JP2013079225A - Method for recovering cyclic polyphenylene ether ether ketone composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method with which it is possible to economically recover, in a short amount of time and with good efficiency, an industrially useful cyclic polyphenylene ether ether ketone composition.SOLUTION: A mixture includes a cyclic polyphenylene ether ether ketone (a) and an organic solvent (b), wherein at least 50 wt.% of a cyclic polyphenylene ether ether ketone (a) is dissolved in the mixture. Then, a solvent (c) different from the organic solvent (b) is added to the mixture to recover the cyclic polyphenylene ether ether ketone composition at the recovery rate of at least 50 wt.% as a solid content.

Description

  The present invention relates to a method for recovering a cyclic polyphenylene ether ether ketone composition. More specifically, the present invention relates to a method for efficiently recovering a cyclic polyphenylene ether ether ketone composition by an economical and simple method.

  Aromatic cyclic compounds can be applied to highly functional materials and functional materials based on the properties resulting from their cyclic properties, for example, properties as compounds with inclusion ability, and high molecular weight linear chains by ring-opening polymerization In recent years, it has attracted attention for its specificity derived from its structure, such as its use as an effective monomer for the synthesis of glassy polymers. 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 the 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 a cyclic polyphenylene ether ether ketone having three or more different repeating numbers m. Does not generate.

  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. Furthermore, in order to recover the cyclic polyphenylene ether ether ketone by this method, a step of preparing an aromatic ketimine compound as a raw material, a step of preparing and purifying the cyclic polyphenylene ether ether ketimine, and the recovered cyclic polyphenylene ether ether ketimine A process that prepares and purifies a cyclic polyphenylene ether ether ketone by hydrolyzing the water is at least essential, and requires a complicated multi-step reaction process. It is.

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

  This invention solves the said subject and makes it a subject to provide the method of collect | recovering cyclic polyphenylene ether ether ketone compositions efficiently by an economical and simple method.

The present invention employs the following means in order to solve such problems.
That is, the present invention is as follows.
1. An organic solvent in a mixture (A) containing at least cyclic polyphenylene ether ether ketone (a) and an organic solvent (b) in which 50% by weight or more of the cyclic polyphenylene ether ether ketone (a) is dissolved A method for recovering a cyclic polyphenylene ether ether ketone composition, comprising adding the solvent (c) different from (b) to recover the cyclic polyphenylene ether ether ketone composition as a solid content.
2. A mixture (B) containing at least a linear polyphenylene ether ether ketone and a cyclic polyphenylene ether ether ketone is contacted with an organic solvent (b) to prepare the mixture (A) as a soluble component of the organic solvent (b). 2. The method for recovering a cyclic polyphenylene ether ether ketone composition according to 1.
3. The cyclic polyphenylene ether ether ketone according to 1 or 2, wherein the organic solvent (b) is a solvent having high solubility in cyclic polyphenylene ether ether ketone and poor solubility in linear polyphenylene ether ether ketone. A method for recovering the composition.
4). The cyclic polyphenylene ether ether ketone composition is a composition containing 60% by weight or more of the cyclic polyphenylene ether ether ketone (a) represented by the general formula (I), wherein the cyclic polyphenylene ether ether ketone (a) Is a mixture of cyclic polyphenylene ether ether ketones having different repeating numbers m, and is a cyclic polyphenylene ether ether ketone composition having a melting point of 270 ° C. or lower. A method for recovering the cyclic polyphenylene ether ether ketone composition according to any one of the above.

(Here, m in (I) is an integer of 2 to 40)
5. The method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of 1 to 4, wherein the cyclic polyphenylene ether ether ketone (a) is a mixture comprising at least three different integers m.
6). The method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of 1 to 5, wherein the cyclic polyphenylene ether ether ketone (a) is a mixture composed of at least three consecutive different integers m. .
7). The cyclic polyphenylene ether ether ketone composition according to any one of 1 to 6, wherein the solvent (c) is mixed with the organic solvent (b) when the solvent (c) is added to the mixture (A). Recovery method.
8). 8. The method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of 1 to 7, wherein the organic solvent (b) is an aprotic polar solvent.
9. The method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of 1 to 8, wherein the organic solvent (b) is an organic amide solvent.
10. The method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of 1 to 9, wherein the solvent (c) is a protic solvent.
11. The method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of 1 to 10, wherein the weight of the solvent (c) added to the mixture (A) is not more than the weight of the organic solvent (b).
12 The cyclic polyphenylene ether ether ketone composition according to any one of 1 to 11, wherein the cyclic polyphenylene ether ether ketone composition is separated by performing solid-liquid separation after adding the solvent (c). Collection method.
13. A method for producing polyphenylene ether ether ketone, comprising subjecting a cyclic polyphenylene ether ether ketone composition obtained by the recovery method according to any one of 13.1 to 12 to heat-opening polymerization.

  According to the present invention, a method for recovering a cyclic polyphenylene ether ether ketone composition can be provided, and more specifically, a method for efficiently recovering a cyclic polyphenylene ether ether ketone composition by an economical and simple method can be provided.

  Hereinafter, the present invention will be described in detail.

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

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

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

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

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

The reduced viscosity (η) of the cyclic polyphenylene ether ether ketone composition of the present invention having the characteristics as described above can be preferably exemplified by 0.1 dL / g or less, and 0.09 dL / g or less. Is more preferable, and it is more preferable that it is 0.08 dL / g or less. Unless otherwise specified, the reduced viscosity in the present invention is obtained by subjecting a concentrated sulfuric acid solution having a concentration of 0.1 g / dL (weight of cyclic polyphenylene ether ether ketone composition / 98% by weight concentrated sulfuric acid) to sulfonation. It is a value measured using an Ostwald viscometer at 25 ° C. immediately after completion of dissolution in order to minimize the influence. The reduced viscosity was calculated according to the following formula.
η = {(t / t0) −1} / C
(Here, t represents the number of seconds passing through the sample solution, t0 represents the number of seconds passing through the solvent (98 wt% concentrated sulfuric acid), and C represents the concentration of the solution.)

(2) Organic solvent (b)
In the present invention, the cyclic polyphenylene ether ether ketone composition is recovered as a solid from the mixture (A) in which 50% by weight or more of the cyclic polyphenylene ether ether ketone present in the mixture is dissolved. ) Is used in preparing the organic solvent (b). Here, the cyclic polyphenylene ether ether ketone is recovered by recovering the cyclic polyphenylene ether ether ketone as a solid content from the mixture in which 50% by weight or more of the cyclic polyphenylene ether ether ketone present in the mixture is dissolved. The cyclic polyphenylene ether ether ketone composition solid can be recovered as a shape excellent in purity improvement and recovery operability of the composition.

  Here, the organic solvent (b) is not particularly limited as long as it is an organic solvent having a solubility capable of dissolving 50% by weight or more of the cyclic polyphenylene ether ether ketone present in the mixture (A). A solvent having high solubility in ether ketone and poor solubility in linear polyphenylene ether ether ketone is preferable. Since the dissolving power of the organic solvent here is affected by various factors such as the temperature, pressure and amount used when dissolving, the selection is not particularly limited as long as it is an organic solvent that meets the above conditions. From the viewpoint of recovering the cyclic polyphenylene ether ether ketone composition by an efficient and simple operation, it is desirable that a large amount of cyclic polyphenylene ether ether ketone can be dissolved with a smaller amount of organic solvent. Examples of the solvent having such characteristics include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, cyclopentane, benzene, toluene, xylene, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1, Halogen solvents such as 1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, ether solvents such as diethyl ether, tetrahydrofuran and diisopropyl ether, ketone solvents such as acetone and methyl ethyl ketone, N-methyl-2-pyrrolidone, N-alkylpyrrolidones such as N-ethyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone, N-methyl-εcaprolactam, caprolactams such as ε-caprolactam, 1,3-dimethyl-2-yl Examples thereof include organic solvents such as aprotic solvents such as midazolidinone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide and the like.

(3) Solvent (c)
In the present invention, the cyclic polyphenylene ether ether ketone is solidified by adding a solvent (c) different from the organic solvent (b) to the mixture containing the cyclic polyphenylene ether ether ketone (a) and the organic solvent (b). Collect as minutes.

  The solvent (c) used here is added to the mixture (A) containing the cyclic polyphenylene ether ether ketone (a) and the organic solvent (b), whereby the cyclic polyphenylene ether ether ketone (a) in the mixture (A) is added. What is necessary is just to have the characteristic which can collect | recover 50 weight% or more, Preferably 70 weight% or more, More preferably, 90 weight% or more, More preferably, 95 weight% or more as solid content. Accordingly, it is necessary that the solvent (c) has a lower solubility in the cyclic polyphenylene ether ether ketone than the organic solvent (b). Moreover, in order to make cyclic polyphenylene ether ether ketone into solid content more efficiently by adding solvent (c), it is desirable that solvent (c) is mixed with organic solvent (b). Solvents having such characteristics are generally highly polar solvents, and the preferred solvent differs depending on the type of organic solvent (b) used, and thus cannot be limited. For example, water, methanol, ethanol, propanol, isopropanol, butanol, hexanol Examples thereof include protic solvents such as alcohols. Since these solvents are particularly polar and have low solubility in cyclic polyphenylene ether ether ketone, they can be suitably used. From the viewpoint of availability, economy, and ease of handling among protic solvents, water, methanol, ethanol Are preferred, and water is particularly preferred.

(4) Linear polyphenylene ether ether ketone The linear polyphenylene ether ether ketone in the present invention is a linear compound represented by the following general formula (II) having paraphenylene ketone and paraphenylene ether as repeating structural units. is there.

  Although there is no restriction | limiting in particular in the repeating number n in Formula (II), 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 linear polyphenylene ether ether ketone in the present invention is not particularly limited, but the reduced viscosity (η) of a general linear polyphenylene ether ether ketone is usually 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.

(5) Mixture (A)
In the present invention, a mixture containing at least the cyclic polyphenylene ether ether ketone (a) and the organic solvent (b), wherein 50% by weight or more of the cyclic polyphenylene ether ether ketone (a) is dissolved in the mixture (A). The cyclic polyphenylene ether ether ketone composition is recovered as a solid content by adding a solvent (c) different from the organic solvent (b).

  In the mixture (A) here, it is preferable that there is no component other than the cyclic polyphenylene ether ether ketone (a) and the organic solvent (b), but other components are included within a range not impairing the essence of the present invention. Also good. As the amount of the third component increases, the purity of the cyclic polyphenylene ether ether ketone composition isolated and recovered by this recovery method tends to decrease. In order to obtain a polyphenylene ether ether ketone composition, it is desired that the third component is small.

  Content of cyclic polyphenylene ether ether ketone (a) in this mixture (A) (weight of cyclic polyphenylene ether ether ketone (a) relative to the total weight of cyclic polyphenylene ether ether ketone (a) and organic solvent (b)) The higher the content, the more preferable, and generally the higher the content, the higher the yield of cyclic polyphenylene ether ether ketone obtained after the recovery operation, and the cyclic polyphenylene ether ether ketone can be efficiently recovered. In this respect, the content of the cyclic polyphenylene ether ether ketone (a) in the mixture (A) is preferably 1% by weight or more, more preferably 2% by weight or more, and still more preferably 5% by weight or more. On the other hand, the upper limit of the content of the cyclic polyphenylene ether ether ketone (a) in the mixture (A) is not particularly limited, but generally the content of the cyclic polyphenylene ether ether ketone tends to be low in solubility in various solvents. If it is too high, an insoluble component tends to be generated, which may cause inconvenience in the recovery operation. The inconvenience in this recovery operation is, for example, that the mixture (sometimes in the form of a slurry containing solid content) becomes non-uniform, the local composition is different, and the quality of the recovered product is lowered. In addition, since the tendency to cause such inconvenience greatly depends on the characteristics of the organic solvent (b) to be used and the conditions for preparing the mixture (A), the inclusion of the cyclic polyphenylene ether ether ketone (a) in the mixture (A) Although the upper limit of the rate cannot be determined, the content is usually 50% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less.

(6) Preparation of mixture (A) The preparation method of mixture (A) in the present invention may be any preparation method as long as the above mixture (A) is obtained. For example, at least linear polyphenylene ether ether ketone and cyclic A preferred method is a method of preparing the mixture (A) as a soluble component of the organic solvent (b) by bringing the mixture (B) containing polyphenylene ether ether ketone into contact with the organic solvent (b). Generally, linear polyphenylene ether ether ketone is known to have high crystallinity and very low solubility in a solvent, and it is known that cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone are Solubility in solvents is greatly different, and cyclic polyphenylene ether ether ketone is generally more soluble in solvents. From this, by the method of bringing the mixture (B) containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone into contact with the organic solvent (b), linear polyphenylene ether ether as a solid content from the mixture (B) is obtained. The ketone can be separated, and a mixture (A) containing at least the cyclic polyphenylene ether ether ketone and the organic solvent (b) can be obtained.

  In this method, the reaction system pressure when the mixture (B) is brought into contact with the organic solvent (b) is not particularly limited, but normal pressure or slight pressure is preferable, and normal pressure is particularly preferable. The system has the advantage that the components of the reactor that build it are inexpensive. From this point of view, it is desirable that the reaction system pressure avoid pressurizing conditions that require expensive pressure resistant containers. By bringing the mixture (B) into contact with the organic solvent (b) at such a reaction system pressure, the cyclic polyphenylene ether ether ketone in the mixture (B) tends to be efficiently extracted and recovered.

  Further, the atmosphere when the mixture (B) is contacted with the organic solvent (b) is not particularly limited, but it is preferably performed in a non-oxidizing atmosphere, and is performed in an inert gas atmosphere such as nitrogen, helium, or argon. Among these, it is particularly preferable to carry out in a nitrogen atmosphere from the viewpoint of economy and ease of handling.

  Although there is no restriction | limiting in the temperature which contacts the said mixture (B) with the organic solvent (b), generally melt | dissolution to the organic solvent (b) of cyclic polyphenylene ether ether ketone contained in a mixture (B) is accelerated, so that temperature is high. In the case of using the preferred organic solvent (b) described above, for example, 20 to 150 ° C. can be exemplified as a specific temperature range.

  The time for which the mixture (B) is brought into contact with the organic solvent (b) varies depending on the type and temperature of the organic solvent (b) to be used and cannot be uniquely limited. However, for example, 1 minute to 50 hours can be exemplified. In the range, the cyclic polyphenylene ether ether ketone tends to be sufficiently dissolved in the organic solvent (b).

  The method for bringing the mixture (B) into contact with the organic solvent (b) may be any known general method, and is not particularly limited. For example, the mixture (B) and the organic solvent (b) are mixed, A method of recovering the soluble part after stirring if necessary, a method of dissolving the cyclic polyphenylene ether ether ketone in the organic solvent (b) simultaneously with showering the organic solvent (b) in the mixture (B) on various filters Any method can be used, such as a method based on the Soxhlet extraction principle. Although there is no restriction | limiting in particular in the usage-amount of the organic solvent (b) at the time of making a mixture (B) and an organic solvent (b) contact, For example, the range of 0.5-100 is illustrated by the bath ratio with respect to the weight of a mixture (B). it can. When the bath ratio is in such a range, the mixture (B) and the organic solvent (b) are easily mixed uniformly, and the cyclic polyphenylene ether ether ketone tends to be sufficiently dissolved in the organic solvent (b). is there. In general, a larger bath ratio is advantageous for dissolving cyclic polyphenylene ether ether ketone in the organic solvent (b), but if it is too large, no further effect can be expected. Benefits may occur. When the contact between the mixture (B) and the organic solvent (b) is repeated, a sufficient effect is often obtained even with a small bath ratio, and the Soxhlet extraction method has a similar effect in principle. In many cases, a sufficient effect can be obtained with a small bath ratio.

  After contacting the mixture (B) and the organic solvent (b), a solution in which the cyclic polyphenylene ether ether ketone is dissolved is obtained in the form of a solid-liquid slurry containing solid linear polyphenylene ether ether ketone. The mixture (A) can be recovered using a solid-liquid separation method. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. For the solid component, when the cyclic polyphenylene ether ether ketone still remains, contact with the organic solvent (b) and recovery of the solution are repeated to obtain a mixture (A ) Can be obtained.

  Moreover, before performing operation which adds solvent (c) to the mixture (A) obtained in this way, and collect | recovers cyclic polyphenylene ether ether ketone composition as solid content, the organic solvent in mixture (A) ( It is also possible to adjust the cyclic polyphenylene ether ether ketone content in the mixture (A) by distilling off b).

(7) Method for recovering cyclic polyphenylene ether ether ketone composition In the present invention, a mixture comprising at least cyclic polyphenylene ether ether ketone (a) and an organic polar solvent (b) comprising cyclic polyphenylene ether ether ketone (a The cyclic polyphenylene ether ether ketone composition is recovered as a solid content by adding a solvent (c) to a mixture (A) in which 50% by weight or more) is dissolved.

  At this time, the mixture (A) is heated in order to avoid the disadvantages in the recovery operation as described in the item (5) and to increase the content of the cyclic polyphenylene ether ether ketone (a) in the mixture (A). It is also possible. As described in the section (2), this temperature varies depending on the characteristics of the organic solvent (b) to be used and cannot be uniquely determined, but is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and 90 ° C. or higher. Is more preferable. On the other hand, the upper limit temperature is preferably not higher than the boiling point at normal pressure of the organic solvent (b) to be used. Within such a temperature range, the cyclic polyphenylene ether ether ketone content in the mixture (A) tends to be stable while maintaining a high content, which is preferable. In preparing the mixture (A), it is possible to perform operations such as stirring and shaking, which is desirable from the viewpoint of maintaining a more uniform state of the mixture. Here, in the mixture (A) comprising the cyclic polyphenylene ether ether ketone (a) and the organic solvent (b), 50% by weight or more of the cyclic polyphenylene ether ether ketone present in the mixture is dissolved. As described above, this has a merit in the recovery of cyclic polyphenylene ether ether ketone. Here, as a method of quantifying the cyclic polyphenylene ether ether ketone dissolved in the mixture (A), for example, the mixture (A) is subjected to a normal solid-liquid separation operation to recover insoluble components, and the weight thereof is calculated. The method of quantifying by calculating | requiring can be illustrated.

  In the present recovery method, the cyclic polyphenylene ether ether ketone dissolved in the solvent (b) is then added to the mixture (A) as described above by adding a solvent (c) different from the organic solvent (b). It is precipitated as a solid and collected. Here, the method of adding the solvent (c) to the mixture (A) is not particularly limited, but an addition method in which a coarse solid content is generated by adding the solvent (c) should be avoided, preferably the mixture A method of dropping the solvent (c) while stirring is preferable. The temperature at which the solvent (c) is added is not limited. However, the lower the temperature, the higher the tendency to form coarse solids when the solvent (c) is added. In view of maintaining uniformity, 50 ° C. or higher can be preferably exemplified. On the other hand, the upper limit temperature is preferably not more than the boiling point at normal pressure of the organic solvent (b) and the solvent (c) to be used. By performing the operation of adding the solvent (c) in such a preferable temperature range, there is a tendency that the recovery operation can be performed by a simpler method from the viewpoint of operation and the viewpoint of equipment.

  Further, in the method for recovering cyclic polyphenylene ether ether ketone according to the present invention, the cyclic polyphenylene ether ether ketone can be efficiently used even with a small amount of solvent as compared with a method conventionally employed as a method for recovering cyclic polyphenylene ether ether ketone. Therefore, the weight of the solvent (c) added to the mixture (A) containing the cyclic polyphenylene ether ether ketone (a) and the organic solvent (b) should be less than the weight of the organic solvent (b). It is also possible. Further, as described above, the solvent (c) added to the mixture containing the cyclic polyphenylene ether ether ketone (a) and the organic solvent (b) by selecting the preferable organic solvent (b) and the solvent (c) in the present invention. The weight of the organic solvent (b) can be 50% by weight or less, more preferably 40% by weight or less, and even more preferably 35% by weight or less. . On the other hand, the lower limit of the weight to which the solvent (c) is added is not particularly limited. However, in order to recover the cyclic polyphenylene ether ether ketone composition as a solid content more efficiently, it is preferably 5% by weight or more and preferably 10% by weight. The above is more preferable. In the present invention, it is possible to recover 50% by weight or more of the cyclic polyphenylene ether ether ketone (a) contained in the mixture (A) as a solid content, but the use of the preferred solvent (c) as described above. In the amount range, 80% by weight or more of the cyclic polyphenylene ether ether ketone (a) tends to be recovered as a solid content, more preferably 90% by weight or more, still more preferably 95% by weight or more, and still more preferably It is also possible to recover 98% by weight or more. In the reprecipitation method conventionally employed as a method for recovering cyclic polyphenylene ether ether ketone, a solution or slurry in which at least a part of cyclic polyphenylene ether ether ketone is dissolved is used as a poor solvent for cyclic polyphenylene ether ether ketone. Although cyclic polyphenylene ether ether ketone has been recovered by the dropping method, the amount of the poor solvent used in this method is generally excessive with respect to the cyclic polyphenylene ether ether ketone solution or slurry. There was a problem that a large amount of waste liquid was generated. Further, in this reprecipitation method, when the amount of poor solvent used is reduced, for example, when the reprecipitation operation is performed within the above-described exemplary range of the preferred solvent usage in the present invention, a coarse solid content is generated. Various inconveniences tended to occur, such as sticking of the component and lowering of the purity of the cyclic polyphenylene ether ether ketone in the obtained solid component. On the other hand, it can be said that the method for recovering cyclic polyphenylene ether ether ketone of the present invention is an extremely excellent method in that it tends to greatly improve the problems of these conventional reprecipitation methods.

  In the mixture of the cyclic polyphenylene ether ether ketone (a), the organic solvent (b) and the solvent (c) obtained by carrying out the above operations (hereinafter sometimes referred to as the mixture (d)) 50% by weight or more of the cyclic polyphenylene ether ether ketone (a) present in is present as a solid content. Therefore, 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. Here, in order to further increase the recovery rate of the cyclic polyphenylene ether ether ketone composition, it is preferable to perform solid-liquid separation after the mixture (d) is in a state of less than 50 ° C., more preferably 40 ° C. or less, More preferably, it is performed at 30 ° C. or lower. Note that the recovery of the cyclic polyphenylene ether ether ketone composition after such a preferable temperature is not only effective in increasing the recovery rate of the cyclic polyphenylene ether ether ketone composition, but also with simpler equipment. It can also be said that it is a preferable condition from the viewpoint that the ether ether ketone composition can be recovered. Although there is no particular lower limit to the temperature of the mixture (d), it is desirable to avoid conditions that cause the viscosity of the mixture (d) to become too high due to a decrease in temperature or conditions that cause solidification. Is most preferably near room temperature.

  By performing such solid-liquid separation, 50% by weight or more of the cyclic polyphenylene ether ether ketone present in the mixture (d) can be isolated and recovered as a solid content. When the solid cyclic polyphenylene ether ether ketone thus separated contains the liquid component (mother liquor) in the mixture (d), the solid cyclic polyphenylene ether ether ketone composition is prepared using various solvents. It is possible to reduce the mother liquor by washing. Here, as various solvents used for washing the solid cyclic polyphenylene ether ether ketone composition, a solvent having low solubility in cyclic polyphenylene ether ether ketone is desirable. For example, the solvent (c) shown in the above item (3) is It can illustrate as a preferable solvent. By additionally performing washing using such a solvent, not only can the amount of mother liquor contained in the solid cyclic polyphenylene ether ether ketone composition be reduced, but also the solvent contained in the cyclic polyphenylene ether ether ketone composition. There is also an effect that impurities soluble in water can be reduced. Examples of this washing method include a method of solid-liquid separation by adding a solvent on a separation filter in which a solid cake is laminated, and a method of solid-liquid separation again after slurrying by adding a solvent to the solid cake and stirring. it can. In addition, the liquid component is removed by subjecting the cyclic polyphenylene ether ether ketone composition in a wet state containing the liquid component, such as the above-described mother liquor or a solvent component obtained by a washing operation, to a general drying treatment, for example. It is also possible to obtain a cyclic polyphenylene ether ether ketone composition in a dry state.

  In addition, it is preferable to perform the atmosphere at the time of performing collection | recovery operation of cyclic polyphenylene ether ether ketone composition in non-oxidizing atmosphere. This not only suppresses the occurrence of undesired side reactions such as crosslinking reaction, decomposition reaction, oxidation reaction, etc. of the cyclic polyphenylene ether ether ketone when the cyclic polyphenylene ether ether ketone composition is recovered. There is a tendency that undesirable side reactions such as oxidative degradation of the solvent (b) and the solvent (c) can be suppressed. The non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with various components subjected to the recovery operation is 5% by volume or less, preferably 2% by volume or less, and more preferably substantially free of oxygen, ie, nitrogen or helium. And an inert gas atmosphere such as argon. Among these, a nitrogen atmosphere is particularly preferred from the viewpoint of economy and ease of handling.

(8) Production method of polyphenylene ether ether ketone The cyclic polyphenylene ether ether ketone composition recoverable by the method of the present invention is used as a polyphenylene ether ether ketone prepolymer, and is converted into polyphenylene ether ether ketone by heat ring-opening polymerization. can do. Here, the polyphenylene ether ether ketone is a linear compound represented by the general formula (II) having paraphenylene ketone and paraphenylene ether as repeating structural units.

  Further, the reduced viscosity (η) of the polyphenylene ether ether ketone obtained by subjecting the cyclic polyphenylene ether ether ketone composition recoverable by the method of the present invention to heat ring-opening polymerization is not particularly limited, but a preferred range is 0.1. -2.5 dL / g, More preferably, it is 0.2-2.0 dL / g, More preferably, 0.3-1.8 dL / g can be illustrated.

  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. When the heating temperature is lower than the melting temperature of the cyclic polyphenylene ether ether ketone, it takes a long time to obtain polyphenylene ether ether ketone by heat ring-opening polymerization. Alternatively, there is a tendency that polyphenylene ether ether ketone cannot be obtained without heating ring-opening polymerization. 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, since the melting point of the cyclic polyphenylene ether ether ketone is high, the ring-opening polymerization requires a long time in the above preferred temperature range. Alternatively, the cyclic polyphenylene ether ether ketone composition having the melting point of 270 ° C. or less is suitable for the above-mentioned preferable temperature range, whereas the thermal ring-opening polymerization does not proceed and the polyphenylene ether ether ketone tends to be not obtained. , The ring-opening polymerization of heat proceeds efficiently, and polyphenylene ether ether ketone is obtained. 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, alkali metal alkoxide such as sodium tert-butoxide, potassium tert-butoxide, or 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, sodium acetate and potassium acetate. Door can be. 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-participating 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.

(9) Use of cyclic polyphenylene ether ether ketone composition Cyclic polyphenylene ether ether ketone composition that can be recovered by the method of the present invention significantly reduces the melt viscosity of the thermoplastic resin by being blended with the thermoplastic resin. It has a strong tendency and exhibits the effect of improving the fluidity of the thermoplastic resin. This is an effect due to the fact that the entanglement between molecules is small because the cyclic polyphenylene ether ether ketone does not have a terminal structure unlike a normal linear compound or linear polymer.

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

  As a method for producing a thermoplastic resin composition obtained by blending such a cyclic polyphenylene ether ether ketone composition and a thermoplastic resin, melt kneading is preferred, and known methods can be used for melt kneading. . 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 described more specifically with reference to the following examples. These examples are illustrative and not limiting.

Various physical properties were measured using high performance liquid chromatography, a differential scanning calorimeter (DSC), an infrared spectroscopic analyzer (IR), and an Ostwald viscometer. Detailed analysis conditions are as follows.
(High performance liquid chromatography)
Apparatus: Shimadzu LC-10Avp series column: Mightysil RP-18GP150-4.6
Detector: Photodiode array detector (UV = 270 nm is used)
Column temperature: 40 ° C
Sample: 0.1 wt% THF solution mobile phase: THF / 0.1 w% trifluoroacetic acid aqueous solution (differential scanning calorimeter)
Device: Seiko Instruments Inc. Robot DSC
(Infrared spectroscopy analyzer)
Equipment: Perkin Elmer System 2000 FT-IR
Sample preparation: KBr method (viscosity measurement)
Viscometer: Ostwald viscometer solvent: 98 wt% sulfuric acid sample concentration: 0.1 g / dL (sample weight / solvent volume)
Measurement temperature: 25 ° C
Reduced viscosity formula: η = {(t / t0) −1} / C
t: Sample solution passage time t0: Solvent passage time C: Solution concentration

[Reference Example 1]
Here, the example which manufactured the cyclic polyphenylene ether ether ketone composition is shown.

  An autoclave equipped with a stirrer was charged with 1.1 kg (5 mol) of 4,4′-difluorobenzophenone, 0.55 kg (5 mol) of hydroquinone, 0.69 kg (5 mol) of potassium carbonate, and 50 L of N-methyl-2-pyrrolidone. 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, the temperature was raised from room temperature to 140 ° C., held at 140 ° C. for 1 hour, then heated to 180 ° C. and held at 180 ° C. for 3 hours, and then 250 ° C. The reaction was carried out by maintaining the temperature at 250 ° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 4.5 g of THF, and a THF-insoluble component was separated and removed by filtration to prepare a high-performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that seven consecutive 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 based on the hydroquinone calculated by the absolute calibration curve method was 15.0%. there were.

  150 kg of a 1% by weight acetic acid aqueous solution was added to 50 kg of the reaction mixture thus obtained, and the mixture was stirred to form a slurry, then heated to 70 ° C. and stirred for 30 minutes. The slurry was filtered through a filter to obtain a solid content. The operation of dispersing the obtained solid content in 50 kg of deionized water, maintaining at 70 ° C. for 30 minutes and filtering to obtain the solid content was repeated three times. The obtained solid content was subjected to vacuum drying at 70 ° C. overnight to obtain about 1.3 kg (mixture (A)) of dry solid.

  Further, 1.3 kg of the dried solid obtained above was subjected to extraction operation at 80 ° C. for 5 hours using 30 kg of chloroform. After the extraction operation, chloroform was distilled off from the extract obtained by solid-liquid separation, and vacuum drying was performed at 70 ° C. for 3 hours to obtain 0.2 kg of a white solid.

  This white solid was confirmed to be a compound comprising a phenylene ether ketone unit from the absorption spectrum in infrared spectroscopic analysis, mass spectral analysis (equipment: Hitachi M-1200H) separated by high-performance liquid chromatography, and MALDI- From the molecular weight information by TOF-MS, this white solid is found to be a cyclic polyphenylene ether ether ketone composition mainly composed of a mixture of seven kinds of cyclic polyphenylene ether ether ketones having a repeating number m of 2 to 8 in succession. It was. Furthermore, as a result of analyzing the obtained cyclic polyphenylene ether ether ketone composition, the weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition was 88%, It has also been found that it has a melting point and the reduced viscosity of the cyclic polyphenylene ether ether ketone composition is less than 0.02 dL / g.

  Further, the solid component insoluble in chloroform obtained by the above chloroform extraction and solid-liquid separation was subjected to vacuum drying at 70 ° C. overnight to obtain 1.1 kg of an off-white solid content. 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. This shows that the mixture (a) prepared by the above method is a mixture containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone.

[Example 1]
Here, the cyclic polyphenylene ether ether ketone composition obtained in Reference Example 1 was used as the cyclic polyphenylene ether ether ketone, N-methyl-2-pyrrolidone was used as the organic solvent (b), and water was used as the solvent (c). An example of recovering the cyclic polyphenylene ether ether ketone composition is shown.

  A mixture (A) containing 2.4% by weight of cyclic polyphenylene ether ether ketone was prepared by adding 100 g of NMP to 2.5 g of the cyclic polyphenylene ether ether ketone composition having a purity of 88% obtained in Reference Example 1, and stirring the mixture. While heating to 100 ° C., it was cooled to 80 ° C. At this time, some insoluble components were present at room temperature, but insoluble portions were not observed when the temperature reached 100 ° C., and further when cooled to 80 ° C., and the ring contained in the mixture (A) under conditions of 80 ° C. or higher. It was confirmed that 50% by weight or more of the formula polyphenylene ether ether ketone was dissolved.

  Next, while stirring the mixture (A) at a system temperature of 80 ° C., 43 g of water was slowly added dropwise over about 25 minutes using a tube pump (the weight of NMP and water in the mixture after completion of the addition of water). The ratio is 70:30). At this time, the temperature of the mixture decreased to about 75 ° C. as the water was dropped, and solids gradually formed in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The slurry was cooled to about 30 ° C. over about 1 hour with stirring, and then stirred for about 30 minutes at 30 ° C. or lower, and then the obtained slurry was suction filtered with a glass filter having an opening of 10 to 16 μm. The obtained solid content (including the mother liquor) was dispersed in about 30 g of water, stirred for 15 minutes at 70 ° C., and then subjected to suction filtration with a glass filter in the same manner as described above four times. The obtained solid content was treated at 70 ° C. for 3 hours in a vacuum dryer to obtain a dry solid.

  As a result of analyzing the dried solid by HPLC, it was confirmed that it was a cyclic polyphenylene ether ether ketone, the recovery rate of the cyclic polyphenylene ether ether ketone was 98.2% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone was It was 89%. Moreover, as a result of analyzing the obtained cyclic polyphenylene ether ether ketone by gas chromatography, it turned out that the content rate of NMP is less than 0.1 weight%. By recovering the cyclic polyphenylene ether ether ketone by a preferred method in the present invention, a high-purity cyclic polyphenylene ether ether ketone composition could be obtained in a high yield.

[Example 2]
The cyclic polyphenylene ether ether ketone composition was the same as in Example 1 except that the amount of water used as the solvent (c) was 54 g (the weight ratio of NMP to water in the mixture after completion of the dropwise addition of water was 65:35). As a result of the recovery, the recovery rate of the cyclic polyphenylene ether ether ketone composition was 99.6% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone composition was 88%. The yield was improved by increasing the amount of the solvent (c) to be used, and although the effect of improving the purity was slightly lowered, a high-purity cyclic polyphenylene ether ether ketone composition could be obtained in a high yield.

[Example 3]
The cyclic polyphenylene ether ether ketone composition was the same as in Example 1 except that the amount of water used as the solvent (c) was 33 g (the weight ratio of NMP to water in the mixture after completion of the dropwise addition of water was 75:25). As a result of the recovery, the recovery rate of the cyclic polyphenylene ether ether ketone composition was 93.6% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone composition was 90%. It was found that a yield of the cyclic polyphenylene ether ether ketone composition with higher purity can be obtained although the yield is slightly reduced by reducing the amount of the solvent (c) used.

[Example 4]
The cyclic polyphenylene ether ether ketone composition was the same as in Example 1 except that the amount of water used as the solvent (c) was 25 g (the weight ratio of NMP to water in the mixture after completion of the dropwise addition of water was 80:20). As a result of the recovery, the recovery rate of the cyclic polyphenylene ether ether ketone composition was 88.9% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone composition was 92%. It was found that a cyclic polyphenylene ether ether ketone composition with extremely high purity can be obtained while the yield is reduced by further reducing the amount of the solvent (c) used.

[Comparative Example 1]
The same operation as in Example 1 was carried out except that the solvent (c) was not added. The recovery rate of the cyclic polyphenylene ether ether ketone composition was 8% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone composition was 93%.

  When the solvent (c) was not added, it was found that only a very small amount of cyclic polyphenylene ether ether ketone composition could be obtained, resulting in a very low yield. Moreover, as a result of analyzing the obtained cyclic polyphenylene ether ether ketone composition using gas chromatography, it was found that 1% by weight or more of NMP was contained, and the removal efficiency of the mother liquor by post-treatment (water washing operation) was improved. It turned out to be bad.

[Comparative Example 2]
Here, an example is shown in which the cyclic polyphenylene ether ether ketone composition is recovered by a known reprecipitation method as a method for recovering the cyclic polyphenylene ether ether ketone composition.

  A mixture containing 2.4 parts by weight of the cyclic polyphenylene ether ether ketone composition is prepared by adding 100 g of NMP to 2.5 g of the cyclic polyphenylene ether ether ketone composition having a purity of 88% obtained in Reference Example 1, and stirring the mixture. The mixture was heated to 100 ° C and then cooled to 80 ° C. This mixed solution was added dropwise to 900 g of water at about 25 ° C. under stirring conditions (the weight ratio of NMP to water in the mixture after completion of the addition of water was 10:90). At this time, the water became milky due to the dropwise addition of the mixed liquid, and the degree of the emulsion became stronger as the dropping was advanced, but it was in a state of being clouded even when the dropping was completed, so it was left at room temperature with stirring for about 5 hours. However, it remained milky. This emulsion was subjected to suction filtration with a glass filter in the same manner as in Example 1. As a result, the filterability was extremely poor and the filtrate was emulsion.

  Hereinafter, as a result of performing the same treatment as in Example 1, the recovery rate of the cyclic polyphenylene ether ether ketone composition was 80% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone composition was 87%. When recovery of cyclic polyphenylene ether ether ketone is performed by a known reprecipitation method as a recovery method of the cyclic polyphenylene ether ether ketone composition, not only a large amount of waste liquid is generated in the recovery operation compared to the present invention. It has been found that the operability in the solid-liquid separation is also significantly deteriorated. Moreover, it turned out that there is no purity improvement effect of cyclic polyphenylene ether ether ketone composition.

[Example 5]
Extraction operation was performed for 5 hours at 100 ° C. using 20.0 g of the mixture (A) prepared by the method described in Reference Example 1 using 120 g of NMP. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (NMP) as filtrate components. As a result of analyzing this mixture (A), it was found that the mixture (A) contained 3.2% by weight (3.0 g) of cyclic polyphenylene ether ether ketone.

  The resulting mixture (A) was heated to 100 ° C. with stirring and then cooled to 80 ° C. At the stage of reaching 100 ° C. and the stage of cooling to 80 ° C., no insoluble part was observed, and it was confirmed that 50% by weight or more of the cyclic polyphenylene ether ether ketone was dissolved.

  Next, while stirring the mixture (A) at an internal temperature of 80 ° C., 41 g of water was slowly added dropwise over about 25 minutes using a tube pump (the weight of NMP and water in the mixture after completion of the addition of water). The ratio is 70:30). At this time, the temperature of the mixture decreased to about 75 ° C. as the water was dropped, and solids gradually formed in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The slurry was cooled to about 30 ° C. over about 1 hour with stirring, and then stirred for about 30 minutes at 30 ° C. or lower, and then the obtained slurry was suction filtered with a glass filter having an opening of 10 to 16 μm. The obtained solid content (including the mother liquor) was dispersed in about 30 g of water, stirred for 15 minutes at 70 ° C., and then subjected to suction filtration with a glass filter in the same manner as described above four times. The obtained solid content was treated at 70 ° C. for 3 hours in a vacuum dryer to obtain a dry solid.

  As a result of analyzing the dried solid by HPLC, it was confirmed that it was a cyclic polyphenylene ether ether ketone, the recovery rate of the cyclic polyphenylene ether ether ketone was 98.0% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone was It was 89%.

  Even if a soluble component obtained by contacting the mixture (B) containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone with the organic solvent (b) is used as the mixture (A), A polyphenylene ether ether ketone composition of the formula can be obtained in high yield.

[Example 6]
20.0 g of the mixture (a) prepared by the method described in Reference Example 1 was subjected to extraction operation at 50 ° C. for 5 hours using 120 g of NMP. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (NMP) as filtrate components. As a result of analyzing the mixture (A), it was found that the mixture (A) contained 3.0% by weight (2.9 g) of cyclic polyphenylene ether ether ketone.

  Using the mixture (A) obtained here, the cyclic polyphenylene ether ether ketone composition was recovered in the same manner as in Example 5. As a result, the recovery rate of the cyclic polyphenylene ether ether ketone was 98.2% by weight. The purity of the resulting cyclic polyphenylene ether ether ketone was 91%.

  When the mixture (B) is brought into contact with the organic solvent (b) to prepare the mixture (A) as a soluble component of the organic solvent (b), the contact temperature between the mixture (B) and the organic solvent (b) is lowered. Thus, it was found that a high-purity cyclic polyphenylene ether ether ketone composition can be obtained in a high yield.

[Reference Example 2]
Here, preparation of polyphenylene ether ether ketone is described with reference to the method described in Examples of Patent Publication 2007-506833.

  In a four-necked flask equipped with a stirrer, a nitrogen blowing tube, a Dean-Stark apparatus, a condenser tube, and a thermometer, 14.0 g (82.4 mmol) of 4,4′-difluorobenzophenone, 8.8 g (80 mmol) of hydroquinone, and diphenyl 49 g of sulfone was charged. When the temperature was raised to 140 ° C. through nitrogen, an almost colorless solution was formed. At this temperature, 8.5 g (80 mmol) of sodium carbonate and 0.2 g (1.6 mmol) of potassium carbonate were added to prepare a mixture. The amount of the organic polar solvent relative to 1.0 mole of the benzene ring component in the mixture is about 0.2 liter.

  The mixture was heated to an internal temperature of 200 ° C., held for 1 hour, heated to 250 ° C., held for 1 hour, further heated to 315 ° C. and held for 3 hours to carry out the reaction. After completion of the reaction, the reaction mixture was allowed to cool to obtain a reaction mixture.

  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 1.8%.

  By washing and removing the by-product salt and diphenylsulfone by washing the reaction mixture with water and acetone, the mixture (i) was obtained by drying in a hot air dryer at 120 ° C.

  About 1.0 g of the obtained mixture (I) was subjected to Soxhlet extraction with 100 g of chloroform at a bath temperature of 80 ° C. for 5 hours, and then a solid component insoluble in chloroform was vacuum-dried at 70 ° C. overnight to form an off-white solid. About 0.97 g of component was obtained. As a result of the analysis, it was confirmed that the polyphenylene ether ether ketone was linear from the absorption spectrum in the infrared spectroscopic analysis. This shows that the mixture (a) prepared by the above method is a mixture containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone.

[Reference Example 3]
Here, preparation of polyphenylene ether ether ketone by referring to the method described in Examples of JP-A-2007-302895 will be described.

  In a four-necked flask equipped with a stirrer, a nitrogen blowing tube, a Dean-Stark device, a condenser tube, and a thermometer, 26.2 g (120.1 mmol) of 4,4′-difluorobenzophenone, 13.2 g (119.9 mmol) of hydroquinone, A mixture was prepared by adding 13.2 g (124.5 mmol) of sodium carbonate, 0.64 g (4.6 mmol) of potassium carbonate, and 69.2 g of diphenylsulfone. The amount of the organic polar solvent relative to 1.0 mole of the benzene ring component in the mixture is about 0.2 liter.

  The mixture was heated to an internal temperature of 320 ° C. and held for 8 hours for reaction. After completion of the reaction, the reaction mixture was allowed to cool to obtain a reaction mixture.

  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 1.9%.

  By washing and removing the by-product salt and diphenylsulfone by washing the reaction mixture with ethanol and water, the mixture (c) was obtained by drying in a hot air dryer at 120 ° C.

  About 1.0 g of the obtained mixture (c) was subjected to Soxhlet extraction with 100 g of chloroform at a bath temperature of 80 ° C. for 5 hours, and then the solid component insoluble in chloroform was vacuum-dried at 70 ° C. overnight to form an off-white solid. About 0.97 g of component was obtained. As a result of the analysis, it was confirmed that the polyphenylene ether ether ketone was linear from the absorption spectrum in the infrared spectroscopic analysis. From this, it can be seen that the mixture (c) prepared by the above method is a mixture containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone.

[Reference Example 4]
Here, preparation of polyphenylene ether ether ketone will be described with reference to the method described in Examples of JP 2010-95614 A.

  In a four-necked flask equipped with a stirrer, a nitrogen blowing tube, a Dean-Stark device, a condenser tube, and a thermometer, 22.4 g (101.5 mmol) of 4,4′-difluorobenzophenone, 11.0 g (100.0 mmol) of hydroquinone, And 164 g of sulfolane were charged. When the temperature was raised to 80 ° C. while introducing nitrogen, an almost colorless solution was formed. At this temperature, 14.0 g (101.0 mmol) of potassium carbonate was added to prepare a mixture. The amount of the organic polar solvent relative to 1.0 mole of the benzene ring component in the mixture is about 0.54 liter.

  The mixture was heated to an internal temperature of 265 ° C., and kept at 265 ° C. for 4 hours to carry out the reaction. After completion of the reaction, the reaction mixture was allowed to cool to obtain a reaction mixture.

  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 5.9%.

  By washing and removing the by-product salt and sulfolane by washing the reaction mixture with water, the mixture was dried in a hot air dryer at 120 ° C. to obtain a mixture (d).

  About 1.0 g of the obtained mixture (d) was subjected to Soxhlet extraction with 100 g of chloroform at a bath temperature of 80 ° C. for 5 hours, and then the solid component insoluble in chloroform was vacuum-dried at 70 ° C. overnight to form an off-white solid. About 0.93 g of component was obtained. As a result of the analysis, it was confirmed that the polyphenylene ether ether ketone was linear from the absorption spectrum in the infrared spectroscopic analysis. This shows that the mixture (d) prepared by the above method is a mixture containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone.

[Example 7]
Here, the recovery of the cyclic polyphenylene ether ether ketone composition from the mixture (i) containing at least the linear polyphenylene ether ether ketone and the cyclic polyphenylene ether ether ketone prepared by the method described in Reference Example 2 will be described.

  20.0 g of the mixture (I) was subjected to extraction operation at 100 ° C. for 5 hours using 120 g of NMP. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (NMP) as filtrate components. As a result of analyzing this mixture (A), it was found that the mixture (A) contained 0.2% by weight (0.2 g) of cyclic polyphenylene ether ether ketone.

  By heating the obtained mixture (A) to 120 ° C. under reduced pressure, 80 g of NMP was distilled off to adjust the content of cyclic polyphenylene ether ether ketone contained in the mixture (A) (1.3 % By weight (0.2 g)).

  The mixture (A) whose cyclic polyphenylene ether ether ketone content was adjusted was heated to 100 ° C. with stirring and then cooled to 80 ° C. At the stage of reaching 100 ° C. and the stage of cooling to 80 ° C., no insoluble part was observed, and it was confirmed that 50% by weight or more of the cyclic polyphenylene ether ether ketone was dissolved.

  Next, while stirring the mixture (A) at an internal temperature of 80 ° C., 6.5 g of water was slowly added dropwise over about 25 minutes using a tube pump (NMP and water in the mixture after completion of the addition of water). The weight ratio is 70:30). At this time, the temperature of the mixture decreased to about 75 ° C. as the water was dropped, and solids gradually formed in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The slurry was cooled to about 30 ° C. over about 1 hour with stirring, and then stirred for about 30 minutes at 30 ° C. or lower, and then the obtained slurry was suction filtered with a glass filter having an opening of 10 to 16 μm. The obtained solid content (including the mother liquor) was dispersed in about 30 g of water, stirred for 15 minutes at 70 ° C., and then subjected to suction filtration with a glass filter in the same manner as described above four times. The obtained solid content was treated at 70 ° C. for 3 hours in a vacuum dryer to obtain a dry solid.

  As a result of analyzing the dried solid by HPLC, it was confirmed that it was a cyclic polyphenylene ether ether ketone, the recovery rate of the cyclic polyphenylene ether ether ketone was 98.0% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone was 92%.

[Example 8]
Here, recovery of the cyclic polyphenylene ether ether ketone composition from the mixture (c) containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone prepared by the method described in Reference Example 3 will be described.

  Extraction operation was performed for 5 hours at 100 ° C. using 20.0 g of the mixture (U) using 120 g of NMP. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (NMP) as filtrate components. As a result of analyzing the mixture (A), it was found that the mixture (A) contained 0.4% by weight (0.4 g) of cyclic polyphenylene ether ether ketone.

  By heating the obtained mixture (A) to 120 ° C. under reduced pressure, 65 g of NMP was distilled off to adjust the content of cyclic polyphenylene ether ether ketone contained in the mixture (A) (1.3 % By weight (0.4 g)).

  The mixture (A) whose cyclic polyphenylene ether ether ketone content was adjusted was heated to 100 ° C. with stirring and then cooled to 80 ° C. At the stage of reaching 100 ° C. and the stage of cooling to 80 ° C., no insoluble part was observed, and it was confirmed that 50% by weight or more of the cyclic polyphenylene ether ether ketone was dissolved.

  Next, while stirring this mixture (A) at an internal temperature of 80 ° C., 12.9 g of water was slowly added dropwise over about 25 minutes using a tube pump (NMP and water in the mixture after completion of the addition of water). The weight ratio is 70:30). At this time, the temperature of the mixture decreased to about 75 ° C. as the water was dropped, and solids gradually formed in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The slurry was cooled to about 30 ° C. over about 1 hour with stirring, and then stirred for about 30 minutes at 30 ° C. or lower, and then the obtained slurry was suction filtered with a glass filter having an opening of 10 to 16 μm. The obtained solid content (including the mother liquor) was dispersed in about 30 g of water, stirred for 15 minutes at 70 ° C., and then subjected to suction filtration with a glass filter in the same manner as described above four times. The obtained solid content was treated at 70 ° C. for 3 hours in a vacuum dryer to obtain a dry solid.

  As a result of analyzing the dried solid by HPLC, it was confirmed that it was a cyclic polyphenylene ether ether ketone, the recovery rate of the cyclic polyphenylene ether ether ketone was 98.1% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone was 92%.

[Example 9]
Here, recovery of the cyclic polyphenylene ether ether ketone composition from the mixture (d) containing at least linear polyphenylene ether ether ketone and cyclic polyphenylene ether ether ketone prepared by the method described in Reference Example 4 will be described.

  20.0 g of the mixture (d) was subjected to extraction operation at 100 ° C. for 5 hours using 120 g of NMP. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (NMP) as filtrate components. As a result of analyzing this mixture (A), it was found that the mixture (A) contained 1.2% by weight (1.2 g) of cyclic polyphenylene ether ether ketone.

  The mixture (A) was heated to 100 ° C. with stirring and then cooled to 80 ° C. At the stage of reaching 100 ° C. and the stage of cooling to 80 ° C., no insoluble part was observed, and it was confirmed that 50% by weight or more of the cyclic polyphenylene ether ether ketone was dissolved.

  Next, while stirring the mixture (A) at a system temperature of 80 ° C., 40.7 g of water was slowly added dropwise over about 25 minutes using a tube pump (NMP and water in the mixture after completion of the dropwise addition of water). The weight ratio is 70:30). At this time, the temperature of the mixture decreased to about 75 ° C. as the water was dropped, and solids gradually formed in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The slurry was cooled to about 30 ° C. over about 1 hour with stirring, and then stirred for about 30 minutes at 30 ° C. or lower, and then the obtained slurry was suction filtered with a glass filter having an opening of 10 to 16 μm. The obtained solid content (including the mother liquor) was dispersed in about 30 g of water, stirred for 15 minutes at 70 ° C., and then subjected to suction filtration with a glass filter in the same manner as described above four times. The obtained solid content was treated at 70 ° C. for 3 hours in a vacuum dryer to obtain a dry solid.

  As a result of analyzing the dried solid by HPLC, it was confirmed that it was a cyclic polyphenylene ether ether ketone, the recovery rate of the cyclic polyphenylene ether ether ketone was 99.0% by weight, and the purity of the recovered cyclic polyphenylene ether ether ketone was It was 91%.

[Example 10]
Here, the cyclic polyphenylene ether ether ketone was obtained by using the cyclic polyphenylene ether ether ketone composition obtained in Reference Example 1 as the cyclic polyphenylene ether ether ketone, using acetone as the organic solvent (b) and water as the solvent (c). The example which collect | recovered the ketone composition is shown.

  100 g of acetone was added to 2.5 g of the cyclic polyphenylene ether ether ketone composition having a purity of 88% obtained in Reference Example 1 to prepare a mixture (A) containing 2.4 wt% of the cyclic polyphenylene ether ether ketone, Warm to 50 ° C. with stirring. At this time, no insoluble part was observed, and it was confirmed that 50% by weight or more of the cyclic polyphenylene ether ether ketone contained in the mixture (A) was dissolved.

  Next, with stirring the mixture (A) at an internal temperature of 50 ° C., 33 g of water was slowly added dropwise over about 25 minutes using a tube pump (the weight of acetone and water in the mixture after completion of the addition of water). The ratio is 75:25). At this time, the temperature of the mixture decreased to about 46 ° C. along with the dropwise addition of water, and solids gradually formed in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The cyclic polyphenylene ether ether ketone composition was recovered from this slurry by the same method as in Example 1. As a result, the recovery rate of the cyclic polyphenylene ether ether ketone was 99.5% by weight, and the recovered cyclic polyphenylene ether was recovered. The purity of the ether ketone was 89%.

[Example 11]
Here, the cyclic polyphenylene ether ether ketone obtained by using the cyclic polyphenylene ether ether ketone composition obtained in Reference Example 1 as the cyclic polyphenylene ether ether ketone, acetone as the organic solvent (b), and methanol as the solvent (c). The example which collect | recovered the ketone composition is shown.

  100 g of acetone was added to 2.5 g of the cyclic polyphenylene ether ether ketone composition having a purity of 88% obtained in Reference Example 1 to prepare a mixture (A) containing 2.4 wt% of the cyclic polyphenylene ether ether ketone, Warm to 50 ° C. with stirring. At this time, no insoluble part was observed, and it was confirmed that 50% by weight or more of the cyclic polyphenylene ether ether ketone contained in the mixture (A) was dissolved.

  Next, while stirring the mixture (A) at an internal temperature of 50 ° C., 67 g of methanol was slowly added dropwise over about 25 minutes using a tube pump (weight of acetone and methanol in the mixture after completion of the addition of water). The ratio is 60:40). At this time, the temperature of the mixture decreased to about 44 ° C. along with the dropwise addition of methanol, and a solid content was gradually generated in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The cyclic polyphenylene ether ether ketone composition was recovered from the slurry by the same method as in Example 1. As a result, the recovery rate of the cyclic polyphenylene ether ether ketone was 91.3% by weight, and the recovered cyclic polyphenylene ether was recovered. The purity of the ether ketone was 92.0%.

[Example 12]
Here, the cyclic polyphenylene ether ether ketone is obtained by using the cyclic polyphenylene ether ether ketone composition obtained in Reference Example 1 as the cyclic polyphenylene ether ether ketone, using THF as the organic solvent (b) and water as the solvent (c). The example which collect | recovered the ketone composition is shown.

  100 g of THF was added to 2.5 g of the cyclic polyphenylene ether ether ketone composition having a purity of 88% obtained in Reference Example 1 to prepare a mixture (A) containing 2.4% by weight of cyclic polyphenylene ether ether ketone, and stirred. While warming to 60 ° C. At this time, no insoluble part was observed, and it was confirmed that 50% by weight or more of the cyclic polyphenylene ether ether ketone contained in the mixture (A) was dissolved.

  Next, while stirring the mixture (A) at an internal temperature of 60 ° C., 33 g of water was slowly added dropwise over about 25 minutes using a tube pump (the weight of THF and water in the mixture after completion of the addition of water). The ratio is 75:25). At this time, the temperature of the mixture decreased to about 54 ° C. along with the dropwise addition of water, and solids gradually formed in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The cyclic polyphenylene ether ether ketone composition was recovered from this slurry by the same method as in Example 1. As a result, the recovery rate of the cyclic polyphenylene ether ether ketone was 99.1% by weight, and the recovered cyclic polyphenylene ether was recovered. The purity of the ether ketone was 90%.

[Example 13]
Here, the cyclic polyphenylene ether ether ketone obtained by using the cyclic polyphenylene ether ether ketone composition obtained in Reference Example 1 as the cyclic polyphenylene ether ether ketone, THF as the organic solvent (b), and methanol as the solvent (c). The example which collect | recovered the ketone composition is shown.

  100 g of THF was added to 2.5 g of the cyclic polyphenylene ether ether ketone composition having a purity of 88% obtained in Reference Example 1 to prepare a mixture (A) containing 2.4% by weight of the cyclic polyphenylene ether ether ketone and stirred. The mixture was warmed to 55 ° C. At this time, no insoluble part was observed, and it was confirmed that 50% by weight or more of the cyclic polyphenylene ether ether ketone contained in the mixture (A) was dissolved.

  Next, while stirring the mixture (A) at a system temperature of 55 ° C., 67 g of methanol was slowly added dropwise over about 25 minutes using a tube pump (the weight of THF and methanol in the mixture after completion of the addition of water). The ratio is 60:40). At this time, the temperature of the mixture was lowered to about 50 ° C. along with the dropwise addition of methanol, and a solid content was gradually generated in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The cyclic polyphenylene ether ether ketone composition was recovered from this slurry by the same method as in Example 1. As a result, the recovery rate of the cyclic polyphenylene ether ether ketone was 90.8% by weight, and the recovered cyclic polyphenylene ether was recovered. The purity of the ether ketone was 92%.

[Example 14]
Here, the cyclic polyphenylene ether ether ketone was obtained by using the cyclic polyphenylene ether ether ketone composition obtained in Reference Example 1 as the cyclic polyphenylene ether ether ketone, using chloroform as the organic solvent (b) and methanol as the solvent (c). The example which collect | recovered the ketone composition is shown.

  100 g of chloroform was added to 2.5 g of the cyclic polyphenylene ether ether ketone composition having a purity of 88% obtained in Reference Example 1 to prepare a mixture (A) containing 2.4 wt% of the cyclic polyphenylene ether ether ketone, Warm to 55 ° C. with stirring. At this time, no insoluble part was observed, and it was confirmed that 50% by weight or more of the cyclic polyphenylene ether ether ketone contained in the mixture (A) was dissolved.

  Next, while stirring the mixture (A) at a system temperature of 55 ° C., 67 g of methanol was slowly added dropwise over about 25 minutes using a tube pump (the weight of chloroform and methanol in the mixture after completion of the dropwise addition of methanol). The ratio is 60:40). At this time, the temperature of the mixture decreased to about 48 ° C. along with the dropwise addition of methanol, and a solid content was gradually generated in the mixture. A coarse solid content was not observed, and the slurry was uniformly dispersed.

  The cyclic polyphenylene ether ether ketone composition was recovered from this slurry by the same method as in Example 1. As a result, the recovery rate of the cyclic polyphenylene ether ether ketone was 95.0%, and the recovered cyclic polyphenylene ether ether was recovered. The purity of the ketone was 93%.

[Example 15]
20.0 g of the mixture (A) prepared by the method described in Reference Example 1 was subjected to extraction operation at 60 ° C. for 5 hours using 120 g of THF. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (THF) as filtrate components. As a result of analyzing the mixture (A), it was found that the mixture (A) contained 3.0% by weight (2.9 g) of cyclic polyphenylene ether ether ketone.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition using the mixture (A) obtained in the same manner as in Example 12, the recovery rate of the cyclic polyphenylene ether ether ketone was 99.1% by weight. The purity of the cyclic polyphenylene ether ether ketone was 92%.

[Example 16]
20.0 g of the mixture (A) prepared by the method described in Reference Example 1 was subjected to extraction operation at 60 ° C. for 5 hours using 120 g of THF. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (THF) as filtrate components. As a result of analyzing the mixture (A), it was found that the mixture (A) contained 3.0% by weight (2.9 g) of cyclic polyphenylene ether ether ketone.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition using the mixture (A) obtained in the same manner as in Example 13, the recovery rate of cyclic polyphenylene ether ether ketone was 91.0%. The purity of the cyclic polyphenylene ether ether ketone was 93%.

[Example 17]
20.0 g of the mixture (I) prepared by the method described in Reference Example 2 was subjected to extraction operation at 50 ° C. for 5 hours using 120 g of acetone. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (acetone) as filtrate components. As a result of analyzing the mixture (A), it was found that the mixture (A) contained 0.2% by weight (0.2 g) of cyclic polyphenylene ether ether ketone.

  By heating the obtained mixture (A) to 50 ° C. under reduced pressure, 80 g of acetone was distilled off to adjust the content of cyclic polyphenylene ether ether ketone contained in the mixture (A) (1. 3% by weight (0.2 g)).

  As a result of recovering the cyclic polyphenylene ether ether ketone composition using the mixture (A) obtained in the same manner as in Example 10, the recovery rate of the cyclic polyphenylene ether ether ketone was 99.5% by weight. The purity of the cyclic polyphenylene ether ether ketone was 93%.

[Example 18]
20.0 g of the mixture (I) prepared by the method described in Reference Example 2 was subjected to extraction operation at 50 ° C. for 5 hours using 120 g of acetone. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (acetone) as filtrate components. As a result of analyzing the mixture (A), it was found that the mixture (A) contained 0.2% by weight (0.2 g) of cyclic polyphenylene ether ether ketone.

  By heating the obtained mixture (A) to 50 ° C. under reduced pressure, 80 g of acetone was distilled off to adjust the content of cyclic polyphenylene ether ether ketone contained in the mixture (A) (1. 3% by weight (0.2 g)).

  As a result of recovering the cyclic polyphenylene ether ether ketone composition using the mixture (A) obtained in the same manner as in Example 11, the recovery rate of cyclic polyphenylene ether ether ketone was 91.5% by weight. The purity of the cyclic polyphenylene ether ether ketone was 93.5%.

[Example 19]
20.0 g of the mixture (c) prepared by the method described in Reference Example 3 was subjected to extraction operation at 50 ° C. for 5 hours using 120 g of acetone. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (acetone) as filtrate components. As a result of analyzing the mixture (A), it was found that the mixture (A) contained 0.4% by weight (0.4 g) of cyclic polyphenylene ether ether ketone.

  The obtained mixture (A) was heated to 50 ° C. under reduced pressure, whereby 70 g of acetone was distilled off to adjust the content of cyclic polyphenylene ether ether ketone contained in the mixture (A) (1. 6% by weight (0.4 g)).

  As a result of recovering the cyclic polyphenylene ether ether ketone composition using the mixture (A) obtained in the same manner as in Example 10, the recovery rate of the cyclic polyphenylene ether ether ketone was 99.4% by weight. The purity of the cyclic polyphenylene ether ether ketone was 93%.

[Example 20]
20.0 g of the mixture (c) prepared by the method described in Reference Example 3 was subjected to extraction operation at 50 ° C. for 5 hours using 120 g of acetone. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (acetone) as filtrate components. As a result of analyzing the mixture (A), it was found that the mixture (A) contained 0.4% by weight (0.4 g) of cyclic polyphenylene ether ether ketone.

  The obtained mixture (A) was heated to 50 ° C. under reduced pressure, whereby 70 g of acetone was distilled off to adjust the content of cyclic polyphenylene ether ether ketone contained in the mixture (A) (1. 6% by weight (0.4 g)).

  As a result of recovering the cyclic polyphenylene ether ether ketone composition using the mixture (A) obtained in the same manner as in Example 11, the recovery rate of cyclic polyphenylene ether ether ketone was 91.5% by weight. The purity of the cyclic polyphenylene ether ether ketone was 94%.

[Example 21]
20.2 g of the mixture (d) prepared by the method described in Reference Example 4 was subjected to extraction operation at 50 ° C. for 5 hours using 120 g of acetone. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (acetone) as filtrate components. As a result of analyzing this mixture (A), it was found that the mixture (A) contained 1.3% by weight (1.2 g) of cyclic polyphenylene ether ether ketone.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition in the same manner as in Example 10 using the mixture (A) obtained here, the recovery rate of cyclic polyphenylene ether ether ketone was 99.0% by weight. The purity of the cyclic polyphenylene ether ether ketone was 94%.

[Example 22]
Extraction operation of 20.0 g of the mixture (d) prepared by the method described in Reference Example 4 was carried out at 50 g for 5 hours using 120 g of acetone. After the extraction operation, solid-liquid separation was performed to obtain 95 g of a mixture (A) containing at least cyclic polyphenylene ether ether ketone and an organic solvent (acetone) as filtrate components. As a result of analyzing this mixture (A), it was found that the mixture (A) contained 1.3% by weight (1.2 g) of cyclic polyphenylene ether ether ketone.

  As a result of recovering the cyclic polyphenylene ether ether ketone composition in the same manner as in Example 11 using the mixture (A) obtained here, the recovery rate of the cyclic polyphenylene ether ether ketone was 92.0% by weight. The purity of the cyclic polyphenylene ether ether ketone was 94%.

[Example 23]
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 1, 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 a thermal characteristic with a melting point of 332 ° C. and a crystallization temperature of 240 ° C. Further, as a result of measuring the reduced viscosity of the black solid, it was found that η was 0.5 dL / g.

Claims (13)

An organic solvent in a mixture (A) containing at least cyclic polyphenylene ether ether ketone (a) and an organic solvent (b) in which 50% by weight or more of the cyclic polyphenylene ether ether ketone (a) is dissolved A method for recovering a cyclic polyphenylene ether ether ketone composition, comprising adding the solvent (c) different from (b) to recover the cyclic polyphenylene ether ether ketone composition as a solid content. A mixture (B) containing at least a linear polyphenylene ether ether ketone and a cyclic polyphenylene ether ether ketone is contacted with an organic solvent (b) to prepare the mixture (A) as a soluble component of the organic solvent (b). The method for recovering a cyclic polyphenylene ether ether ketone composition according to claim 1. The cyclic polyphenylene ether according to claim 1 or 2, wherein the organic solvent (b) is a solvent having high solubility in cyclic polyphenylene ether ether ketone and poor solubility in linear polyphenylene ether ether ketone. A method for recovering the ether ketone composition. The cyclic polyphenylene ether ether ketone composition is a composition containing 60% by weight or more of the cyclic polyphenylene ether ether ketone (a) represented by the general formula (I), wherein the cyclic polyphenylene ether ether ketone (a) Is a mixture of cyclic polyphenylene ether ether ketones having different repeating numbers m, and is a cyclic polyphenylene ether ether ketone composition having a melting point of 270 ° C. or lower. 4. A method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of 3 above.

(Here, m in (I) is an integer of 2 to 40) The cyclic polyphenylene ether ether ketone (a) is a mixture composed of at least three different integers m, and the cyclic polyphenylene ether ether ketone composition according to any one of claims 1 to 4, Method. The cyclic polyphenylene ether ether ketone (a) is a mixture composed of at least three consecutive different integers m, at least in the cyclic polyphenylene ether ether ketone composition according to any one of claims 1 to 5. Collection method. The cyclic polyphenylene ether ether ketone according to any one of claims 1 to 6, wherein the solvent (c) is mixed with the organic solvent (b) when the solvent (c) is added to the mixture (A). A method for recovering the composition. The method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of claims 1 to 7, wherein the organic solvent (b) is an aprotic polar solvent. The method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of claims 1 to 8, wherein the organic solvent (b) is an organic amide solvent. The method for recovering a cyclic polyphenylene ether ether ketone composition according to any one of claims 1 to 9, wherein the solvent (c) is a protic solvent. The recovery of the cyclic polyphenylene ether ether ketone composition according to any one of claims 1 to 10, wherein the weight of the solvent (c) added to the mixture (A) is not more than the weight of the organic solvent (b). Method. The cyclic polyphenylene ether ether ketone composition according to any one of claims 1 to 11, wherein the cyclic polyphenylene ether ether ketone composition is separated by performing solid-liquid separation after adding the solvent (c). Collection method of things. A method for producing a polyphenylene ether ether ketone, comprising subjecting the cyclic polyphenylene ether ether ketone composition obtained by the recovery method according to claim 1 to heat-opening polymerization.