JPH03265629A - Production of aromatic poly(thio)ether ketone - Google Patents

Abstract

PURPOSE:To obtain the title high-mol. wt. crosslinkage-free compound easily under mild conditions by reacting a specified aromatic compound with a specified aromatic dicarboxylic acid dihalide under specified conditions and converting the obtained aromatic polymer into an aromatic poly(thio)ether ketone by treatment in the presence of water. CONSTITUTION:An aromatic compound of formula I [wherein X1 and X2 are each O or S; Ar1 and Ar2 are each a monovalent aromatic residue; Ar3 and Ar4 are each a bivalent aromatic residue; and A is a skeletal unit of formula II (wherein R1 and R2 are each halogen except F)] is reacted with an aromatic dicarboxylic acid dihalide of formula III (wherein R3 to R10 are each H, halogen, a hydrocarbon group or alkoxy; Y is a direct bond, O or S; Z is halogen; and m is 0-3) in the presence of a Lewis acid in an organic solvent to obtain an aromatic polymer having repeating units of formula IV (wherein Ar1 to Ar4 are each a bivalent aromatic residue). The obtained polymer is treated in the presence of water to convert it into an aromatic poly(thio)ether ketone having repeating units of formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing aromatic poly(thio)-thyl ketones. More details include mechanical properties, electrical properties, heat resistance, il! Aromatic poly(thio) useful as engineering plastics with excellent chemical properties and dimensional stability.
This invention relates to a method for producing ether ketone.

(Prior art) Various methods have been proposed for the synthesis of aromatic poly(thio)etherketones, and they can be roughly divided into synthesis methods using electrophilic substitution reactions and synthesis methods using nucleophilic substitution reactions. . Examples of the former include 1) a method in which diphenyl ether is reacted with isophthalic acid and/or terephthalic acid or their acid halides using a Friedel-Craft catalyst such as anhydrous aluminum chloride or anhydrous iron chloride (for example, the method described in U.S. Pat. ,065,205 specification,
British Patent No. 971, Specification No. 227, JP-A-59-1
No. 59826), or a method of reacting diphenyl ether with isophthalic acid and/or terephthalic acid or their acid halides using phosphorus pentoxide/methanesulfonic acid or phosphorus pentoxide/trifluoromethanesulfonic acid as a catalyst [e.g. Kaisho 58-871
No. 27, M, [Ieda] et al., Macromolecular Chemistry Rapid Communication (Akromo1.Che+*, Rapid, C
ommun) 5.833 (I985)] 2) A method of reacting phenoxybenzoyl or its acid halide using a Friedelkraff catalyst such as anhydrous aluminum chloride or hydrogen fluoride/boron trifluoride (for example, Japanese Patent Publication No. 45 -18311 Publication, U.S. Patent No. 3,442,857, British Patent No. 1,387
, 303 specification), or a method of reacting phenoxybenzoic acid or its acid halide in polyphosphoric acid [for example, Iwakura et al., Journal of Polymer Science (J, Polymer, 5ci) Part-1, 6
, 3345 (I968)] 3) A method of reacting diphenyl ether and phosgene using a Friedelkraff catalyst such as anhydrous aluminum chloride [for example, JP-A-61-221228;
Publication No. 61-221229, No. 62-1469
No. 23, No. 82-241922, C, S, Marvel et al., Journal of Polymer Science, Polymer Chemistry Edition (J, Polymer, Sci; Po
1ylI1. Chem, Ed) 23.2205 (I
985).

Examples of the latter include: 1) A method in which dihalogenobenzophenone and an alkali metal salt of dihydric phenol or a silyl ether compound are reacted in a high boiling point aprotic polar solvent [for example, JP-A-61-197632; 61-221227
Publication No. 61-213219, No. 62
-7729 publication, 62-7730 publication, 62-7730 publication
Publication No. 2-148523, A., G. Phanfam (
A, G. Farnham) et al., Journal of Polymer Science (J, Polymer, 5cienc)
e) Part-1, 5, 2375 (I967), T.E. ALtwood et al.
Polymer, 25. (8), 1096
(I981), Hans Earl Kricheldorff (
Polymer (Hans R, Krcheldorf) et al.
Polymer) 25, 1151 (I984) 2) A method of reacting an alkali metal salt of halophenol in a high boiling point aprotic polar solvent (for example, JP-A No. 5
3-10696).

(111! Problems to be Solved by the Invention) However, aromatic poly(thio)etherketones obtained by these synthetic methods generally have rigid molecular chains and are crystalline polymers, so they have poor solubility in solvents. is extremely inferior. Therefore, under relatively mild synthesis conditions such as those used in electrophilic substitution reactions, the polymer precipitates during the pentapolymerization process, making it difficult to obtain a high molecular weight product. Methods such as copolymerization have been attempted to obtain high molecular weight materials, but the crystallinity of the resulting polymers is impaired or the heat resistance is reduced.

In addition, as another attempt to obtain high molecular weight substances, a method using a highly corrosive special solvent system such as hydrogen fluoride/boron trifluoride has been proposed, but this method uses a special material for the reaction vessel. It has the disadvantage that it requires the use of other materials.

On the other hand, in the synthesis method of poly(thio)etherketone by nucleophilic substitution reaction, an expensive raw material such as difluorobenzophenone having a more active fluorine group is used as a leaving group in order to obtain a high molecular weight product. With,
For example, it is necessary to carry out the reaction in a high boiling point solvent such as diphenyl sulfone at a high temperature of 300° C. or higher, which has many disadvantages from an economic point of view. Furthermore, the polymer thus obtained has the disadvantage that by-product acids such as highly corrosive fluorine salts tend to remain. Furthermore, since the reaction temperature is high, it also has the disadvantage that undesirable side reactions such as gelation are likely to occur during the reaction.

Also diphenyl ether and bis(trichloromethyl)
A method of reacting benzene with Friedelkrach catalyst in the presence of a Friedelkrach catalyst [D. Raabe, H. H. Horhold et al., Acta, Polymerica]
36. (I1), 603 (I985) are also known. However, the polymer obtained by this method has a molecule j of 13,000 or less, and other physical properties are not described.

According to the results of additional tests conducted by the present inventors, the obtained polymer was a low molecular weight polymer that contained a crosslinked structure and was unsatisfactory in terms of practical physical properties. Raabe et al. also describe that under synthesis conditions with a high monomer concentration, a gel component is generated during the reaction, and it is presumed that the resulting polymer has a crosslinked structure.

(Means for Solving the Problems) As a result of intensive research to solve the drawbacks of the above-mentioned conventional techniques, the present inventors have discovered that a specific aromatic compound and an aromatic dicarboxylic acid civalide are combined in the presence of a Lewis acid. By reacting in an organic solvent and then treating the product in the presence of water, a high molecular weight aromatic poly(thio)etherketone containing no gel content and no crosslinked structure can be easily obtained. I found out that this invention is a distant relative.

That is, the present invention is based on the general formula (I) % formula % () [wherein Xl and X2 represent an oxygen atom or an alkoxy group which may be the same or different, and A r + and A, 2 are the same and A + 3 and A r a represent monovalent aromatic residues which may also be different, A + 3 and A r a represent divalent aromatic residues, and A represents a main chain unit represented by 1 C-2 (however, , R1 and A represent a halogen atom excluding a fluorine atom, which may be the same or different.)] and the aromatic compound represented by the general formula (II) R1 (wherein -R3 to RIII are hydrogen atoms , represents a halogen atom, a hydrocarbon group or an alkoxy group, Y is a direct bond,
wl represents an elementary atom or an alkoxy group, Z represents a halogen atom, and m is an integer of O to 3. ) is reacted in an organic solvent in the presence of a Lewis acid to form a main chain unit represented by the general formula (I[[) (where R7 and A are the same). ), R3-R411 represents a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group, and Y
represents a straight hydrocarbon group or an alkoxy group, and m is O~
It is an integer up to 3. ] By producing an aromatic polymer having a repeating unit represented by formula (IV) [wherein -Ar+ to Ar4 are the same or different], the polymer is then treated in the presence of water. XI and X2 represent an oxygen atom or an alkoxy group which may be the same or different; A represents a divalent aromatic residue which may be the same or different;

R9 of R5R5R+ (wherein A r + to A r < represent divalent aromatic residues which may be the same or different; Xl and X2 represent an oxygen atom or an alkoxy group which may be the same or different; , R3-R11I represents a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group, Y represents a straight hydrocarbon group or an alkoxy group, and m is an integer from O to 3.) It relates to a method for producing an aromatic poly(thio)etherketone, which comprises converting the aromatic poly(thio)etherketone into an aromatic poly(thio)etherketone having the following properties.

The 11th step of the present invention, which is the production of an aromatic polymer having a repeating unit represented by general formula (m), consists of an aromatic compound represented by general formula (I) and a general formula (If).
This reaction is carried out by reacting an aromatic dicarbonylmonosybalide represented by the formula in an organic solvent in the presence of a Lewis acid.

Examples of the aromatic compound represented by the general formula (I) used in the present invention include 1,1'-bis(4-phenoxyphenyl)dichloromethane, 1,1'-bis(3-phenoxyphenyl)dichloromethane, l, 1 '-Bis (4
-phenoxyphenyl)dibromomethane, 1,1'-bis(3-phenoxyphenyl)dibromomethane, 1.1
'-bis(4-phenoxyphenyl) short methane,
1.1'-bis(3-phenoxyphenyl) short methane, 1, 1'-bis(4-phenylthiophenyl)dichloromethane, 1. P-his(3-phenylthiophenyl)dichloromethane, 1,1'-bis(4-phenylthiophenyl)dibromomethane, I,1'-bis(3-phenylthiophenyl)dibromomethane, 1,1'-bis (4-phenylthiophenyl) short methane, 1.1
Examples include '-bis(3-phenylthiophenyl) short methane, but are not necessarily limited to these. These aromatic compounds may be used alone or in combination.

In addition, these aromatic compounds may be separately purified by autoclaving, but in general, many of these aromatic compounds are unstable to moisture or light, so the corresponding carbonyl compound ( For example, 1,1'-bis(4
-phenoxyphenyl) dichloromethane, a method using the corresponding carbonyl compound (4,4'-diphenoxybenzophenone, etc.) directly may be used. That is, the corresponding carbonyl compound is synthesized by the usual method and 1f
tl! After that, the aromatic compound represented by the general formula (I) used in the present invention is converted into the aromatic compound represented by the general formula (I) using phosphorus halide, and the aromatic compound is not taken out from the reaction system.
A predetermined amount of aromatic dicarboxylic acid dichloride is added to this and subjected to polymerization. This method is more economically advantageous.

The aromatic dicarboxylic acid civalide represented by the general formula (n) used in the present invention includes terephthalic acid dichloride, isophthalic acid dichloride, diphenylmethane-4,4'-dicarbonyl dichloride, and diphenyl-4,4'-dicarbonyl dichloride. , diphenyl ether-4,4'-dicarbonyl dichloride, benzophenone-4,4'-dicarbonyl dichloride, naphthalene-2,6-dicarbonyl dichloride, naphthalene-1,4-dicarbonyl dichloride, terephthalic acid dibromide, isophthalic acid Examples include dibromide, but are not necessarily limited to these.

Further, these aromatic dicarboxylic acid cybarides may be used alone or in combination.

The amount of aromatic dicarboxylic acid cybalide represented by general formula (II) to be used is 0.5 to 10.0 molar ratio to the aromatic compound represented by general formula (I). Preferably 0.8-2
, more preferably from 0.9 to 1.1.

If the molar ratio is less than 0.5 or more than 10, it is difficult to obtain a high molecular weight aromatic poly(thio)etherketone.

Lewis acids used in the present invention include, but are not necessarily limited to, aluminum chloride, aluminum bromide, ferric chloride, tin chloride, titanium tetrachloride, boron trifluoride, and antimony pentachloride. It's not something you can do.

These Lewis acids may be used alone or in combination. The amount of these Lewis acids used is 0.1 to 20, preferably 1 to 15, more preferably 2 to 7 in molar ratio to the aromatic dicarboxylic acid cybaride represented by general formula (n). When the molar ratio is less than 0.1, it is difficult to obtain a high molecular weight aromatic poly(thio)etherketone. Moreover, when it exceeds 20, it is not preferable from an economic point of view.

Aromatic compounds represented by general formula (I) and general formula (If
) The reaction temperature with the aromatic dicarboxylic acid cybaride represented by is -50°C to 100°C, preferably -10°C to 8°C.
The temperature is 0°C, more preferably -10°C to 50°C. If the reaction temperature is less than 150° C., the reaction proceeds but is slow and uneconomical. On the other hand, if the reaction temperature exceeds 100°C, aromatic poly(thio)etherketone having a crosslinked structure tends to be produced, which is undesirable. Examples of organic solvents used in the reaction with the aromatic dicarboxylic acid cybaride shown above include nitrobenzene, dichloromethane, 1,2-dichloroethane, carbon disulfide, 1,2-dichlorobenzene, and chloroform.

These organic solvents may be used alone or in combination. What is the amount of organic solvent used?

Considering the economical aspect, the amount is up to 2Q, preferably up to 1.5ff per mol of the aromatic compound represented by the general formula (I).

The second step of the present invention is a method of treating an aromatic polymer having a repeating unit represented by general formula (m) to obtain an aromatic poly(thio)etherketone represented by general formula (IV). , in the presence of water under heterogeneous or homogeneous conditions. Heterogeneous conversion is generally caused by excess water;
This is optionally carried out by treatment in the presence of an organic solvent and a dilute acid catalyst. The amount of water used is sufficient as long as it is the amount necessary to convert the aromatic polymer represented by the general formula (III) into the aromatic poly(thio)etherketone represented by the general formula (rV). However, the weight ratio of water to aromatic polymer is preferably 1-1000.

Larger amounts of water can also be used. Optional organic solvents include N-methylpyrrolidone, N,N'-
Examples include dimethylacetamide.

Also, the acid catalyst preferably has 0.0001 of the water present.
It can be used at concentrations from 0.005% to 2011%, most preferably from 0.005% to 2% by weight. Suitable acid catalysts include strong mineral acids such as hydrochloric acid, nitric acid, fluorosulfonic acid, sulfuric acid, and the like, and strong organic acids such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, and the like. The conversion temperature is preferably 0°C to 300°C, more preferably 50°C to 250°C. In general, the conversion rate is faster at higher temperatures. Conversion reaction time is complete within seconds or up to several hours.

The aromatic poly(thio)etherketone obtained in the present invention is soluble in 97% concentrated sulfuric acid and contains substantially no gel content. Further, the logarithmic viscosity (η, h) of the aromatic poly(thio)etherketone is 0.6 or more, preferably 0.6 or more.
It is 7 or more. When the logarithmic viscosity of the aromatic poly(thio)etherketone is less than 0.6, the strength when formed into a molded article or film is low and it does not have practical physical properties.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Note that the aromatic poly(thio)etherketone (polymer) obtained by the present invention is extremely difficult to dissolve in general organic solvents, so it is difficult to determine its average molecular weight. Therefore, the logarithmic viscosity measured in concentrated sulfuric acid was used as a measure of molecular weight. Logarithmic viscosity (η, .h
) is measured at 30°C at a concentration of 0.5 g/J in 97% concentrated sulfuric acid and calculated using the following formula (%). However, - (I: Outflow time of the solvent in the viscosity needle t: Solution outflow time C; polymer solution concentration, 0
．． 5g/di Furthermore, the physical properties of the polymer were measured as follows. Thermal properties are PERKIN-ELMER 7
DSC measurements were performed using the mold series. Mechanical properties are determined by press-molding the polymer at 360°C to 400°C.
Manufactured by Toyo Baldwin, TENSILON/[I
Tensile test measurements were carried out using TM-1-2500.

Infrared absorption spectroscopy (IR) is performed by Hitachi, Ltd. 11
The measurement was carried out using a Model 270-50 infrared spectrophotometer. 13
C-NMR spectrum analysis (I3C-NMR) was carried out using a G5X400 nuclear magnetic resonance spectrometer manufactured by JEOL, using tetramethylsilane (TMS) as an internal standard and deuterated chloroform solvent.

Comparative Example 1 9.161 g (0,025 mol) of 4,4'-diphenoxybenzophenone and 3.045 g (0,000 mol) of 4,4'-diphenoxybenzophenone were placed in a 500 IIll four-sided flask equipped with a stirrer, thermometer, and nitrogen inlet. ,015 mol), isophthalic acid dichloride 2.030 g (0.01
0 mol) and 150 ml of dichloromethane were added thereto, and the mixture was cooled to 0°C. While stirring the mixture, 10.0 g (0,075 mol) of anhydrous aluminum chloride was added. Thereafter, the temperature in the system was gradually raised, and the reaction was carried out at 10 to 25° C. with stirring for 24 hours. After the reaction is complete.

The reaction was stopped by pouring into 500 ml of methanol. The obtained polymer was washed twice with methanol 500+al, once each with 5% boiling @ acid aqueous solution and boiling m demineralized water, washed with acetone, and vacuum dried at 100° C. overnight. The obtained polymer was a white powder with a yield of 12.0
g (yield 96.8%). In addition, the polymer is 9
It was completely dissolved in 7% concentrated sulfuric acid and contained no gel content. The logarithmic viscosity of the polymer was 0.49. The R spectrum is shown in Figure 1. In addition, the results of single element analysis are shown below.

C: 79.77% (79,83%), H: 4.10% (
(4,06%) However, the numbers in parentheses are theoretical values.

From the above results, the structure of the obtained polymer was as shown below.

As a result of DSC analysis, the crystal melting point (Tm) was 345.6°C.
The heat of fusion (ΔHa) was 8.2 cal/g.

Comparative Example 2 In Comparative Example 1, terephthalic acid dichloride was 3.55
The reaction and analysis were carried out in the same manner as in Comparative Example 1, except that 3 g (0,0175 mol) of isophthalic acid dichloride and 1.523 g (0,0075 mol) of isophthalic acid dichloride were used. As a result, Polymer 1 having the same structure as Comparative Example 1 and having a logarithmic viscosity of 0.55
1.6 g (yield 93.5%) was obtained. As a result of DSC analysis, the crystal melting point (T+a) was 386.3℃, and the heat of fusion (△
Ha) was 7.6 cal/g.

Example 1 (continuous method) 9.161 g (0,025 mol) of 4,4'-diphenoxybenzophenone and 5 mol of phosphorus pentachloride were placed in a 500 ml four-tube flask equipped with a stirrer, a thermometer, and a nitrogen inlet under a nitrogen stream. Add .727g (0,0275 mol) and 1
The temperature was raised to 00°C and the reaction was continued for 30 minutes. Thereafter, the system was kept at 100° C. and the pressure was reduced (I00 m+lHz or less), and by-produced phosphorus oxytrichloride and remaining phosphorus pentachloride were removed from the system over a period of 30 minutes. Thereafter, the temperature inside the system was cooled to room temperature. The IR spectrum and 13C-NMR spectrum of the product are shown in Figures 2 and 3, respectively. For comparison, the IR spectrum of 4,4'-diphenoxybenzophenone and H'3c-
The NMR spectra are shown in FIGS. 4 and 5, respectively. It is clear from Figure 312 and Figure 3 that < 1650c
tn-' (IR) and 194. lppm (I3C
The absorption peak based on the carbonyl bond of -NMR) completely disappeared, and a new peak of 570c11.520cm-' (I
An absorption peak based on the dichloromethylene structure was confirmed at 91.6 ppm (3C-NMR).

From the above results, the synthesis of the desired 1,1'-bis(4-phenoxyphenyl)dichloromethane was confirmed.

In a 500 ml four-tube flask equipped with a heavy-duty stirrer, a thermometer, and a nitrogen inlet, 9.181 g (0,025 mol) of 4,4'-diphenoxybenzophenone and 5 mol of phosphorus pentachloride were added under a nitrogen stream. Add .727g (0,0275mol), 1
The temperature was raised to 00'C, and the reaction was allowed to continue for 30 minutes. After that, the pressure inside the system was reduced (loOa+m
Hg or less), and by-produced phosphorus oxytrichloride and remaining phosphorus pentachloride were removed from the system over a period of 30 minutes.

Thereafter, the temperature inside the system was cooled to 0°C. 3.04% of terephthalic acid dichloride was added to the above reaction system cooled to 0°C.
Section 5 (0,015 mol), isophthalic acid dichloride 2
．． 030 g (0,010 mol), dichloromethane 150
I put w+1. While stirring the mixture, 18.7 g (0.125 mol) of anhydrous aluminum chloride was gradually added. After reacting at 0°C for an hour, the temperature in the system was gradually raised and the reaction was carried out at 10°C for 18 hours with stirring. After the reaction was completed, the contents were poured into 500 ml of methanol to stop the reaction.

The aromatic polymer obtained was filtered and ground, and washed twice with 500 ml of methanol and once with 500 ml of distilled water. Thereafter, the pulverized aromatic polymer was added to 500 ml of a 0.2% sulfuric acid aqueous solution, and a conversion treatment was carried out at 175° C. for 2 hours. After conversion treatment, boil 11JI51 salt water 500ml
Washed twice. Then wash with acetone and heat to 130'C.
It was vacuum dried overnight. The obtained polymer was a white powder, and the yield was 12.0 g (yield 96.0%). The Beilstein test result was negative, confirming that the polymer did not contain chlorine.

Further, the polymer was completely dissolved in 97% concentrated sulfuric acid, and no gel content was present. Logarithmic viscosity was 0.89.

The IR spectrum of this polymer is shown in Figure 6.
The absorption peak based on the dichloromethylene structure at 70c11.520 cm-' completely disappeared, and the IR spectrum of the polyetherketone of Comparative Example 1 (FIG. 1) was the same. In addition, the results of elemental analysis are shown below.

C; 79.78% (79,83%), )l; 4.07%
(4,06%) However, the numbers in parentheses are theoretical values.

From the above results, it was found that the structure of the obtained polymer was as shown below.

Additionally, the results of DSC analysis showed a sharp crystal peak, with a crystal melting point (Tm) of 343.2°C and a heat of fusion (ΔHm).
) 8.1 cal/g.

As a result of press molding at 380°C, a milky white tough film was obtained and had the following mechanical properties.

Tensile strength: LO90Kg/cm2, elongation at break: 41
% Example 2 Dan-1 Kingoki stirrer, thermometer 5 1.1'-Bis(4
-phenoxyphenyl) dichloromethane 9.161 g (
0,025 mol), terephthalic acid dichloride 3.04
5g (0,015 mol), isophthalic acid dichloride 2
．． 030 g (0,010 mol), dichloromethane 150
ml was added and the inside of the system was cooled to 0°C.

While stirring the mixture, add anhydrous aluminum chloride 16-7
g (0,125 mol) were added gradually. After reacting at 0°C for 1 hour, the temperature in the system was gradually increased to 19°C at 10°C.
The reaction was allowed to proceed with stirring for a period of time. After the reaction was completed, the contents were poured into 500g+1 methanol to stop the reaction.

The obtained aromatic polymer was filtered and ground, and washed twice with 500 ml of methanol and once with 500 ml of distilled water.

Thereafter, the pulverized aromatic polymer was added to 500 ml of a 0.2% sulfuric acid aqueous solution, and a conversion treatment was performed at 175° C. for 2 hours. After the conversion treatment, washing was performed twice with boiling demineralized water 500+*1. Thereafter, it was washed with acetone and vacuum dried at 130°C overnight. The obtained polymer is a white powder,
The yield is 12. bc (yield 97.6%).

The Beilstein test result was negative, confirming that the polymer did not contain chlorine.

Further, the polymer was completely dissolved in 97% concentrated sulfuric acid, and no gel content was present.The logarithmic viscosity was 0.87.

The IR spectrum of this polymer was identical to that of the polyetherketone of Example 1 (Figure 6) and was essentially identical to the polymer of Example 1.

In addition, the results of DSC analysis showed a sharp crystal peak, the crystal melting point (Tm) was 344.5°C, and the heat of fusion (ΔHm)
It was 9.2 cal/g.

As a result of press molding at 380°C, a milky white tough film was obtained and had the following mechanical properties.

Tensile strength; 1010Kz/cm2. Breaking elongation: 5
8z Examples 3 to 5 were synthesized in the same manner as in Example 1. The results are shown in Table 2.

(Margin below) Examples 6-8 Shown in the table.

(The following is a blank space) (Effects of the invention) As described above, according to the present invention, under mild conditions,
Furthermore, high molecular weight aromatic poly(thio) does not contain a crosslinked structure.
Etherketones can be produced.

[Brief explanation of drawings]

1 [Figure 1 is the IR spectrum of the polymer obtained in Comparative Example 1, and Figures 2 and 11 to 3 are the IR spectra of the polymer obtained in Comparative Example 1.
The IR spectrum and NMR spectrum of 4-phenoxyphenyl)dichloromethane are shown, respectively, and Figures 4 and 5 show the I of 4,4'-diphenoxybenzophenone.
The R spectrum and NMR spectrum are shown respectively, and the sixth
The figure shows an IR spectrum of the polymer obtained in Example 1.

Claims (1)

[Claims] General formula (I) Ar_1-X_1-Ar_3-A-Ar_4-X_2-
Ar_2 (I) [wherein X_1 and X_2 represent oxygen atoms or sulfur atoms which may be the same or different; Ar_1 and Ar_2 represent monovalent aromatic residues which may be the same or different; , Ar_3 and Ar_
4 represents a divalent aromatic residue, and A represents a main chain unit represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 and R
_2 represents a halogen atom excluding a fluorine atom, which may be the same or different. )] and the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_3 to R_1_0 represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, Y represents a direct bond, an oxygen atom or a sulfur atom, Z represents a halogen atom, and m is an integer of 0 to 3. The reaction produces the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [In the formula, Ar_1 to Ar_4 represent divalent aromatic residues which may be the same or different, and X_1 and X_2 represents an oxygen atom or a sulfur atom, which may be the same or different, and A represents a main chain unit represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 and R
_2 represents a halogen atom excluding a fluorine atom, which may be the same or different. ), R_3 to R_1_0 represent a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group, Y represents a direct bond, an oxygen atom or a sulfur atom, and m is an integer from 0 to 3. ] By producing an aromatic polymer having a repeating unit represented by the formula and then treating the polymer in the presence of water, the general formula (IV) ▲Mathematical formula, chemical formula, table, etc.▼(IV) (In the formula, Ar_1 to Ar_4 represent divalent aromatic residues which may be the same or different, X_1 and X_2 represent oxygen atoms or sulfur atoms which may be the same or different, and R_3 to R_1_0 are represents a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group, Y represents a direct bond, an oxygen atom or a sulfur atom, and m is an integer from 0 to 3. A method for producing an aromatic poly(thio)etherketone, which comprises converting it into a (thio)etherketone.