for 30 minutes to obtain a light yellow transparent tough resin. The resin was completely insoluble in various solvents.

Example 2 The amount of bisphenol A of Example 1 was adjusted to 41.07 parts, 2- (3.5
-Dihydroxyphenyl) -2-oxazoline in an amount of 3.
The reaction and post-treatment were carried out in the same manner as in Example 1 except that the amount was 58 parts. The obtained polymer had ηsp / c = 0.58 and Tg = 189 ° C., and Tm could not be observed.

Next, 10 parts of the polymer and 0.1 part of benzenesulfonic acid were dissolved in 40 parts of chloroform to prepare a film by a casting method. Then, the film was heated at 230 ° C. for 30 minutes to obtain a light yellow transparent tough resin. The resin was completely insoluble in various solvents.

Example 3 4-fluoro-3 '-(p-fluorobenzoyl) benzophenone 4.83 parts, hydroquinone 1.32 parts, 2- (3,5
-Dihydroxyphenyl) -2-oxazoline 0.54 parts,
2.07 parts of anhydrous potassium carbonate and 12.2 parts of sulfolane were placed in a reactor equipped with a stirrer and a distillation system, and the system was replaced with nitrogen, and then reacted at 200 ° C. for 60 minutes under a nitrogen atmosphere under normal pressure. Then, the temperature was raised to 230 ° C., 90 minutes, 250 ° C., 60 minutes, 270 ° C., and reacted for 60 minutes. Next, the reaction product was cooled and then poured into methanol, and the precipitate was crushed into chips, which were then extracted and dried in the same manner as in Example 1. The obtained polymer is η
sp / c = 0.96, Tg = 154 ° C., and Tm was not detected.

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

Example 4 4,4'-Dichlorodiphenylsulfone 51.69 g, 2,6-dichlorobenzonitrile 3,44 g, 2- (3,5-dihydroxyphenyl) -2-oxazoline 1.79 parts, bisphenol A4
3.36 parts, anhydrous potassium carbonate 60.81 parts, dimethylsulfoxide 176 parts, toluene 50 parts are stirred and Dean-Stark.
A reactor equipped with a trap was put into the system, and the system was heated so that the internal temperature became 150 ° C. while blowing nitrogen into the system, and the reaction was carried out for 5 hours while distilling water off. Then, the obtained reaction product is poured into methanol to be solidified and then pulverized to obtain chips having a particle size of 500 μm or less. The chips are subjected to extraction treatment under methanol reflux three times and water reflux three times to obtain dimethyl sulfoxide and The inorganic salt was removed. Then, it was dried at 100 ° C. for 4 hours. The obtained polymer had ηsp / c = 0.60 and Tg = 184 ° C., and Tm could not be observed. Then, 10 parts of this polymer and 0.1 part of benzenesulfonic acid were mixed well and heated at 250 ° C. for 10 minutes to obtain a light yellow transparent tough resin. Further, this resin was completely insoluble in various solvents.

Example 5 4,4'-Dichlorodiphenylsulfone 6.46 parts, 2- (2,6
-Difluorophenyl) -2-oxazoline 0.46 parts, 4,
4'-Dihydroxydiphenyl 4.66 parts, anhydrous potassium carbonate 3.46 parts, and dimethylsulfoxide 11 parts were placed in a reactor equipped with a stirrer and a distillation system, and the system was replaced with nitrogen, and then the mixture was replaced with nitrogen under atmospheric pressure at 220 ° C for 60 minutes. It was made to react. Then 250
The reaction was carried out at 120 ° C for 120 minutes. Next, the reaction product was cooled and then poured into methanol, and the precipitate was crushed into chips, which were then extracted and dried in the same manner as in Example 1. The obtained polymer had ηsp / c = 0.52 and Tg = 212 ° C., and Tm could not be detected. Then, 10 parts of this polymer and 0.1 part of ethyl p-toluenesulfonate were thoroughly mixed and heated at 250 ° C. for 10 minutes to obtain a light yellow transparent tough resin. Further, this resin was completely insoluble in various solvents.

Claims (3)

(57) [Claims] 1. The following formulas (I), (II) and / or (II)
I) and -O-Ar -... (I) In the aromatic polyether composed of, at least a part of Ar is represented by the following formula (IV) Or at least a part of Z is the following formula (V) [Where X ₁ is the same as the definition of the above formula (IV). ] The reduced viscosity (concentration 1.0 g / dl) measured at 30 ° C. in N-methyl-2-pyrrolidone is 0.25.
The above is an aromatic polyether. 2. The following formula (VI) The aromatic dihydroxy compound containing at least a part of the aromatic dihydroxy compound represented by, a dihalogen compound in which substantially equimolar halogen is activated with respect to the aromatic dihydroxy compound, and a halogen if necessary The reaction with an activated halogenophenol in the presence of an alkali.
A method for producing the aromatic polyether described. 3. The following formula (VII) And a halogen-activated aromatic dihalogeno compound containing at least a portion of the halogen-activated aromatic dihalgeno compound, and a substantially equimolar amount of aromatic dihydroxy with respect to the aromatic dihalogeno compound. The method for producing an aromatic polyether according to claim 1, wherein the compound is reacted with a halogenophenol in which halogen is activated, if necessary, in the presence of an alkali.