JP2016204265A - Method for producing monomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a monomer having good hue from a polymer using as a raw material a monomer represented by Formula (I) in a short period of time.SOLUTION: The method for producing a monomer represented by Formula (I) by the following steps: (1) a step of mixing a solvent including at least one kind selected from an ether solvent, a ketone solvent and a hydrocarbon solvent, a polymer and a metal hydroxide aqueous solution and decomposing the polymer to produce a decomposition liquid; (2) a step of recovering a crude product of a monomer from the decomposition liquid; and (3) a step of purifying the crude product of the monomer. (Rand Rare H, a 1-10C alkyl group, a 6-10C cycloalkyl or aryl group; X is a 2-6C alkylene group which may be branched, a 6-10C cycloalkylene or arylene group; n and m are an integer of 1 to 5)SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a monomer by decomposing a polymer with an aqueous metal hydroxide solution.

Polycarbonate, polyester or polyester carbonate has excellent mechanical properties, electrical properties, heat resistance, cold resistance, transparency, hydrolysis resistance, etc. Optical lens, optical disk, liquid crystal panel, head lamp panel The demand for these materials is increasing year by year. As the demand for these polymers increases, many of the polymer products that are discarded are processed by methods such as incineration or filling in the ground. This not only accelerates the depletion of petroleum resources due to the increased demand for polymers, but also promotes the deterioration of the global environment. Therefore, it has become important to reuse (recycle) discarded plastic.
The methods for recycling plastic are as follows: (1) Thermal recycling in which plastic is recovered as thermal energy, (2) Material recycling in which plastic is mixed and processed at a certain ratio in the product, and (3) Plastic is chemically processed. There is chemical recycling that decomposes and returns to plastic raw materials for reuse in plastic manufacturing. However, because thermal recycling incinerates plastic to extract heat, carbon dioxide and water are generated, essentially destroying the global environment and reducing resources. Material recycling has the least environmental impact and is environmentally desirable in terms of resource consumption, but the products that can be mixed are limited, the proportion that can be mixed into the products is small, and the amount that can be recycled is limited. Since chemical recycling decomposes plastics into raw materials, it can be used for manufacturing as it is, and is an industrially useful recycling method.

As a method of chemically recycling polycarbonate, a method of decomposing polycarbonate with an excess of an alkaline aqueous solution has been known for a long time. For example, in Patent Document 1, polycarbonate and 1-30% aqueous alkali solution are put in a pressure vessel without using an organic solvent, hydrolyzed at 100 ° C. or higher, preferably 150 ° C. or higher, acidified, and then dissolved in methanol. Then, the activated carbon treatment is performed to remove the coloring components, and then reprecipitation is performed to obtain white bisphenol.
Patent Document 2 discloses a method in which polycarbonate scrap is saponified with a bulk or a solution, an unsaponified component is separated, a saponified mixture is phosgenated, and used in a polycarbonate polymerization step without any purification and treatment steps. Yes.
Patent Document 3 discloses a method of recovering an aromatic dihydroxy compound and a diaryl carbonate by decomposing a polycarbonate with phenol in the presence of an alkali catalyst.
Patent Document 4 discloses a method for obtaining a dialkyl carbonate and an aromatic dihydroxy compound by performing a transesterification reaction in a toluene, xylene, benzene or dioxane solvent using a small amount of alkali as a catalyst.
Patent Document 5 proposes a method of transesterifying a polycarbonate with a lower alcohol in the presence of a tertiary amine in the presence of a solvent such as an alkyl chloride, an ether or an aromatic hydrocarbon solvent and a tertiary amine to obtain an aromatic dihydroxy compound and a dialkyl carbonate. Has been.

Further, Patent Document 6 discloses a method in which a polycarbonate is dissolved in a halogenated hydrocarbon solvent and then decomposed with a metal hydroxide aqueous solution to obtain an aromatic dihydroxy compound metal salt aqueous solution, and a solid fragrance from the aromatic dihydroxy compound metal salt aqueous solution. A method for obtaining a group hydroxy compound is shown.
However, since the method described in Patent Document 1 uses a thin alkaline aqueous solution, the reaction becomes high temperature, and a large amount of water is used in the post-treatment, and the yellow coloring component is reprecipitated from a mixed solvent of methanol and water. Therefore, the waste liquid treatment is very complicated.

Since the method described in Patent Document 2 is used in a polymerization reaction without a purification step, additives, colorants, and the like used as almost essential components in plastics are mixed in the polycarbonate production process, which affects product quality. .
In the methods described in Patent Documents 3 to 5, not only the decomposition and solvent separation and recovery steps are complicated, but also unnecessary by-products are generated.
The method described in Patent Document 6 requires the addition of an antioxidant in order to prevent oxidation of the aromatic hydroxy compound under basic conditions, and in order to take it out as a high-purity solid, an acid is added to the fragrance. It is necessary to deposit the group hydroxy compound.
In addition, the methods described in Patent Documents 1 to 6 are polycarbonates using bisphenol A as a raw material, and 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene in that it has a phenolic hydroxyl group. There is no knowledge about a polymer made from a monomer having a hydroxyl group bonded to an alkylene chain represented by —CH ₂ CH ₂ OH, such as (hereinafter sometimes abbreviated as BPEF).

Japanese Patent Publication No. 40-016536 Japanese Patent Laid-Open No. 54-048869 Japanese Patent Application Laid-Open No. 06-056885 Japanese Patent Laid-Open No. 10-259151 JP 2002-212335 A JP 2005-126358 A

  An object of the present invention is to provide a method for producing a monomer having a good hue and containing almost no coloring component in a short time from a polymer having a monomer represented by the following formula (I) as a raw material. .

(In Formula (I), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. X is an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, n and m are each independently an integer of 1 to 5 .)

The present inventors examined a method for recovering a monomer from a polymer using a monomer represented by the following formula (I) such as BPEF as a raw material. As a result, it has been found that the monomer represented by the following formula (I) has a hydroxyl group bonded to an alkylene chain such as —CH ₂ CH ₂ OH, and is therefore contained and recovered in the organic layer, not the aqueous layer. It was.

  In addition, a polymer containing a monomer residue represented by the following formula (I) is easily cleaved at the time of decomposition, and one end represented by the following formula (Ia) is phenolic as an impurity. It has been found that impurities which are hydroxyl groups and impurities whose both ends represented by the following formula (Ib) are phenolic hydroxyl groups are produced, and that these are causes of coloring. These impurities were expected to be difficult to separate because of their approximate structure, but the monomer represented by formula (Ia) or (Ib) can be easily separated by washing the organic layer with water. I found. As a result, it was found that a monomer having a small coloring component can be obtained.

(In Formula (I), Formula (Ia) and Formula (Ib), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or a carbon atom. X is an aryl group having 6 to 10. X is an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, n and m is an integer of 1-5 each independently.)

  It has also been found that the quality of a polymer using the monomer as a raw material is comparable to the quality of a polymer produced using a commercially available monomer.

That is, according to this invention, the method of obtaining a monomer from the polymer shown below is provided.
1. A method for producing a monomer represented by the following formula (I) by decomposing a polymer containing a monomer residue represented by the following formula (1) with an aqueous metal hydroxide solution,

(In Formula (I), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. X is an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, n and m are each independently an integer of 1 to 5 .)

(1) A step of decomposing a polymer by mixing an organic solvent containing at least one selected from the group consisting of an ether solvent, a ketone solvent and a hydrocarbon solvent, a polymer and a metal hydroxide aqueous solution to obtain a decomposition solution containing a monomer (Decomposition process),
(2) a step of recovering a crude monomer product from the decomposition solution (recovery step), and (3) a step of purifying the crude monomer product (purification step),
The manufacturing method of the said monomer containing.
2. 2. The method according to item 1, wherein the polymer is polycarbonate, polyester or polyester carbonate.
3. 2. The method according to item 1, wherein the monomer is 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
4). 2. The method according to item 1 above, wherein the metal hydroxide is sodium hydroxide and / or potassium hydroxide.
5. 2. The method according to item 1, wherein the organic solvent contains at least 50% by weight of at least one selected from the group consisting of an ether solvent, a ketone solvent and a hydrocarbon solvent.
6). 2. The method according to item 1, wherein the organic solvent is at least one solvent selected from the group consisting of toluene, xylene, tetrahydrofuran, dioxane, acetone, 2-butanone, 4-methyl-2-pentanone and cyclohexanone.
7). 2. The production method according to item 1 above, wherein the decomposition temperature in the decomposition step is 25 to 90 ° C.
8). 2. The method according to item 1 above, wherein the concentration of the aqueous metal hydroxide solution in the decomposition step is 15 to 48% by weight.
9. 2. The method according to item 1, wherein the recovery step includes a step of cooling the decomposition liquid and recovering the precipitated monomer crude product.
10. 2. The method according to item 1, wherein the recovery step is a step of recovering the crude product of the monomer from the organic solvent layer after separating the decomposition solution from the aqueous phase and the organic solvent phase.
11. 11. The method according to item 10, wherein the recovery step includes a step of washing the separated organic solvent layer with water.
12 The purification step includes a recrystallization step of dissolving the crude monomer product in a recrystallization solvent containing at least one selected from the group consisting of an ether solvent, a ketone solvent, a hydrocarbon solvent, and an alcohol solvent, and then depositing the monomer. The manufacturing method of the preceding clause 1.
13. The recrystallization solvent is at least one solvent selected from the group consisting of toluene, xylene, tetrahydrofuran, dioxane, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, methanol, ethanol, 2-propanol, and 2-butanol. 13. The production method according to item 12 above.
14 13. The production method according to item 12 above, comprising a step of washing the organic solvent layer with water before the recrystallization step.
15. The monomer is 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, and 9- (4- (2-hydroxyethoxy) phenyl) -9- (4-hydroxyphenyl) fluorene in the monomer 2. The method according to item 1 above, wherein the content is 0.2% or less.
16. Polycarbonate, polyester, or polyester carbonate polymerized using the monomer according to item 15 as a raw material.
17. A lens, sheet or film obtained from the polymer according to item 16 above.
18. 9,9-bis (4- (2-hydroxyethoxy) phenyl) having a content of 9- (4- (2-hydroxyethoxy) phenyl) -9- (4-hydroxyphenyl) fluorene of 0.2% or less Fluorene.

  According to the present invention, a monomer having a good hue and containing almost no coloring component can be produced in a short time from a polymer using a monomer represented by the following formula (I) as a raw material. According to the present invention, a monomer having a good hue that can be used as a polymer raw material can be produced with high purity.

(In Formula (I), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. X is an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, n and m are each independently an integer of 1 to 5 .)

  Hereinafter, the method for producing a monomer from the polymer of the present invention will be specifically described sequentially.

<Manufacturing method of monomer>
The production method of the present invention includes a decomposition step, a recovery step, and a purification step.

<(1) Decomposition process>
In the decomposition step, an organic solvent containing at least one selected from the group consisting of an ether solvent, a ketone solvent, and a hydrocarbon solvent, a polymer, and a metal hydroxide aqueous solution are mixed to decompose the polymer to obtain a decomposition solution containing a monomer. It is a process.
(polymer)
The polymer is a polymer containing a monomer residue represented by the following formula (I). That is, it is a polymer obtained using the monomer represented by the formula (I) as one of the raw materials. Examples of the polymer include polycarbonate, polyester, or polyester carbonate.

In formula (I), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

  Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the cycloalkyl group having 6 to 10 carbon atoms include a cyclohexyl group and a cyclooctyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.

X is an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.
Examples of the alkylene group having 2 to 6 carbon atoms that may be branched include an ethylene group, a propylene group, and a butylene group. Examples of the cycloalkylene group having 6 to 10 carbon atoms include a cyclohexylene group and a cyclooctylene group. Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group and a naphthalenediyl group.
n and m are each independently an integer of 1 to 5. n and m are each preferably an integer of 1 to 2 independently.

  Specifically, the monomer represented by the formula (I) used in the present invention is 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2 -Hydroxyethoxy) -2-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2 -Ethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-ethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropyl Phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9, 9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis ( 4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2 -Hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2, -Dimethylpropoxy) phenyl) fluorene, 9,9-bis (4- (6-hydroxy-3-oxapentyloxy) phenyl) fluorene, 9,9-bis (4- (9-hydroxy-3,6-dioxa) Octyloxy) phenyl) fluorene, and the like. Among these, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is particularly preferable.

The polymer used in the present invention is preferably a polycarbonate, polyester or polyester carbonate obtained using 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF) as one of the raw materials.
The content of the monomer residue represented by the formula (I) in the polymer is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more. It is.

(Organic solvent)
The organic solvent used in the decomposition step is an organic solvent containing at least one selected from the group consisting of ether solvents, ketone solvents, and hydrocarbon solvents. The organic solvent is preferably at least one solvent selected from the group consisting of toluene, xylene, tetrahydrofuran, dioxane, acetone, 2-butanone, 4-methyl-2-pentanone and cyclohexanone.
The organic solvent used in the decomposition step is preferably used as a mixed solvent. A mixed solvent of toluene and cyclohexanone or toluene and 2-butanone is preferable, and toluene and cyclohexanone are particularly preferable. When cyclohexanone is used as a solvent, the polymer can be smoothly decomposed in the decomposition step without causing the polymer to adhere to the inner wall of the kettle or between the polymers to form a lump.

The composition ratio of the mixed solvent is preferably an organic solvent containing at least 50% by weight of at least one selected from the group consisting of ether solvents, ketone solvents and hydrocarbon solvents. An organic solvent containing at least 50% by weight of an aromatic hydrocarbon solvent is more preferable. For example, in the case of a mixed solvent of toluene: cyclohexanone, 50 to 90:50 to 10 is preferable, and 75 to 85:25 to 15 is more preferable. When the ratio of cyclohexanone is larger than 50% by weight, the dissolved BPEF hardly precipitates and the yield decreases. When it is less than 10% by weight, it is difficult to obtain the effect of preventing adhesion of the polymer.
The amount of the organic solvent used is preferably in the range of 100 to 600 parts by weight, more preferably 130 to 300 parts by weight, and particularly preferably 150 to 170 parts by weight with respect to 100 parts by weight of the polymer. When the amount of the solvent is less than 100 parts by weight, the initial mixing may be insufficient, and the solvent may not be sufficiently swelled or dissolved, resulting in a long time until the decomposition reaction is completed. On the other hand, when the amount is more than 600 parts by weight, the concentration of carbonate bonds and ester bonds in the reaction system is lowered, the decomposition reaction rate is lowered, the decomposition reaction time is lengthened, and the solvent recovery cost is increased.

  In the decomposition step, a phase transfer catalyst can be appropriately added and used in order to prevent the polymers from adhering to each other to form lumps. As the phase transfer catalyst, a quaternary ammonium salt is preferably used, and examples thereof include tetraethylammonium bromide, benzyltriethylammonium chloride, benzyltributylammonium chloride, and methyltrioctylammonium chloride. Of these, benzyltriethylammonium chloride is preferred. These can be used alone or in admixture of two or more. The amount of the phase transfer catalyst used is preferably 10 to 30 parts by weight with respect to 100 parts by weight of the polymer. If the amount used is less than 10 parts by weight, the effect of preventing mass formation cannot be obtained.

The metal hydroxide aqueous solution used for decomposing the polymer is preferably sodium hydroxide or potassium hydroxide, and particularly preferably sodium hydroxide. The amount of metal hydroxide used is preferably 4.1 to 12.4 moles per mole of carbonate and ester bonds of the polymer. If the amount used is less than 4.1 mol, the decomposition reaction is very slow, and if it exceeds 12.4 mol, the cost increases, and the amount of the metal hydroxide aqueous solution discharged when BPEF is isolated and recovered is also high. Increased and economically undesirable.
In the decomposition reaction, the polymer may be dissolved in advance in an organic solvent containing at least one selected from the group consisting of an ether solvent, a ketone solvent, and a hydrocarbon solvent, or a reactor that performs the decomposition reaction without dissolving all of them. It may be thrown into.

In the present invention, the metal hydroxide is used in the form of an aqueous solution. The concentration of the metal hydroxide is preferably 10 to 48% by weight, more preferably 20 to 40% by weight, and still more preferably 23 to 38% by weight.
When the concentration of the metal hydroxide is lower than 10% by weight, the decomposition rate becomes slow and it takes a very long time to complete the reaction, so that the processing efficiency is remarkably deteriorated. On the other hand, when the concentration of the metal hydroxide exceeds 48% by weight, the metal hydroxide is easily precipitated and becomes a slurry. When the slurry becomes a slurry, the reaction is slowed down.

  For example, in the case of BPEF represented by the following formula (I-1), 9- (4 -(2-hydroxyethoxy) phenyl) -9- (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxyphenyl) fluorene represented by the following formula (Ib-1) It becomes easy to produce a compound and adversely affects quality. In particular, 9- (4- (2-hydroxyethoxy) phenyl) -9- (4-hydroxyphenyl) fluorene represented by the following formula (Ia-1) is difficult to be removed in the purification process, and thus easily remains in the recovered BPEF. .

  In this invention, 25-90 degreeC is preferable and the temperature which performs a decomposition reaction has more preferable 30-50 degreeC. When it is less than 25 ° C., the decomposition reaction time becomes long, and the processing efficiency is remarkably inferior. When the temperature exceeds 90 ° C., 9- (4- (2-hydroxyethoxy) phenyl) -9- (4-hydroxyphenyl) fluorene represented by the formula (Ia-1) during the decomposition treatment, and the formula (Ib Coloring components such as 9,9-bis (4-hydroxyphenyl) fluorene represented by -1) are easily generated, and BPEF represented by the formula (I-1) with good quality cannot be obtained.

In the present invention, the time for the decomposition reaction is preferably 3 to 12 hours, and more preferably 4 to 6 hours. When it is less than 3 hours, the decomposition reaction is not completed, and the yield decreases. Moreover, when it exceeds 12 hours, it will become easy to produce | generate a coloring component during a decomposition process.
The polymer decomposition method in the present invention is an interfacial reaction, and a polymer dissolved or swollen in an organic solvent containing at least one selected from the group consisting of an ether solvent, a ketone solvent, and a hydrocarbon solvent is a metal hydroxide aqueous solution. And is decomposed by contact at the interface. This reaction is irreversible, carbonate bond in polycarbonate, polyester bond in polyester, carbonate bond and ester bond in polyester carbonate, and aromatic diol such as BPEF, aliphatic diol such as ethylene glycol and dihydroxy compound metal salt, dicarboxylic acid Decomposes into acid metal salt, carbonate metal salt, etc.

<(2) Recovery process>
The recovery step is a step of recovering the crude monomer product represented by the formula (I) from the decomposition solution.
In the case of polyester carbonate derived from the monomer represented by the formula (I) and terephthalic acid, first, water is added to the decomposition solution after the decomposition reaction to dissolve the dicarboxylic acid (terephthalic acid) metal salt and carbonate metal salt. . The amount of water to be added is more than the amount that completely dissolves the solid, but if too much is added, the amount of waste liquid to be discharged increases and the cost increases, so the minimum amount that completely dissolves the metal salt is preferable. . Specifically, the amount of water added is preferably 1800 to 3000% by weight and more preferably 2200 to 2700% by weight with respect to the dicarboxylic acid metal salt.
Here, the decomposition solution containing the aqueous layer and the organic solvent layer can be cooled to precipitate the crude monomer product represented by the formula (I). Examples of the method for filtering the crude product of the monomer represented by the formula (I) obtained as a solid include a filter, a centrifuge, and a centrifugal sedimentation device. The liquid content after filtration by the centrifuge is preferably 25% by weight or less.

In addition, when there is a monomer represented by the formula (I) that does not dissolve after adding water to the decomposition solution, it is heated to 40 to 90 ° C. and completely dissolved, and an aqueous solution of an organic solvent phase and a metal salt in the reactor. It can be separated into two phases. These two phases are separated by a liquid-liquid separator such as a decanter. However, if the separation is insufficient in the liquid-liquid separator, the metal salt cannot be removed and affects the quality of the product. It is preferable to remove it as much as possible. As this method, a known method such as contact with a washing tower, separation with a stirrer, liquid-liquid separator, or centrifugal separator can be used.
The organic solvent phase contains impurities other than the monomer represented by the formula (I), for example, a polymer-derived dicarboxylate, carbonate, metal catalyst and the like. These impurities can be removed by repeating the washing several times until they are brought into contact with pure water and the conductivity of the aqueous phase is 50 μS / cm or less.
By cooling the obtained organic solvent phase, the monomer represented by the solid formula (I) can be precipitated. A preferred method for precipitating the monomer represented by the formula (I) is to dissolve the monomer represented by the formula (I) by heating to 40 to 90 ° C. in the presence of an organic solvent, and then to 30 ° C. or lower. This is a method of cooling and precipitating the monomer represented by the formula (I). According to this method, the monomer represented by the formula (I) that cannot be completely dissolved in the organic solvent phase is obtained as a slurry, and the monomer represented by the formula (I) can be obtained by filtering the slurry. it can.

The amount of the organic solvent is not less than the amount that the monomer represented by the formula (I) is completely dissolved during heating, but if it is too much, the proportion of the monomer represented by the formula (I) that does not precipitate while being dissolved during cooling. The amount of the monomer represented by the formula (I) is completely dissolved, so that the minimum amount is preferable. Specifically, the amount of the organic solvent to be added is preferably 410% by weight or less with respect to the monomer represented by the formula (I).
Examples of the method for filtering the monomer represented by the formula (I) obtained as a solid include a filter, a centrifuge, and a centrifugal sedimentation device. A centrifuge is preferable because the liquid content after filtration is low.

<(3) Purification step>
The purification step is a step for purifying the crude product of the monomer represented by the formula (I).
First, the solid product of the monomer represented by the formula (I) is transferred to a stirring vessel, and at least one selected from the group consisting of an ether solvent, a ketone solvent, a hydrocarbon solvent, and an alcohol solvent is added and stirred. By heating, the monomer represented by the formula (I) is completely dissolved. Specifically, the amount of the organic solvent to be added is preferably 250 to 1000% by weight, more preferably 260 to 350% by weight with respect to the monomer represented by the formula (I).
Next, it is preferable to add pure water to the organic phase and perform washing with stirring. Specifically, the amount of pure water added is preferably 20 parts by weight to 100 parts by weight, more preferably 40 parts by weight to 60 parts by weight with respect to the monomer represented by the formula (I). .

  In the organic phase, the inorganic impurities of the metal derived from the metal hydroxide used in the polymerization catalyst and decomposition step of the polymer other than the monomer represented by the formula (I) and the monomer represented by the formula (Ia), A monomer represented by the formula (Ib) is included. These impurities can be removed by contact with pure water and washing. The stirring is stopped and the mixture is allowed to stand to separate into two phases of an organic phase and an aqueous solution of a metal salt in a stirring tank. The two phases are separated by a liquid-liquid separator such as a decanter. However, if the separation is insufficient in the liquid-liquid separator, the metal salt cannot be removed and affects the product. The aqueous phase is preferably removed until the electric conductivity of the aqueous phase is 20 μS / cm or less. In particular, when the sodium content remains, the hue of the resin obtained by polymerization deteriorates. Sodium is 100 ppm or less, preferably 30 ppm or less, particularly preferably 10 ppm or less. As this method, a known method such as contact with a washing tower, separation with a stirrer, liquid-liquid separator, or centrifugal separator can be used.

By cooling the organic phase, the solid monomer represented by the formula (I) can be precipitated. A preferred method for precipitating the monomer represented by the formula (I) is to dissolve the monomer represented by the formula (I) by heating to 40 to 90 ° C. in the presence of an organic solvent, and then to 30 ° C. or lower. This is a method of cooling and precipitating the monomer represented by the formula (I). According to this method, the monomer represented by the formula (I) that cannot be completely dissolved in the organic phase is obtained as a slurry, and the purified crystal of the monomer represented by the formula (I) is obtained by filtering the slurry. be able to.
The obtained purified crystals of the monomer represented by the formula (I) may be further purified.

Examples of the organic solvent used for repurification include an organic solvent containing at least one selected from the group consisting of an ether solvent, a ketone solvent, a hydrocarbon solvent, and an alcohol solvent. Preferably, it is at least one solvent selected from the group consisting of toluene, xylene, tetrahydrofuran, dioxane, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, methanol, ethanol, 2-propanol, and 2-butanol. . More preferably, methanol, ethanol, 2-propanol, 2-butanol, etc. are mentioned, More preferably, it is methanol.
When a more polar solvent is used, impurities such as the monomer represented by the formula (Ia) and the monomer represented by the formula (Ib) can be easily removed, and hydrocarbons such as toluene and xylene can be removed. In the case of using a solvent, it is preferably used by mixing with a highly polar solvent.
An adsorbent may be used for the purpose of adsorbing impurities in the organic phase. Examples of the adsorbent include activated carbon, activated clay, and acid clay, and activated carbon is particularly preferable. The amount of the adsorbent used is preferably 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the monomer represented by the formula (I). If the amount used is less than 0.5 parts by weight, the effect of removing impurities cannot be obtained, and if it is more than 5.0 parts by weight, the cost increases, which is economically undesirable.

A specific re-purification method is as follows. A solid purified crystal of the monomer represented by formula (I) is transferred to a stirring tank, an alcohol-based organic solvent is added, and the mixture is heated while stirring, and represented by formula (I). The monomer is completely dissolved. The adsorbent is charged there and stirred. The organic solvent phase contains impurities (bisphenol fluorene, monophenol fluorene, etc.) other than the monomer represented by the formula (I), and coloring components. These impurities can be removed by performing an adsorbent treatment. After removing the adsorbent by filtration, the obtained organic phase is cooled to 30 ° C. or lower, so that the monomer represented by the solid formula (I) can be precipitated. The monomer represented by the formula (I) that cannot be completely dissolved in the organic phase is obtained as a slurry, and the monomer represented by the formula (I) can be obtained by filtering the slurry. The amount of the alcohol-based organic solvent is not less than the amount that the monomer represented by the formula (I) is completely dissolved during heating, but if it is too much, the monomer represented by the formula (I) that does not precipitate while being dissolved during cooling. Therefore, the minimum amount of the monomer in which the monomer represented by the formula (I) is completely dissolved is preferable.
Specifically, the amount of the alcohol-based organic solvent to be added is preferably 400 to 4000% by weight with respect to the monomer represented by the formula (I).

The present invention is a method for obtaining a monomer by decomposing a polymer. In order to recover a monomer having a good hue, a series of steps of (1) decomposition step, (2) recovery step, and (3) purification step are used. is necessary.
In the decomposition step, a specific organic solvent (at least one selected from the group consisting of an ether solvent, a ketone solvent and a hydrocarbon solvent) and a metal hydroxide (alkali) are used, and the alkali concentration has a specific range of 10 to 48. It is preferable to carry out the decomposition at a weight percentage of 25 to 95 ° C. and a decomposition time of 3 to 12 hours. Under these conditions, it is possible to suppress the by-product of impurities that cause coloring.
In the purification step, impurities that cause coloration are obtained by recrystallization using a specific solvent of the crude product (at least one selected from the group consisting of ether solvents, ketone solvents, hydrocarbon solvents, and alcohol solvents). As a result, a monomer having the desired purity and melted Hazen color number can be obtained.

The monomer represented by the formula (I) recovered by the method of the present invention can be reused in the production process of the polymer. As a method of re-use, it can be used as it is by a melt polymerization method.
The monomer represented by the formula (I) recovered by the method of the present invention preferably has a content of the monomer represented by the formula (Ia) of 0.2% or less, and is 0.15% or less. It is more preferable. A resin obtained using such a monomer is excellent in hue and is preferable.
Further, the recovered monomer represented by the formula (I) and a commercially available monomer represented by the formula (I) may be used together for the production of a polymer. The method of mixing the recovered monomer represented by the formula (I) and the commercially available monomer represented by the formula (I) may be any of solids, solids and liquids, and methods of mixing liquids. .

<Polycarbonate>
Polycarbonate can be produced using the recovered monomer represented by the formula (I). The polycarbonate preferably contains a unit represented by the following formula (II).

  Polycarbonate is a resin obtained by reacting a dihydroxy component containing at least BPEF with a carbonate component in the presence of a basic compound catalyst.

  The hydroxy component may contain other copolymer components other than BPEF. Other copolysynthesis includes 1,1′-biphenyl-4,4′-diol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) Ether, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 2,2-bis (4-hydroxyphenyl) propane 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) ) Hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis ( 4-hydroxy-3-methylphenyl) fluorene, α, ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane Aromatic diols such as 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol. In addition, aliphatic diols such as ethylene glycol, tricyclo [5.2.1.0 (2,6)] decane dimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol And cycloaliphatic diols such as pentacyclopentadecane dimethanol, cyclopentane-1,3-dimethanol, spiroglycol, isosorbide, and isomannide. These may be used alone or in combination of two or more. Among these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A: BPA) is particularly mentioned.

Examples of the carbonic acid diester include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and dinaphthyl carbonate. Among them, diphenyl carbonate is preferable. These aromatic carbonic acid diesters may be used alone or in combination of two or more.
The content of the unit represented by the formula (II) in the polycarbonate is preferably 30 mol% or more, more preferably 40 to 100 mol%, still more preferably 50 to 90 mol% of the total dihydroxy component. By setting the content of the unit represented by the formula (II) in the above range, a polycarbonate excellent in optical properties, moldability, and mechanical properties is obtained.
The molecular weight of the polycarbonate is preferably 7,000 to 100,000, more preferably 8,000 to 30,000, and still more preferably 8,000 to 14,000. The molecular weight is measured by the solution viscosity method.
Polycarbonate can be produced by an ordinary polycarbonate production method. For example, a reaction between diol and phosgene or a transesterification reaction between diol and bisaryl carbonate is preferably employed.

In the reaction of diol and phosgene, the reaction is performed in the presence of an acid binder and a solvent in a non-aqueous system. Examples of the acid binder include pyridine, dimethylaminopyridine, tertiary amine and the like. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is desirable to use a terminal terminator such as phenol or p-tert-butylphenol as the molecular weight regulator. The reaction temperature is usually 0 to 40 ° C., and the reaction time is preferably several minutes to 5 hours.
In the transesterification reaction, a diol and bisaryl carbonate are mixed in the presence of an inert gas, and in the presence of a mixed catalyst comprising an alkali metal compound catalyst or an alkaline earth metal compound or both, it is usually 120 to 350 under reduced pressure. The reaction is carried out at ° C, preferably 150-300 ° C. The degree of vacuum is changed stepwise, and finally the alcohol produced at 133 Pa or less is distilled out of the system. The reaction time is usually about 1 to 4 hours. However, when the polymerization temperature is higher than 350 ° C., phenyl vinyl ether and acetaldehyde are easily produced as by-products, and when the polymerization temperature is lower than 120 ° C., the reaction does not proceed, which is not preferable.
As a polymerization catalyst, an alkali metal compound or an alkaline earth metal compound may be used as a main component, and a nitrogen-containing basic compound may be used as a subsidiary component if necessary.

  The alkali metal compound used as the catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate. Sodium stearate, potassium stearate, lithium stearate, sodium salt, potassium salt, lithium salt of bisphenol A, sodium benzoate, potassium benzoate, lithium benzoate and the like. Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate , Calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.

Nitrogen-containing basic compounds used as promoters include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine Etc.
These catalysts may be used alone or in combination of two or more, and the amount of these polymerization catalysts used is in a ratio of 10 ⁻⁹ to 10 ⁻³ mol with respect to 1 mol of the total diol component. . However, when the catalyst amount is more than the above, phenyl vinyl ether and acetaldehyde are easily produced as by-products, and the hue is deteriorated, which is not preferable. Moreover, you may add antioxidant, a heat stabilizer, etc. for a hue improvement.

After completion of the polymerization reaction, the polycarbonate may have its catalyst removed or deactivated in order to maintain thermal stability and hydrolysis stability. For alkali metal compounds or alkaline earth metal compounds, generally, a method of deactivating a catalyst by adding a known acidic substance is preferably carried out. Specific examples of these deactivating substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, butyl p-toluenesulfonate, and hexyl p-toluenesulfonate. Aromatic sulfonic acid esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite Phosphites such as di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, phosphorus Phosphate esters such as dibutyl acid, dioctyl phosphate, monooctyl phosphate, diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, etc. Phosphonic acids, phosphonic esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, tetrabutylphosphonium dodecylbenzenesulfonate, etc. Aromatic sulfonates, stearic acid chloride, benzoyl chloride, organic halides such as p-toluenesulfonic acid chloride, alkylsulfuric acid such as dimethylsulfuric acid, and organic halides such as benzyl chloride are preferably used. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient, which is not preferable. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, since heat resistance falls and it becomes easy to color a molded object, it is unpreferable.
After catalyst deactivation, a step of devolatilizing and removing low-boiling compounds in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C may be provided.

<Polyester>
Polyester can be produced using the recovered monomer represented by the formula (I). The polyester preferably contains a unit represented by the following formula (III).

In the formula, Y is a unit derived from a dicarboxylic acid component such as a phenylene group, a naphthalenediyl group, or an alkylene group. Polyester is a resin obtained by reacting a diol component containing at least BPEF with a dicarboxylic acid component containing dicarboxylic acid and / or a reactive derivative thereof.
Each of the diol component and the dicarboxylic acid component may be a single component, or each may contain two or more compounds.

  Other diol compounds that can be used with BPEF include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol (1,4-butanediol), hexanediol, neopentyl glycol, and octanediol. , Straight chain or branched C2-12 alkylene glycol such as decanediol, tricyclo [5.2.1.0 (2,6)] decane dimethanol, cyclohexane-1,4-dimethanol, decalin- Examples include alicyclic diols such as 2,6-dimethanol, norbornane dimethanol, pentacyclopentadecane dimethanol, cyclopentane-1,3-dimethanol, spiroglycol, isosorbide, and isomannide. Further, (poly) oxyalkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol and the like can be mentioned. These diols can be used singly or in combination of two or more.

A preferred example of the diol used in combination with BPEF is a linear or branched C2-10 alkylene glycol, more preferably a linear or branched C2-6 alkylene glycol, and still more preferably ethylene glycol. , Propylene glycol, tetramethylene glycol (1,4-butanediol) and other linear or branched C2-4 alkylene glycols. A particularly preferred diol component is ethylene glycol.
Diols such as ethylene glycol other than BPEF are useful as copolymerization components for enhancing polymerization reactivity and imparting flexibility to the resin. In addition, since a refractive index, heat resistance, and water absorption may fall by introduction | transduction of a copolymerization component, generally the smaller the copolymerization ratio is better at those points.

  Examples of the dicarboxylic acid include alkanedicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. Moreover, alkene dicarboxylic acids, such as maleic acid and fumaric acid, are mentioned. Moreover, cycloalkane dicarboxylic acid, such as cyclohexane dicarboxylic acid, is mentioned. Further, di- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, and adamantane dicarboxylic acid can be used. Also included are terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, etc.) biphenyl dicarboxylic acid (2,2′-biphenyldicarboxylic acid, etc.). It is done.

Furthermore, acid anhydrides such as hexahydrophthalic anhydride and tetrahydrophthalic anhydride are listed. Further, lower (C1-4) alkyl esters such as dimethyl ester and diethyl ester can be mentioned. Moreover, derivatives capable of forming an ester such as acid halides corresponding to dicarboxylic acids are listed.
These dicarboxylic acids may be used individually by 1 type, or may be used in combination of 2 or more type. Of these, cyclohexanedicarboxylic acid and terephthalic acid are preferable because they are inexpensive and easily available industrially.

In the polyester, the content of the unit represented by the formula (III) is 60 mol% or more, preferably 60 to 100 mol%, more preferably 60 to 90 mol%, based on all units. By setting the ratio of the unit represented by the formula (II) within the above range, the polyester is excellent in optical properties such as refractive index. In terms of strength, the higher the BPEF content, the higher the elastic modulus and the better. On the other hand, if it is too high, the tensile elongation decreases, so the content of the unit represented by the formula (III) is 90 mol% or less. Is preferred. Therefore, the content of the unit represented by the formula (III) is more preferably 90 to 60 mol%.
In the polyester, the content of repeating units derived from BPEF is 30 mol% or more, preferably 30 to 50 mol%, more preferably 30 to 45 mol%, based on all units. By setting the ratio of the repeating unit derived from BPEF within the above range, the polyester has excellent optical properties. In terms of strength, the higher the content of BPEF, the higher the elastic modulus and the better. However, polyesters must have a composition ratio of diol component and dicarboxylic acid component and / or dicarboxylic acid component containing these reactive derivatives to be 50:50. Since the molecular weight is not sufficient, the content of the structural unit derived from BPEF represented by the following formula is more preferably 30 to 50 mol%.

The molecular weight of the polyester is preferably 7,000 to 100,000, more preferably 8,000 to 30,000, and still more preferably 8,000 to 14,000. The molecular weight is measured by the solution viscosity method.
Polyester is a dicarboxylic acid component (dicarboxylic acid and / or ester-forming dicarboxylic acid derivative) and a diol component containing BPEF, such as a transesterification method, a melt polymerization method such as a direct polymerization method, a solution polymerization method, an interfacial polymerization method, etc. It can be obtained by reacting according to various methods. Among these, a melt polymerization method using no reaction solvent is preferable.

The transesterification method, which is one of the melt polymerization methods, is a method in which a polyester is obtained by reacting a dicarboxylic acid ester with a diol compound in the presence of a catalyst and transesterifying while distilling off the generated alcohol. Used in the synthesis of polyester.
As a catalyst for the transesterification reaction, it is desirable to use at least one metal compound. Examples of the metal element contained in the preferred metal compound include sodium, potassium, calcium, titanium, lithium, magnesium, manganese, zinc, tin, and cobalt. Among these, calcium and manganese compounds are preferable because of high reactivity and good color tone of the resulting resin. The amount of the transesterification catalyst used is ^10-9 to ^10-3 mol per mol of the diol compound.

The direct polymerization method is a method in which a polyester is obtained by performing a dehydration reaction between a dicarboxylic acid and a diol compound to form an ester compound, and then performing an ester exchange reaction while distilling off excess diol compound under reduced pressure. It is. The direct polymerization method has the advantage that no distillate of alcohol is used unlike the transesterification method, and an inexpensive dicarboxylic acid can be used as a raw material.
As a catalyst for the polymerization reaction in carrying out these melt polymerization methods, it is preferable to use at least one metal compound. Preferred metal elements include titanium, germanium, antimony, aluminum and the like. Among these, titanium and germanium compounds are particularly preferable for optical resins because of their high reactivity and excellent transparency and color tone of the resulting resin. The usage-amount of a polymerization catalyst is used in the ratio of 10 ^<-9 > ^-10 <^-3> mol with respect to the produced | generated polyester.

Further, when the polyester of the present invention is produced, it is preferable to use an equimolar or more phosphorus compound after the transesterification reaction in order to facilitate the polymerization reaction. Examples of phosphorus compounds include phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and the like. Among these, trimethyl phosphate is particularly preferable. The usage-amount of a phosphorus compound is used in the ratio of 10 ^<-9 > ^-10 <^-3> mol with respect to the polyester to produce | generate.

In the transesterification reaction, the copolymer components used as needed are charged into a reaction vessel equipped with a heating device, a stirrer and a distillation pipe, and the reaction catalyst is added and the temperature is increased while stirring in an atmospheric pressure inert gas atmosphere. Then, the reaction is allowed to proceed while distilling off by-products such as methanol produced by the reaction. The reaction temperature is 150 ° C. to 270 ° C., preferably 160 ° C. to 260 ° C., and the reaction time is usually 3 to 7 hours.
The polymerization reaction is carried out, for example, using a product after completion of the transesterification reaction in a reaction vessel equipped with a heating device, a stirrer, a distilling tube, and a vacuum addition device. If these conditions are satisfied, the polymerization reaction can be continued in the same reaction vessel used in the transesterification reaction.

The polymerization reaction is performed, for example, after adding a catalyst to the reaction vessel containing the product after completion of the transesterification reaction, while gradually raising the temperature and reducing the pressure in the reaction vessel. The pressure in the tank is finally reduced from atmospheric pressure to 0.4 kPa or less, preferably 0.2 kPa or less. The temperature in the tank is raised from 220 to 230 ° C., and finally raised to 250 to 350 ° C., preferably 260 to 320 ° C. After reaching a predetermined torque, the reaction product is extruded from the bottom of the tank. to recover. In a usual case, the reaction product is extruded into water as a strand, cooled and then cut to obtain a polyester in pellet form. However, when the temperature of the polymerization reaction is 320 ° C. or higher, by-products are easily generated.
After completion of the polymerization reaction, a step of devolatilizing and removing the low boiling point compound in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C. may be provided.

<Polyester carbonate>
Polyester carbonate can be produced using the recovered monomer represented by the formula (I). The polyester carbonate preferably contains units represented by the following formulas (II) and (III). In formula (III), Y is a unit derived from a dicarboxylic acid component such as a phenylene group, a naphthalenediyl group, or an alkylene group.

  The polyester carbonate is preferably a resin containing a diol component containing at least BPEF, a dicarboxylic acid and a carbonate ester component, and a mixed catalyst comprising a basic compound catalyst, a transesterification catalyst, or both. Each of the dihydroxy component, the dicarboxylic acid component, and the carbonic acid diester component may be a single component or may contain two or more types of compounds.

  Examples of the diol component that can be used with BPEF include aliphatic diols such as ethylene glycol. Also tricyclo [5.2.1.0 (2,6)] decane dimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecane dimethanol, cyclopentane. Examples include alicyclic diols such as -1,3-dimethanol and spiroglycol. In addition, 1,1′-biphenyl-4,4′-diol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) ether, bis (4 -Hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 2,2-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- Bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexaful Ropropane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy) -3-methylphenyl) fluorene, α, ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, 4, Examples include aromatic diols such as 4 ′-[1,3-phenylenebis (1-methylethylidene) hydroxyphenyl) -1-phenylethane and bisphenol A. You may use these individually or in combination of 2 or more types.

  Dicarboxylic acid compounds include terephthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, ethylmalonic acid and other aliphatic dicarboxylic acids, isophthalic acid, tert-butylisophthalic acid And monocyclic aromatic dicarboxylic acids such as acids. Moreover, polycyclic aromatic dicarboxylic acids, such as naphthalene dicarboxylic acid, anthracene dicarboxylic acid, and phenanthrene dicarboxylic acid, are mentioned. Moreover, biphenyl dicarboxylic acid, such as 2,2'-biphenyl dicarboxylic acid, is mentioned. Moreover, alicyclic dicarboxylic acids, such as 1, 4- cyclodicarboxylic acid and 2, 6-decalin dicarboxylic acid, are mentioned. You may use these individually or in combination of 2 or more types. Of these, terephthalic acid is preferred. In addition, acid chlorides and esters are used as these derivatives.

Examples of the carbonate precursor used in the production of the polyester carbonate of the present invention include phosgene, diphenyl carbonate, bischloroformate of the above dihydric phenols, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl. Examples thereof include carbonate and dinaphthyl carbonate. Of these, diphenyl carbonate is preferred.
In the polyester carbonate, the total of the units represented by the formulas (II) and (III) is contained in a proportion of 30 mol% or more, preferably 40 to 100 mol%, more preferably 50 to 90 mol% in all units. . By setting the total of the units represented by the formulas (II) and (III) within the above range, a polyester carbonate having excellent optical properties such as a refractive index is obtained.
From the above, it is more preferable that the total content of the units represented by the formulas (II) and (III) is 50 to 90 mol% with respect to all units contained in the resin.

The proportion of the unit represented by the formula (II) in the polyester carbonate is preferably 50 to 95 mol%, more preferably 60 to the total amount of the units represented by the formulas (II) and (III). 90 mol%, more preferably 70-90 mol%.
In the polyester carbonate, the content of repeating units derived from BPEF represented by the following formula is 30 mol% or more, preferably 40 to 100 mol%, more preferably 50 to 90 mol%, based on all units. In terms of optical properties, the higher the content of BPEF, the higher the refractive index, which is preferable. On the other hand, if the content is too high, the tensile elongation decreases, so the content of BPEF is preferably 90 mol% or less.

  The molecular weight of the polyester carbonate is preferably 7,000 to 100,000, more preferably 8,000 to 30,000, and still more preferably 8,000 to 14,000. The molecular weight is measured by the solution viscosity method.

As a method for producing polyester carbonate, a method used for producing ordinary polyester carbonate is arbitrarily adopted. For example, a reaction between a diol and a dicarboxylic acid or dicarboxylic acid chloride and phosgene, or a transesterification reaction between a diol, a dicarboxylic acid, and a bisaryl carbonate is preferably employed.
In the reaction of diol, dicarboxylic acid or its acid chloride with phosgene, the reaction is performed in a non-aqueous system in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine, dimethylaminopyridine, tertiary amine and the like. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is desirable to use a terminal terminator such as phenol or p-tert-butylphenol as the molecular weight regulator. The reaction temperature is usually 0 to 40 ° C., and the reaction time is preferably several minutes to 5 hours.

In the transesterification reaction, a diol and a dicarboxylic acid or a diester thereof and a bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is usually performed at 120 to 350 ° C., preferably 150 to 300 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the alcohols produced at 1 mmHg or less are distilled out of the system. The reaction time is usually about 1 to 4 hours. However, when the polymerization temperature is 350 ° C. or higher, phenyl vinyl ether and acetaldehyde are easily produced as by-products, which is not preferable.
In the transesterification reaction, a polymerization catalyst can be used to promote the reaction. As such a polymerization catalyst, an alkali metal compound, an alkaline earth metal compound or a heavy metal compound may be used as a main component, and a nitrogen-containing basic compound may be used as a subsidiary component if necessary.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate. , Potassium stearate, lithium stearate, sodium salt of bisphenol A, potassium salt, lithium salt, sodium benzoate, potassium benzoate, lithium benzoate and the like. Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate , Calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.

Examples of the nitrogen-containing basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine and the like.
Other transesterification catalysts include zinc, tin, zirconium, lead, titanium, germanium, antimony, osmium, and aluminum salts, such as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II ), Tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, acetic acid Lead (IV), titanium tetrabutoxide (IV), etc. are used.
These catalysts may be used alone or in combination of two or more, and the amount of these polymerization catalysts used is 10-9 to 10-3 moles per mole of the total of diol and dicarboxylic acid. Used. These may be used alone or in combination of two or more. In the transesterification reaction, a diaryl carbonate having an electron-withdrawing substituent may be added at a later stage or after completion of the polycondensation reaction in order to reduce the hydroxy end group. Furthermore, an antioxidant or a heat stabilizer may be added to improve the hue.

In the polyester carbonate of the present embodiment, the catalyst may be removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolysis stability. For alkali metal compounds or alkaline earth metal compounds, generally, a method of deactivating a catalyst by adding a known acidic substance is preferably carried out. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate. Esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, phosphorous acid Phosphorous esters such as di-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphoric acid Phosphate esters such as dioctyl and monooctyl phosphate, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid , Phosphonic esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, and aromatics such as tetrabutylphosphonium dodecylbenzenesulfonate Sulfonates, stearic acid chloride, benzoyl chloride, organic halides such as p-toluenesulfonic acid chloride, alkylsulfuric acid such as dimethyl sulfate, and organic halides such as benzyl chloride are preferably used. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient, which is not preferable. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, since heat resistance falls and it becomes easy to color a molded object, it is unpreferable.

After catalyst deactivation, a step of devolatilizing and removing low-boiling compounds in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C may be provided.
Polymers obtained by the production method of the present invention include heat stabilizers, antioxidants, mold release agents (fatty acid esters, etc.), lubricants, plasticizers, antistatic agents, whitening agents, ultraviolet absorbers, weathering agents, antibacterial agents Agents, pigments, dyes, fillers, reinforcing agents, polymers such as other resins and rubbers, and modifiers such as flame retardants can be appropriately added and used.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Unless indicated otherwise, parts represent parts by weight. The evaluation was performed by the following method.

(1) BPEF purity, impurity amount:
Using a mixture of eluent methanol / water on a column of Kromasil 100-5-C18 4.6 × 150 mm, column temperature 40 ° C., detector 254 nm, 60% methanol water / methanol (100/0) → (gradient ) → 60% methanol water / methanol (12/88 after 20 minutes) → 60% methanol water / methanol (13/87 after 30 minutes). The measurement was performed by dissolving 10 mg of the monomer in 10 ml of methanol and then filtering with a PTFE filter having a pore size of 0.2 μm. The impurity was defined as the content of the detected LC peak area.
(2) BPEF hue (melted Hazen color number)
15 g of purified crystals are weighed in a test tube with an inner diameter of 25 mm, heated and dissolved at 270 ° C. for 30 minutes in a block heater in the atmosphere, and then diluted with Wako Pure Chemicals chromaticity standard solution (1000) according to JISK0071-1. The prepared standard colorimetric solution was compared with the naked eye to obtain a Hazen color number.
(3) Pellet b value The polymer pellet (a pellet shape is 4 mm in length and a diameter of about 1-3 mm) was put into the glass cell, and the pellet hue was measured using Nippon Denshoku color difference meter SE-2000.

[Example 1]
(Disassembly process)
Carbonate unit (BPEF derived from 221 parts of sodium hydroxide, 410 parts of ion-exchanged water and 9,9-bis (4- (2-hydroxyphenyl) fluorene) in a glass reactor equipped with a stirrer, thermometer and cooling pipe Derivative) A polymer 450 mainly composed of polyester carbonate (PEC) of ester unit (DMT derivative) (II) (molar ratio (I) :( II) = 82: 18) derived from (I) and dimethyl terephthalate 576 parts of toluene and 144 parts of cyclohexanone were added thereto, and the temperature was raised to 40 ° C. and stirred for 4 hours.

(Recovery process)
To the resulting slurry-like decomposition solution, 1238 parts of ion-exchanged water was added to dissolve the solid, and the lower aqueous layer was separated. The remaining organic layer was washed with ion-exchanged water at 65 ° C. or higher until the conductivity of the washing water became 20 μS / cm or less. The obtained solution was cooled to 20 ° C. or lower with stirring to precipitate crystals. The precipitated crystals were collected by filtration to obtain 478 parts of white wet crystals (purity 98.8%), which was a crude product of BPEF.

(Purification process)
478 parts of the obtained crude product, 1080 parts of toluene and 120 parts of 2-butanone were charged into a glass reactor equipped with a stirrer, a thermometer and a condenser, and heated to 75 ° C. with stirring to completely dissolve the solid. . The solution was washed with ion-exchanged water at 65 ° C. or higher until the washing water conductivity was 10 μS / cm or lower. The organic layer was advantech No. After removing insolubles using 5C filter paper, the resulting solution was cooled to 20 ° C. with stirring to precipitate crystals. The precipitated crystals were taken out by filtration and dried under reduced pressure to obtain 325 parts of white crystals (yield 78.4%, purity 99.5%, molten Hazen color number 50) as purified crystals of BPEF.
The content of 9- (4- (2-hydroxyethoxy) phenyl) -9- (4-hydroxyphenyl) fluorene represented by formula (Ia) (single terminal phenol in Table 1) is 0.12%. Met.

[Example 2]
In the decomposition step, the charge amount of ion exchange water for decomposition reaction is 664 parts, the charge amount of toluene is 360 parts, the charge amount of cyclohexanone is 90 parts, the reaction temperature is 50 ° C., the reaction time is 11 hours, and in the recovery step Except that the amount of ion-exchanged water for dissolution was changed to 984 parts, the same operation as in Example 1 was performed, and 322 parts of white crystals (yield 77.7%, purity 99.5%, molten Hazen color number 60) )

[Example 3]
In the decomposition step, exactly the same as Example 2 except that the amount of ion exchange water for decomposition reaction was 664 parts, the reaction temperature was 50 ° C., the reaction time was 11 hours, and the amount of ion exchange water for dissolution was 984 parts. Thus, 322 parts of white crystals (yield 75.9%, purity 99.6%, melted Hazen color number 60) were obtained.

[Example 4]
Except that cyclohexanone was used instead of 2-butanone in the purification step, the same operation as in Example 3 was performed, and 303 parts of white crystals (yield 73.1%, purity 99.4%, molten Hazen color number 70). )

[Example 5]
(Purification process)
478 parts of the crude product obtained in exactly the same manner as in Example 1 and 4050 parts of methanol were charged into a glass reactor equipped with a stirrer, thermometer and condenser, and heated to 65 ° C. with stirring to obtain a solid. It was completely dissolved. The solution was heated to 60 ° C. using Advantech No. After removing insolubles using 5C filter paper, the resulting solution was cooled to 20 ° C. with stirring to precipitate crystals. The precipitated crystals were taken out by filtration and then dried under reduced pressure to obtain 234 parts of white crystals (yield 56.6%, purity 99.5%, molten Hazen color number 60) as purified crystals of BPEF.

[Example 6]
In the decomposition step, the same operation as in Example 2 was performed except that 2-butanone was used instead of cyclohexanone, and 320 parts of white crystals (yield 77.2%, purity 99.5%, molten Hazen color number 70) were obtained. Obtained.

[Example 7]
In the decomposition step, the same operation as in Example 2 was carried out except that the amount of toluene charged was 2579 parts and cyclohexanone was not used, and 256 parts of white crystals (yield 61.9%, purity 99.2%, molten Hazen) A color number of 70) was obtained.

[Example 8]
The same operation as in Example 1 was performed except that the amount of decomposition ion-exchanged water for decomposition reaction was 239 parts in the decomposition step, and the amount of ion-exchanged water for dissolution was 1409 parts in the recovery step, and 289 parts of white crystals (Yield 69.9%, purity 99.3%, molten Hazen color number 70).

[Example 9]
In the decomposition step, 221 parts by weight of sodium hydroxide is added to 365 parts by weight of potassium hydroxide, the amount of ion exchange water for decomposition reaction is 664 parts, the reaction time is 6 hours, and in the recovery step, ion exchange water for dissolution is charged. Except for changing the amount to 450 parts, the same operation as in Example 1 was carried out to obtain 325 parts of white crystals (yield 78.4%, purity 99.5%, molten Hazen color number 50).

[Example 10]
(Purification process)
325 parts of recrystallized white crystals obtained in exactly the same manner as in Example 1, 1350 parts of methanol and 150 parts of 2-butanone were charged into a glass reactor equipped with a stirrer, thermometer and cooling tube while stirring. The temperature was raised to 65 ° C. to completely dissolve the solid. The solution was treated with activated carbon at 60 ° C., and cooled to 20 ° C. or lower with stirring after the activated carbon filtration to precipitate crystals. The precipitated crystals were taken out by filtration and dried under reduced pressure to obtain 229 parts of white crystals (yield 55.3%, purity 99.6%, molten Hazen color number 25) as repurified crystals of BPEF.

[Example 11]
In the decomposition step, carbonate units derived from BPEF (BPEF derivative) (I) and ester unit components derived from dimethyl terephthalate (DMT derivative) (II) ((I) :( II) = 82: 18) Polyester carbonate is derived from a carbonate unit (BPEF derivative) (I) derived from BPEF and 2,2-bis (4-hydroxyphenyl) propane represented by the following formula (IV) in place of the main polymer. The same procedure as in Example 3 was performed except that the polycarbonate of the carbonate unit (BPA derivative) ((I) :( III) = 80: 20) was used, and 273 parts of white crystals (purified crystals of BPEF) were obtained. The ratio was 75.0%, the purity was 99.5%, and the melted Hazen color number was 70).

[Comparative Example 1]
In the decomposition step, except that 1400 parts of dichloromethane was used instead of toluene and cyclohexanone, and the reaction time was 40 hours, the same operation as in Example 2 was performed, and 289 parts of white crystals (yield 69.8%, purity 98) 8% and a melted Hazen color number of 80).

[Comparative Example 2]
Crude crystals obtained by performing exactly the same operations as in the decomposition step and recovery step of Example 2 were dried under reduced pressure to give 349 parts of white crystals (yield 84.3%, purity 98.3%, melted Hazen color number). 80) was obtained.

[Example 12] (Polycarbonate)
BPEF 140.32 parts by weight of the recrystallized product of Example 1 in Table 1, 18.27 parts by weight of 2,2-bis (4-hydroxyphenyl) propane (BPA), diphenyl carbonate (hereinafter abbreviated as “DPC”) 87.80 parts by weight and sodium hydrogen carbonate 5.0 × 10 ⁻⁴ parts by weight are placed in a reactor equipped with a stirrer and a distillation apparatus, and after substituting with nitrogen three times, under a nitrogen atmosphere of 101 KPa. Heated to 215 ° C. and stirred for 20 minutes. After complete dissolution, it was adjusted to 20 KPa over 15 minutes, and kept at 215 ° C. and 20 KPa for 20 minutes to conduct a transesterification reaction. Further, the temperature was raised to 240 ° C. at a rate of 37.5 ° C./hr, and held at 240 ° C. and 16 KPa for 10 minutes. Then, it adjusted to 1.3 KPa over 10 minutes, and hold | maintained at 240 degreeC and 1.3 KPa for 10 minutes. Furthermore, it was made 130 Pa or less over 40 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 240 ° C. and 130 Pa or less. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced resin was extracted while pelletizing. The b value of the pellet was 3.2.

[Example 13] (Polyester carbonate)
BPEF 140.32 parts by weight, DMT 15.54 parts by weight, DPC 54.84 parts by weight, titanium tetrabutoxide 13.6 × 10 ⁻³ parts by weight of the recrystallized product of Example 1 in Table 1 were equipped with a stirrer and a distillation apparatus. The mixture was placed in a reaction kettle, heated to 180 ° C. under a nitrogen atmosphere, and stirred for 20 minutes. Thereafter, the degree of vacuum was adjusted to 20 KPa over 20 minutes, the temperature was raised to 250 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was performed. Thereafter, while maintaining the temperature at 250 ° C., the pressure was reduced to 130 Pa or less over 120 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 250 ° C. and 130 Pa or less. Thereafter, the produced resin was extracted while pelletizing. The pellet had a b value of 4.5.

[Reference Example] (Polyester carbonate)
BPEF (commercially available from Honshu Chemical Industry, purity 99.5%, molten Hazen color number 40)) 140.00 parts by weight, DMT 15.54 parts by weight, DPC 54.84 parts by weight, titanium tetrabutoxide 13.6 × 10 ^{− 3} parts by weight was put into a reaction kettle equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under a nitrogen atmosphere, and stirred for 20 minutes. Thereafter, the degree of vacuum was adjusted to 20 KPa over 20 minutes, the temperature was raised to 250 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was performed. Thereafter, while maintaining the temperature at 250 ° C., the pressure was reduced to 130 Pa or less over 120 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 250 ° C. and 130 Pa or less. Thereafter, the produced resin was extracted while pelletizing. The b value of the pellet was 4.3.

[Comparative Example 3] (Polyester carbonate)
BPEF 140.00 parts by weight, DMT 15.54 parts by weight, DPC 54.84 parts by weight, titanium tetrabutoxide 13.6 × 10 ⁻³ parts by weight of the recrystallized product of Comparative Example 1 in Table 1 were equipped with a stirrer and a distillation apparatus. The mixture was placed in a reaction kettle, heated to 180 ° C. under a nitrogen atmosphere, and stirred for 20 minutes. Thereafter, the degree of vacuum was adjusted to 20 KPa over 20 minutes, the temperature was raised to 250 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was performed. Thereafter, while maintaining the temperature at 250 ° C., the pressure was reduced to 130 Pa or less over 120 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 250 ° C. and 130 Pa or less. Thereafter, the produced resin was extracted while pelletizing. The pellet had a b value of 14.5 and was colored tan.
In the resins of Examples 12 and 13, there are few BPEF impurities in the resin, the hue after polymerization is extremely good, and a resin having a b value equivalent to that of the reference example using a commercially available BPEF is obtained. On the other hand, Comparative Example 3 is inferior in the color after polymerization due to many impurities of 9- (4- (2-hydroxyethoxy) phenyl) -9- (4-hydroxyphenyl) fluorene in the resin.

  According to the production method of the present invention, a monomer having a good hue that can be used as a polymer raw material can be obtained. Moreover, the quality of the polymer obtained using this monomer is comparable to the quality of the polymer produced using a commercially available monomer. Therefore, the polymer is useful as an optical member such as various optical lenses such as a camera lens, a projector lens, and a pickup lens, an optical disc, an optical film, a plastic substrate, an optical card liquid crystal panel, a headlamp lens, and an OPC binder.

Claims (18)

A method for producing a monomer represented by the following formula (I) by decomposing a polymer containing a monomer residue represented by the following formula (1) with an aqueous metal hydroxide solution,

(In Formula (I), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. X is an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, n and m are each independently an integer of 1 to 5 .)
(1) A step of decomposing a polymer by mixing an organic solvent containing at least one selected from the group consisting of an ether solvent, a ketone solvent and a hydrocarbon solvent, a polymer and a metal hydroxide aqueous solution to obtain a decomposition solution containing a monomer (Decomposition process),
(2) a step of recovering a crude monomer product from the decomposition solution (recovery step), and (3) a step of purifying the crude monomer product (purification step),
The manufacturing method of the said monomer containing.   The production method according to claim 1, wherein the polymer is polycarbonate, polyester or polyester carbonate.   The production method according to claim 1, wherein the monomer is 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.   The production method according to claim 1, wherein the metal hydroxide is sodium hydroxide and / or potassium hydroxide.   The production method according to claim 1, wherein the organic solvent contains 50% by weight or more of at least one selected from the group consisting of an ether solvent, a ketone solvent and a hydrocarbon solvent.   The production method according to claim 1, wherein the organic solvent is at least one solvent selected from the group consisting of toluene, xylene, tetrahydrofuran, dioxane, acetone, 2-butanone, 4-methyl-2-pentanone and cyclohexanone.   The method according to claim 1, wherein the decomposition temperature in the decomposition step is 25 to 90 ° C.   The method according to claim 1, wherein the concentration of the metal hydroxide aqueous solution in the decomposition step is 15 to 48% by weight.   The method according to claim 1, wherein the recovery step includes a step of cooling the decomposition solution and recovering the precipitated monomer crude product.   The method according to claim 1, wherein the recovery step is a step of recovering a crude monomer product from the organic solvent layer after separating the aqueous phase and the organic solvent phase from the decomposition solution.   The method according to claim 10, wherein the recovery step includes a step of washing the separated organic solvent layer with water.   The purification step includes a recrystallization step of dissolving the crude monomer product in a recrystallization solvent containing at least one selected from the group consisting of an ether solvent, a ketone solvent, a hydrocarbon solvent, and an alcohol solvent, and then depositing the monomer. The manufacturing method according to claim 1.   The recrystallization solvent is at least one solvent selected from the group consisting of toluene, xylene, tetrahydrofuran, dioxane, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, methanol, ethanol, 2-propanol, and 2-butanol. The manufacturing method according to claim 12.   The manufacturing method of Claim 12 including the process of washing an organic-solvent layer with water before a recrystallization process.   The monomer is 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, and 9- (4- (2-hydroxyethoxy) phenyl) -9- (4-hydroxyphenyl) fluorene in the monomer The production method according to claim 1, wherein the content is 0.2% or less.   A polycarbonate, polyester or polyester carbonate polymerized using the monomer according to claim 15 as a raw material.   A lens, sheet or film obtained from the polymer of claim 16.   9,9-bis (4- (2-hydroxyethoxy) phenyl) having a content of 9- (4- (2-hydroxyethoxy) phenyl) -9- (4-hydroxyphenyl) fluorene of 0.2% or less Fluorene.