JP5966559B2 - Method for recovering polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone composition - Google Patents

Description

  The present invention relates to a method for recovering a highly pure cyclic polyphenylene ether ether ketone composition from a mixture containing at least polyphenylene ether ether ketone, cyclic polyphenylene ether ether ketone and an organic polar solvent by a 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.

  As a method for recovering cyclic polyphenylene ether ether ketone, for example, a polyphenylene ether ether ketone mixture containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone is extracted with chloroform, and further, a chloroform soluble component is extracted with methylene chloride. Has disclosed a method of silica gel chromatography purification using a non-patent document 1 (for example, see Non-Patent Document 1). Although this method can surely recover high-purity cyclic polyphenylene ether ether ketone, it is a recovery method that requires the use of a large amount of a chlorinated solvent with a large environmental impact such as chloroform and methylene chloride. It can be said that this method has poor industrial feasibility. Further, in Non-Patent Document 1, as a raw material for the synthesis of cyclic polyphenylene ether ether ketone, for example, as shown in the following formula, a linear polyphenylene ether ether ketone oligomer having hydroxyl groups at both ends and a linear shape having fluorine groups at both ends Since polyphenylene ether ether ketone oligomer is used, the obtained cyclic polyphenylene ether ether ketone has a repeating number m of 3 and / or 6, and does not produce a cyclic polyphenylene ether ether ketone having a repeating number m. .

  In addition, as a method for recovering cyclic polyphenylene ether ether ketone by a method other than the silica gel chromatography described above, for example, a polyphenylene ether ether ketone mixture containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone is extracted with acetone. A method of recrystallizing and purifying the solid content obtained by removing acetone from the extract with dimethyl sulfoxide (DMSO) has been disclosed (for example, see Non-Patent Document 2). Even in this method, it is possible to recover high-purity cyclic polyphenylene ether ether ketone. However, it is necessary to use a large amount of DMSO, which is a recrystallization solvent, with respect to cyclic polyphenylene ether ether ketone. Since most of the cyclic polyphenylene ether ether ketone is lost, it is difficult to say that it is an industrially usable recovery method. Further, in Non-Patent Document 2, as shown in the following formula, as a raw material for producing cyclic polyphenylene ether ether ketone, linear polyphenylene ether ether ketone having hydroxyl groups at both ends and 4,4′-difluorobenzophenone are used. Therefore, the obtained cyclic polyphenylene ether ether ketone is described as a mononuclear body of a cyclic dimer (m = 2).

  As another method for recovering cyclic polyphenylene ether ether ketone, N-phenyl (4,4′-difluorodiphenyl) ketimine and hydroquinone are reacted as shown in the following formula, and then the reaction product is subjected to acidic conditions. A method for recovering cyclic polyphenylene ether ether ketone by hydrolysis, further extraction with tetrahydrofuran (THF) and reprecipitation of methanol is disclosed (for example, see Non-patent Document 3).

  However, in general, aromatic ketimine compounds are less reactive than the corresponding aromatic ketone compounds, and further the reaction is carried out under ultra-dilute conditions. Therefore, even after completion of the cyclic polyphenylene ether ether ketimine synthesis reaction, Low molecular weight linear oligomers that are difficult to separate from polyphenylene ether ether ketimine remain, and this method only yielded low-purity cyclic polyphenylene ether ether ketone containing a large amount of impurities. Further, in order to recover linear 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 ketimine At least the process of preparing and purifying cyclic polyphenylene ether ether ketone by hydrolyzing the water is essential, and a complicated multi-step reaction process is required. is there.

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 collect | recovering cyclic polyphenylene ether ether ketone compositions with high purity by the method which can be utilized simply and industrially.

The present invention employs the following means in order to solve such problems.
That is, the present invention is as follows.
1. A mixture (a) comprising at least a polyphenylene ether ether ketone represented by the general formula (I), a cyclic polyphenylene ether ether ketone represented by the general formula (II) and an organic polar solvent , wherein the mixture in the mixture (a) A method for recovering a polyphenylene ether ether ketone and a cyclic polyphenylene ether ether ketone composition from a mixture (a) having an organic polar solvent of 1.20 liters to 100 liters with respect to 1.0 mole of a benzene ring component , From the mixture (a), the organic polar solvent is distilled off to 0.10 liter or more and 1.0 liter or less with respect to 1.0 mole of the benzene ring component , and at least polyphenylene ether ether ketone, cyclic polyphenylene ether ether ketone and Prepare a mixture (b) containing an organic polar solvent Degree, and recovery methods of a mixture (b) the polyphenylene ether ketone polyphenylene ether ketone and cyclic polyphenylene ether ether ketone composition characterized in that it comprises a step of performing solid-liquid separation at a temperature region becomes insoluble.

(Here, n in (I) is 10 to 10,000, and m in (II) is an integer of 2 to 40.)
2. 2. The polyphenylene according to 1, comprising a step of obtaining a cyclic polyphenylene ether ether ketone composition as a solid from a filtrate component obtained by performing solid-liquid separation in a temperature range in which the polyphenylene ether ether ketone is insoluble. Method for recovering ether ether ketone and cyclic polyphenylene ether ether ketone composition.
3. The polyphenylene ether ether ketone and the cyclic compound according to any one of 1 to 2, wherein the cyclic polyphenylene ether ether ketone in the mixture (a) is 4 parts by weight or more with respect to 100 parts by weight of the polyphenylene ether ether ketone. A method for recovering a polyphenylene ether ether ketone composition.
4). As the mixture (a), a mixture (a) containing at least a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base (A) and an organic polar solvent is added to 1.0 mol of the benzene ring component in the mixture (a). The polyphenylene ether ether ketone and the cyclic polyphenylene ether ether ketone according to any one of 1 to 3, wherein a mixture obtained by heating and reacting using 1.20 liters or more of an organic polar solvent is used. A method for recovering the composition.
5. Method for recovering the mixture (A) further Formula polyphenylene ether ketone and cyclic polyphenylene ether ether ketone composition 4, wherein the containing polyphenylene ether ketone of formula (I).
6). As the mixture (a), at least the polyphenylene ether ketone represented by the general formula (I), the basic compound (B) and a mixture containing an organic polar solvent (c) a mixture obtained by heating by reacting The method for recovering a polyphenylene ether ether ketone and a cyclic polyphenylene ether ether ketone composition according to any one of 1 to 3, wherein:
7). The method for recovering a polyphenylene ether ether ketone and a cyclic polyphenylene ether ether ketone composition according to any one of 1 to 6 , wherein the temperature at which the organic polar solvent is distilled off is 180 ° C or higher.
8). The polyphenylene ether according to any one of 1 to 7 , wherein the cyclic polyphenylene ether ether ketone composition recovered from the filtrate component obtained by solid-liquid separation contains 60% by weight or more of the cyclic polyphenylene ether ether ketone. Method for recovering ether ketone and cyclic polyphenylene ether ether ketone composition.
9.1 to 8 to obtain a Liwa type polyphenylene ether ketone composition by the recovery method according to any one of, and then the production method of the polyphenylene ether ketone, characterized in that the heating ring-opening polymerization.

  ADVANTAGE OF THE INVENTION According to this invention, the simple collection | recovery method of cyclic polyphenylene ether ether ketone composition with high purity can be provided.

  Hereinafter, the present invention will be described in detail.

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

  Although there is no restriction | limiting in particular in the repeating number n in Formula (I), the range of 10-10000 can be illustrated, the range of 20-5000 is preferable, and the range of 30-1000 can be illustrated more preferably.

The reduced viscosity (η) of the polyphenylene ether ether ketone in the present invention is not particularly limited, but the reduced viscosity (η) of a general polyphenylene ether ether ketone is usually in the range of 0.1 to 2.5 dL / g. Can be illustrated, preferably 0.2 to 2.0 dL / g, more preferably 0.3 to 1.8 dL / g. In general, the higher the reduced viscosity of polyphenylene ether ether ketone, that is, the higher the molecular weight of polyphenylene ether ether ketone, the lower the solubility in organic polar solvents. Therefore, the separation efficiency from cyclic polyphenylene ether ether ketone by solid-liquid separation increases. Although there is an advantage that it becomes high, if the reduced viscosity is in the above-mentioned range, it can be used without an essential problem. Unless otherwise specified, the reduced viscosity in the present invention is concentrated sulfuric acid having a concentration of 0.1 g / dL (weight of polyphenylene ether ether ketone or cyclic polyphenylene ether ether ketone composition / 98% by weight of concentrated sulfuric acid). The value of the solution measured using an Ostwald viscometer at 25 ° C. immediately after completion of dissolution in order to minimize the effect of sulfonation. The reduced viscosity was calculated according to the following formula.
η = {(t / t0) −1} / C
(Where t is the number of seconds that the sample solution passes, t0 is the number of seconds that the solvent (98 wt% concentrated sulfuric acid) passes, and C is the concentration of the solution).

  The cyclic polyphenylene ether ether ketone composition in the present invention is a composition containing cyclic polyphenylene ether ether ketone, and is an impurity component in the cyclic polyphenylene ether ether ketone composition, that is, other than cyclic polyphenylene ether ether ketone. As a component, linear polyphenylene ether ether ketone can be mainly mentioned.

  As a method for producing the polyphenylene ether ether ketone used in the present invention, any method can be used as long as it can produce a polyphenylene ether ether ketone having the above-described known characteristics. For example, at least a dihalogenated aromatic ketone compound, a base, It is possible to use a production method by heating and reacting a mixture containing a dihydroxy aromatic compound and an organic polar solvent.

(2) Cyclic polyphenylene ether ether ketone In the present invention, the cyclic polyphenylene ether ether ketone is a cyclic compound represented by the following general formula (II) having paraphenylene ketone and paraphenylene ether as repeating structural units. is there.

  The range of the repeating number m in Formula (II) is 2-40, 2-30 are more preferable, 2-15 are more preferable, and 2-10 can be illustrated as an especially preferable range. Since the melting point of the cyclic polyphenylene ether ether ketone tends to increase as the repeating number m increases, the repeating number m is preferably set in 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 (II) 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. The cyclic polyphenylene ether ether ketone having each repeating number m can be analyzed by component separation by high performance liquid chromatography, and the composition of the cyclic polyphenylene ether ether ketone, that is, each of the cyclic polyphenylene ether ether ketones included in the cyclic polyphenylene ether ether ketone. The weight fraction of the cyclic polyphenylene ether ether ketone having the repeating number m can be calculated from the peak area ratio of each cyclic polyphenylene ether ether ketone in high performance liquid chromatography.

  As a method for producing the cyclic polyphenylene ether ether ketone used in the present invention, any method can be used as long as it can produce a cyclic polyphenylene ether ether ketone having the above-mentioned characteristics, but at least a dihalogenated aromatic ketone compound is preferred as a preferred method. , A production method by heating and reacting a mixture containing a base, a dihydroxy aromatic compound, and an organic polar solvent, at least a polyphenylene ether ether ketone, a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base (A), and A production method by heating and reacting a mixture containing an organic polar solvent, or a production method by heating and reacting a mixture containing at least polyphenylene ether ether ketone, a basic compound and an organic polar solvent is used. Bets are possible.

(3) Organic polar solvent The organic polar solvent in the present invention is not particularly limited as long as it does not substantially cause undesirable side reactions such as decomposition of polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone. 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 include nitrile solvents such as benzonitrile, diaryl ethers such as diphenyl ether, ketones such as benzophenone and acetophenone, and mixtures thereof. Among these, N-methyl-2-pyrrolidone, 1,3-dimethyl -2-Imidazolid Organic amide solvents are preferred, such as down, N- methyl-2-pyrrolidone are particularly preferably used. 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.

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

Here, X in the general formula (III) is a halogeno group selected from fluorine, chlorine, bromine, iodine, astatine and the like, and the two halogeno groups included in the general formula (III) 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. These dihalogenated aromatic ketone compounds may be used singly or as a mixture of two or more types without any problem.
(5) Dihydroxy aromatic compound The dihydroxy aromatic compound used in the preferred method of preparing the mixture (a) of the present invention is an aromatic compound represented by the general formula (IV).

  Although there is no restriction | limiting in particular in the repeating number q in general formula (IV) here, the hydroquinone which is q = 0 can be mentioned as a preferable specific example. Moreover, although there is no restriction | limiting in particular about the upper limit of the repeating number q in General formula (IV), 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.

  The amount of these dihydroxy aromatic compounds used is preferably in the range of 0.8 to 1.2 mol, and in the range of 0.9 to 1.1 mol, relative to 1.0 mol of the dihalogenated aromatic ketone compound. More preferably, the range of 0.95 to 1.05 mol is further more preferable, and the range of 0.98 to 1.03 mol is particularly preferable. By making the amount of dihydroxy aromatic compound used within the above preferred range, the decomposition reaction of the generated cyclic polyphenylene ether ether ketone can be suppressed, and the cyclic polyphenylene ether ether ketone composition contains cyclic polyphenylene ether ether ketone. This is preferable because the amount tends to be high.

(6) Base (A)
Examples of the base (A) used in the preparation method of the preferred mixture (a) 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 such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, etc. alkali metal bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, etc. Alkaline earth metal bicarbonates or alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide Of alkaline earth metals such as Among these, from the viewpoint of ease of handling and reactivity, carbonates such as sodium carbonate and potassium carbonate, and bicarbonates such as sodium bicarbonate and potassium bicarbonate are preferable, and sodium carbonate, carbonate Potassium is further preferred, and potassium carbonate is more preferably used. These may be used alone or in combination of two or more. These bases (A) 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.

(7) Basic compound (B)
As the basic compound (B) in the present invention, known inorganic bases and organic bases can be widely used. Examples of inorganic bases include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, and other alkali metal or alkaline earth metal carbonates, lithium hydrogen carbonate, sodium hydrogen carbonate, carbonate Alkali metal or alkaline earth metal bicarbonates such as potassium hydrogen, rubidium bicarbonate, cesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide Alkali metal or alkaline earth metal hydroxides such as rubidium, cesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium phosphate, sodium phosphate, potassium phosphate, rubidium phosphate, cesium phosphate , Calcium phosphate, strontium phosphate, alkali metal phosphate such as barium phosphate, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, calcium fluoride, fluoride Strontium, barium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, calcium chloride, strontium chloride, barium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, Alkali metal or alkali such as calcium bromide, strontium bromide, barium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, calcium iodide, strontium iodide, barium iodide Alkali metal or alkaline earth metal hydrides such as earth metal halides, lithium hydride, sodium hydride, potassium hydride, rubidium hydride, cesium hydride, calcium hydride, strontium hydride, barium hydride , Alkali metals, ammonia and the like. Examples of the organic base include sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, alkali alkoxide such as sodium tert-butoxide, potassium tert-butoxide or phenoxide, lithium acetate, sodium acetate, potassium acetate, acetic acid. Alkali metal acetates such as rubidium and cesium acetate, primary amines such as methylamine, ethylamine and butylamine, secondary amines such as dimethylamine and diethylamine, tertiary amines such as triethylamine and tributylamine, aniline and pyridine The organic amine compound can be given as a specific example. Among these, from the viewpoint of reactivity, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium bromide, Alkali metal halides such as sodium bromide, potassium bromide, rubidium bromide, cesium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide are preferred, and among these, lithium fluoride Alkali metal fluorides such as sodium fluoride, potassium fluoride, rubidium fluoride, and cesium fluoride can be given as more preferred specific examples. These may be used alone or in combination of two or more.

  Other preferred specific examples include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and other alkali metal or alkaline earth metal carbonates, lithium hydrogen carbonate, Examples can include alkali metal or alkaline earth metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, calcium bicarbonate, strontium bicarbonate, and barium bicarbonate, among these Sodium carbonate and potassium carbonate are more preferable, and potassium carbonate can be mentioned as a more preferable specific example. These may be used alone or in combination of two or more.

(8) Preparation method of mixture (a) In the present invention, polyphenylene ether is passed through a step of distilling off the organic polar solvent from the mixture (a) containing at least polyphenylene ether ether ketone, cyclic polyphenylene ether ether ketone and organic polar solvent. Ether ketone and cyclic polyphenylene ether ether ketone are recovered.

  Here, the mixture (a) is not particularly limited as long as it is a mixture containing at least polyphenylene ether ether ketone, cyclic polyphenylene ether ether ketone and an organic polar solvent, but from the viewpoint of production efficiency of the cyclic polyphenylene ether ether ketone composition. To 4 parts by weight or more of cyclic polyphenylene ether ether ketone with respect to 100 parts by weight of polyphenylene ether ether ketone, preferably 6 parts by weight or more, more preferably 8 parts by weight or more. The upper limit of the amount of the cyclic polyphenylene ether ether ketone in the mixture (a) is not limited, but preferably contains 70 parts by weight or less of the cyclic polyphenylene ether ether ketone with respect to 100 parts by weight of the polyphenylene ether ether ketone. More preferably, it contains 40 parts by weight or less. Furthermore, the amount of the organic polar solvent in the mixture (a) is preferably 1.20 liters or more, more preferably 1.30 liters or more, and still more preferably with respect to 1.0 mol of the benzene ring component in the mixture (a). Means a thing of 1.50 liters or more. Although there is no restriction | limiting in particular in the upper limit of the quantity of the organic polar solvent in a mixture (a), It is preferable that it is 100 liters or less with respect to 1 mol of benzene ring components in a mixture (a), 50 liters or less are more preferable, More preferably, it is 20 liters or less. In addition, the amount of the organic polar solvent here is based on the volume of the solvent under normal temperature and normal pressure.

  As a method for preparing the mixture (a) in the present invention, any method can be used as long as the mixture having the above composition can be prepared. However, as a preferable method, (x) at least a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base (A ) And a mixture (a) containing an organic polar solvent by heating to react, (y) at least polyphenylene ether ether ketone, dihalogenated aromatic ketone compound, dihydroxy aromatic compound, base (A) and organic Production method by heating and reacting mixture (i) containing polar solvent, (z) Heating and reacting mixture (c) containing at least polyphenylene ether ether ketone, basic compound (B) and organic polar solvent The manufacturing method by this can be illustrated. Hereinafter, the details of the preferred production method of the mixture (a) will be described.

(8) -1. Manufacturing method (x), (y)
A preferred method for producing the mixture (a) is a method (x) in which at least a mixture (a) containing at least a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base (A), and an organic polar solvent is heated and reacted. An example is a method (y) in which a polyphenylene ether ether ketone, a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base (A), and a mixture (a) containing an organic polar solvent are heated and reacted.

  When the mixture (a) is produced by these preferred methods, the amount of the organic polar solvent in the mixture is preferably 1.20 liters or more per 1.0 mol of the benzene ring component in the mixture (a) or (b). More preferably, it contains 1.30 liters or more, more preferably 1.50 liters or more, and particularly preferably 2.0 liters or more. Further, the upper limit of the amount of the organic polar solvent in the mixture is not particularly limited, but is preferably 100 liters or less, more preferably 50 liters or less, relative to 1.0 mol of the benzene ring component in the mixture, 30 liters or less is more preferable, and 20 liters or less is particularly preferable. Increasing the amount of the organic polar solvent tends to improve the selectivity of the cyclic polyphenylene ether ether ketone, but if it is too much, the amount of cyclic polyphenylene ether ether ketone produced per unit volume of the reaction vessel will decrease. There is a tendency, 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 at normal temperature and normal pressure, and the amount of the organic polar solvent used in the reaction mixture is the dehydration operation from the amount of the organic polar solvent introduced into the reaction system. It is the amount obtained by subtracting the amount of the organic polar solvent excluded from the reaction system due to the above. 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. Furthermore, in the production method (y), since polyphenylene ether ether ketone used for the reaction is also a raw material that can be a constituent component of cyclic polyphenylene ether ether ketone, it is necessary to consider the number of moles of the benzene ring component in the polyphenylene ether ether ketone. . Here, polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone are polymers containing three benzene rings in a repeating unit. Therefore, the “number of moles” of the benzene ring component contained in these polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone is “the number of repeating units of polyphenylene ether ether ketone × 3”. For example, one molecule of polyphenylene ether ether ketone having a polymerization degree of 100 is calculated as 300 moles of benzene ring component instead of 1 mole. In addition, a component that cannot become a cyclic polyphenylene ether ether ketone constituent due to a reaction such as toluene is regarded as 0 mol of a benzene ring component.

  The use amount of the base (A) in the production method (x) (y) of the mixture (a) is preferably equal to or more than the stoichiometric ratio with respect to the dihydroxy aromatic compound, and the specific use of the base (A) For example, when the amount of a divalent base such as sodium carbonate or potassium carbonate used is Y mol and the amount of a monovalent base such as sodium hydrogen carbonate or potassium hydrogen carbonate is Z mol, a mixture (a (Y + 2Z) is preferably in the range of 1.0 to 1.10 mol, preferably in the range of 1.00 to 1.05 mol, relative to 1.0 mol of the dihydroxy aromatic compound used in the production of It is more preferable that it is in the range of 1.00 mol to 1.03 mol. When the amount of the base (A) used in the preferred production method (x) or (y) of the mixture (a) is within these suitable ranges, a metal salt of a dihydroxy aromatic compound can be sufficiently produced. Furthermore, it is also preferable because it is possible to suppress the progress of an undesirable reaction such as a decomposition reaction of the generated cyclic polyphenylene ether ether ketone by a large excess of base.

  In addition, when the mixture (a) is produced by the production method (x) or (y), a metal salt of a dihydroxy aromatic compound separately prepared from the dihydroxy aromatic compound and the base (A) can be used. In some cases, the preferred base (A) described above can be added to provide an excess of base. The excess amount of the supplied base (A) 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 for producing the mixture (a). Preferably, it 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 (A) in 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.

  Method for producing mixture (a) by reacting by heating mixture (a) containing at least polyphenylene ether ether ketone, dihalogenated aromatic ketone compound, dihydroxy aromatic compound, base (A), and organic polar solvent (y ), The amount of polyphenylene ether ether ketone used is such that the reaction mixture at the start of the reaction, that is, when the conversion rate of the dihalogenated aromatic ketone compound charged in the reaction system is 0, contains polyphenylene ether ether ketone. A good formula is the main structural unit of polyphenylene ether ether ketone

Is preferably in the range of 0.1-30 repeat unit moles per mole of dihydroxy aromatic compound, more preferably in the range of 0.25-20 repeat unit moles, and 0.5-15 repeats A range of unit moles is more preferred, and a range of 1 to 10 repeating unit moles is particularly preferred. When the amount of polyphenylene ether ether ketone used is in a preferred range, cyclic polyphenylene ether ether ketone tends to be obtained in a high yield, and the reaction tends to proceed in a short time.

  Mixture (a) containing at least dihalogenated aromatic ketone compound, dihydroxy aromatic compound, base (A), and organic polar solvent, or at least polyphenylene ether ether ketone, dihalogenated aromatic compound, dihydroxy aromatic compound, base (A ), And the mixture (i) containing an organic polar solvent is heated to react with the dihalogenated aromatic ketone compound, dihydroxy aromatic compound, base (A), organic polar solvent, or polyphenylene ether used in the reaction. Although it cannot be uniquely determined because it diversifies depending on the type and amount of ether ketone, it is usually 120 to 350 ° C., preferably 150 to 330 ° C., more preferably 200 to 320 ° C. Furthermore, in the manufacturing method of the mixture (a) by manufacturing method (y), the range of 250-300 degreeC can be illustrated as an especially preferable range. In these preferable temperature ranges, higher reaction rates tend 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 defined 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.

  A mixture (a) containing at least a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base (A) and an organic polar solvent, or at least a polyphenylene ether ether ketone, a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base ( A) When the mixture (a) containing an organic polar solvent is heated and reacted, the mixture (a) or (a) accelerates the reaction, components that do not substantially inhibit the reaction other than the essential components, and the reaction. It is also possible to add components having an effect. In the preferred production methods (x) and (y) of these mixtures (a), there is no limitation on the preparation method of the essential components. However, in the preferred production method (y), at least polyphenylene ether ether ketone, dihydroxy aromatic compound, base A method in which (A) and a dihalogenated aromatic compound or a dihalogenated aromatic compound and an organic polar solvent are additionally added to the reaction mixture obtained by heating and reacting the mixture containing the organic polar solvent and heated to react is also preferable. It can be mentioned as a method. 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, various well-known polymerization systems and reaction systems such as a batch system and a continuous system 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.

  In addition, in the above reaction, when a large amount of water is present in the reaction system, adverse effects such as a reduction in the reaction rate and the generation of a side reaction product that is difficult to separate from the cyclic polyphenylene ether ether ketone tend to be manifested. . The amount of water present in the system during the reaction is preferably 3.0% by weight or less, more preferably 1.0% by weight or less, and more preferably 0.5% by weight or less. The content is particularly preferably 0.3% by weight or less. Therefore, the water content in this preferred range can be reduced by excluding the water produced when the hydrate or aqueous mixture is used as the base (A) or the water produced as a by-product from the reaction, if necessary. The following is preferable. Here, the amount of water present in the system is a weight fraction with respect to the total weight of the reaction mixture, and the amount of water can be measured by the Karl Fischer method. Although there is no restriction | limiting in particular in the time which performs a dehydration operation, After mixing essential components in (i) manufacturing method (x) or (y), or (ii) After mixing essential components other than a dihalogenated aromatic ketone compound It is preferable that Here, when the dehydration operation is performed by the method according to (ii), the mixture (a) is produced by adding a dihalogenated aromatic ketone compound or a dihalogenated aromatic ketone compound and an organic polar solvent after the dehydration operation. As a method for removing water, any method can be used as long as water can be removed from the reaction system, and examples thereof include dehydration by high-temperature heating and azeotropic distillation using an azeotropic solvent, and in particular, from the viewpoint of dehydration efficiency. A preferred method is an azeotropic distillation method. Here, the azeotropic solvent used in the azeotropic distillation is an organic compound that can form an azeotropic mixture with water, and the boiling point of the azeotropic mixture is lower than the boiling point of the organic polar solvent used in the reaction. Specific examples include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene and xylene, and inert chlorinated aromatic compounds such as chlorobenzene and dichlorobenzene, among which toluene and xylene Can be mentioned as a preferred azeotropic solvent. In addition, the amount of azeotropic solvent cannot be specified unconditionally because the amount required to form an azeotrope with water varies depending on the amount of water present in the system and the type of solvent. It is preferred to use an excess of solvent over that required to remove water as an azeotrope, specifically 0.2 liters or more per 1.0 mole of dihydroxylated aromatic compound in the mixture. Preferably, 0.5 liter or more is more preferable, and 1.0 liter or more is more preferable. Further, the upper limit of the amount of azeotropic solvent is not particularly limited, but it is preferably 20.0 liters or less, more preferably 10.0 liters or less, relative to 1.0 mol of the dihydroxylated aromatic compound in the mixture. Preferably, it is 5.0 liters or less. When the amount of the azeotropic solvent used is too large, the polarity in the mixture decreases, so the reaction efficiency between the base and the dihydroxy aromatic compound tends to decrease. Here, the amount of the azeotropic solvent is based on the volume of the solvent under normal temperature and pressure. In addition, when performing azeotropic distillation of water using the principle of the Dean-Stark device, the amount of azeotropic solvent in the reaction system can always be kept constant, so the amount of azeotropic solvent used can be further reduced. It is. The temperature at which water is removed from the reaction system cannot be uniquely determined because the boiling point of the azeotrope with water differs depending on the type of azeotropic solvent, but it is above the boiling point of the azeotrope with water and is It is preferable that it is below the boiling point of the organic polar solvent used for this, Specifically, the range of 60-170 degreeC can be illustrated, Preferably it is 80-170 degreeC, More preferably, it is 100-170 degreeC, More preferably, it is 120-170 degreeC. The range of can be illustrated. The removal of water may be either a method of performing a constant temperature within a preferable temperature range, a method of increasing the temperature stepwise, or a method of changing the temperature continuously. Furthermore, it is also a preferable method to carry out the azeotropic distillation under reduced pressure. By performing the azeotropic distillation under reduced pressure, water tends to be removed more efficiently.

  The azeotropic solvent is preferably excluded from the system after azeotropic distillation. The time for removing the azeotropic solvent from the system is preferably after the end of the azeotropic distillation of water. Further, when the dehydration operation is performed by the method according to (ii) above, the removal of the azeotropic solvent is performed by dihalogenated aromatics. It is preferable to carry out the step before adding the ketone compound or the dihalogenated aromatic ketone compound and the organic polar solvent. If a large amount of the azeotropic solvent remains in the system, the polarity of the reaction system decreases, and the reaction rate of cyclic polyphenylene ether ether ketone formation tends to decrease. Therefore, it is desirable to perform an operation for removing the azeotropic solvent. The amount of the azeotropic solvent remaining in the system during the cyclic polyphenylene ether ether ketone formation reaction is preferably 20% or less with respect to the organic polar solvent used for preparing the mixture (a), and is preferably 10% or less. Is more preferably 8% or less, and particularly preferably 6% or less. It is important to remove the azeotropic solvent so that it is below this preferred range. As a method for removing the azeotropic solvent, a method by distillation is preferable, and an inert gas such as nitrogen, helium, or argon may be used as a carrier gas. In addition, distillation under reduced pressure is also a preferable method, and the azeotropic solvent tends to be removed more efficiently. The temperature at which the azeotropic solvent is removed may be any temperature as long as the azeotropic solvent can be excluded from the reaction system. Can be exemplified by the range of 120 to 170 ° C, more preferably 140 to 170 ° C. The removal of the azeotropic solvent may be performed either at a constant temperature in a preferred temperature range, a method of increasing the temperature stepwise, or a type of continuously changing the temperature.

(8) -2. Manufacturing method (z)
Another preferred production method of the mixture (a) is a production method (z) by heating and reacting a mixture (c) containing at least polyphenylene ether ether ketone, a basic compound (B) and an organic polar solvent. Can do.

  The amount of the organic polar solvent in the mixture (c) when the mixture (a) is produced by this method is not particularly limited, but preferably 1.20 liters or more with respect to 1.0 mol of the benzene ring component in the mixture. More preferably, it contains 1.30 liters or more, more preferably 1.50 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 100 liters or less, more preferably 50 liters or less, and more preferably 20 liters or less, relative to 1.0 mol of the benzene ring component in the mixture. More preferably, it is more preferably 10 liters or less. When the amount of the organic polar solvent used is increased, the amount of cyclic polyphenylene ether ether ketone produced tends to decrease, and the time required for the reaction tends to increase. Therefore, from the viewpoint of achieving both the production selectivity of cyclic polyphenylene ether ether ketone and productivity, the use range of the organic polar solvent described above can be exemplified as a preferred range. Here, the amount of the organic polar solvent is an amount obtained by subtracting the amount of the organic polar solvent excluded from the reaction system by dehydration operation or the like from the amount of the organic polar solvent introduced into 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".

  Use amount of basic compound (B) in production method (z) of mixture (a) by heating and reacting mixture (c) containing at least polyphenylene ether ether ketone, basic compound (B) and organic polar solvent Is not particularly limited, but is the main structural unit of polyphenylene ether ether ketone

Is preferably in the range of 0.001 to 10 mol, more preferably in the range of 0.01 to 5 mol, and more preferably in the range of 0.05 to 1 mol. More preferably, it is in the range. Use of basic compound (B) in production method (z) of mixture (a) by heating and reacting mixture (c) containing at least polyphenylene ether ether ketone, basic compound (B) and organic polar solvent When the amount is within the above preferred range, the cyclic polyphenylene ether ether ketone tends to be obtained in a high yield, and the reaction tends to proceed in a short time.

  When the mixture (c) containing at least polyphenylene ether ether ketone, basic compound (B), and organic polar solvent is reacted by heating, water can be added to the mixture (c) in addition to the essential components. Although there is no restriction | limiting in particular in the moisture content at this time, It is preferable that it exists in the range of 0.01-100 mol with respect to 1 mol of basic compounds (B) to be used, The range of 0.1-50 mol is more preferable, A range of 0.5 to 10 mol can be more preferably exemplified. When the amount of water used is in the above preferred range, the cyclic polyphenylene ether ether ketone tends to be obtained in a high yield, and the cyclic polyphenylene ether ether ketone contained in the cyclic polyphenylene ether ether ketone composition is particularly likely to be obtained. The content rate tends to increase. Moreover, as a basic compound (B) preferably used in the manufacturing method (z) of a cyclic polyphenylene ether ether ketone composition, an alkali metal halide, an alkali metal carbonate, or an alkali metal bicarbonate is mentioned. Even when any of these preferable basic compounds (B) is used, the above-mentioned effect appears by adding water. Among them, an alkali metal carbonate and / or an alkali metal bicarbonate is used as the basic compound (B). When used, the above-mentioned effects due to the addition of water tend to appear more prominently. Therefore, when a cyclic polyphenylene ether ether ketone composition is produced by the method according to production method (z) using alkali metal carbonate and / or alkali metal bicarbonate as the basic compound (B), the mixture ( Adding water to c) can be exemplified as a more preferred embodiment.

  The reaction temperature at which the mixture (c) containing at least polyphenylene ether ether ketone, basic compound (B) and organic polar solvent is heated to react is the basic compound (B) used in the reaction, the organic polar solvent, and further polyphenylene. Although it cannot be uniquely determined because it varies depending on the type and amount of ether ether ketone, it is usually 120 to 350 ° C, preferably 150 to 330 ° C, more preferably 200 to 320 ° 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 on the reaction time, but the reaction proceeds sufficiently even within 40 hours, preferably within 10 hours, more preferably within 6 hours.

  When the mixture (c) containing at least polyphenylene ether ether ketone, the basic compound (B), and the organic polar solvent is heated and reacted, the mixture (c) contains components that do not substantially inhibit the reaction other than the above components, It is also possible to add a component having 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.

  Typical reaction formulas of the production methods (x), (y), and (z) of the mixture (a) described above are shown below.

(9) Distillation of organic polar solvent In order to recover the polyphenylene ether ether ketone and the cyclic polyphenylene ether ether ketone composition by the method of the present invention, it is essential to distill off the organic polar solvent from the mixture (a). It is.

  As a method for distilling off the organic polar solvent, any method can be used as long as the organic polar solvent can be excluded from the reaction system from the mixture (a) and the amount of the organic polar solvent contained in the mixture (a) can be reduced. As a preferred method, a method of distilling an organic polar solvent under reduced pressure or under pressure, a method of removing the solvent by filtration, a method of removing the solvent by flash transfer, a substance having a strong affinity with the solvent is added. Examples thereof include a method of developing phase separation and substantially removing the solvent from the reaction system. Among them, a method of distilling the organic polar solvent under reduced pressure or increased pressure, and a method of removing the solvent by flash transfer are more preferable. A method of distilling the organic polar solvent under pressure or under pressure is more preferable. Further, when distilling the organic polar solvent under reduced pressure or under pressure, an inert gas such as nitrogen, helium or argon may be used as a carrier gas.

  In addition, the temperature at which the organic polar solvent is distilled off varies depending on the type of the organic polar solvent and the composition of the mixture (a), and cannot be uniquely determined, but is preferably 180 to 320 ° C. 190-310 degreeC is more preferable, and the range of 200-300 degreeC can be illustrated as a still more preferable range. In this temperature range, most of the polyphenylene ether ether ketone is dissolved in the organic polar solvent, and it can be expected that the molecular chain growth reaction of the polyphenylene ether ether ketone proceeds during the distillation. Furthermore, since the organic polar solvent is distilled off, the concentration of the growth terminal in the system increases, and as a result, the molecular chain growth reaction is considered to proceed at an accelerated rate. Therefore, the polyphenylene ether ether ketone oligomer contained in the mixture (a) has a high molecular weight while the organic polar solvent is distilled off, and the amount of polyphenylene ether ether ketone oligomer contained in the mixture (b) is finally reduced. Here, the polyphenylene ether ether ketone oligomer refers to those having an average molecular weight lower than that of the above-mentioned polyphenylene ether ether ketone, and the polyphenylene ether ether ketone oligomer is in the range of 2 to 20 as the number of repetitions n in the following general formula (I). The range of 2-18 is preferable, and the range of 2-15 is more preferable.

  The polyphenylene ether ether ketone oligomer having a repeating number n in this preferred range is similar to the cyclic polyphenylene ether ether ketone in properties such as solubility in various solvents, and is difficult to separate from the cyclic polyphenylene ether ether ketone. A compound. Therefore, it is preferable that the amount of these polyphenylene ether ether ketone oligomers remaining in the mixture (b) is small.

  Further, the distillation may be either one-stage distillation performed at a constant temperature, multi-stage distillation in which the temperature is raised stepwise, or distillation in the form of continuously changing the temperature.

  Since the time required for the distillation depends on the type and amount of the organic polar solvent used or the distillation temperature, it cannot be generally specified, but is preferably 0.1 hours or more, more preferably 0.3 hours or more, and 5 hours or more is more preferable. By setting it as this preferable time or more, high molecular weight of the polyphenylene ether ether ketone oligomer contained in the mixture (a) tends to proceed easily. Furthermore, after distilling off the organic polar solvent, the reaction is continued at the same temperature or higher to increase the molecular weight of the polyphenylene ether ether ketone oligomer, and the cyclic polyphenylene ether contained in the cyclic polyphenylene ether ether ketone composition. Since the ether ether ketone content tends to be high, it is preferable to use such means.

  When distilling off the organic polar solvent, if the organic polar solvent is distilled off excessively, the polyphenylene ether ether ketone tends to precipitate and solidify, and the viscosity of the mixture (b) tends to increase and the operability tends to deteriorate. is there. Therefore, the amount of the organic polar solvent to be distilled off cannot be uniquely determined because it varies depending on the type of the organic polar solvent, the amount used in the reaction, etc. It is preferably 0.10 liters or more, more preferably 0.15 liters or more, and even more preferably 0.20 liters or more with respect to 1.0 mol of the benzene ring component in b).

  On the other hand, if the amount of the organic polar solvent distilled off is too small, the effect of the present invention tends to be reduced. Therefore, the amount of the organic polar solvent to be distilled off cannot be uniquely determined because it varies depending on the kind of the organic polar solvent, the amount used in the reaction, etc. The distillate is preferably distilled off to 1.0 liter or less, more preferably 0.8 liter or less to 1.0 mol relative to 1.0 mol of the benzene ring component in the mixture (b). More preferably, the solvent is distilled off to 5 liters or less.

  Moreover, before distilling off the organic polar solvent, it is also possible to perform an operation of removing a component insoluble at a temperature at which the polyphenylene ether ether ketone is dissolved by solid-liquid separation (2). By performing this operation, the viscosity of the mixture (b) obtained by distilling off the organic polar solvent is lowered, and the operability tends to be improved.

  Here, the temperature at which the solid-liquid separation (2) is performed is not particularly limited as long as the polyphenylene ether ether ketone is dissolved, but is preferably in the range of 200 to 350 ° C, more preferably in the range of 220 to 300 ° C, The range of 230-280 degreeC is still more preferable. Within such a temperature range, polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone are less likely to be decomposed or altered, and organic polar solvents are less likely to be degraded or altered. In such a preferable temperature range, the solubility of polyphenylene ether ether ketone in an organic polar solvent is improved, so that the solution component tends to be uniform, and the viscosity of the solution component tends to decrease as the temperature increases. The separability in solid-liquid separation (2) tends to be improved.

  Although there is no restriction | limiting in particular in the pressure at the time of performing solid-liquid separation (2) in the temperature range where polyphenylene ether ether ketone becomes soluble, 2.0 MPa or less is preferable at a gauge pressure, and 1.0 MPa or less is more preferable. In general, as the pressure increases, it is necessary to increase the pressure resistance of the device that performs solid-liquid separation, and such a device is required to have a high degree of sealing performance at each part constituting it. Since the cost increases, it is preferable to perform solid-liquid separation at a lower pressure.

  Moreover, the method of performing solid-liquid separation (2) is not specifically limited, A well-known method can be employ | adopted, It is the filtration by pressure filtration and vacuum filtration which are filtration using a filter, and separation by the specific gravity difference of solid content and a solution. Centrifugation, sedimentation, and a combination of these can be employed. A decanter separation method in which sedimentation separation is performed before the filtration operation is also a preferable method. The filter used for filtration operation should just be stable on the conditions which perform solid-liquid separation (2), for example, a wire sieve and a sintered plate can be used conveniently. In addition, the mesh size or pore size of this filter varies widely depending on the viscosity, pressure, temperature, particle size of the solid component in the slurry, and purity of the resulting filtrate (solid content). Can be adjusted.

(10) Recovery of polyphenylene ether ether ketone In the present invention, the mixture (b) obtained by distilling off the organic polar solvent is subjected to solid-liquid separation in a temperature range in which the polyphenylene ether ether ketone is insoluble, and an insoluble component is obtained. The polyphenylene ether ether ketone is recovered as a soluble component, and the cyclic polyphenylene ether ether ketone is recovered as a soluble component.

  The temperature at which solid-liquid separation is performed is not particularly limited as long as the polyphenylene ether ether ketone is insoluble, but a temperature range of 20 to 200 ° C is preferable, a range of 50 to 150 ° C is more preferable, and a range of 80 to 120 ° C is preferable. Further preferable examples can be given. In this preferred temperature range, polyphenylene ether ether ketone tends to be present as a solid, while cyclic polyphenylene ether ether ketone tends to be dissolved in an organic polar solvent. Therefore, by performing solid-liquid separation in this temperature range, it is possible to easily separate the polyphenylene ether ether ketone as a solid component and the cyclic polyphenylene ether ether ketone dissolved in an organic polar solvent.

  Although there is no restriction | limiting in the pressure at the time of performing solid-liquid separation, 2.0 MPa or less can be illustrated as a preferable pressure range with a gauge pressure, 1.0 MPa or less is more preferable, 0.8 MPa or less is more preferable, 0.5 MPa or less is preferable. It can be illustrated as a more preferable range. In general, as the pressure increases, it is necessary to increase the pressure resistance of the device that performs solid-liquid separation, and such a device is required to have a high degree of sealing performance at each part constituting it. Expenses will increase. In the preferred pressure range, generally available solid-liquid separation equipment can be used.

  In addition, a method for performing solid-liquid separation is not particularly limited, and a known method can be employed, and pressure filtration or vacuum filtration that is filtration using a filter, centrifugation that is separation due to a difference in specific gravity between a solid content and a solution, Furthermore, a method combining these can be employed. A decanter separation method in which sedimentation separation is performed before the filtration operation is also a preferable method. The filter used for the filtration operation is not particularly limited as long as it is stable under the conditions for solid-liquid separation. For example, a commonly used filter medium such as a wire mesh filter, a sintered plate, a filter cloth, or filter paper can be used in the process. In addition, the pore size of this filter can be adjusted over a wide range depending on the viscosity, pressure, temperature of the slurry used for the solid-liquid separation operation, the particle size of the solid component in the slurry, and the purity of the resulting filtrate (solid content). Can do. In particular, the particle diameter of the polyphenylene ether ether ketone recovered as a solid content from the slurry in this solid-liquid separation operation, that is, the mesh diameter or the pore diameter depending on the particle diameter of the solid content present in the slurry subjected to solid-liquid separation. It is effective to select the filter pore size. The average particle diameter (median diameter) of the polyphenylene ether ether ketone in the slurry subjected to solid-liquid separation can vary widely depending on the composition, temperature, concentration, etc. of the slurry, but as long as the present inventors can know, the average The particle size tends to be 1 to 300 μm. Therefore, 0.1-100 micrometers can be illustrated as a preferable average hole diameter of a filter hole diameter, 0.25-20 micrometers is preferable, and 0.5-15 micrometers can be illustrated as a more preferable range. Furthermore, there is no particular limitation on the atmosphere in which the solid-liquid separation is performed here, but it can be exemplified as a preferable method performed in an inert atmosphere such as nitrogen, helium, and argon. As a result, undesired reactions such as decomposition of polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone are unlikely to occur, and decomposition and alteration of organic polar solvents tend not to occur.

  According to the solid-liquid separation here, most of the polyphenylene ether ether ketone contained in the mixture (b) can be separated as a solid content, preferably 80% or more, more preferably 90% or more, and still more preferably 95. % Or more can be recovered as solids. In addition, when the solid polyphenylene ether ether ketone separated by solid-liquid separation contains an organic polar solvent (mother liquor) containing cyclic polyphenylene ether ether ketone, the solid content is washed with a fresh solvent. Thus, the residual amount of cyclic polyphenylene ether ether ketone in the solid content can be reduced. As this method, there are a method of adding a fresh solvent on a filter in which a solid cake is laminated and solid-liquid separation, a method of adding a fresh solvent to a solid cake and stirring to make a slurry, and then a solid-liquid separation. Although it can illustrate, it is preferable to perform the conditions which perform these operation according to the preferable conditions employ | adopted for solid-liquid separation mentioned above. In addition, the solvent used here should just be a thing which can dissolve cyclic polyphenylene ether ether ketone, Preferably an organic polar solvent can be illustrated.

  In the case where an alkali metal halide salt is contained in the solid component recovered by the solid-liquid separation, the alkali metal halide salt can be removed by a known method. Examples of the removing method include a method of contacting with a second solvent in which the alkali metal halide salt is soluble. Here, the alkali metal halide salt is a solid component such as one produced when preparing the mixture (a), or an alkali metal halide salt introduced into the reaction system at an optional stage such as during or after the reaction. Includes all alkali metal halide salts present therein. Alkali metal halide salts include any combination of alkali metals, i.e., lithium, sodium, potassium, rubidium and cesium, and halogens, i.e., fluorine, chlorine, bromine, iodine and astatine. Examples include lithium, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, potassium iodide, cesium fluoride, and the like.

  As the second solvent used when removing the alkali metal halide salt from the solid component, a solvent in which the alkali metal halide salt is soluble is preferable, for example, alcohol solvents such as methanol and ethanol and water can be exemplified, and water is particularly preferable. preferable.

  There is no particular limitation on the temperature at which the alkali metal halide salt is removed from the solid component, but the upper limit is preferably set to the reflux condition temperature under normal pressure of the second solvent to be used. 20-100 degreeC can be illustrated as a preferable temperature range, More preferably, 25-80 degreeC can be illustrated.

  As a method of bringing the solid component into contact with the second solvent, a method in which the second solvent is added to the filter on which the solid component is laminated to perform solid-liquid separation, or a method in which the second solvent is added to the solid component and stirred. An example is a method of solid-liquid separation after slurrying. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. It is also possible to reduce the content of the alkali metal halide salt by bringing the polyphenylene ether ether ketone thus obtained into contact with the second solvent again.

  Since the polyphenylene ether ether ketone thus obtained contains the second solvent, it can be dried under normal pressure and / or reduced pressure as desired. The drying temperature is preferably in the range of 50 to 200 ° C, more preferably in the range of 70 to 150 ° C. The drying atmosphere may be any of an inert atmosphere such as nitrogen, helium, and argon, a reduced pressure, an oxidizing atmosphere such as oxygen and air, and a mixed atmosphere of air and nitrogen. It is also a preferred method to dry under reduced pressure, after removing most of the solvent and then drying again under reduced pressure. The drying time is preferably 0.5 to 50 hours, more preferably 1 to 30 hours, and further preferably 1 to 20 hours.

  The polyphenylene ether ether ketone obtained by the present invention is excellent in heat resistance, chemical resistance, flame retardancy, electrical properties and mechanical properties.

(11) Recovery of cyclic polyphenylene ether ether ketone Cyclic polyphenylene ether ether ketone is obtained by removing the organic polar solvent from the solid-liquid separation filtrate obtained by performing the above mixture (b) in a temperature region in which polyphenylene ether ether ketone is insoluble. A composition can be obtained. There is no particular limitation on the method for obtaining the cyclic polyphenylene ether ether ketone composition by removing the organic polar solvent from the filtrate component, and the filtrate component is in contact with a solvent having low solubility in the polyphenylene ether ether ketone component and miscible with the organic polar solvent. The method of recovering the cyclic polyphenylene ether ether ketone composition, after removing a part or most of the organic polar solvent of the filtrate by an operation such as distillation, and having low solubility in the polyphenylene ether ether ketone component and the organic polarity A method of recovering a cyclic polyphenylene ether ether ketone composition by contacting with a solvent miscible with the solvent, cooling the filtrate to deposit a cyclic polyphenylene ether ether ketone composition, and depositing the cyclic polyphenylene ether ether ketone composition How to recover, filter The organic polar solvent was removed by heating under normal pressure or, a method of recovering a cyclic polyphenylene ether ether ketone composition. Among them, after removing a part or most of the organic polar solvent by an operation such as distillation, it is brought into contact with a solvent that has low solubility in the polyphenylene ether ether ketone component and is miscible with the organic polar solvent, and then cyclic polyphenylene ether ether. A method of recovering the ketone composition is preferred. In addition, the solvent having such characteristics is generally a solvent having a relatively high polarity, and the preferred solvent differs depending on the type of the organic polar solvent used. However, for example, water, methanol, ethanol, propanol, isopropanol, butanol can be used. , Alcohols typified by hexanol, acetone, ketones typified by methyl ethyl ketone, acetates typified by ethyl acetate and butyl acetate can be exemplified, and water, methanol and acetone are preferred from the viewpoint of availability and economy. Water is particularly preferred. By performing the treatment with such a solvent, it is possible to reduce the amount of the organic polar solvent or by-product salt contained in the cyclic polyphenylene ether ether ketone composition. Since the cyclic polyphenylene ether ether ketone composition is precipitated as a solid component by this treatment, the cyclic polyphenylene ether ether ketone composition can be recovered using a known solid-liquid separation method. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. These series of treatments can be repeated several times as necessary, and this tends to further reduce the amount of organic polar solvent and by-product salt contained in the cyclic polyphenylene ether ether ketone composition. is there. In the method of recovering the cyclic polyphenylene ether ether ketone composition by contacting with a solvent that is poorly soluble in the polyphenylene ether ether ketone component and miscible with the organic polar solvent, preferably at least 70% by weight, More preferably, it is desirable to remove 95% by weight or more of the organic polar solvent.

  Moreover, as another preferable method of removing the organic polar solvent from the filtrate, a method of removing the organic polar solvent by heating at normal pressure or lower can be exemplified. The filtrate containing the cyclic polyphenylene ether ether ketone obtained as described above may contain a solid depending on the temperature. In this case, the solid is soluble in the organic polar solvent when the organic polar solvent is removed. It is desirable to recover together with the components. In the method of removing the organic polar solvent by heating at normal pressure or lower, the removal of the organic polar solvent is at least 50 wt% or more, preferably 70 wt% or more, more preferably 90 wt% or more, and even more preferably 95 wt%. It is desirable to remove more than% organic polar solvent. Although the temperature at which the organic polar solvent is removed by heating depends on the characteristics of the organic polar solvent to be used, it cannot be uniquely limited, but a range of 20 to 150 ° C, preferably 40 to 120 ° C can be selected. Further, the pressure for removing the organic polar solvent is preferably not more than normal pressure, which makes it possible to remove the organic polar solvent at a lower temperature.

  The cyclic polyphenylene ether ether ketone composition thus obtained has a high purity containing 60% by weight or more, preferably 65% by weight or more, more preferably 70% by weight or more of the cyclic polyphenylene ether ether ketone. Industrially having a different property from the obtained linear polyphenylene ether ether ketone is highly useful.

  In particular, the cyclic polyphenylene ether ether ketone composition recovered by the method of the present invention has a melting solution temperature of 270 ° C. or lower, and has a feature that the melting solution temperature is significantly lower than that of the corresponding linear polyphenylene ether ether ketone. Have

(12) Production method of polyphenylene ether ether ketone The cyclic polyphenylene ether ether ketone composition of the present invention can be used as a polyphenylene ether ether ketone prepolymer and can be converted into polyphenylene ether ether ketone by heat ring-opening polymerization. . Here, the polyphenylene ether ether ketone is a linear compound represented by the general formula (I) having paraphenylene ketone and paraphenylene ether as repeating structural units. As described above, since the cyclic polyphenylene ether ether ketone composition recovered by the method of the invention has a low melt solution temperature of 270 ° C. or lower, the process temperature for obtaining a high degree of polymerization is set low. be able to. That is, it is advantageous from the viewpoint that the energy required for processing can be reduced. Further, the reduced viscosity (η) of the polyphenylene ether ether ketone obtained by subjecting the cyclic polyphenylene ether ether ketone composition of the present invention to heat ring-opening polymerization is not particularly limited, but the preferred range is 0.1 to 2.5 dL. / G, more preferably 0.2 to 2.0 dL / g, still more preferably 0.3 to 1.8 dL / g. The heating temperature when the cyclic polyphenylene ether ether ketone composition is converted to polyphenylene ether ether ketone by heating ring-opening polymerization is preferably equal to or higher than the temperature at which the cyclic polyphenylene ether ether ketone composition melts, If it is such temperature conditions, there will be no restriction | limiting in particular. If the heating temperature is lower than the melting temperature of the cyclic polyphenylene ether ether ketone, it takes a long time to obtain the polyphenylene ether ether ketone by the heat ring-opening polymerization, or the polyphenylene ether ether ketone does not proceed without the heat ring-opening polymerization. There is a tendency to become unobtainable. The temperature at which the cyclic polyphenylene ether ether ketone composition melts is the composition and molecular weight of the cyclic polyphenylene ether ether ketone, the weight fraction of the cyclic polyphenylene ether ether ketone contained in the cyclic polyphenylene ether ether ketone composition, Furthermore, since it changes depending on the environment during heating, it cannot be uniquely shown.For example, it is possible to grasp the melt temperature by analyzing a cyclic polyphenylene ether ether ketone composition with a differential scanning calorimeter. is there. As a minimum of heating temperature, 150 degreeC or more can be illustrated, Preferably it is 180 degreeC or more, More preferably, it is 200 degreeC or more, More preferably, it is 220 degreeC or more. In this temperature range, the cyclic polyphenylene ether ether ketone composition melts and tends to be obtained in a short time. On the other hand, if the temperature of the ring-opening polymerization is too high, crosslinking reaction or decomposition between cyclic polyphenylene ether ether ketone, between polyphenylene ether ether ketone produced by heating, or between polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone, etc. It is desirable to avoid a temperature at which such an undesirable side reaction is remarkably generated, because an undesirable side reaction typified by the reaction tends to easily occur and the characteristics of the obtained polyphenylene ether ether ketone may be deteriorated. . As an upper limit of heating temperature, 500 degrees C or less can be illustrated, Preferably it is 400 degrees C or less, More preferably, it is 360 degrees C or less, More preferably, it is 335 degrees C or less, More preferably, it is 300 degrees C or less. Below this temperature range, adverse effects on the properties of the resulting polyphenylene ether ether ketone due to undesirable side reactions tend to be suppressed. When a known cyclic polyphenylene ether ether ketone is used, the cyclic polyphenylene ether ether ketone has a high melting point, so that it takes a long time for the heat-opening polymerization in the above-mentioned preferable temperature range, or the heat-opening polymerization proceeds. However, the cyclic polyphenylene ether ether ketone composition having the melting point of 270 ° C. or less is effective in the above-mentioned preferable temperature range, while the polyphenylene ether ether ketone is not easily obtained. Proceeds to obtain polyphenylene ether ether ketone. In the method for producing polyphenylene ether ether ketone of the present invention, it is possible to carry out heat-opening polymerization at a temperature not higher than the melting point of the obtained polyphenylene ether ether ketone.

  Although the reaction time differs depending on the weight fraction and composition ratio of the cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition to be used, the heating temperature, the heating ring-opening polymerization method and the like, it cannot be uniformly defined. It is preferable to set so as not to cause undesired side reactions such as the crosslinking reaction described above, and the range of 0.01 to 100 hours can be exemplified, 0.05 to 20 hours are preferable, and 0.05 to 10 hours are preferable. More preferred. By setting it as these preferable reaction time, it exists in the tendency which can suppress the bad influence on the characteristic of the polyphenylene ether ether ketone obtained by progress of unfavorable side reactions, such as a crosslinking reaction.

  The process for producing polyphenylene ether ether ketone by heat-opening polymerization of the cyclic polyphenylene ether ether ketone composition of the present invention can be carried out in the absence of a catalyst or in the presence of a catalyst. The catalyst herein is not particularly limited as long as it is a compound having an effect of accelerating the ring-opening polymerization reaction of the cyclic polyphenylene ether ether ketone composition in the present invention, and is a photopolymerization initiator, a radical polymerization initiator, a cation. Known catalysts such as a polymerization initiator, an anionic polymerization initiator, and a transition metal catalyst can be used, and among these, an anionic polymerization initiator is preferable. Examples of the anionic polymerization initiator include inorganic alkali metal salts or organic alkali metal salts. Examples of the inorganic alkali metal salts include alkali metal halides such as sodium fluoride, potassium fluoride, cesium fluoride, and lithium chloride. Examples of the organic alkali metal salt include sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide and other alkali metal alkoxides, sodium phenoxide, potassium phenoxide, sodium Examples include alkali metal phenoxides such as -4-phenoxyphenoxide and potassium-4-phenoxyphenoxide, and alkali metal acetates such as lithium acetate and sodium acetate potassium acetate. Can. Further, it is presumed that these anionic polymerization initiators exhibit a catalytic action by nucleophilic attack on the cyclic polyphenylene ether ether ketone composition. Therefore, it is possible to use a compound having a nucleophilic attack ability equivalent to those of these anionic polymerization initiators as a catalyst. Examples of such a compound having a nucleophilic attack ability include a polymer having an anion polymerizable terminal. Can do. These anionic polymerization initiators may be used alone or in combination of two or more. By performing the ring-opening polymerization of the cyclic polyphenylene ether ether ketone composition in the presence of these preferred catalysts, polyphenylene ether ether ketone tends to be obtained in a short time. Specifically, the heating time of the heat ring-opening polymerization 2 hours or less, further 1 hour or less, 0.5 hours or less.

  The amount of catalyst used varies depending on the molecular weight of the target polyphenylene ether ether ketone and the type of catalyst, but is usually a formula that is the main structural unit of cyclic polyphenylene ether ether ketone.

0.001 to 20 mol%, preferably 0.005 to 15 mol%, and more preferably 0.01 to 10 mol% with respect to 1 mol of the repeating unit. By adding a catalyst amount in this preferable range, the ring-opening polymerization of the cyclic polyphenylene ether ether ketone composition tends to proceed in a short time.

  Regarding the addition of these catalysts, they may be added as they are, but it is preferable to uniformly disperse them after adding the catalyst to the cyclic polyphenylene ether ether ketone composition. Examples of the uniform dispersion method include a mechanical dispersion method and a dispersion method using a solvent. Specific examples of the mechanical dispersion method include a pulverizer, a stirrer, a mixer, a shaker, and a method using a mortar. Specific examples of the method of dispersing using a solvent include a method of dissolving or dispersing the cyclic polyphenylene ether ether ketone composition in an appropriate solvent, adding a catalyst thereto, and then removing the solvent. In addition, when the catalyst is dispersed, when the catalyst is a solid, more uniform dispersion is possible, so that the average particle size of the polymerization catalyst is preferably 1 mm or less.

  The ring-opening polymerization of the cyclic polyphenylene ether ether ketone composition can be carried out either in a solvent or under a substantially solvent-free condition, but the temperature can be raised in a short time, and the reaction Since the speed is high and the polyphenylene ether ether ketone tends to be easily obtained in a short time, it is preferably carried out under conditions substantially free of a solvent. The term “substantially solvent-free conditions” here means that the solvent in the cyclic polyphenylene ether ether ketone composition is 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less. .

  Moreover, as a heating method, it is possible to carry out by a method using a normal polymerization reaction apparatus, in a mold for producing a molded article, or by using an extruder or a melt kneader. Any apparatus having a mechanism can be used without any particular limitation, and known methods such as a batch method and a continuous method can be employed.

  The atmosphere during the ring-opening polymerization of the cyclic polyphenylene ether ether ketone composition is preferably a non-oxidizing atmosphere, and is preferably performed under reduced pressure. Moreover, when it carries out under pressure reduction conditions, it is preferable to make it the pressure reduction conditions after making the atmosphere in a reaction system once non-oxidizing atmosphere. Unfavorable side reactions such as cross-linking reactions and decomposition reactions between cyclic polyphenylene ether ether ketones, between polyphenylene ether ether ketones produced by ring-opening polymerization, and between polyphenylene ether ether ketones and cyclic polyphenylene ether ether ketones. It tends to be possible to suppress the occurrence of. Note that the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the cyclic polyphenylene ether ether ketone is 5% by volume or less, preferably 2% by volume or less, and more preferably contains substantially no oxygen, that is, nitrogen or helium. In addition, it refers to an inert gas atmosphere such as argon, and among these, a nitrogen atmosphere is particularly preferred from the viewpoint of economy and ease of handling. The reduced pressure condition means that the reaction system is lower than the atmospheric pressure, and the upper limit is preferably 50 kPa or less, more preferably 20 kPa or less, and even more preferably 10 kPa or less. An example of the lower limit is 0.1 kPa or more, and 0.2 kPa or more is more preferable. When the decompression condition is at least the preferred lower limit, the cyclic compound having a low molecular weight contained in the cyclic polyphenylene ether ether ketone composition is less likely to be volatilized, while when it is less than the preferred upper limit, undesirable side reactions such as a crosslinking reaction tend not to occur.

  The above-described heating of the cyclic polyphenylene ether ether ketone can be performed in the presence of a fibrous substance. Here, the fibrous substance is a thin thread-like substance, and an arbitrary substance having a structure elongated like a natural fiber is preferable. By converting the cyclic polyphenylene ether ether ketone composition to polyphenylene ether ether ketone in the presence of the fibrous material, a composite material structure composed of the polyphenylene ether ether ketone and the fibrous material can be easily prepared. . Since such a structure is reinforced with a fibrous material, it tends to be superior in mechanical properties, for example, compared to the case of polyphenylene ether ether ketone alone.

  Here, among the various fibrous materials, it is preferable to use reinforcing fibers composed of long fibers, which makes it possible to highly reinforce the polyphenylene ether ether ketone. In general, when creating a composite material structure composed of a resin and a fibrous substance, the resin and the fibrous substance tend to become poorer due to the high viscosity when the resin is melted. In many cases, composite materials cannot be produced and expected mechanical properties do not appear. Here, wetting is the physical state of the fluid material and the solid substrate so that substantially no air or other gas is trapped between the fluid material such as a molten resin and the solid substrate such as a fibrous compound. It means that there is good and maintained contact. Here, the lower the viscosity of the fluid substance, the better the wetting with the fibrous substance. Since the cyclic polyphenylene ether ether ketone composition of the present invention has a significantly lower viscosity when melted than a general thermoplastic resin, for example, polyphenylene ether ether ketone, the wettability with the fibrous material tends to be good. It is in. After the cyclic polyphenylene ether ether ketone composition and the fibrous material form good wetting, the cyclic polyphenylene ether ether ketone composition is converted to polyphenylene ether ether ketone according to the method for producing polyphenylene ether ether ketone of the present invention. Therefore, it is possible to easily obtain a composite material structure in which the fibrous material and polyphenylene ether ether ketone form good wetting.

As described above, the fibrous material is preferably a reinforcing fiber composed of long fibers, and the reinforcing fiber used in the present invention is not particularly limited. However, as the reinforcing fiber that is suitably used, generally, a high-performance reinforcing fiber is used. And fibers having good heat resistance and tensile strength. For example, the reinforcing fiber includes glass fiber, carbon fiber, graphite fiber, aramid fiber, silicon carbide fiber, alumina fiber, and boron fiber. Among these, carbon fiber and graphite fiber, which have good specific strength and specific elastic modulus and are recognized to make a great contribution to weight reduction, can be exemplified as the best. Any type of carbon fiber or graphite fiber can be used as the carbon fiber or graphite fiber depending on the application, but a high strength and high elongation carbon fiber having a tensile strength of 450 kgf / mm ² and a tensile advance of 1.6% or more. Is the most suitable. In the case of using long fiber-like reinforcing fibers, the length is preferably 5 cm or more. In the range of this length, it becomes easy to sufficiently develop the strength of the reinforcing fiber as a composite material. Carbon fiber and graphite fiber may be used in combination with other reinforcing fibers. Moreover, the shape and arrangement | sequence of a reinforced fiber are not limited, For example, even if it is a single direction, a random direction, a sheet form, a mat form, a textile form, and a braid form, it can be used. In particular, for applications that require high specific strength and specific elastic modulus, an array in which reinforcing fibers are aligned in a single direction is the most suitable, but a cloth-like array that is easy to handle. Is also suitable for the present invention.

  The conversion of the cyclic polyphenylene ether ether ketone composition into the polyphenylene ether ether ketone can also be performed in the presence of a filler. Examples of the filler include non-fibrous glass, non-fibrous carbon, and inorganic fillers such as calcium carbonate, titanium oxide, and alumina.

(13) Use of cyclic polyphenylene ether ether ketone composition The cyclic polyphenylene ether ether ketone composition of the present invention has a strong tendency to greatly reduce the melt viscosity of a thermoplastic resin by being blended with the thermoplastic resin. The effect of improving the fluidity of the thermoplastic resin is exhibited. This is an effect due to the fact that the entanglement between molecules is reduced because cyclic polyphenylene ether ether ketone does not have a terminal structure unlike ordinary linear compounds and linear polymers.

  The thermoplastic resin here may be any resin that can be melt-molded. For example, a polyamide resin, a polyester resin, a polyacetal resin, a polycarbonate resin, a polyphenylene ether resin, or a polyphenylene ether resin is blended or grafted with another resin. Modified polyphenylene ether resin modified by polymerization, polyarylate resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyketone resin, polyetherketone resin, polyetheretherketone resin, polyimide resin, polyamideimide resin, polyether Imide resin, thermoplastic polyurethane resin, high density polyethylene resin, low density polyethylene resin, linear low density polyethylene resin, polypropylene resin, polymethylpentene resin Cyclic olefin resin, poly 1-butene resin, poly 1-pentene resin, polymethyl pentene resin, ethylene / α-olefin copolymer, (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid) Acid ester), and a copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester). Polyolefin, block copolymer of conjugated diene and vinyl aromatic hydrocarbon, hydride of block copolymer of conjugated diene and vinyl aromatic hydrocarbon, polyvinyl chloride resin, polystyrene resin, polyacrylate resin, polymethacrylic acid Mainly composed of acrylic resin such as ester resin and acrylonitrile Acrylonitrile copolymer, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, cellulose resin such as cellulose acetate, vinyl chloride / ethylene copolymer, vinyl chloride / vinyl acetate copolymer, Examples thereof include ethylene / vinyl acetate copolymers and saponified ethylene / vinyl acetate copolymers, which may be used alone or in combination as a polymer alloy.

  The cyclic polyphenylene ether ether ketone composition of the present invention and these thermoplastic resins can be mixed at an arbitrary ratio, but a preferable constituent ratio is 70 to 99.9% by weight of a thermoplastic resin, and a cyclic polyphenylene ether ether ketone composition. 0.1 to 30% by weight of the product, more preferably 90 to 99.9% by weight of the thermoplastic resin, and 0.1 to 10% by weight of the cyclic polyphenylene ether ether ketone composition, more preferably the thermoplastic resin. Examples include 95 to 99.5% by weight and cyclic polyphenylene ether ether ketone composition 0.5 to 5% by weight.

  As a method for producing such a thermoplastic resin composition comprising the cyclic polyphenylene ether ether ketone composition of the present invention and a thermoplastic resin, it is preferable to use melt kneading, and a known method is used for melt kneading. be able to. For example, using a Banbury mixer, rubber roll machine, kneader, single-screw or twin-screw extruder, etc., it can be melt-kneaded at a temperature equal to or higher than the melting temperature of the thermoplastic resin and cyclic polyphenylene ether ether ketone composition to obtain a resin composition. . Among these, a twin screw extruder can be exemplified as a preferable method. As kneading methods, 1) a method of kneading thermoplastic resin and cyclic polyphenylene ether ether ketone at once, and 2) preparing a resin composition (master pellet) containing cyclic polyphenylene ether ether ketone at a high concentration in the thermoplastic resin. Then, a method of adding the resin composition and the thermoplastic resin so as to obtain a prescribed concentration and melt-kneading (master pellet method) can be exemplified, and any kneading method may be used. The cyclic polyphenylene ether ether ketone composition of the present invention is characterized by a low melting point of 270 ° C. or lower. Therefore, since it can be set at the time of melt-kneading when producing the thermoplastic resin composition, it tends to be easy to melt-knead with the thermoplastic resin.

  The thermoplastic resin composition thus obtained can be molded by any method such as commonly known injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc. It can be processed into products and used. As molded products, it can be used as injection molded products, extrusion molded products, blow molded products, films, sheets, fibers, etc., as films, as various films such as unstretched, uniaxially stretched, biaxially stretched, as fibers, It can be used as various fibers such as undrawn yarn, drawn yarn, and super-drawn yarn.

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

  Various physical properties were measured using high performance liquid chromatography and an infrared spectroscopic analyzer (IR), and quantitative analysis of cyclic polyphenylene ether ether ketone was performed using high performance liquid chromatography. Detailed analysis conditions are as follows.

(High performance liquid chromatography)
The cyclic polyphenylene ether ether ketone content in the reaction solution and the cyclic polyphenylene ether ether ketone composition was calculated by quantitative analysis by high performance liquid chromatography (HPLC).

The measurement conditions for HPLC are shown below.
Device: LC-10Avp series column manufactured by Shimadzu Corporation: Mightysil RP-18GP150-4.6
Detector: Photodiode array detector (UV = 270 nm used)
Column temperature: 40 ° C
Sample: 0.1 wt% THF solution mobile phase: THF / 0.1 w% trifluoroacetic acid aqueous solution (consumption measurement of dihalogenated aromatic ketone compound)
The consumption of the dihalogenated aromatic ketone compound was calculated by performing quantitative analysis by gas chromatography (GC) analysis. GC measurement conditions are shown below.
Device: GC17-A manufactured by Shimadzu Corporation
Column: TC-17 0.32mmφ × 60m 0.5μm thickness (GL Science Co., Ltd.)
Carrier gas flow rate: 1.44 mL / min
Column inlet pressure: 140 kPa
Column oven: 250 ° C
Split ratio: 10: 1
Detector: Flame ionization detection method (FID method)
Injection amount: 5 μm
(Infrared spectroscopy analyzer)
Equipment: Perkin Elmer System 2000 FT-IR
Sample preparation: KBr method (molecular weight measurement of polyphenylene ether ether ketone)
The weight average molecular weight of polyphenylene ether ether ketone was calculated in terms of polystyrene by gel permeation chromatography (GPC) with reference to Macromolecules 2009, 42, 1955.

[Reference Example 1]
In a 1 liter autoclave equipped with a stirrer, were added 4.91 '(50 mmol) of 4,4'-difluorobenzophenone, 5.51 g (50 mmol) of hydroquinone, 6.91 g (50 mmol) of anhydrous potassium carbonate, and 500 mL of N-methyl-2-pyrrolidone. Prepared. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of benzene ring component in the mixture is 3.33 liters.

  After sealing the reaction vessel under nitrogen gas at room temperature and normal pressure, while stirring at 400 rpm, the temperature was raised from room temperature to 200 ° C., held at 200 ° C. for 5 minutes, then heated to 250 ° C. and heated at 250 ° C. for 2 minutes. The reaction was carried out while maintaining the time. After completion of the reaction, the mixture (a) was prepared by cooling to room temperature.

  About 0.2 g of the mixture (a) is weighed, diluted with about 4.5 g of THF, and an analytical sample is prepared by separating and removing THF-insoluble components by filtration. Gas chromatography and high performance liquid chromatography of the mixture (a) Analysis was carried out. As a result, it was confirmed that seven types of cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 8 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 16.0%. Further, the consumption rate of the monomer 4,4′-difluorobenzophenone is 100%. From this, in the mixture (a) prepared by this method, the cyclic polyphenylene is used with respect to 100 parts by weight of the polyphenylene ether ether ketone. It can be seen that 19.0 parts by weight of ether ether ketone is contained. Moreover, it turns out that the mixture (a) contains 3.3 liters of NMP with respect to 1.0 mol of benzene ring components.

[Reference Example 2]
After diluting 500 g of the reaction solution obtained in Reference Example 1 with about 1500 g of ion-exchanged water, the deposited components were collected by filtration with a glass filter. The filter-on component was dispersed in about 300 g of ion-exchanged water, stirred at 70 ° C. for 30 minutes, and again subjected to the same filtration and recovery operation three times in total to obtain a white solid. This was subjected to vacuum drying at 80 ° C. for 8 hours to obtain a dry solid.

  The obtained solid material was charged into a cylindrical filter paper, and Soxhlet extraction was performed for about 5 hours using chloroform as a solvent, thereby removing low molecular weight components contained in the solid content.

  The solid component remaining in the cylindrical filter paper after the extraction operation was subjected to vacuum drying at 70 ° C. for 8 hours to obtain 11.3 g of a dry solid. As a result of the analysis, it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 19000 from the absorption spectrum in infrared spectroscopic analysis.

[Example 1]
The mixture (a) obtained by the method described in Reference Example 1 was extracted, charged into an autoclave equipped with a valve, and heated so that the internal temperature was 250 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 424 g of the solvent was distilled off over 30 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 423 g of NMP. Thereby, it turned out that the mixture (b) contains 0.59 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a glass filter having a pore diameter of 10 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The obtained white solid was 2.81 g.

  This white solid was confirmed to be a compound comprising a phenylene ether 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 molecular weight information by -TOF-MS, this white powder is a cyclic polyphenylene ether ether ketone composition mainly composed of a mixture of five cyclic polyphenylene ether ether ketones having a repeating number m of 2 to 6 It was found (the yield based on hydroquinone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 19.5%). Further, the weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 78%. 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.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times the amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain 12.0 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 23,000.

[Example 2]
The mixture (a) obtained by the method described in Reference Example 1 was extracted, charged into an autoclave equipped with a valve, and heated so that the internal temperature was 250 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 424 g of the solvent was distilled off over 30 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 423 g of NMP. Thereby, it turned out that the mixture (b) contains 0.59 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a membrane filter (manufactured by PTFE) having a pore diameter of 1 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times weight of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The obtained white solid was 2.58 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (The yield based on hydroquinone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 17.9%). The weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 85%.

  Further, the component separated as a solid content by solid-liquid separation was added to and dispersed in about 5 times weight of deionized water, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 11.8 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 23,000.

[Example 3]
The mixture (a) obtained by the method described in Reference Example 1 was extracted, charged into an autoclave equipped with a valve, and heated so that the internal temperature was 220 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 220 ° C., and 421 g of the solvent was distilled off over 50 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 421 g of NMP. Thereby, it turned out that the mixture (b) contains 0.60 liter of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a glass filter having a pore diameter of 10 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The white solid obtained was 2.92 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (The yield based on hydroquinone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 20.3%). The weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 75%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 12.0 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 21,000.

[Example 4]
The mixture (a) obtained by the method described in Reference Example 1 was extracted, charged into an autoclave equipped with a valve, and heated so that the internal temperature was 190 ° C. Next, 426 g of the solvent was distilled off over 70 minutes under reduced pressure while maintaining the internal temperature at 190 ° C. After completion of the evaporation of the solvent, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 426 g of NMP. Thereby, it turned out that the mixture (b) contains 0.57 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a glass filter having a pore diameter of 10 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The obtained white solid was 2.98 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (Yield based on hydroquinone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 20.7%). The weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 72%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times the amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 11.9 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 19,700.

[Example 5]
The mixture (a) obtained by the method described in Reference Example 1 was extracted, charged into an autoclave equipped with a valve, and heated so that the internal temperature was 250 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 364 g of the solvent was distilled off over 40 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 364 g of NMP. Thereby, it turned out that the mixture (b) contains 0.97 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a glass filter having a pore diameter of 10 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The obtained white solid was 2.95 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (Yield based on hydroquinone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 20.5%). The weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 75%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times the amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 11.9 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 21,500.

[Example 6]
The mixture (a) obtained by the method described in Reference Example 1 was extracted, charged into an autoclave equipped with a valve, and heated so that the internal temperature was 250 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 364 g of the solvent was distilled off over 40 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 364 g of NMP. Thereby, it turned out that the mixture (b) contains 0.97 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a membrane filter (manufactured by PTFE) having a pore diameter of 1 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The obtained white solid was 2.76 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (Yield based on hydroquinone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 19.2%). Moreover, the weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 80%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 11.6 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 21,500.

[Comparative Example 1]
The mixture (a) obtained in Reference Example 1 was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a glass filter having a pore diameter of 10 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The white solid obtained was 3.17 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (The yield based on hydroquinone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 22.0%). The weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 69%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 12.0 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 19000.

  Comparison between Example 1 and Comparative Example 1 shows that the organic polar solvent is distilled off after completion of the reaction, whereby the content of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition is increased. It can be seen that the weight average molecular weight of the polyphenylene ether ether ketone in the form of a polymer increases.

[Reference Example 3]
Here, it describes about the synthesis | combination according to the manufacturing method of the polyphenylene ether ether ketone by the general method as described in the Example of patent publication 2007-506833.

  In a four-necked flask equipped with a stirrer, a nitrogen blowing tube, a Dean-Stark device, a condenser tube, and a thermometer, 22.5 g (103 mmol) of 4,4′-difluorobenzophenone, 11.0 g (100 mmol) of hydroquinone, and 49 g of diphenylsulfone Was charged. The amount of diphenylsulfone relative to 1.0 mole of benzene ring component in the mixture is about 0.16 liter. When the temperature was raised to 140 ° C. through nitrogen, an almost colorless solution was formed. At this temperature, 10.6 g (100 mmol) of anhydrous sodium carbonate and 0.28 g (2 mmol) of anhydrous potassium carbonate were added. The temperature was raised to 200 ° C and held for 1 hour, raised to 250 ° C and held for 1 hour, then raised to 315 ° C and held for 3 hours.

  As a result of analyzing the obtained reaction mixture by high performance liquid chromatography, the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was less than 1%, which was a trace amount.

  The reaction mixture was allowed to cool, pulverized, and washed with water and acetone to wash away by-product salts and diphenylsulfone. The obtained polymer was dried at 120 ° C. in a hot air dryer to obtain a powder.

  About 1.0 g of the obtained powder 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 small amount of a chloroform-soluble component. The yield of the recovered chloroform-soluble component based on hydroquinone used in the reaction was 1.2%. As a result of analyzing the recovered chloroform soluble component by high performance liquid chromatography, it was found that the cyclic soluble polyphenylene ether ether ketone and linear polyphenylene ether ether ketone oligomer were contained in the chloroform soluble component. . The linear polyphenylene ether ether ketone oligomer is similar to the cyclic polyphenylene ether ether ketone in properties such as solvent solubility and is difficult to separate from the cyclic polyphenylene ether ether ketone. Further, the cyclic polyphenylene ether ether ketone mixture contained in the recovered chloroform-soluble component has a repetition number m = 4, 5 and the weight fraction of the cyclic polyphenylene ether ether ketone having the repetition number m = 4. Accounted for 80% or more. The recovered chloroform soluble component had a melting point of about 320 ° C. This is presumed to be due to the high content of cyclic polyphenylene ether ether ketone tetramer (m = 4) occupying the chloroform-soluble component obtained by this method.

  In the above Soxhlet extraction, a solid component insoluble in chloroform was vacuum-dried overnight at 70 ° C. to obtain an off-white solid content of about 0.98 g. As a result of the analysis, it was confirmed that it was a linear polyphenylene ether ether ketone from the absorption spectrum in infrared spectroscopic analysis. As a result of measuring the reduced viscosity, it was found that this linear polyphenylene ether ether ketone had a reduced viscosity of 0.75 dL / g.

[Reference Example 4]
Here, it describes about the manufacturing method (y) of the mixture (a) using the linear polyphenylene ether ether ketone (reduced viscosity; 0.75 dL / g) obtained by the method by the reference example 3. FIG.

  In a 1 L autoclave equipped with a stirrer, 4,4′-difluorobenzophenone 2.2 g (10 mmol), hydroquinone 1.1 g (10 mmol), anhydrous potassium carbonate 1.4 g (10 mmol) were obtained by the method described in Reference Example 3. 11.5 g (40 mmol) of linear polyphenylene ether ether ketone and 500 mL of N-methyl-2-pyrrolidone were charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of benzene ring component in the mixture is 3.33 liters.

  After sealing the reaction vessel under nitrogen gas at room temperature and normal pressure, while stirring at 400 rpm, the temperature was raised from room temperature to 140 ° C., held at 140 ° C. for 1 hour, then heated to 180 ° C. and heated at 180 ° C. After the reaction was completed, the mixture was heated to 250 ° C. and then held at 250 ° C. for 5 hours to carry out the reaction, and then cooled to room temperature to prepare a mixture (a).

  About 0.2 g of the mixture (a) is weighed, diluted with about 4.5 g of THF, and an analytical sample is prepared by separating and removing THF-insoluble components by filtration. Gas chromatography and high performance liquid chromatography of the mixture (a) Analysis was carried out. As a result, it was confirmed that seven kinds of cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 8 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture was 8.5% (here cyclic The yield of the polyphenylene ether ether ketone mixture is the amount of the benzene ring component contained in the produced cyclic polyphenylene ether ether ketone mixture and the benzene contained in the polyphenylene ether ether ketone, hydroquinone, and 4,4′-difluorobenzophenone used in the reaction. Calculated by comparison of the amount of ring components). Further, the consumption rate of the monomer 4,4′-difluorobenzophenone is 100%. In the mixture (a) prepared by this method, the cyclic polyphenylene ether is used with respect to 100 parts by weight of the polyphenylene ether ether ketone. It can be seen that 9.3 parts by weight of ether ketone is contained. Moreover, it turns out that the mixture (a) contains 3.3 liters of NMP with respect to 1.0 mol of benzene ring components.

[Reference Example 5]
After diluting 500 g of the reaction solution obtained in Reference Example 4 with about 1500 g of ion-exchanged water, the precipitated components were collected by filtration with a glass filter. The filter-on component was dispersed in about 300 g of ion-exchanged water, stirred at 70 ° C. for 30 minutes, and again subjected to the same filtration and recovery operation three times in total to obtain a white solid. This was subjected to vacuum drying at 80 ° C. for 8 hours to obtain a dry solid.

  The obtained solid content was charged into a cylindrical filter paper and subjected to Soxhlet extraction for about 5 hours using chloroform as a solvent to remove low molecular weight components contained in the solid content.

  The solid component remaining in the cylindrical filter paper after the extraction operation was subjected to vacuum drying at 70 ° C. for 8 hours to obtain 12.4 g of a dry solid. As a result of the analysis, it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 16000 from the absorption spectrum in the infrared spectroscopic analysis.

[Example 7]
The mixture (a) obtained by the method described in Reference Example 4 was extracted, charged into an autoclave equipped with a valve, and heated to an internal temperature of 250 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 428 g of the solvent was distilled off over 40 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 428 g of NMP. Thereby, it turned out that the mixture (b) contains 0.56 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a glass filter having a pore diameter of 10 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The obtained white solid was 2.88 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (The yield based on the polyphenylene ether ether ketone, hydroquinone, and 4,4′-difluorobenzophenone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 20.0%). Moreover, the weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 76%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times the amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 13.2 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 21,000.

[Example 8]
The mixture (a) obtained by the method described in Reference Example 4 was extracted, charged into an autoclave equipped with a valve, and heated to an internal temperature of 250 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 428 g of the solvent was distilled off over 40 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 428 g of NMP. Thereby, it turned out that the mixture (b) contains 0.56 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a membrane filter (manufactured by PTFE) having a pore diameter of 1 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The obtained white solid was 2.70 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (The yield based on the polyphenylene ether ether ketone, hydroquinone and 4,4′-difluorobenzophenone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 18.8%). The weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 81%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times the amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 11.7 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 21,000.

[Reference Example 6]
Here, the production method (z) of the mixture (a) using the linear polyphenylene ether ether ketone (reduced viscosity; 0.75 dL / g) obtained by the method according to Reference Example 3 will be described.

  A 1 liter autoclave equipped with a stirrer was charged with 14.4 g (50 mmol) of polyphenylene ether ether ketone obtained by the method described in Reference Example 3, 1.52 g (10 mmol) of cesium fluoride, and 500 mL of N-methyl-2-pyrrolidone. It is. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of benzene ring component in the mixture is 3.33 liters.

  After the reaction vessel was sealed under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 140 ° C. while stirring at 400 rpm, held at 140 ° C. for 1 hour, then heated to 180 ° C. and then heated to 180 ° C. The reaction was carried out by maintaining the time, then raising the temperature to 230 ° C. and holding at 230 ° C. for 5 hours. After completion of the reaction, the mixture (a) was prepared by cooling to room temperature.

  About 0.2 g of the mixture (a) is weighed, diluted with about 4.5 g of THF, and an analytical sample is prepared by separating and removing THF-insoluble components by filtration. Gas chromatography and high performance liquid chromatography of the mixture (a) Analysis was carried out. As a result, it was confirmed that seven cyclic polyphenylene ether ether ketones having a repetition number m = 2 to 8 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture was 13.7% (here cyclic The yield of the polyphenylene ether ether ketone mixture was calculated by comparing the amount of cyclic polyphenylene ether ether ketone produced with the amount of polyphenylene ether ether ketone used in the reaction. This shows that the mixture (a) prepared by this method contains 15.9 parts by weight of cyclic polyphenylene ether ether ketone with respect to 100 parts by weight of polyphenylene ether ether ketone. Moreover, it turns out that the mixture (a) contains 3.3 liters of NMP with respect to 1.0 mol of benzene ring components.

[Reference Example 7]
After diluting 500 g of the reaction solution obtained in Reference Example 6 with about 1500 g of ion-exchanged water, the precipitated components were collected by filtration with a glass filter. The filter-on component was dispersed in about 300 g of ion-exchanged water, stirred at 70 ° C. for 30 minutes, and again subjected to the same filtration and recovery operation three times in total to obtain a white solid. This was subjected to vacuum drying at 80 ° C. for 8 hours to obtain a dry solid.

  The obtained solid content was charged into a cylindrical filter paper and subjected to Soxhlet extraction for about 5 hours using chloroform as a solvent to remove low molecular weight components contained in the solid content.

  The solid component remaining in the cylindrical filter paper after the extraction operation was subjected to vacuum drying at 70 ° C. for 8 hours to obtain 11.7 g of a dry solid. As a result of the analysis, it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 18,000 from the absorption spectrum in the infrared spectroscopic analysis.

[Example 9]
The mixture (a) obtained by the method described in Reference Example 6 was extracted, charged into an autoclave equipped with a valve, and heated so that the internal temperature was 250 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 429 g of the solvent was distilled off over 45 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 429 g of NMP. Thereby, it turned out that the mixture (b) contains 0.55 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a glass filter having a pore diameter of 10 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The obtained white solid was 2.88 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (The yield based on the polyphenylene ether ether ketone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 20.0%). Moreover, the weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 76%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 12.4 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 21,000.

[Reference Example 8]
In a 1 liter autoclave equipped with a stirrer, 11.24 g (51.5 mmol) of 4,4′-difluorobenzophenone, 5.51 g (50 mmol) of hydroquinone, 6.91 g (50 mmol) of anhydrous 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 3.27 liters.

  After sealing the reaction vessel under nitrogen gas at room temperature and normal pressure, while stirring at 400 rpm, the temperature was raised from room temperature to 200 ° C., held at 200 ° C. for 5 minutes, then heated to 250 ° C. and heated at 250 ° C. for 2 minutes. The reaction was carried out while maintaining the time. After completion of the reaction, the mixture (a) was prepared by cooling to room temperature.

  About 0.2 g of the mixture (a) is weighed, diluted with about 4.5 g of THF, and an analytical sample is prepared by separating and removing THF-insoluble components by filtration. Gas chromatography and high performance liquid chromatography of the mixture (a) Analysis was carried out. As a result, it was confirmed that seven types of cyclic polyphenylene ether ether ketones having a repeating number m = 2 to 8 were formed, and the yield of the cyclic polyphenylene ether ether ketone mixture with respect to hydroquinone was 16.0%. Further, the consumption rate of the monomer 4,4′-difluorobenzophenone is 100%. From this, in the mixture (a) prepared by this method, the cyclic polyphenylene is used with respect to 100 parts by weight of the polyphenylene ether ether ketone. It can be seen that 19.0 parts by weight of ether ether ketone is contained. Moreover, it turns out that the mixture (a) contains 3.3 liters of NMP with respect to 1.0 mol of benzene ring components.

[Reference Example 9]
After diluting 500 g of the reaction solution obtained in Reference Example 8 with about 1500 g of ion-exchanged water, the precipitated components were collected by filtration with a glass filter. The filter-on component was dispersed in about 300 g of ion-exchanged water, stirred at 70 ° C. for 30 minutes, and again subjected to the same filtration and recovery operation three times in total to obtain a white solid. This was subjected to vacuum drying at 80 ° C. for 8 hours to obtain a dry solid.

  The obtained solid content was charged into a cylindrical filter paper and subjected to Soxhlet extraction for about 5 hours using chloroform as a solvent to remove low molecular weight components contained in the solid content.

  The solid component remaining in the cylindrical filter paper after the extraction operation was subjected to vacuum drying at 70 ° C. for 8 hours to obtain 11.3 g of a dry solid. As a result of the analysis, it was a linear polyphenylene ether ether ketone and the weight average molecular weight was 20000 from the absorption spectrum in the infrared spectroscopic analysis.

[Example 10]
The mixture (a) obtained by the method described in Reference Example 8 was extracted, charged into an autoclave equipped with a valve, and heated so that the internal temperature was 250 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 424 g of the solvent was distilled off over 40 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 424 g of NMP. Thereby, it turned out that the mixture (b) contains 0.57 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a glass filter having a pore diameter of 10 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The white solid obtained was 2.49 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (The yield based on the hydroquinone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 17.3%). The weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 86%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 12.0 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was linear polyphenylene ether ether ketone and the weight average molecular weight was 25,000.

[Example 11]
The mixture (a) obtained by the method described in Reference Example 8 was extracted, charged into an autoclave equipped with a valve, and heated so that the internal temperature was 250 ° C. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 424 g of the solvent was distilled off over 40 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature, and the mixture (b) was recovered.

  Analysis of the distilled solvent by gas chromatography revealed that it contained 424 g of NMP. Thereby, it turned out that the mixture (b) contains 0.57 liters of NMP per 1.0 mol of benzene ring components.

  The recovered mixture (b) was heated and stirred under nitrogen so that the temperature of the reaction solution was 100 ° C. After maintaining at 100 ° C. for 20 minutes, solid-liquid separation was performed using a membrane filter (manufactured by PTFE) having a pore diameter of 1 μm.

  The filtrate component obtained by solid-liquid separation was dropped into about 8 times amount of deionized water, and the precipitated insoluble component was recovered. The obtained solid component was dried under reduced pressure at 80 ° C. for 8 hours to obtain a white solid. The obtained white solid was 2.43 g.

  Moreover, as a result of analyzing by the method of Example 1, as for the white solid, cyclic polyphenylene ether ether ketone composition which has five types of continuous cyclic polyphenylene ether ether ketone mixtures of repetition number m = 2-6 as a main component. (The yield based on hydroquinone used in the reaction of the cyclic polyphenylene ether ether ketone composition was 16.9%). The weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 88%.

  Further, the component separated as a solid content by solid-liquid separation was added to about 5 times amount of deionized water and dispersed, and then heated to 70 ° C. and stirred for 15 minutes. The slurry was filtered through a glass filter (average pore diameter of 10 to 16 μm) to obtain a solid content. The obtained solid content was dispersed in about 5 times amount of deionized water, and the obtained solid content was vacuum dried at 120 ° C. for 5 hours to obtain about 12.0 g of a dry solid.

  As a result of analysis of the obtained solid content, it was found from the absorption spectrum in infrared spectroscopic analysis that it was linear polyphenylene ether ether ketone and the weight average molecular weight was 25,000.

[Example 12]
Here, the ring-opening polymerization of the cyclic polyphenylene ether ether ketone composition obtained by the recovery method of the present invention will be described.

  In the cyclic polyphenylene ether ether ketone composition obtained by the method described in Example 2, the formula-(O-Ph-O-Ph-CO-Ph)-which is the main structural unit of the cyclic polyphenylene ether ether ketone is repeated. 100 mg of a powder in which 5 mol% of cesium fluoride was mixed with respect to the unit was charged into a glass ampule, and the inside of the ampule was replaced with nitrogen. The ampule was placed in an electric furnace adjusted to 350 ° C. and heated for 60 minutes, and then the ampule was taken out and cooled to room temperature to obtain a black solid.

  As a result of analyzing a black solid using a differential scanning calorimeter, it was found that it had thermal characteristics with a melting point of 333 ° C. and a crystallization temperature of 246 ° C. Further, as a result of measuring the reduced viscosity of the black solid, it was found that η was 0.67 dL / g.

Claims (9)

A mixture (a) comprising at least a polyphenylene ether ether ketone represented by the general formula (I), a cyclic polyphenylene ether ether ketone represented by the general formula (II) and an organic polar solvent , wherein the mixture in the mixture (a) A method for recovering a polyphenylene ether ether ketone and a cyclic polyphenylene ether ether ketone composition from a mixture (a) having an organic polar solvent of 1.20 liters to 100 liters with respect to 1.0 mole of a benzene ring component , From the mixture (a), the organic polar solvent is distilled off to 0.10 liter or more and 1.0 liter or less with respect to 1.0 mole of the benzene ring component , and at least polyphenylene ether ether ketone, cyclic polyphenylene ether ether ketone and Prepare a mixture (b) containing an organic polar solvent Degree, and recovery methods of a mixture (b) the polyphenylene ether ketone polyphenylene ether ketone and cyclic polyphenylene ether ether ketone composition characterized in that it comprises a step of performing solid-liquid separation at a temperature region becomes insoluble.

(Here, n in (I) is 10 to 10,000, and m in (II) is an integer of 2 to 40.) 2. A step of obtaining a cyclic polyphenylene ether ether ketone composition as a solid from a filtrate component obtained by performing solid-liquid separation in a temperature range in which the polyphenylene ether ether ketone is insoluble. Of recovering polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone composition. The polyphenylene ether ether ketone according to any one of claims 1 to 2, wherein the cyclic polyphenylene ether ether ketone in the mixture (a) is 4 parts by weight or more with respect to 100 parts by weight of the polyphenylene ether ether ketone. A method for recovering a cyclic polyphenylene ether ether ketone composition. As the mixture (a), a mixture (a) containing at least a dihalogenated aromatic ketone compound, a dihydroxy aromatic compound, a base (A) and an organic polar solvent is added to 1.0 mol of the benzene ring component in the mixture (a). A polyphenylene ether ether ketone and a cyclic polyphenylene ether according to any one of claims 1 to 3, wherein a mixture obtained by reacting by using 1.20 liters or more of an organic polar solvent and heating is used. A method for recovering the ether ketone composition. Wherein said mixture (A), further recovery method of claim 4 polyphenylene ether ketone and cyclic polyphenylene ether ether ketone composition, wherein it contains a polyphenylene ether ketone represented by the above general formula (I) . As the mixture (a), at least the polyphenylene ether ketone represented by the general formula (I), the basic compound (B) and a mixture containing an organic polar solvent (c) a mixture obtained by heating by reacting The method for recovering a polyphenylene ether ether ketone and a cyclic polyphenylene ether ether ketone composition according to claim 1, wherein: The method for recovering a polyphenylene ether ether ketone and a cyclic polyphenylene ether ether ketone composition according to any one of claims 1 to 6 , wherein the temperature at which the organic polar solvent is distilled off is 180 ° C or higher. Solid-liquid cyclic polyphenylene ether ether ketone composition recovered from the resulting filtrate components by separation, according to any one of claims 1 to 7, characterized in that it comprises a cyclic polyphenylene ether ether ketone 60 wt% or more A method for recovering a polyphenylene ether ether ketone and a cyclic polyphenylene ether ether ketone composition. Any give by Liwa type polyphenylene ether ketone composition to the recovery method according to either then heated ring-opening polymerization method for producing the polyphenylene ether ether ketone, characterized by the claims 1-8.