JPH0245520A - Production of crystal aromatic poly(thio)ether ketone - Google Patents

Abstract

PURPOSE:To obtain the subject polymer, excellent in mechanical, electrical properties, heat, chemical resistance, etc., and useful as engineering plastics by reacting specific two kinds of aromatic compounds in the presence of a Friedel-Crafts catalyst and hydrolyzing the resultant product. CONSTITUTION:The objective polymer obtained by reacting an aromatic compound expressed by formula I (X1 and X2 are O or S; Ar1 to Ar3 are bifunctional aromatic residue) [e.g., 1,4-bis(p-phenoxybenzoyl)benzene] with an aromatic compound expressed by formula II (R1 to R6 are halogen; Ar4 is bifunctional aromatic residue) [e.g., 1,4-bis(trichloromethyl)benzene] in the presence of a Friedel-Crafts catalyst (e.g., aluminum chloride) and hydrolyzing the resultant product.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a crystalline aromatic poly(thio)etherketone. More specifically, the present invention relates to a method for producing crystalline aromatic poly(thio)etherketone useful as engineering plastics having excellent mechanical properties, electrical properties, heat resistance, chemical resistance, dimensional stability, etc.

[Conventional technology]

Various methods have been proposed for the synthesis of aromatic poly(thio)etherketones, which can be roughly divided into synthesis methods using electrophilic substitution reactions and synthesis methods using nucleophilic substitution reactions. Examples of the former include l) a method of reacting diphenyl ether 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, as described in US Pat. Specification No. 3,065,205,
British Patent No. 971,227, JP-A-59-15
9826), 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 (for example, Kaisho 58-8712
Publication No. 7, M Ueda et al., Macromolecular Chemistry 7. Rapiuto Communication (MakroIllol, Chell, R
apidCoIIlmun) 5, 833 (1
985)) 2) A method in which phenoxybenzoic acid or its acid halide is reacted using a Friedelkraff catalyst such as anhydrous aluminum chloride or hydrogen fluoride/boron trifluoride (for example, Japanese Patent Publication No. 18311/1983, US Patent No. 3,442,857, British Patent No. 1
, 387, 303), or a method in which phenoxybenzoic acid or its acid halide is reacted in polyphosphoric acid (for example, Iwakura et al., Journal Otsu Polymer.
Science (J, Polymer, Sci) Pa
rt-1,6,:l345 (1968) ), 3) A method in which diphenyl ether and phosgene are reacted using a Friedelkraff catalyst such as anhydrous aluminum chloride (for example, JP-A No. 61-221228, No. 61-
No. 221229, No. 62-146923, No. 62-241922, Sea Nis Marvel <C
, S, Marvel) et al., Journal of Polymer Science, Polymer Chemistry Edition (J, Polymer, Sci; Polym,
Chem.

Ed) Sen, 2205 (+985)), etc.

Examples of the latter include l) a method in which a dihalogenobentzphenone and an alkali metal salt of a 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, 61-213219, 62-7729, 62-7730, 62-+4852:
Publication No. 1, A.C. Funfam (A, G, F
Arnham et al., Journal of Polymer Science (J, Polymer, 5science)
Part-1, 5, 2375 (1967), T.E. Atwood (T.E.

ALtwood) et al., Boria-(Polymer
) 25. (8).

1096 (1981), 1lans R, Kr1cheldorf
) et al., Polymcr 25.1151 (
+984) ), 2) A method of reacting an alkali metal salt of halophenol in a high boiling point aprotic polar solvent (
For example, the method described in Japanese Patent Application Laid-Open No. 5:1-10696) can be mentioned.

(Problem to be solved by the invention) However, these aromatic poly(thio)etherketones generally have rigid molecular chains and are crystalline polymers, so they have extremely poor solubility in solvents. Synthesis conditions at relatively mild temperatures, such as those used in electron substitution reactions, have the disadvantage that it is difficult to obtain high molecular weight products because the polymer precipitates during the polymerization process.In order to obtain high molecular weight products, copolymerization, etc. The method of fluoride/
Some methods have been proposed that use a special highly corrosive solvent system such as boron fluoride, which has the drawback of requiring the use of a special material for the reaction vessel.

On the other hand, in the synthesis method of poly(thio)etherketone by nucleophilic substitution reaction, in order to obtain a polymer, an expensive raw material such as difluorobenzophenone having a more active fluorine group is used as a leaving group, and , in a high boiling point solvent such as diphenyl sulfone, 2
It is necessary to carry out the reaction at a high temperature of 00° C. or higher, and it has many disadvantages from an economic point of view. In addition, the polymers obtained in this way have the disadvantage that by-products such as highly corrosive fluorine salts tend to remain, and these residual salts can cause undesirable side reactions such as gelation during polymer molding. It also has the disadvantage of being easy to deal with.

On the other hand, diphenyl ether and bis(trichloromethyl)
A method for obtaining polyetherketone by reacting benzene with benzene in the presence of a Friedelkraff catalyst and then hydrolyzing it [D. Raabe, H. Herhold.

It, If, 1lorhold) et al., Acta Poly+5erica: 1
6. (11), 603 (+985)) are known. However, this method does not mention any physical properties such as crystallinity of the obtained polymer, and the results of additional tests by the present inventors show that the obtained polymer exhibits crystallinity including a crosslinked structure. There were no low molecular weight polymers. Raabe et al. also describe that under synthesis conditions with a high monomer concentration, a gel fraction is generated during the reaction, and it is presumed that the resulting crosslinked structure is formed.

[Means to solve the problem]

As a result of extensive research in order to solve the drawbacks of the above-mentioned conventional techniques, the present inventors have discovered that a specific aromatic compound and an aromatic compound having two trihalogenomethyl groups are prepared in the presence of a free-solat fluorocarbon catalyst. The present invention was accomplished by discovering that a crystalline aromatic poly(thio)etherketone can be easily obtained by hydrolyzing the product after the reaction.

That is, the present invention is based on the general formula (I) (wherein x1 and x2 represent oxygen atoms or sulfur atoms which may be rotated or different, and Ar+, Ar2 and Ar3 represent divalent aromatic residues. ) and the aromatic compound represented by the general formula (II) (wherein R1-R6 represent a halogen atom, Ar,
.

represents a divalent aromatic residue. ] The present invention relates to a method for producing a crystalline aromatic poly(thio)etherketone, which comprises reacting an aromatic compound represented by the following formula in the presence of a Friedelkraff catalyst, and then hydrolyzing the product.

The aromatic compounds represented by the general formula (I) used in the present invention include 1,4-bis(P-phenoxybensoyl)benzene, 1,3-bis(P-phenoxybenzoyl)benzene, 1,4 -His(P-phenylthiobenzoyl)benzene 1,3-bis(P-phenylthiobenzoyl)benzene, 4,4゛-bis(P-phenoxybenzoyl)biphenyl, 3,4°-bis(P
-phenoxybenzoyl)biphenyl, 3,3゛-bis(P-phenoxybenzoyl)biphenyl, 4.4°-
Bis(P-phenylthiobenzoyl)biphenyl, 3,
Examples include, but are not necessarily limited to, 4'-bis(P-phenylthiobenzoyl)biphenyl, 3.3'-bis(P-phenylthiobenzoyl)biphenyl, and the like.

These aromatic compounds may be used alone or in combination.

Further, the aromatic compound having two trihalogenomethyl groups represented by the general formula (II) used in the present invention includes 1,4-bis(trichloromethyl)benzene, 1,3-bis(trichloromethyl) Benzene, ■, 4-bis(trichloromethyl)benzene, 1
．． 3-bis(trichloromethyl)henzene, 4,4°-
Examples include, but are not necessarily limited to, bis(trichloromethyl)biphenyl, 3,4'-bis(trichloromethyl)biphenyl, and 3,3'-bis(trichloromethyl)biphenyl. Further, these aromatic compounds having two trihalogenomethyl groups may be used alone or in combination.

- The use of an aromatic compound having two trihalogenomethyl groups represented by formula (II) is as follows: - Formula (I)
0.5 to 10 in molar ratio to the aromatic compound represented by
, preferably 0.8 to Z, more preferably 0.9 to 1
．． It is 1. If the molar ratio is less than 0.5 or more than 10, it is difficult to obtain a crystalline polymer.

The free sol cod fluorocatalyst used in the present invention includes:
Examples include, but are not limited to, aluminum chloride, aluminum bromide, ferric chloride, stannic cyclide, titanium tetrachloride, boron trifluoride, and antimony pentachloride.

These Friedelkraff catalysts may be used alone or in combination. The amount of these Friedel Krach catalysts to be used is 0.1 to 20, preferably 1 to 15, and more Preferably it is 2-7. It is difficult to obtain crystalline Bommer when the molar ratio is less than 0.1 or more than 20.

Aromatic compounds represented by general formula (I) and general formula (rl
) The reaction temperature with the aromatic compound having two trihalogenomethyl groups is -so'c to 100°C1
Preferably the temperature is -IO°C to 80°C, more preferably -10°C to 50°C. If the reaction temperature is lower than -50°C, the reaction will proceed, but it will be slow and uneconomical. On the other hand, if the reaction temperature exceeds 100° C., it is undesirable because a polymer having a crosslinked structure tends to be formed.

In addition, examples of solvents used when reacting the aromatic compound represented by the general formula (I) with the aromatic compound having two trihalogenomethyl groups represented by the general formula (II) include nitrobenzene, carbon disulfide, , 1.2
-Dichlorobenzene, chloroform, etc. are used.

These solvents may be used alone or in combination. The amount of solvent to be used is 2 moles, preferably 1 mole of the aromatic compound represented by the general formula (I).
．． It's only 5 sentences.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Note that the logarithmic viscosity (η
i nh) in 97% concentrated sulfuric acid, 1. Og/clQ
The concentration was measured at 30°C.

Example 1 100 ta! with stirrer, thermometer and nitrogen inlet. ;
1.4-bis(
P-phenoxybenzoyl)benzene 4.705g (0
, 01 mol), 1.128 g (0.01 mol) of 1,4-his(trichloromethyl)benzene, and 90 tv of nitrobenzene were added, and the mixture was cooled to 5°C. While stirring the mixture, add 7.14 g of anhydrous ferric chloride (0,0
44 mol) was added. Thereafter, the temperature in the system was gradually raised to 10° C. and the reaction was carried out with stirring for 48 hours.

The resulting dark red reaction solution was poured into one glass of water to stop the reaction. The obtained polymer was mixed with ethanol Son ys9.
After washing twice with 5% boiling hydrochloric acid aqueous solution and boiling demineralized water, the sample was washed twice with acetone, and vacuum dried at 100°C overnight. The obtained polymer was a white powder, and the yield was 4.5 g. Also, the logarithmic viscosity is 0.14
As a result of the Bellstein reaction test, it was confirmed that almost no halogen was present. DSC (differential scanning calorimetry) measurements revealed that this polymer was a crystalline aromatic polyetherketone with a crystalline melting point of 340°C and a glass transition temperature (Tg) of 156°C.

Example 2 The reaction was carried out in the same manner as in Example 1, except that 1,3-bis(trichloromethyl)benzene was used instead of 1,4-bis(trichloromethyl)benzene, and the logarithmic viscosity was 0. .17 polymer 4.65 was obtained.

According to DSC measurement, this polymer has a crystalline melting point of 280°C.
It was a crystalline aromatic polyetherketone with a glass transition temperature (Tg) of 150°C.

(Effects of the Invention) As described above, according to the present invention, crystalline aromatic poly(thio)etherketone can be easily produced.

Claims (1)

[Claims] General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X_1 and X_2 represent oxygen atoms or sulfur atoms, which may be the same or different,
_2 and Ar_3 represent divalent aromatic residues. ] Aromatic compounds represented by the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 to R_6 represent halogen atoms, and Ar
_4 represents a divalent aromatic residue. 1. A method for producing a crystalline aromatic poly(thio)etherketone, which comprises reacting an aromatic compound represented by the following formula in the presence of a Friedel-Crafts catalyst, and then hydrolyzing the product.