JP2012229177A - Process for producing cyclic polyphenylene ether etherketone composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel cyclic polyphenylene ether etherketone composition which overcomes problems of the prior arts suffering from a high melting point and poor workability; and a process for producing a novel polyphenylene ether etherketone composition.SOLUTION: The process for producing the cyclic polyphenylene ether etherketone composition includes: reacting a mixture (A) including at least (a) a dihalogenated aromatic ketone compound, (b) a dihydroxy aromatic compound, (c) a base, and (d) an organic polar solvent, whereby a cyclic polyphenylene ether etherketone composition containing different repeat number of cyclic polyphenylene ether etherketones and having a melting point of 270°C or lower is produced. The component (a) is used in an amount ranging from 1.00 to 1.10 moles relative to 1.0 mole of the component (b) in the mixture (A).

Description

  The present invention relates to a method for producing a cyclic polyphenylene ether ether ketone composition. More specifically, the present invention relates to a method for efficiently producing a cyclic polyphenylene ether ether ketone composition having an excellent molding processability at a low temperature and a low melting point by an economical and simple method.

  Aromatic cyclic compounds can be applied to highly functional materials and functional materials based on properties resulting from their cyclic properties, for example, properties as compounds with inclusion ability, and high molecular weight linear forms by ring-opening polymerization In recent years, it has attracted attention due to its specificity derived from its structure, such as its use as an effective monomer for polymer synthesis. Cyclic polyphenylene ether ether ketone also belongs to the category of aromatic cyclic compounds and is a notable compound as described above.

  Examples of the method for producing cyclic polyphenylene ether ether ketone include linear polyphenylene ether ether ketone oligomers having hydroxyl groups at both ends and linear polyphenylene ether ether ketone oligomers having fluorine groups at both ends as shown in the following formula. The method of making it react is reported (for example, nonpatent literature 1).

  In this method, an oligomer having a long chain length is used as a raw material, so that the obtained cyclic polyphenylene ether ether ketone composition contains almost no low molecular weight oligomer, while cyclic polyphenylene ether ether ketone has Only cyclic polyphenylene ether ether ketone having a repeating number m of 3 and / or 6 and a melting point exceeding 270 ° C. can be obtained. More specifically, a cyclic polyphenylene ether ether ketone obtained from a linear oligomer (both terminal hydroxyl group oligomer composed of 4 units of benzene ring component and fluorine terminal oligomer composed of 5 terminals of benzene ring component) It is described that it is composed only of a cyclic trimer (m = 3) and a cyclic hexamer (m = 6), which are cyclic polyphenylene ether ether ketones having melting points at 360 ° C. and 324 ° C., respectively. .

  The same authors also disclosed a method for producing a cyclic polyphenylene ether ether ketone (for example, Non-Patent Document 2).

  The cyclic polyphenylene ether ether ketone obtained by this method is a monomer of a cyclic dimer (m = 2), and has a melting point of 440 ° C. or higher. Thus, the use of linear polyphenylene ether ether ketone oligomer as a raw material for the synthesis of cyclic polyphenylene ether ether ketone is for the purpose of obtaining cyclic polyphenylene ether ether ketone having a desired repeat number m with high purity. In this method, a cyclic polyphenylene ether ether ketone composition characterized in that it is a mixture comprising different numbers of repeating units m in the present invention and has a melting point of 270 ° C. or lower. It is difficult to manufacture. In addition, since the synthesis of the cyclic polyphenylene ether ether ketone described in Non-Patent Documents 1 and 2 is carried out by a reaction under a pseudo high dilution condition, the production selectivity of the cyclic polyphenylene ether ether ketone is high, but the ultra-dilute state Since it is essential to maintain the reaction, it takes a very long time for the reaction, and further, it is also necessary to separately prepare the oligomers of both terminal hydroxyl groups and both terminal fluorine groups used in the cyclic polyphenylene ether ether ketone synthesis raw material, It was difficult to say that it was an industrially usable production method of cyclic polyphenylene ether ether ketone.

  In addition, a method using an aromatic imine compound as a raw material for producing cyclic polyphenylene ether ether ketone has also been reported (for example, Non-Patent Document 3). In Non-Patent Document 3, a cyclic polyphenylene ether ether ketimine is prepared from N-phenyl (4,4′-difluorodiphenyl) ketimine and hydroquinone as shown in the following formula, and then the cyclic polyphenylene ether ether ketimine is subjected to acidic conditions. A method for obtaining a cyclic polyphenylene ether ether ketone by hydrolysis is disclosed.

  In general, aromatic ketimine compounds are less reactive than the corresponding aromatic ketone compounds, and the reaction is performed under ultra-dilute conditions. Therefore, even after completion of the cyclic polyphenylene ether ether ketimine synthesis reaction, the cyclic polyphenylene ether A low molecular weight linear oligomer that is difficult to separate from ether ketimine remains. Therefore, in this method, only a low-purity product containing a large amount of impurities was obtained as a cyclic polyphenylene ether ether ketone composition. Furthermore, in order to produce a cyclic polyphenylene ether ether ketone by this method, a step of preparing an aromatic ketimine compound as a raw material, a step of preparing and purifying a cyclic polyphenylene ether ether ketimine, and a recovered cyclic polyphenylene ether ether The process of preparing and purifying cyclic polyphenylene ether ether ketone by hydrolyzing ketimine is at least essential, and a complicated multi-step reaction process is essential, so cyclic polyphenylene ether ether that can be utilized industrially It was difficult to say that it was a method for producing a ketone composition. Further, although the non-patent document 3 has no description about the melting point of the cyclic polyphenylene ether ether ketone, it contains a large amount of linear polyphenylene ether ether ketone having a high melting point as an impurity. Unlike the cyclic polyphenylene ether ether ketone composition of the present invention, the ether ketone composition is considered to have a high melting point.

  Moreover, the manufacturing method of cyclic polyphenylene ether ether ketone using the phenylene ether oligomer as a raw material is also disclosed (for example, patent document 1).

  Patent Document 1 describes that a cyclic polyphenylene ether ketone can be prepared by a one-step reaction by reacting 1,4-diphenoxybenzene in the presence of a Lewis acid. The synthesis methods of polyphenylene ether ketone compounds can be broadly divided into two types: synthesis methods based on ether bond formation by aromatic nucleophilic substitution reaction and synthesis methods based on ketone bond formation by aromatic electrophilic substitution reaction. The cyclic polyphenylene ether ketone synthesis route described in Patent Document 1 is included in the latter. One of the problems when using an aromatic electrophilic substitution reaction in the polyphenylene ether ketone synthesis reaction is that the regioselectivity of the reaction is low. Therefore, it can be presumed that the cyclic polyphenylene ether ketone obtained by the method described in Patent Document 1 is a low-purity cyclic polyphenylene ether ketone containing an ortho-form and a meta-form in addition to the target para-form. Also, Patent Document 1 does not describe any melting point of the cyclic polyphenylene ether ketone obtained.

Chinese Patent No. 1015199399

Macromolecules 1996, 29, 5502 Macromol. Chem. Phys. 1996, 197, 4069 Polymer Bulletin, 1999, 42, 245

  This invention solves the subject of the said prior art, and makes it a subject to provide the method of manufacturing efficiently cyclic | annular polyphenylene ether ether ketone composition in a short time by the economical and simple method.

In response to the above problems, the present invention
1. At least (a) a dihalogenated aromatic ketone compound,
(B) a dihydroxy aromatic compound,
(C) a base, and (d) an organic polar solvent,
To produce a cyclic polyphenylene ether ether ketone composition having a cyclic polyphenylene ether ether ketone represented by the general formula (I) and having a different integer m, and having a melting point of 270 ° C. or lower. A cyclic polyphenylene ether ether ketone composition characterized by using (a) in the range of 1.00 to 1.10 moles per 1.0 mole of (b) in the mixture (a) Manufacturing method,

(In formula (I), m represents an integer of 2 to 40.)
2. 2. The cyclic polyphenylene ether ether ketone composition according to 1 above, wherein (a) is used in the range of 1.01 to 1.05 mol per 1.0 mol of (b) in the mixture (a). Manufacturing method,
3. The method for producing a cyclic polyphenylene ether ether ketone composition according to 1 or 2 above, wherein the cyclic polyphenylene ether ether ketone is a mixture comprising at least three consecutive different integers m,
4). 4. The cyclic polyphenylene according to any one of 1 to 3 above, wherein the cyclic polyphenylene ether ether ketone composition contains 60% by weight or more of the cyclic polyphenylene ether ether ketone represented by the general formula (I). Method for producing ether ether ketone composition,
5. The cyclic polyphenylene ether ether ketone composition according to any one of 1 to 4 above, wherein an organic polar solvent is used in an amount of 1.2 to 10 liters per 1 mole of the benzene ring component in the mixture (a). A manufacturing method is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of cyclic polyphenylene ether ether ketone composition can be provided, More specifically, the method of manufacturing cyclic polyphenylene ether ether ketone composition efficiently in a short time by an economical and simple method is provided. it can.

  Embodiments of the present invention will be described below.

  The cyclic polyphenylene ether ether ketone in the present invention is a cyclic compound represented by the following general formula (I) having paraphenylene ketone and paraphenylene ether as repeating structural units.

  The range of the repeating number m in the formula (I) is 2 to 40, more preferably 2 to 20, further preferably 2 to 15, and 2 to 10 can be exemplified as a particularly preferable range. Since the melting point of the cyclic polyphenylene ether ether ketone tends to increase as the number of repetitions m increases, the number of repetitions m is preferably within the above range from the viewpoint of melting the cyclic polyphenylene ether ether ketone at a low temperature. .

  The cyclic polyphenylene ether ether ketone represented by the formula (I) is preferably a mixture having a different repeating number m, and is a cyclic polyphenylene ether ether ketone mixture having at least three different repeating numbers m. More preferably, the mixture is more preferably a mixture of 4 or more repetitions m, and particularly preferably a mixture of 5 or more repetitions m. Furthermore, it is particularly preferable that these repeating numbers m are continuous. Compared to a single compound having a single repeating number m, the melting point of a mixture comprising a different repeating number m tends to be lower, and compared to a cyclic polyphenylene ether ether ketone mixture comprising two different repeating numbers m. In addition, the melting point of a mixture composed of three or more types of repeating number m tends to be further lowered, and the melting point of a mixture consisting of continuous repeating number m is lower than that of a mixture consisting of discontinuous repeating number m. There is a tendency. Here, cyclic polyphenylene ether ether ketone having each repeating number m can be analyzed by component separation by high performance liquid chromatography, and further included in the composition of cyclic polyphenylene ether ether ketone, ie, cyclic polyphenylene ether ether ketone. The weight fraction of the cyclic polyphenylene ether ether ketone having each repeating number m can be calculated from the peak area ratio of each cyclic polyphenylene ether ether ketone in the high performance liquid chromatography. In the present invention, high purity means that the weight fraction of cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition is high, and low purity means that in the cyclic polyphenylene ether ether ketone composition. It means that the weight fraction of cyclic polyphenylene ether ether ketone is low. Moreover, the production amount of the cyclic polyphenylene ether ether ketone in the mixture (a) can be calculated from the area ratio of high performance liquid chromatography, and the yield can be determined from the ratio with respect to the charged hydroquinone amount.

  Furthermore, the cyclic polyphenylene ether ether ketone composition of the present invention has a melting point of 270 ° C. or lower, and has a feature that the melting point is significantly lower than that of the corresponding linear polyphenylene ether ether ketone. The melting point is preferably 250 ° C. or lower, and more preferably 230 ° C. or lower. The lower the melting point of the cyclic polyphenylene ether ether ketone composition, the lower the processing temperature, and the process for obtaining a high degree of polymerization using the cyclic polyphenylene ether ether ketone as the polyphenylene ether ether ketone prepolymer. Since the temperature can be set low, it is advantageous from the viewpoint that the energy required for processing can be reduced. Here, the melting point of the cyclic polyphenylene ether ether ketone composition can be measured by observing the endothermic peak temperature using a differential scanning calorimeter.

  Further, the cyclic polyphenylene ether ether ketone composition in the present invention is a cyclic polyphenylene ether ether ketone composition containing 60% by weight or more of cyclic polyphenylene ether ether ketone, and more preferably 65% by weight or more. Preferably, it is more preferably 70% by weight or more, and even more preferably 75% by weight or more. As an impurity component in the cyclic polyphenylene ether ether ketone composition, that is, a component other than the cyclic polyphenylene ether ether ketone, linear polyphenylene ether ether ketone can be mainly exemplified. Since this linear polyphenylene ether ether ketone has a high melting point, the melting point of the cyclic polyphenylene ether ether ketone composition tends to increase as the weight fraction of the linear polyphenylene ether ether ketone increases. Therefore, when the weight fraction of the cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition is in the above range, the cyclic polyphenylene ether ether ketone composition tends to have a low melting point. The cyclic polyphenylene in the cyclic polyphenylene ether ether ketone composition is also obtained from the viewpoint that when the ether ether ketone composition is used as a polyphenylene ether ether ketone prepolymer, a polyphenylene ether ether ketone having a sufficiently high degree of polymerization can be obtained. The ether ether ketone weight fraction is preferably in the above range.

  Next, the raw material used with the manufacturing method for obtaining the cyclic polyphenylene ether ether ketone composition of this invention is demonstrated.

  The dihalogenated aromatic ketone compound used in the present invention is an aromatic ketone compound represented by the general formula (II).

  Here, X in the general formula (II) is a halogeno group selected from fluorine, chlorine, bromine, iodine, astatine and the like, and further, the two halogeno groups included in the general formula (II) are the same or different. There is no problem even if it is a halogeno group. Specific examples of these dihalogenated aromatic ketone compounds include 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 4,4'-diiodobenzophenone, 4-fluoro- 4'-chlorobenzophenone, 4-fluoro-4'-bromobenzophenone, 4-fluoro-4'-iodinated benzophenone, 4-chloro-4'-bromobenzophenone, 4-chloro-4'-iodinated benzophenone, 4- Examples include bromo-4′-iodinated benzophenone. Among these, 4,4′-difluorobenzophenone is preferable from the viewpoint of reactivity, and 4,4′-dichlorobenzophenone is preferable from the viewpoint of economy, and 4,4′-difluorobenzophenone is particularly preferable. As an example.

  In the production of the cyclic polyphenylene ether ether ketone composition of the present invention, the halogeno group in these dihalogenated aromatic ketone compounds acts as a leaving group. Therefore, it is also possible to use an aromatic ketone compound having a substituent having a leaving group ability equivalent to these halogens, and examples of the substituent having such a leaving group ability include a nitro group, A specific example is 4′-dinitrobenzophenone.

  In the production of the cyclic polyphenylene ether ether ketone composition of the present invention, the above-mentioned dihalogenated aromatic ketone compound or dinitrated aromatic ketone compound may be used alone or as a mixture of two or more kinds. There is no problem.

  The dihydroxy aromatic compound used in the present invention is an aromatic compound represented by the general formula (III).

  Here, the repeating number q in the general formula (III) is not particularly limited, but hydroquinone in which q = 0 can be given as a preferred specific example. Moreover, although there is no restriction | limiting in particular about the upper limit of the repeating number q in General formula (III), The dihydroxy aromatic compound which is q = 2 or less can be mentioned as a preferable dihydroxy aromatic compound. These dihydroxy aromatic compounds may be used alone or as a mixture of two or more.

  In the production of the cyclic polyphenylene ether ether ketone composition in the present invention, the amount of (a) dihalogenated aromatic ketone compound used is 1.00 to 1.1.0 per 1.0 mol of (b) dihydroxy aromatic compound. It must be in the range of 10 mol, preferably in the range of 1.00 to 1.07 mol, more preferably in the range of 1.01 to 1.05 mol, 1.01 to 1.03 mol Is most preferable. The hydroxy end group of the linear polyphenylene ether ether ketone is considered to cause the ring opening of the cyclic structure of the cyclic polyphenylene ether ether ketone, but (a) a dihalogenated aromatic ketone compound and (b) a dihydroxy aromatic compound By controlling the amount used, the concentration of the hydroxy end group can be controlled, and side reactions such as the ring-opening reaction of the produced cyclic polyphenylene ether ether ketone can be suppressed. Furthermore, since the production of linear polyphenylene ether ether ketone oligomer that is difficult to separate from cyclic polyphenylene ether ether ketone can be suppressed, cyclic polyphenylene ether ether ketone can be obtained with high yield and high purity.

  Examples of the base used in the production of the cyclic polyphenylene ether ether ketone composition of the present invention include alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate, calcium carbonate, strontium carbonate, and barium carbonate. Alkaline earth metal carbonates, alkali hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate Earth metal bicarbonate or alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide Arca Examples include hydroxides of earth metals, and carbonates such as sodium carbonate and potassium carbonate, and bicarbonates such as sodium bicarbonate and potassium bicarbonate are preferable from the viewpoint of ease of handling and reactivity. Sodium carbonate and potassium carbonate are more preferable, and potassium carbonate is more preferably used. These may be used alone or in combination of two or more. These bases are preferably used in the form of anhydrides, but can also be used as hydrates or aqueous mixtures. Here, the aqueous mixture refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component.

  The organic polar solvent used in the production of the cyclic polyphenylene ether ether ketone composition of the present invention may be one that does not substantially cause undesirable side reactions such as reaction inhibition and decomposition of the produced cyclic polyphenylene ether ether ketone. There are no particular restrictions. Specific examples of such organic polar solvents include N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), 1, Nitrogen-containing polar solvents such as 3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide, tetramethylurea, sulfoxide-sulfone solvents such as dimethyl sulfoxide (DMSO), dimethyl sulfone, diphenyl sulfone, sulfolane, Examples thereof include nitrile solvents such as benzonitrile, diaryl ethers such as diphenyl ether, ketones such as benzophenone and acetophenone, and mixtures thereof. These are preferably used because of their high reaction stability. Among them, N-methyl-2-pyrrolidone and dimethyl sulfoxide are preferred, and N-methyl-2-pyrrolidone is particularly preferred. These organic polar solvents are excellent in stability in a high temperature region, and can be said to be preferable organic polar solvents from the viewpoint of availability.

  The amount of the organic polar solvent in the mixture when producing the cyclic polyphenylene ether ether ketone composition of the present invention is preferably 1.2 liters or more with respect to 1.0 mol of the benzene ring component in the mixture (a), More preferably, it contains 1.3 liters or more, more preferably 1.5 liters or more, and particularly preferably 2.0 liters or more. The upper limit of the amount of the organic polar solvent in the mixture is not particularly limited, but is preferably 10.0 liters or less, more preferably 8.0 liters or less, relative to 1.0 mol of the benzene ring component in the mixture. 5.0 liters or less is particularly preferable. Increasing the amount of organic polar solvent tends to improve the selectivity of cyclic polyphenylene ether ether ketone formation, but if too much, the amount of cyclic polyphenylene ether ether ketone produced per unit volume of the reaction vessel decreases. And the time required for the reaction tends to increase. Therefore, from the viewpoint of achieving both the production selectivity of the cyclic polyphenylene ether ether ketone and the productivity, the use range of the organic polar solvent described above is preferable. The amount of the organic polar solvent here is based on the volume of the solvent under normal temperature and normal pressure, and the amount of the organic polar solvent used in the reaction mixture is dehydration operation from the amount of the organic polar solvent introduced into the reaction system. Is the amount obtained by subtracting the amount of the organic polar solvent excluded from the reaction system. In addition, the benzene ring component in the mixture here is a benzene ring component contained in a raw material that can become a cyclic polyphenylene ether ether ketone constituent by reaction, and the “number of moles” of the benzene ring component in these raw materials is “ "Number of benzene rings constituting the compound". For example, 1 mol of 4,4′-difluorobenzophenone is 2 mol of benzene ring component, 1 mol of hydroquinone is 1 mol of benzene ring component, and a mixture containing 1 mol of 4,4′-difluorobenzophenone and 1 mol of hydroquinone is benzene ring component 3 Calculated as a mixture containing moles.

  In the production method of the cyclic polyphenylene ether ether ketone composition of the present invention, a method of reacting with a dihydroxy aromatic compound and a base, or a metal salt of a dihydroxy aromatic compound separately prepared from the dihydroxy aromatic compound and a base is used. Can be mentioned as a preferred method.

  The amount of the base used in the method of reacting with the dihydroxy aromatic compound and the base is preferably equal to or more than the stoichiometric ratio with respect to the dihydroxy aromatic compound, and the specific amount of the base used is, for example, sodium carbonate or When the amount of divalent base such as potassium carbonate used is Y mol and the amount of monovalent base such as sodium hydrogen carbonate or potassium hydrogen carbonate is Z mol, a cyclic polyphenylene ether ether ketone composition is produced. (Y + 2Z) is preferably in the range of 1.00 to 1.10 mol, and in the range of 1.00 to 1.05 mol, relative to 1.0 mol of the dihydroxy aromatic compound used in the process. Is more preferable, and a range of 1.00 mol to 1.03 mol is more preferable. In the production method of the cyclic polyphenylene ether ether ketone composition of the present invention, the amount of the base used in producing the cyclic polyphenylene ether ether ketone composition is within these preferred ranges, so that the metal salt of the dihydroxy aromatic compound is reduced. It is preferable because it can be sufficiently produced, and the progress of an undesirable reaction such as a decomposition reaction of the produced cyclic polyphenylene ether ether ketone by a large excess of base can also be suppressed.

  In addition, when producing the cyclic polyphenylene ether ether ketone composition of the present invention, when using a metal salt of a dihydroxy aromatic compound separately prepared from a dihydroxy aromatic compound and a base, the above-mentioned preferred base is added, Excess base can be supplied. The excess amount of the supplied base is such that (Y + 2Z) is in the range of 0 to 0.10 mol with respect to 1.0 mol of the dihydroxy aromatic compound used to produce the cyclic polyphenylene ether ether ketone composition. Is preferably in the range of 0 to 0.05 mol, more preferably in the range of 0 to 0.03 mol. By making the excess amount of the base within a suitable range, it is possible to suppress the progress of an undesirable reaction such as a decomposition reaction of cyclic polyphenylene ether ether ketone, which is preferable.

  The reaction temperature of the mixture (a) in the present invention cannot be uniquely determined because it varies depending on the type and amount of the dihalogenated aromatic ketone compound, dihydroxy aromatic compound, base, and organic polar solvent used in the reaction. The range is usually 120 to 350 ° C, preferably 130 to 320 ° C, more preferably 140 to 300 ° C. In this preferable temperature range, a higher reaction rate tends to be obtained. The reaction may be either a one-step reaction performed at a constant temperature, a multi-stage reaction in which the temperature is raised stepwise, or a reaction in which the temperature is continuously changed.

The reaction time depends on the type and amount of the raw material used or the reaction temperature, and thus cannot be specified unconditionally, but is preferably 0.1 hour or longer, more preferably 0.5 hour or longer, and further preferably 1 hour or longer. preferable. By setting it as this preferable time or more, it exists in the tendency which can reduce an unreacted raw material component fully. On the other hand, there is no particular upper limit for the reaction time, but the reaction proceeds sufficiently even within 40 hours, preferably within 10 hours, more preferably within 6 hours.
In the present invention, it is also possible to add to the mixture (a) components other than the essential components that do not substantially inhibit the reaction and components that have an effect of accelerating the reaction. Moreover, there is no restriction | limiting in particular in the method of performing reaction, However, It is preferable to carry out on stirring conditions. Furthermore, in the method for producing the cyclic polyphenylene ether ether ketone composition of the present invention, various known polymerization methods and reaction methods such as a batch method and a continuous method can be employed. In addition, the atmosphere in the production is preferably a non-oxidizing atmosphere, preferably in an inert atmosphere such as nitrogen, helium, and argon, and preferably in a nitrogen atmosphere in view of economy and ease of handling.

  The cyclic polyphenylene ether ether ketone composition of the present invention can be obtained by separating and recovering from the reaction mixture obtained by the above production method. The reaction mixture obtained by the above production method contains at least cyclic polyphenylene ether ether ketone, linear polyphenylene ether ether ketone and an organic polar solvent, and other components such as unreacted raw materials, by-product salts, water, azeotropic solvents, etc. May be included. There is no particular limitation on the method for recovering the cyclic polyphenylene ether ether ketone from such a reaction mixture. For example, if necessary, after removing a part or most of the organic polar solvent by an operation such as distillation, the polyphenylene ether ether ketone is removed. The cyclic polyphenylene ether ether ketone is mixed with an organic polar solvent having low solubility in the components, and is contacted with a solvent having a solubility in the by-product salt under heating as necessary. The method of collect | recovering as a mixed solid with can be illustrated. Solvents having such characteristics are generally relatively polar solvents, and preferred solvents differ depending on the type of organic polar solvent and by-product salt used, but are not limited. For example, water, methanol, ethanol, propanol, isopropanol , Alcohols represented by butanol and hexanol, acetone, ketones represented by methyl ethyl ketone, acetates represented by ethyl acetate, butyl acetate, etc., and water, methanol and Acetone is preferred and water is particularly preferred.

  By performing the treatment with such a solvent, it is possible to reduce the amount of organic polar solvent or by-product salt contained in the mixed solid of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone. Since both cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone are precipitated as solid components by this treatment, a mixture of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone is recovered by a known solid-liquid separation method. As a result, the amount of organic polar solvent and by-product salt contained in the mixed solid of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone tends to be further reduced.

  Moreover, as a processing method by said solvent, there exists the method of mixing a solvent and a reaction mixture, and it is also possible to stir or heat suitably as needed. Although there is no restriction | limiting in particular in the temperature at the time of processing with a solvent, The range of 20-220 degreeC is preferable, and the range of 50-200 degreeC is further more preferable. In such a range, for example, by-product salt can be easily removed, and the treatment can be performed at a relatively low pressure, which is preferable. Here, when water is used as the solvent, the water is preferably distilled water or deionized water, but if necessary, formic acid, acetic acid, propionic acid, butyric acid, chloroacetic acid, dichloroacetic acid, acrylic acid, crotonic acid, Organic acidic compounds such as benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, and alkali metal salts and alkaline earth metal salts thereof, sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, silicic acid, etc. It is also possible to use an aqueous solution containing an inorganic acidic compound and ammonium ions. If the mixed solid of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone obtained after this treatment contains the solvent used in the treatment, it is dried as necessary to remove the solvent. Is also possible.

  In the recovery method described above, the cyclic polyphenylene ether ether ketone is recovered as a mixture with the linear polyphenylene ether ether ketone to obtain a cyclic polyphenylene ether ether ketone composition. In order to further increase the content of cyclic polyphenylene ether ether ketone in this composition, a method for separating and recovering cyclic polyphenylene ether ether ketone from this mixture includes, for example, cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone. Separation method that utilizes the difference in solubility of, more specifically, a solvent having high solubility in cyclic polyphenylene ether ether ketone and poor solubility in linear polyphenylene ether ether ketone is heated as necessary. And a method of obtaining a cyclic polyphenylene ether ether ketone as a solvent-soluble component by contacting with the mixture of the cyclic polyphenylene ether ether ketone and the linear polyphenylene ether ether ketone. In general, linear polyphenylene ether ether ketone is known to have high crystallinity and very low solubility in a solvent, and it is known that cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone are soluble in a solvent. Since the difference in solubility is large, it is possible to efficiently obtain cyclic polyphenylene ether ether ketone by the separation method using the difference in solubility.

  The solvent used here is not particularly limited as long as it can dissolve cyclic polyphenylene ether ether ketone, but cyclic polyphenylene ether ether ketone dissolves in the environment where dissolution is performed, but linear polyphenylene ether ether ketone dissolves. Solvents that are difficult to resist are preferred, and solvents that do not dissolve linear polyphenylene ether ether ketone are more preferred. The reaction system pressure when the mixture of the cyclic polyphenylene ether ether ketone and the linear polyphenylene ether ether ketone is brought into contact with the solvent is preferably normal pressure or slight pressure, and particularly preferably normal pressure. Has the advantage that the reactor components that build it are inexpensive. From this point of view, it is desirable that the reaction system pressure avoid pressurizing conditions that require expensive pressure resistant containers. As the solvent to be used, those which do not substantially cause an undesirable side reaction such as decomposition or crosslinking of the polyphenylene ether ether ketone component are preferable, and a solvent which is preferable when the operation of bringing the mixture into contact with the solvent is performed, for example, under normal pressure reflux conditions. As hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cyclopentane, benzene, toluene, xylene, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene Halogen solvents such as 2,6-dichlorotoluene, ether solvents such as diethyl ether, tetrahydrofuran and diisopropyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, Examples include polar solvents such as limethyl phosphoric acid and N, N-dimethylimidazolidinone, among which benzene, toluene, xylene, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene 2,6-dichlorotoluene, diethyl ether, tetrahydrofuran, diisopropyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, trimethyl phosphoric acid, N, N-dimethylimidazolidinone are preferred, toluene, More preferred examples are xylene, chloroform, methylene chloride and tetrahydrofuran.

  There is no particular restriction on the atmosphere in which the mixture of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone is brought into contact with the solvent, but it is preferably carried out in a non-oxidizing atmosphere, and nitrogen, helium, argon, etc. It is preferably carried out under an active atmosphere, and among these, it is particularly preferred to carry out under a nitrogen atmosphere from the viewpoint of economy and ease of handling.

  The temperature at which the mixture of the cyclic polyphenylene ether ether ketone and the linear polyphenylene ether ether ketone is brought into contact with the solvent is not particularly limited, but generally the higher the temperature, the more the dissolution of the cyclic polyphenylene ether ether ketone in the solvent is promoted. It tends to be. As described above, since the contact of the mixture of the cyclic polyphenylene ether ether ketone and the linear polyphenylene ether ether ketone with the solvent is preferably carried out under normal pressure, the upper limit temperature is the reflux of the solvent used under atmospheric pressure. It is preferable to set the temperature, and in the case of using the above-mentioned preferable solvent, for example, a temperature range of 20 to 150 ° C. can be exemplified.

  The time for contacting the mixture of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone with the solvent cannot be uniquely limited because it varies depending on the type and temperature of the solvent used. In such a range, the cyclic polyphenylene ether ether ketone tends to be sufficiently dissolved in the solvent.

  The method of bringing the mixture into contact with the solvent may be any known general method, and is not particularly limited. For example, a mixture of a cyclic polyphenylene ether ether ketone and a linear polyphenylene ether ether ketone is mixed with the solvent, Any method such as a method of collecting the solution part after stirring as necessary, a method of dissolving the cyclic polyphenylene ether ether ketone in the solvent at the same time as showering the solvent in the above mixture on various filters, or a method based on the Soxhlet extraction method principle is used. be able to. There is no particular limitation on the amount of the solvent used when the mixture of the cyclic polyphenylene ether ether ketone and the linear polyphenylene ether ether ketone is brought into contact with the solvent. For example, the range of 0.5 to 100 is exemplified by the bath ratio with respect to the weight of the mixture. it can. When the bath ratio is in such a range, the mixture and the solvent are easily mixed uniformly, and the cyclic polyphenylene ether ether ketone tends to be sufficiently dissolved in the solvent. In general, a larger bath ratio is advantageous for dissolving cyclic polyphenylene ether ether ketone in the solvent, but if it is too large, no further effect can be expected, and conversely an economic disadvantage due to an increase in the amount of solvent used occurs. Sometimes. In addition, when the contact between the mixture and the solvent is repeated, a sufficient effect is often obtained even with a small bath ratio, and the Soxhlet extraction method has a similar effect in principle, so in this case also with a small bath ratio. In many cases, sufficient effects can be obtained.

  After contacting the mixture of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone with a solvent, the solution in which cyclic polyphenylene ether ether ketone is dissolved is a solid-liquid slurry containing solid linear polyphenylene ether ether ketone. When obtained, it is preferable to recover the solution part using a known solid-liquid separation method. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. By removing the solvent from the solution thus separated, the cyclic polyphenylene ether ether ketone can be recovered. On the other hand, if the cyclic polyphenylene ether ether ketone still remains for the solid component, it is also possible to obtain cyclic polyphenylene ether ether ketone in a higher yield by repeating contact with the solvent and recovery of the solution again. is there.

  The solvent can be removed from the solution containing the cyclic polyphenylene ether ether ketone obtained as described above to obtain the cyclic polyphenylene ether ether ketone as a solid component. Here, the removal of the solvent can be exemplified by, for example, a method of heating and treating under normal pressure, or solvent removal using a membrane, but in terms of obtaining a cyclic polyphenylene ether ether ketone more efficiently and efficiently. A method of removing the solvent by heating at normal pressure or lower is preferred. In addition, the solution containing the cyclic polyphenylene ether ether ketone obtained as described above may contain a solid depending on the temperature, but the solid in this case also belongs to the cyclic polyphenylene ether ether ketone. It is preferable to recover the solvent together with components soluble in the solvent at the time of removing the solvent, so that the cyclic polyphenylene ether ether ketone can be obtained in a high yield. Here, the solvent is preferably removed by at least 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight or more. Although the temperature at which the solvent is removed by heating depends on the type of the solvent used, it cannot be uniquely limited, but a range of 20 to 150 ° C., preferably 40 to 120 ° C. can be selected. In addition, the pressure for removing the solvent is preferably normal pressure or lower, which makes it possible to remove the solvent at a lower temperature.

  The cyclic polyphenylene ether ether ketone composition obtained by the method of the present invention has a high purity and usually contains 60% by weight or more of cyclic polyphenylene ether ether ketone, and generally obtained linear polyphenylene ether ether ketone and Has high utility value even industrially with different characteristics.

  The present invention will be specifically described below with reference to examples. These examples are illustrative and not limiting.

  Various physical properties are measured using high performance liquid chromatography, differential scanning calorimeter (DSC), infrared spectroscopic analyzer (IR), Ostwald viscometer, and quantitative analysis of cyclic polyphenylene ether ether ketone is performed by high performance liquid. Performed by chromatography. Detailed analysis conditions are as follows.

(High performance liquid chromatography)
Apparatus: LC-10Avp series column manufactured by Shimadzu Corporation: Mightysil RP-18GP150-4.6
Detector: Photodiode array detector (UV = 270 nm is used)
Column temperature: 40 ° C
Sample: 0.1 wt% THF solution mobile phase: THF / 0.1 w% trifluoroacetic acid aqueous solution.

(Differential scanning calorimeter)
Apparatus: Robot DSC manufactured by Seiko Instruments Inc.

(Infrared spectroscopy analyzer)
Apparatus: Perkin Elmer System 2000 FT-IR
Sample preparation: KBr method.

[Example 1]
In a 1 L reaction vessel equipped with a stirring blade, 10.91 g (50 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50 mmol) of hydroquinone, 6.91 g (50 mmol) of potassium carbonate, and 500 mL of N-methyl-2-pyrrolidone. Prepared. The amount of N-methyl-2-pyrrolidone relative to 1.0 mol of the benzene ring component in the mixture (a) is 3.3 liters. After replacing the inside of the can with nitrogen, the temperature was raised to 200 ° C. in a sealed state, held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 2 hours for reaction. After completion of the reaction, a reaction mixture was prepared by cooling to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 6 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 11.4%.

  50 g of the reaction mixture thus obtained was collected, and 150 g of a 1% by weight aqueous acetic acid solution was added. After stirring to form a slurry, the mixture was heated to 70 ° C. and stirring was continued for 30 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The operation of dispersing the obtained solid content in 50 g of deionized water, maintaining at 70 ° C. for 30 minutes and filtering to obtain the solid content was repeated three times. The obtained solid was subjected to vacuum drying at 70 ° C. overnight to obtain about 14.4 g of a dry solid.

  Furthermore, 1.0 g of the dry solid obtained above was subjected to Soxhlet extraction with 100 g of chloroform at a bath temperature of 80 ° C. for 5 hours. Chloroform was removed from the obtained extract using an evaporator to obtain a solid content. After adding 2 g of chloroform to this solid content, it was added dropwise to 30 g of methanol as a dispersion using an ultrasonic cleaner. The resulting precipitated component was filtered off using a filter paper having an average pore size of 1 μm and then vacuum-dried at 70 ° C. for 3 hours to obtain about 0.13 g of a white solid.

This white powder was confirmed to be a compound comprising a phenylene ether ketone unit from the absorption spectrum in infrared spectroscopic analysis, mass spectrum analysis (equipment: Hitachi M-1200H) divided into components by high performance liquid chromatography, and MALDI- According to the molecular weight information by TOF-MS (apparatus; AXIMA-TOF ² manufactured by Shimadzu Corporation), this white powder is a cyclic compound mainly composed of a mixture of five cyclic polyphenylene ether ether ketones having a repetition number m of 2-6. It was found to be a polyphenylene ether ether ketone composition. Moreover, the weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 83.0%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of such a cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 160 ° C.

[Example 2]
In a 1 L reaction vessel equipped with a stirring blade, 11.42 g (50.5 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50.0 mmol) of hydroquinone, 6.91 g (50.0 mmol) of potassium carbonate, N-methyl -2-pyrrolidone 500 mL was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mol of the benzene ring component in the mixture (a) is 3.3 liters. After replacing the inside of the can with nitrogen, the temperature was raised to 200 ° C. in a sealed state, held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 2 hours for reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five cyclic polyphenylene ether ether ketones having a repetition number m = 2 to 6 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 13.5%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether ether ketone composition in the cyclic polyphenylene ether ether ketone composition was recovered. The weight fraction of the ether ether ketone mixture was 80.3%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of this cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 162 ° C.

[Example 3]
In a 1 L reaction vessel equipped with a stirring blade, 11.4 g (51.0 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50.0 mmol) of hydroquinone, 6.91 g (50.0 mmol) of potassium carbonate, N-methyl -2-pyrrolidone 500 mL was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mol of the benzene ring component in the mixture (a) is 3.3 liters. After replacing the inside of the can with nitrogen, the temperature was raised to 200 ° C. in a sealed state, held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 2 hours for reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 6 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 16.0%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether ether ketone composition in the cyclic polyphenylene ether ether ketone composition was recovered. The weight fraction of the ether ether ketone mixture was 83.0%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of this cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 160 ° C.

[Example 4]
In a 1 L reaction vessel equipped with a stirring blade, 11.46 g (52.5 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50.0 mmol) of hydroquinone, 6.91 g (50.0 mmol) of potassium carbonate, N-methyl -2-pyrrolidone 500 mL was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of benzene ring component in the mixture is 3.2 liters. While passing through nitrogen, the temperature was raised to 200 ° C., held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 2 hours for reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 6 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 13.8%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether in the cyclic polyphenylene ether ether ketone composition was obtained. The weight fraction of the ether ketone mixture was 72.1%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of this cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 161 ° C.

[Example 5]
In a 1 L reaction vessel equipped with a stirring blade, 11.67 g (51.0 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50.0 mmol) of hydroquinone, 6.91 g (50.0 mmol) of potassium carbonate, N-methyl -2-pyrrolidone 500 mL was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of the benzene ring component in the mixture is 3.3 liters. After replacing the inside of the can with nitrogen, the temperature was raised to 200 ° C. in a sealed state, held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 2 hours for reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five consecutive cyclic polyphenylene ether ether ketones having a repetition number m = 2 to 6 were produced. The yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 12.8%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether in the cyclic polyphenylene ether ether ketone composition was obtained. The weight fraction of the ether ketone mixture was 68.1%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of this cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 168 ° C.

[Example 6]
In a 1 L reaction vessel equipped with a stirring blade, 12.00 g (55.0 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50.0 mmol) of hydroquinone, 6.91 g (50.0 mmol) of potassium carbonate, N-methyl -2-pyrrolidone 500 mL was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of benzene ring component in the mixture is 3.1 liters. While passing through nitrogen, the temperature was raised to 200 ° C., held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 2 hours for reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 6 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 11.6%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether in the cyclic polyphenylene ether ether ketone composition was obtained. The weight fraction of the ether ketone mixture was 65.2%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of this cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 169 ° C.

[Example 7]
In a 1 L reaction vessel equipped with a stirring blade, 11.4 g (51.0 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50.0 mmol) of hydroquinone, 6.91 g (50.0 mmol) of potassium carbonate, N-methyl -2-Pyrrolidone 200 mL was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mol of the benzene ring component in the mixture is 1.3 liters. While passing through nitrogen, the temperature was raised to 200 ° C., held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 5 hours for reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 6 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 8.3%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether in the cyclic polyphenylene ether ether ketone composition was obtained. The weight fraction of the ether ketone mixture was 70.5%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of this cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 165 ° C.

[Example 8]
In a 1 L reaction vessel equipped with a stirring blade, 5.54 g (25.5 mmol) of 4,4′-difluorobenzophenone, 2.75 g (25.0 mmol) of hydroquinone, 3.46 g (25.0 mmol) of potassium carbonate, N-methyl 375 mL of 2-pyrrolidone was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of the benzene ring component in the mixture is 5.0 liters. While passing through nitrogen, the temperature was raised to 200 ° C., held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 4 hours to carry out the reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five consecutive cyclic polyphenylene ether ether ketones having a repetition number m = 2 to 6 were formed. The yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 15.9%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether in the cyclic polyphenylene ether ether ketone composition was obtained. The weight fraction of the ether ketone mixture was 80.7%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of this cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 160 ° C.

[Example 9]
In a 1 L reaction vessel equipped with a stirring blade, 3.71 g (17.0 mmol) of 4,4′-difluorobenzophenone, 1.84 g (16.7 mmol) of hydroquinone, 2.31 g (16.7 mmol) of potassium carbonate, N-methyl -2-pyrrolidone 500 mL was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of the benzene ring component in the mixture is 9.9 liters. While passing through nitrogen, the temperature was raised to 200 ° C., held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 6 hours to carry out the reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 6 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 18.8%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether in the cyclic polyphenylene ether ether ketone composition was obtained. The weight fraction of the ether ketone mixture was 72.3%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of this cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 165 ° C.

[Comparative Example 1]
In a 1 L reaction vessel equipped with a stirring blade, 10.36 g (47.5 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50.0 mmol) of hydroquinone, 6.91 g (50.0 mmol) of potassium carbonate, N-methyl -2-pyrrolidone 500 mL was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of the benzene ring component in the mixture is 3.4 liters. While passing through nitrogen, the temperature was raised to 200 ° C., held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 2 hours for reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five consecutive cyclic polyphenylene ether ether ketones having a repetition number m = 2 to 6 were produced. The yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 5.1%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether in the cyclic polyphenylene ether ether ketone composition was obtained. The weight fraction of the ether ketone mixture was 58.8%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of such a cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 175 ° C.

[Comparative Example 2]
In a 1 L reaction vessel equipped with a stirring blade, 12.22 g (56.0 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50.0 mmol) of hydroquinone, 6.91 g (50.0 mmol) of potassium carbonate, N-methyl -2-pyrrolidone 500 mL was charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of benzene ring component in the mixture is 3.1 liters. While passing through nitrogen, the temperature was raised to 200 ° C., held at 200 ° C. for 5 minutes, then heated to 250 ° C. and held at 250 ° C. for 2 hours for reaction. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 3.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that five cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 6 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 6.2%.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition from the reaction mixture (a) thus obtained by the method described in Example 1, the cyclic polyphenylene ether in the cyclic polyphenylene ether ether ketone composition was obtained. The weight fraction of the ether ketone mixture was 52.7%. In addition, components other than cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition were linear polyphenylene ether ether ketone oligomers.

  As a result of measuring the melting point of this cyclic polyphenylene ether ether ketone composition, it was found to have a melting point of 173 ° C.

  From the comparison between Examples 1 to 6 and Comparative Examples 1 and 2, when producing cyclic polyphenylene ether ether ketone, (a) and (b) in the mixture (a) are used within the molar ratio range of the present invention. Thus, it is clear that cyclic polyphenylene ether ether ketone can be obtained with high purity and high yield.

Claims (5)

At least (a) a dihalogenated aromatic ketone compound,
(B) a dihydroxy aromatic compound,
(C) a base, and (d) an organic polar solvent,
To produce a cyclic polyphenylene ether ether ketone composition having a cyclic polyphenylene ether ether ketone represented by the general formula (I) and having a different integer m, and having a melting point of 270 ° C. or lower. A cyclic polyphenylene ether ether ketone composition characterized by using (a) in the range of 1.00 to 1.10 moles per 1.0 mole of (b) in the mixture (a) Manufacturing method.

(In formula (I), m represents an integer of 2 to 40.) The cyclic polyphenylene ether ether ketone composition according to claim 1, wherein (a) is used in the range of 1.01-1.05 mol per 1.0 mol of (b) in the mixture (a). Manufacturing method. The method for producing a cyclic polyphenylene ether ether ketone composition according to claim 1 or 2, wherein the cyclic polyphenylene ether ether ketone is a mixture comprising at least three consecutive different integers m. The cyclic polyphenylene ether ether ketone composition contains 60% by weight or more of the cyclic polyphenylene ether ether ketone represented by the general formula (I) in the cyclic polyphenylene ether ether ketone composition. A method for producing a polyphenylene ether ether ketone composition. 5. The cyclic polyphenylene ether ether ketone composition according to claim 1, wherein the organic polar solvent is used in an amount of 1.2 to 10 liters per 1 mole of the benzene ring component in the mixture (a). Manufacturing method.