JPH04183720A - Production of aromatic poly(thio)ether ketone - Google Patents

Abstract

PURPOSE:To obtain the subject ketone, excellent in mechanical and electrical properties, etc., and useful as engineering plastics by using an aromatic monocarboxylic acid halide having a specific structural formula as a molecular weight modifier. CONSTITUTION:An aromatic compound expressed by formula II [X1 and X2 are 0 or S; Ar1 and Ar2 are monofunctional aromatic residue; Ar3 and Ar4 are bifunctional aromatic residue; A is backbone chain units expressed by formula III (R1 and R2 are halogen except F)] is reacted with an aromatic dicarboxylic acid dihalide expressed by formula IV (R3 to R10 are H, halogen, etc.; Y is direct bond, O or S; Z is halogen; m is 0-3) in the presence of anhydrous ferric chloride using an aromatic monocarboxylic acid halide expressed by formula I (R11 to R15 are H, halogen, hydrocarbon or alkoxy; Z is halogen) as a molecular weight modifier and the resultant polymer is then treated in the presence of water to afford the objective ketone expressed by formula V (Y is direct bond, O or S).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides Il! of aromatic poly(thio)etherketones.
Decide how to make it. More specifically, aromatic poly(thio) is useful as an engineering plastic with excellent mechanical properties, electrical properties, heat resistance, chemical resistance, and 1-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 $971, Specification No. 227, JP-A-59-
159826), or diphenyl ether,
A method of reacting isophthalic acid and/or terephthalic acid or their acid halides using phosphorus pentoxide/methanesulfonic acid or phosphorus pentoxide/trifluoromethanesulfonic acid as a catalyst [for example, JP-A-58-87
No. 127, M, Ieda et al., Macromol, Chem, Rapid, C.
ommun) 5.833 (I985)] 2) A method of reacting phenoxybenzoic acid or its acid halide using a Friedelkraff catalyst such as anhydrous aluminum chloride or hydrogen fluoride/boron trifluoride (for example, -18311, U.S. Patent No. 3,442,857, British Patent II 1,3
87,303), or a method of reacting phenoxybenzoic acid or its acid halide in polyphosphoric acid [for example, Iwakura et al., Journal of Polymer Science (J, Polyner, 5ci) Part-1
, q, 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
lym, Chem, Ed) 23,2205 (L98
5)] etc.

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
No. 81-213219, 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, Pol
ymer, 5science) Part-14, 237
5 (I967), T.E. Atwood (T.E.
Polymer, 2
5. (8), 109B (I981), Hans R, Kr1che
Polymer 2
5,11501984) C2) Methods such as a method in which an alkali metal salt of halophenol is reacted in a high boiling point aprotic polar solvent (for example, JP-A-53-10696) can be mentioned.

(Problem to be solved by the invention) However, the aromatic poly(
Since thio)ether ketones generally have rigid molecular chains and are crystalline polymers, they have extremely poor solubility in solvents. Therefore, under relatively mild synthesis conditions such as those used in electrophilic substitution reactions, the polymer precipitates during the polymerization 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 a polymer, a method using a special highly corrosive solvent system such as hydrogen fluoride/boron trifluoride has been proposed.

This method has the disadvantage that a special material must be used for the reaction vessel.

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-products 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]
3B, (I1), 603 (I985)] are also known. However, the polymer obtained by this method has a molecular weight of 1. ooo 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 with unsatisfactory practical physical properties including a crosslinked structure6.Also, Raabe et al.
It is stated that under synthesis conditions with a high monomer concentration, a gel component is generated during one reaction, and it is assumed that the resulting polymer has a crosslinked structure.

In order to solve the drawbacks of these conventional techniques, a specific aromatic compound and an aromatic dicarboxylic acid civalide are reacted in an organic solvent in the presence of a Lewis acid, and then the product is treated in the presence of water. By.

A method for easily obtaining a high molecular weight aromatic poly(thio)etherketone that does not contain a gel component and does not have a crosslinked structure has also been proposed [for example, Japanese Patent Application No. 2-65594].
There was a problem in that polymer precipitation occurred during polymerization, making it extremely difficult to take out the polymer. As a result of stacking, certain aromatic compounds.

By reacting aromatic dicarboxylic acid cybalide in the presence of a specific Lewis acid in an organic solvent at a temperature range of 0 to 100°C, and further using aromatic monocarboxylic acid chloride as a molecular weight regulator, after the reaction is completed. It has been found that the polymer can be easily obtained in solution form without precipitation from the reaction system. Furthermore, by recovering the polymer from the solution and treating the obtained polymer in the presence of water, a high molecular weight aromatic poly(thio)etherketone containing no gel content and having no crosslinked structure can be obtained. They discovered this and completed the present invention.

That is, the present invention is based on the general formula (I) %Formula %(I) [wherein, X+ and X2 represent an oxygen atom or a sulfur atom which may be the same or different, and A r + and A
r 2 represents a monovalent aromatic residue which may be the same or different, A r 3 and A ra represent a divalent aromatic residue, A is the main chain represented by C- represents the unit (however, R+ and R2
represent halogen atoms, excluding fluorine atoms, which may be the same or different. ) and the general formula (■) Re R5RI9R9 (wherein, R3 to Rye represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, and Y represents a direct bond, an oxygen atom, or a sulfur atom). (where Z represents a halogen atom and m is an integer of 0 to 3) is reacted in an organic solvent in the presence of anhydrous ferric chloride as a specific Lewis acid. In the general formula (m) Re R5R1@R9 c, Ar+ to Ar a represent divalent aromatic residues which may be the same or different, and Xl and X2 are oxygen groups which may be the same or different. represents an atom or a sulfur atom, and A represents a main chain unit represented by I C- (provided that R+ and R2
represent halogen atoms, excluding fluorine atoms, which may be the same or different. ), R3-R111 is a hydrogen atom,
represents a halogen atom, a hydrocarbon group or an alkoxy group, Y represents a direct bond, an oxygen atom or a sulfur atom, m
By producing an aromatic polymer having a repeating unit represented by U, where is an integer from O to 3, and then treating the polymer in the presence of water.

General formula (IV) Re Rs R+eR9 (wherein A r + to ArA represent divalent aromatic residues which may be the same or different, X+ and X2 are oxygen atoms or sulfur which may be the same or different represents an atom, R3 to Ry1+ represent a hydrogen atom, )) a rogen 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. , ) to an aromatic poly(thio)etherketone having a repeating unit represented by
In the method for obtaining thio)etherketone, general formula (V) is used as a molecular weight regulator (wherein, R to R+s represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, and Z2 represents a halogen atom). The present invention relates to a method for producing an aromatic poly(thio)etherketone, which is characterized by using an aromatic monocarboxylic acid halide represented by the following.

The first step of the present invention, which is the production of an aromatic polymer having a repeating unit represented by the general formula (m), consists of an aromatic compound represented by the general formula ([) and a repeating unit represented by the general formula (II). This reaction is carried out by reacting the aromatic dicarboxylic acid cybalide with a specific Lewis acid in an organic solvent.

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, 1.1 '-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 + 1.1'-bis( 3-phenylthiophenyl) dichloromethane + 1.1'-bis(4-phenylthiophenyl) dibromomethane, 1.
1'-bis(3-phenylthiophenyl) dibromomethane, 1, 1'-bis(4-phenylthiophenyl) short methane, 1. Examples include, but are not limited to, L'-bis(3-phenylthiophenyl) short methane. These aromatic compounds may be used alone or in combination.

In addition, these aromatic compounds may be synthesized and purified separately, but in general, many of these aromatic compounds are unstable to moisture or light, so the corresponding carbonyl compounds (e.g. , 1,1'-bis(4
-phenoxyphenyl) dichloromethane, a method using the corresponding carbonyl compound (4,4'-diphenoxybenzophenone, etc.) directly may be used. That is, after synthesizing and purifying the corresponding carbonyl compound by conventional methods.

After converting the aromatic compound represented by the general formula (I) used in the present invention using phosphorus halide, etc., this aromatic compound is not taken out from the reaction system, and a predetermined amount of aromatic dicarboxylic acid dichloride is added to it. In addition, it is subjected to polymerization. This method is more economically advantageous.

The aromatic dicarboxylic acid civalide represented by the general formula (■) 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, inphthalic 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 aromatic monocarboxylic acid halide represented by the general formula (V) used in the present invention includes benzoic acid chloride, benzoic acid bromide, 2-methylbenzoic acid chloride, 3-methylbenzoic acid chloride, and 4-methylbenzoic acid chloride. , 2-chlorobenzoic acid chloride, 3-
Examples include, but are not limited to, chlorobenzoic acid chloride and 4-chlorobenzoic acid chloride.

Further, these aromatic monocarboxylic acid halides may be used alone or in combination.

The amount of the aromatic dicarboxylic acid cybaride represented by the general formula (n) to be used is 0.5 to 1O1, preferably 0.8 to 2, in molar ratio to the aromatic compound represented by the general formula (I).
More preferably, it is 0.9 to 1.1.

It is difficult to obtain a high molecular weight aromatic poly(thio)etherketone in any range where the molar ratio is less than 0.5 or more than 1O.

Further, the amount of the aromatic monocarboxylic acid halide represented by the general formula (V) to be used is 0.2 to 0 in molar ratio to the aromatic dicarboxylic acid civalide represented by the general formula (II).
．． 0001, preferably 0.1 to 0.01. It is difficult to obtain a high molecular weight aromatic poly(thio)etherketone in any range where the molar ratio is less than 0.0001 or more than 0.2.

The particular Lewis acid used in the present invention is anhydrous ferric chloride. The amount of anhydrous ferric chloride to be used is determined by the general formula (n)
The molar ratio to the aromatic dicarboxylic acid cybaride represented by is 0.1 to 20, preferably 1 to 15, more preferably 2 to 7. If the molar ratio is less than 0.1,
High molecular weight aromatic poly(thio)etherketones are difficult to obtain. 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 (II)
The reaction temperature with the aromatic dicarboxylic acid cybaride represented by ) is 0°C to 100°C, preferably 20°C to 80°C, and more preferably 50°C to 70°C. If the reaction temperature is less than 0° C., the reaction progresses 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 not preferable.

Furthermore, examples of organic solvents used when reacting the aromatic compound represented by the general formula (I) with the aromatic dicarboxylic acid civalide represented by the general formula (I[) include nitrobenzene, dichloromethane, 1,2-dichloroethane, Carbon disulfide, 2-dichlorobenzene, chloroform, etc. are used.

These organic solvents may be used alone or in combination. The amount of organic solvent to be used is up to 2, preferably up to 1.5, per mole of the aromatic compound represented by general formula (I), considering economic aspects.

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 (m) into the aromatic poly(thio)etherketone represented by the general formula (IV). However, the weight ratio of water to aromatic polymer is preferably 1 to 1,000.

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.
Suitable acid catalysts include strong mineral acids such as hydrochloric acid, 611m, fluorosulfonic acid, sulfuric acid, etc., and p-toluene. Includes strong organic acids such as sulfonic acid, trifluoromethanesulfonic acid, and the like. The temperature for conversion is preferably 0°C to 300°C
, more preferably 50°C to 250°C. -The conversion rate is numerically 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. The logarithmic viscosity (η, .wa) of the obtained polymer was determined at 30°C at a concentration of 0.5 g/2 in 97% concentrated sulfuric acid.
Measured with the following calculation formula rnh" ↓ 1! ("
"-C However, -(I; Outflow time t of the solvent in the viscosity needle; Outflow time C of the polymer solution in the viscometer; Polymer solution concentration, 0.
5/dl Comparative Example 1 9.161 g (0,025 mol) of 4,4'-diphenoxybenzophenone and pentachloride were placed in a 500+ AL four-eye flask equipped with a stirrer, thermometer, and nitrogen inlet under a nitrogen stream. Phosphorus 5, 127 g (0,0275 mol) was added, the temperature was raised to 100'C, and the reaction was continued for 30 minutes.Then, while maintaining the system at 100'C, the pressure was reduced (l
The by-product phosphorus oxytrichloride and the 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. 3.045 g (0,015 moles) of terephthalic acid dichloride, 2.030 g (0,010 moles) of isophthalic acid dichloride, and 150 g (1 mol) of dichloromethane were placed in the reaction system which had been cooled to 0°C. While stirring the mixture, add 16.7 g (0,125 fl) of anhydrous aluminum chloride.
was added gradually. After reacting at 0°C for 1 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 completion of the reaction, the polymer had precipitated and could be easily taken out from the reactor. There wasn't. The obtained aromatic polymer was poured into 500 ml of methanol (5) to stop the reaction, crushed, and then mixed twice with 500 ml of methanol and 500 ml of distilled water.
Washed once with Il+1. After that, the above-mentioned pulverized aromatic polymer was added to 500+nl of 0.2% sulfuric acid aqueous solution.
Conversion was carried out at 5° C. for 2 hours. After the conversion treatment, washing was carried out twice with 500 ml of boiling demineralized water. Thereafter, it was washed with acetone and vacuum dried at 130°C overnight. The obtained polymer was a white powder with a yield of 12.0 (yield 96,
O illusion, F7: nh was 0.85.

Example 1 9.161 g of 1,1'-his(4-phenoxyphenyl)dichloromethane (0,0
25 mol), terephthalic acid dichloride 3.045 g (
0,015 mol), isophthalic acid dichloride 2.03
0 (0,010 f), benzoic acid chloride 0.28
1 g (0,002 mol) and 150 ml of dichloromethane were added, and the inside of the system was cooled to 0°C. While stirring the mixture,
12.2 g (0.07 fl.) of anhydrous ferric chloride were slowly added. After carrying out the nB reaction at 0°C for 1 hour, the temperature in the system was gradually raised and the reaction was carried out at 60°C for 8 hours with stirring.

After the reaction was completed, Polymer 1 did not precipitate and was a highly viscous solution that could be easily taken out from the reactor.

The obtained solution was poured into 500 ml of methanol to stop the reaction, and the aromatic polymer was separated and ground, and washed twice with 500 ml of methanol and once with 500 ml of distilled water.

Thereafter, the pulverized aromatic polymer was charged into 500 m+1 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 500w+1 boiling demineralized water. Thereafter, it was washed with acetone and vacuum dried at 130'C overnight. The obtained polymer was a white powder with a yield of 12.1. (yield 97.6%), '7:
nh was 1.02.

Example 2 In a 500 ml four-eye flask equipped with a stirrer, a temperature needle, and a nitrogen inlet, 9.161. (0,0
25 fl), terephthalic acid dichloride 3.045 g (
0.01 iron), isophthalic acid dichloride 2.030
(0,010 mol), benzoyl chloride 0.21b
After adding 150 g of dichloromethane and 1 liter of dichloromethane, the inside of the system was cooled to 0°C. While stirring the mixture,
12.2 [(0,075+l) of anhydrous ferric chloride was slowly added. After reacting at 0°C for 1 hour, the temperature in the system was gradually raised and the reaction was carried out at 60°C for 8 hours with stirring6.
After the reaction was completed, the polymer did not precipitate and was a highly viscous solution that could be easily taken out from the reactor.

The resulting solution was poured into 500 ml of methanol to stop the reaction, and the aromatic polymer was separated and ground, and washed twice with 500 ml of methanol and once with 500+ nl 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 process, it was washed twice with 500 ml of boiling demineralized water, followed by washing with acetone and vacuum drying at 130° C. overnight. The obtained polymer was a white powder with a yield of 12.1 g (yield 97.6%) and η. h
was 0.96.

(Effects of the Invention) As described above, according to the present invention, the polymer can be obtained in the form of a solution after polymerization under mild conditions without precipitation, and the polymer can be easily recovered. further converting the polymer,
High molecular weight aromatic poly(thio)etherketones can be produced.

Claims (1)

[Claims] General formula (I) A_r_1-X_1-A_r_3-A-A_r_4-X
_2-A_r_2(I) [where X_1 and X_2
represent oxygen atoms or sulfur atoms which may be the same or different, A_r_1 and A_r_2 represent monovalent aromatic residues which may be the same or different, and A_r_
3 and A_r_4 represent divalent aromatic residues, and A represents the 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. By reacting in a solvent, the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [In the formula, A_r_1 to A_r_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, A_r_1 to A_r_4 represent divalent aromatic residues which may be the same or different, and X_1 and
2 represents an oxygen atom or a sulfur 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, m is 0-3
is an integer up to . ) in the method of obtaining aromatic poly(thio)etherketone by converting it into aromatic poly(thio)etherketone having a repeating unit represented by the formula (V) as a molecular weight regulator. ▼(V) (In the formula, R_1_1 to R_1_5 represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, and Z_2
represents a halogen atom. ) A method for producing an aromatic poly(thio)etherketone, which is characterized by using an aromatic monocarboxylic acid halide represented by: