JP2008115139A - Method for continuous production of 9,9-bis(4-hydroxyphenyl)fluorenes by using clathrate crystal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a high-quality product by making the production process continuous. <P>SOLUTION: The production process contains a reaction step to form a 9,9-bis(4-hydroxyphenyl)fluorenes, a dehydration step to dehydrate the reaction product obtained by the reaction step, a concentration step to concentrate the 9,9-bis(4-hydroxyphenyl)fluorenes, a crystallization step to crystallize a clathrate compound from a mixture of a solvent and the concentrated liquid, a crystallized product separation step to separate the slurry, the mother liquor and the washing liquid, a solvent removing step to remove the solvent from the slurry containing the clathrate compound obtained by the crystallized product separation step, a solvent purifying step to purify at least a part of the liquid containing the solvent obtained by the solvent removing step, the mother liquor obtained by the crystallized product separation step and the washing liquid, and a phenols purifying step to purify at least a part of the liquid obtained by the solvent purifying step. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for continuously producing fluorene derivatives, particularly 9,9-bis (4-hydroxyphenyl) fluorenes useful as raw materials for optical lenses, films, optical fibers, optical disks, heat-resistant resins, engineering plastics and the like.

In recent years, there has been a strong demand for materials having higher heat resistance, transparency, and higher refractive index than conventional products in polymers (for example, polycarbonate resins, epoxy resins, polyester resins, etc.) using bisphenols as raw materials. Yes. 9,9-bis (4-hydroxyphenyl) fluorenes, which are a kind of fluorene derivatives, are promising as polymer raw materials having excellent optical properties such as high refractive index, low birefringence, transparency and heat resistance, and are used for automobiles. Headlamp lenses, CDs, CD-ROM pickup lenses, Fresnel lenses, fθ lenses for laser printers, optical lenses such as camera lenses, projection lenses for rear projection televisions, retardation films, films such as diffusion films, plastic optical fibers, optical disk substrates It is expected as a raw material.
Examples of 9,9-bis (4-hydroxyphenyl) fluorenes include 9,9-bis (4-hydroxyphenyl) fluorene; 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (3-hydroxy-6-methylphenyl) fluorene, 9,9-bis (2-hydroxy-4-methylphenyl) fluorene, 9 9,9-bis (alkylhydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-2-methylphenyl) fluorene; 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (dialkylhydroxyl) such as 9-bis (4-hydroxy-3,5-di-tert-butylphenyl) fluorene Phenyl) fluorene; 9,9-bis (cycloalkylhydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene; 9,9-bis (4-hydroxy-3-phenylphenyl) And 9,9-bis (arylhydroxyphenyl) fluorene such as fluorene.
As a method for producing these, a method is known in which a fluorenone and a phenol are subjected to a condensation reaction in the presence of a catalyst.
As a condensation reaction, a method is known in which fluorenone obtained by air oxidation of fluorene is used as a starting material, and a condensation reaction with phenol is performed using hydrogen chloride gas and mercaptopropionic acid as catalysts (Patent Documents 1 and 2). .
Patent Document 3 includes a method in which sulfuric acid having a sulfuric acid content higher than 70% is used as a catalyst used in the method for producing 9,9-bis (4-hydroxyphenyl) fluorene, and β-mercaptopropionic acid is used as a cocondensation agent. It has been.
When these reaction steps are used, the reaction product contains a mineral acid that is a water-soluble catalyst in addition to the target component, and it is necessary to remove it in a subsequent step.
Patent Document 4 proposes a method in which a sulfonic acid type cation exchange resin is used as a catalyst without using a water-soluble catalyst such as hydrochloric acid or sulfuric acid. Inventions using an ion exchange resin without using a mineral acid have been made (Patent Document 5 and Patent Document 6).
Even when such a reaction step is used, the reaction products include 9,9-bis (4-hydroxyphenyl) fluorenes, unreacted phenols and fluorenone and a cocatalyst, water produced by the reaction, and by-products. Organisms are included and some means of separation is required. As the separation means, methods such as extraction / liquid-liquid separation, distillation, and crystallization have been proposed.
In Patent Document 7, in a method for producing a fluorene derivative in which fluorenone and phenol are subjected to a condensation reaction in the presence of thiols and hydrochloric acid, an extractant is added to the resulting reaction mixture to distribute the target compound to the organic layer. A method of adding a crystallization solvent to the organic layer and crystallization separation as an inclusion compound has been proposed.
Patent Document 8 describes a method of precipitating crystals using a solvent that forms an adduct (clathrate compound) as a separation method after the synthesis of 9,9-bis (4-hydroxyphenyl) fluorene.
Patent Document 9 proposes a method using a low fatty acid alcohol and water as a separation method for the same purpose, and Patent Document 10 proposes a method using a mixed solvent of a low fatty acid alcohol and an aromatic hydrocarbon.
Patent Document 11 discloses aliphatic hydrocarbons or aromatics having 6 to 12 carbon atoms as a method for producing 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (same as biscresol fluorene, hereinafter referred to as BCF). A method of performing crystallization using a group hydrocarbon or a mixed solvent thereof has been proposed. Patent Document 12 proposes a method for crystallization using a mixed solvent containing a lower aliphatic alcohol having 1 to 3 carbon atoms and a lower aliphatic ketone having 3 to 7 carbon atoms when purifying biscresols. ing.
Even if only the reaction process is continued from the above known technology, separation of generated water, separation of cocatalyst, separation of unreacted phenols, separation of the crystallization solvent constituting the clathrate compound are necessary, and industrialization is intended. In this case, continuation including a plurality of separation steps is required. In order to recycle and reuse the useful components recovered in the separation process, it is necessary to improve the product recovery rate while suppressing impurities, but the composition of the impurities generated in each separation process and the reuse destination respectively. There is no literature mentioning the characteristics of this process, and no effective continuous production method has been proposed yet.
Further, for example, in an example in which the inclusion compound of BCF is crystallized, a mixed solution of the reaction product or the residue of the organic layer and the crystallization solvent is heated and dissolved at a temperature equal to or lower than the boiling point of the solvent. Although the method which cools the obtained solution to 10 degreeC is described (patent document 13), in order to industrialize, since the container which has a huge heat-transfer surface is required, continuous manufacture was difficult .
JP-A-62-230741 (Patent No. 1611498) Japanese Patent Laid-Open No. 10-265423 (Patent No. 3500488) Japanese Patent Application Laid-Open No. 61-103846 JP-A-5-000980 JP 45-10337 A (Patent No. 585576) JP-A-57-35533 (Patent No. 1468745) JP 2002-047227 A (Patent 3490960) JP-A-62-230741 (Patent No. 1611498) JP-A-4-41450 JP-A-4-41451 Japanese Patent Laid-Open No. 10-265423 (Patent No. 3500488) JP 10-245352 A (Patent No. 3512242) JP 2003-221352 A

  Therefore, the main problem to be solved by the present invention is to provide a method for continuously producing 9,9-bis (4-hydroxyphenyl) fluorenes. Another object is to provide a continuous process for producing 9,9-bis (4-hydroxyphenyl) fluorenes that provides advantages such as a large crystal grain size and excellent crystal quality.

  As a result of research, the present inventors have found a method for continuously producing 9,9-bis (4-hydroxyphenyl) fluorenes by a series of organically coupled steps, and in particular, include in the crystallization step. It has been found that an increase in the size of the apparatus can be suppressed by evaporating a solvent (acetone or the like) constituting the contact compound under heat insulation.

The present invention that has solved the above problems is as follows.
[Invention of Claim 1]
The continuous manufacturing method of 9,9-bis (4-hydroxyphenyl) fluorene characterized by including the following processes.
9,9-bis (4-hydroxyphenyl) is subjected to a condensation reaction of 9-fluorenone with phenol selected from phenol and alkylphenol using a sulfonic acid type cation exchange resin as a catalyst. A reaction process for producing fluorenes,
A dehydration step of removing water from the reaction product obtained from the reaction step to obtain a phenol solution containing 9,9-bis (4-hydroxyphenyl) fluorenes;
A concentration step of separating phenols from the solution containing 9,9-bis (4-hydroxyphenyl) fluorenes obtained in the dehydration step and concentrating 9,9-bis (4-hydroxyphenyl) fluorenes;
A crystallization step of mixing a solvent with the concentrated liquid obtained in the concentration step and crystallizing an inclusion compound composed of 9,9-bis (4-hydroxyphenyl) fluorenes and the solvent,
A crystallization product separation step of separating the crystal containing the inclusion compound from the crystallization product obtained in the crystallization step and washing the separated crystal;
A solvent removal step of removing the solvent from the slurry containing the clathrate compound obtained in the crystallization product separation step,
A solvent purification step for purifying at least a part of the liquid containing the solvent obtained in the solvent removal step, the mother liquor obtained in the crystallization product separation step, and the washing solution;
A phenol purification step in which at least a part of the liquid obtained in the solvent purification step is purified and supplied to the reaction step.

[Invention of Claim 2]
The 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein at least a part of the mother liquor and the washing liquid obtained in the crystallization product separation step are mixed with the concentrate obtained in the concentration step. Continuous manufacturing method.

[Invention of Claim 3]
The continuous 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein at least a part of the liquid containing the solvent obtained in the solvent removal step is mixed with the concentrated liquid obtained in the concentration step. Production method.

[Invention of Claim 4]
2. At least a part of the liquid obtained in the solvent purification step is supplied to the concentration step together with a solution containing 9,9-bis (4-hydroxyphenyl) fluorenes obtained in the dehydration step. Of 9,9-bis (4-hydroxyphenyl) fluorenes.

[Invention of Claim 5]
The method for continuously producing 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein a liquid containing phenols obtained in the concentration step is supplied to the reaction step.

[Invention of Claim 6]
The method for continuously producing 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein in the crystallization step, the inclusion compound is crystallized by evaporating the solvent under adiabatic conditions.

[Invention of Claim 7]
The continuous production method of 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein in the crystallization step, at least a part of the solvent evaporated under adiabatic conditions is cooled and refluxed to the crystallization step. .

The continuous production method of the present invention increases the production efficiency of 9,9-bis (4-hydroxyphenyl) fluorenes, and can suppress the raw material basic unit at a low cost compared with the conventional batch production method. Product purity and recovery rate equivalent to or better than the batch manufacturing method can be realized.
Incidentally, although the crystal grain size obtained by the conventional batch process was about 50 μm, the grain size of the inclusion crystal obtained by this process (both adiabatic cooling crystallization and indirect cooling crystallization) is A colorless and transparent crystal having a particle size of about three times as large as about 140 to 160 μm is obtained, and the crystal particle size is large.
Thus, the clathrate crystal obtained by this process has a large crystal grain size and a low turbidity, so that the mother liquor is little involved in the crystal and the crystal purity is high. Further, in this process, since the amount of the mother liquor adhering to the crystal is small, the crystal can be washed continuously and efficiently, so that a high purity product can be easily obtained.

Next, the present invention will be described with reference to the drawings. First, representative examples will be shown, and then the scope of application of the present invention will be described.
<First Embodiment>
FIG. 1 is a process diagram according to a first embodiment for producing 9,9-bis (4-hydroxyphenyl) fluorenes according to the present invention.
In FIG. 1, 1 is a reaction process, 2 is a dehydration process, 3 is a concentration process, 5 is a crystallization process, 6 is a crystallization product separation process, 7 is a solvent removal process, 8 is a solvent purification process, and 9 is a phenol. Each of the purification steps is shown.

すなわち、１モルのフルオレノンに２モルのオルトクレゾールが反応し、１モルのＢＣＦと１モルの水が発生する。
反応工程１で得られた反応生成物は、目的物である９，９−ビス（４−ヒドロキシフェニル）フルオレン類のほか、未反応のフェノール類及び助触媒を含む。更に、少量の９，９−ビス（４−ヒドロキシフェニル）フルオレン類の異性体、二量体、三量体、ビスフェノール類、トリスフェノール類、クロマン化合物等の副生物を含む。
フェノール類としてオルトクレゾールを選択した場合の副生物の例として、ＢＣＦの２量体（以下ＷＢＣＦと表記する）が挙げられる。ＷＢＣＦは次のような構造で表される。

In the reaction step 1, 9-fluorenone and phenols are reacted in the presence of a catalyst to obtain a reaction product containing 9,9-bis (4-hydroxyphenyl) fluorenes. As the catalyst, a sulfonic acid type cation exchange resin is used without using a mineral acid such as hydrochloric acid or sulfuric acid. Further, if necessary, conventional thiols as co-catalysts such as mercaptocarboxylic acid (thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc. ), Alkyl mercaptan (such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl mercaptan), aralkyl mercaptan (such as benzyl mercaptan) or a salt thereof. In particular, using a sulfonic acid type cation exchange resin in reaction step 1 does not require an acid catalyst neutralization step with an alkali or an extraction step with an organic solvent. Contributes to The usage-amount of phenols is 2-50 mol with respect to 1 mol of fluorenones, Preferably it is 6-30 mol. The reaction temperature is 30 to 150 ° C, preferably 60 to 120 ° C.
This reaction is expressed as follows when, for example, ortho-cresol is selected as the phenol.

That is, 2 mol of orthocresol reacts with 1 mol of fluorenone to generate 1 mol of BCF and 1 mol of water.
The reaction product obtained in the reaction step 1 contains unreacted phenols and a cocatalyst in addition to the target 9,9-bis (4-hydroxyphenyl) fluorenes. Furthermore, a small amount of by-products such as isomers, dimers, trimers, bisphenols, trisphenols, and chroman compounds of 9,9-bis (4-hydroxyphenyl) fluorenes are included.
An example of a by-product when ortho-cresol is selected as the phenol is BCF dimer (hereinafter referred to as WBCF). The WBCF is represented by the following structure.

The reaction product obtained in the reaction step 1 is supplied to the dehydration step 2 through the line 13.
In the dehydration step 2, an aqueous phenolic solution containing a large amount of water is discharged out of the system through the line 14, and the dehydrated reaction product is supplied to the concentration step 3 through the line 15. In the concentration step 3, excess unreacted phenols are removed. Generally, an evaporator can be used for the concentration step 3, and the separated phenols are preferably condensed and then returned to the reaction step 1 through the line 16. Returning the vapor in the concentration step 3 to the reaction step 1 through the line 16 contributes to reducing the calorific value in the phenol purification step 9 described later. In the dehydration step 2 and the concentration step 3, the operation temperature needs to be 180 ° C. or lower, preferably 120 ° C. or lower in order to prevent coloring and deterioration of the final product. Therefore, these steps are operated under vacuum. Therefore, in the concentration step 3, the liquid is concentrated to such a concentration that does not cause crystals to precipitate at this operating temperature and maintains a viscosity that does not hinder transportation.
The concentrated solution obtained in the concentration step 3 passes through the line 17 and is used as a polar solvent (ketones such as acetone, alcohols such as methanol, ethers such as diisopropyl ether. Is mixed with acetone) and fed to the crystallization step 5 through the line 18.

In the crystallization step 5, crystallization can be performed using an appropriate method or apparatus. For example, an indirect cooling crystallization can in which the refrigerant is passed through the jacket and the liquid is indirectly cooled may be used, but in order to require a large heat transfer surface and increase the size of the crystallization apparatus, It is preferable to use an adiabatic cooling crystallization can that is cooled by evaporating the solvent at the bottom in order to reduce the size of the crystallization apparatus. In the case of using an adiabatic cooling crystallization can, it is desirable to condense the evaporated solvent with a heat exchanger and supply it again to the crystallization step 5 through the line 19. In this case, the solvent may be replenished to the line 19 from the line 35b.
The slurry containing the clathrate compound obtained in the crystallization step 5 is supplied to the crystallization product separation step 6 through the line 20. In the crystallization product separation step 6, any separator that can perform solid-liquid separation may be used. As such a separator, a centrifuge or a filter is generally used. However, a filter is used because of the required power, ease of maintenance, and easy handling of the mother liquor and the cleaning liquid separately. It is desirable to use it. The use of a horizontal belt filter as the filter is particularly excellent in cleaning and filtration characteristics. The case where a horizontal belt filter is used will be described. In the crystallization product separation step 6 using a filter, it is desirable to use a purified solvent obtained in a solvent purification step 8 described later as a cleaning liquid and supplied through a line 28. Further, since the solvent is lost as a whole system, a new solvent may be supplied. In replenishing the solvent, the purified solvent and a new solvent may be mixed and then supplied to the crystallization product separation step 6. However, the new solvent may be used for cake washing without mixing. The mother liquid obtained by supplying the slurry to the horizontal belt filter and the washing liquid obtained by further washing the filtered crystals remaining after the mother liquid separation with the solvent are supplied to the solvent purification step 8 through the line 21 and the line 22, respectively. Is done. The washing crystals remaining after the washing liquid separation can be supplied to the solvent removal step 7 through the line 23.

  In the solvent removal step 7, the solvent included in the washed crystal and the solvent constituting the clathrate compound with 9,9-bis (4-hydroxyphenyl) fluorenes are removed. 9-bis (4-hydroxyphenyl) fluorenes are obtained as a product. In general, a heat dryer can be used for removing the solvent, and the modification of the product due to the heating must be suppressed as much as possible. Therefore, a solvent having a boiling point as low as possible should be selected. It is also effective to use a carrier gas such as nitrogen. A part of the solvent removed in the solvent removal step 7 in the case of using a heating dryer is purged out of the system through the line 36 in order to prevent the low-boiling point components from circulating and the rest passes through the line 24. To the solvent purification step 8. In this case, the solvent may be combined with the cleaning liquid and supplied to the solvent purification step 8 through the line 22.

  The mother liquid passing through the line 21 and the washing liquid passing through the line 22 contain the solvent constituting the clathrate compound, and these are supplied to the solvent purification step 8. A part of the liquid supplied to the solvent purification step 8 is mixed with the concentrated liquid passing through the line 17 through the line 26 and supplied to the crystallization step 5. If the mother liquor contains a large amount of phenols, the concentration of phenols separated and reduced in the concentration step 3 will be increased once more, so only a part of the washing solution is mixed with the concentrate through the line 26. Is desirable. As described above, mixing a part of the washing liquid separated in the crystallization product separation step 6 with the concentrate brings an advantage of reducing the calorific value in the solvent purification step 8. A part of the solvent recovered in the solvent purification step 8 is removed from the system through the line 27 (combustion treatment if necessary) to prevent the low-boiling components from circulating and accumulated, and the rest is separated from the crystallization product through the line 28. Supplied to step 6;

The remaining solution after recovering the solvent mainly contains phenols, but includes unrecovered solvent, 9,9-bis (4-hydroxyphenyl) fluorenes, unreacted fluorenone, reaction byproducts, and the like. It is. This solution is discharged from the solvent purification step 8 through a line 29 and branched into a line 30 and a line 31. Since the solution contains a product, it is desirable to supply a part to the concentration step 3 through the line 30 according to the required recovery rate. Further, the remainder is supplied to the phenol purification step 9 through the line 31. Supplying the purified solvent to the concentration step 3 through the line 30 brings the advantage of reducing the caloric intensity in the phenol purification step 9. Furthermore, the product recovery rate can be increased. Moreover, this is also a preferred mode for controlling the concentration of the target component at the outlet of the concentration step 3.
As the phenol purification step 9, it is desirable to use vacuum distillation because phenols (for example, cresol) have a high boiling point. The solution passing through the line 31 is subjected to the phenol purification step 9 to remove light components in the line 32 and heavy components in the line 33, and is supplied to the reaction step 1 through the line 34 as purified phenols.

<Second Embodiment>
FIG. 2 is a process diagram according to the second embodiment.
The difference between the second embodiment and the first embodiment is that, in the case of using an adiabatic cooling crystallization can as the crystallization step 5, the evaporated solvent is circulated through 19b. Through the line 19a, it can be recycled while being combined with the liquid mixture from the line 18. In the latter case, depending on the temperature and the solvent concentration, crystals may be precipitated by contact with the mixed solution. However, if there is no precipitation, it can be sufficiently employed.
Another difference is that a part of the solvent removed in the solvent removal step 7 is supplied to the solvent purification step 8 through the line 24a and is directly mixed with the concentrate through the line 24b. Mixing part of the solvent removed in the solvent removal step 7 with the concentrate directly through the line 24 b provides the advantage of reducing the caloric intensity in the solvent purification step 8.

<Third Embodiment>
FIG. 3 is a process diagram according to the third embodiment.
The difference of the third embodiment from the first embodiment is that the vapor in the concentration step 3 is supplied to the phenol purification step 9 through the line 16, and the mother liquor obtained in the crystallization product separation step 6 And a point where the washing liquid is supplied to the solvent purification step 8 in part, a part of the solvent recovered in the solvent purification step 8 is mixed with the concentrate obtained in the concentration step 3, and the solvent is supplied to the crystallization step 5. The remaining solution after the recovery is supplied to the phenol purification step 9 through the line 29 in its entirety.

<Disclosure scope of the present invention>
The phenols used in the present invention are phenol or alkylphenol, and for example, 2-C _1-4 alkylphenol (such as ortho-cresol) can be preferably used.
As the reactor, a packed column of ion exchange resin can be used, and the reaction heat generated can be removed by warm water passing through a jacket by using the liquid as a down flow.
As the ion exchange resin used as a catalyst, a strongly acidic sulfonic acid type cation exchange resin can be used, and the cation exchange resin needs to be insoluble in water. When the sulfur compound is present in the reaction system, this cation exchange resin can be left as it is, but when it is not present, a part of the sulfonic acid group of the cation exchange resin is neutralized with the sulfur compound. It is preferred to use a treated ion exchange resin. Even in the former case, an ion exchange resin obtained by neutralizing a part of the sulfonic acid group with a sulfur compound may be used. Other ion exchange resins that can be used are those described in the patent literature described in this specification.
As a polar solvent to be present in the crystallization step, a solvent that forms an inclusion crystal with 9,9-bis (4-hydroxyphenyl) fluorenes is used. The crystallization solvent can be composed of at least one polar solvent selected from alcohols such as methanol, ketones such as acetone, and ethers such as diisopropyl ether.

Examples and comparative examples are shown below to clarify the effects of the present invention.
[Example 1]
In accordance with the process shown in FIG. 1, 9,9-bis (4-hydroxyphenyl) was prepared using 9-fluorenone as a raw material and ortho-cresol as a phenol and β-mercaptopropionic acid (hereinafter referred to as βMPA) as a co-catalyst. ) The raw material basic unit when continuously producing BCF as fluorenes was calculated using PRO / II (product name) which is a simulator of Invensys. As a simulation parameter, the annual production amount was 4000 t / y. Based on the results of the reaction experiment using the sulfonic acid type ion exchange resin, the conversion rate of BCF is 99%, but considering the operational fluctuations, the conversion rate of BCF is 95% and the selectivity is 97%. All the by-products were set to WBCF. The purity of the raw material ortho-cresol was 99.7 wt% (designated phenol or the like as an impurity), and the purity of the raw material acetone was 99.6 wt% (designated water or the like as an impurity). The raw material molar ratio was 20 for orthocresol / fluorenone and 40 for fluorenone / βMPA. The solubility curve for acetone of the “inclusion compound of acetone and BCF” was approximated as a logarithmic function based on the actually measured values.
As a result, each raw material unit was 0.680 kg / kg BCF for orthocresol, 0.530 kg / kg BCF for fluorenone, and 0.024 kg / kg BCF for acetone. The utility unit was 1.2 kg / kg BCF for low pressure steam, 4.1 kg / kg BCF for medium pressure steam, and 0.20 Ton / kg BCF for cooling water. The amount of waste was 0.0514 kg / kg BCF for wastewater, 0.020 kg / kg BCF for light waste, 0.020 kg / kg BCF for medium waste, and 0.13 kg / kg BCF for heavy waste.

[Comparative Example 1]
When the same raw material was used and manufactured in a batch mode, that is, in a 2 L glass reactor equipped with a stirrer, a cooler, and a thermometer, 70 g of 99% pure fluorenone, 250 g of orthocresol, 0.4 g of βMPA, and The reaction was performed by charging 15 g of concentrated sulfuric acid and stirring at 55 ° C. for 6 hours. As a result of confirmation by HPLC, the residual amount of fluorenone was 0.1% or less. To the obtained reaction mixture, 300 g of toluene and 80 g of water were added, and neutralized by adding a 32% aqueous sodium hydroxide solution until the pH was about 7, and then the aqueous layer was removed. The organic layer was heated to 80 ° C. and then washed 3 times with 80 g of water. After recovering 300 g of toluene from the organic layer by distillation under reduced pressure, 400 ml of a toluene-acetone mixed solvent (mixing ratio 1: 4) was added to the organic layer, and the mixture was stirred at 70 ° C. for 1 hour. Crystallization gave 140 g of the desired product, BCF. In this case, the BCF recovery rate was 89%, the BCF purity was 99.7 wt%, and the TS concentration in the product was 6.2 ppm. The crystal grain size was about 50 μm, and the standard deviation of the DRY crystal grain size distribution was 0.244. The basic unit of raw materials is 0.924 kg / kg BCF for orthocresol, 0.529 kg / kg BCF for fluorenone, 0.003 kg / kg BCF for βMPA, 0.091 kg / kg BCF for 98% sulfuric acid, 1.063 kg / kg BCF for acetone, and toluene for It was 0.15 kg / kg BCF. The utility unit was 6.062 kg / kg BCF for steam and the amount of waste was 2.533 kg / kg BCF for waste water.

[Example 2]
According to the process shown in FIG. 3, the raw material basic unit was calculated to be 0.825 kg / kg BCF for orthocresol, 0.563 kg / kg BCF for fluorenone, and 0.024 kg / kg BCF for acetone, as calculated by the simulator as in Example 1. . The utility unit was 1.2 kg / kg BCF for low pressure steam, 4.8 kg / kg BCF for medium pressure steam, and 0.36 Ton / kg BCF for cooling water. The amount of waste was 0.055 kg / kg BCF for wastewater, 0.020 kg / kg BCF for light waste, 0.020 kg / kg BCF for medium waste, and 0.32 kg / kg BCF for heavy waste.

[Example 3 and Example 4]
In accordance with the process shown in FIG. 1, 9-fluorenone and orthocresol as phenols are used as raw materials, βMPA is used as a cocatalyst, and BCF is continuously added as 9,9-bis (4-hydroxyphenyl) fluorenes. Manufactured. The reaction was carried out in a reactor having a packed bed of sulfonic acid type cation exchange resin. In the crystallization process, when the indirect cooling crystallizer was used (Example 3) and when the adiabatic cooling crystallizer was used (Example 4), the obtained crystals were examined. The results shown are obtained. The crystallizer used was a double propeller crystal can with a volume of 30 liters and a diameter of 250 mm. In the indirect cooling crystallizer (Example 3), normal pressure was maintained, the temperature difference ΔT in the jacket and the crystal can was adjusted to 5 ° C., and the temperature in the crystal can was maintained at 29 ° C. In the adiabatic cooling crystallizer (Example 4), the pressure inside the crystal can was kept at 140 Torr, and the temperature was kept at 28 ° C. A Shimadzu laser diffraction flow rate distribution analyzer (SALD-2000J) was used for analysis of crystal grain size and particle size distribution. Water and a surfactant were used as the dispersion material.

  From Examples 3 and 4 and Comparative Example 1, the crystals obtained by the continuous process have a sharper particle size distribution than the products of the existing batch process. From this, it is expected that the continuous process has better filterability and higher cleaning efficiency than the products of the existing process, and is likely to achieve the target product quality.

It is process drawing of 1st Embodiment for manufacturing 9,9-bis (4-hydroxyphenyl) fluorene by this invention. It is process drawing of 2nd Embodiment. It is process drawing of 3rd Embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Reaction process, 2 ... Dehydration process, 3 ... Concentration process, 5 ... Crystallization process, 6 ... Crystallization product separation process, 7 ... Solvent removal process, 8 ... Solvent purification process, 9 ... Phenol purification process.

Claims (7)

The continuous manufacturing method of 9,9-bis (4-hydroxyphenyl) fluorene characterized by including the following processes.
9,9-bis (4-hydroxyphenyl) is subjected to a condensation reaction of 9-fluorenone with phenol selected from phenol and alkylphenol using a sulfonic acid type cation exchange resin as a catalyst. A reaction process for producing fluorenes,
A dehydration step of removing water from the reaction product obtained from the reaction step to obtain a phenol solution containing 9,9-bis (4-hydroxyphenyl) fluorenes;
A concentration step of separating phenols from the solution containing 9,9-bis (4-hydroxyphenyl) fluorenes obtained in the dehydration step and concentrating 9,9-bis (4-hydroxyphenyl) fluorenes;
A crystallization step of mixing a solvent with the concentrated liquid obtained in the concentration step and crystallizing an inclusion compound composed of 9,9-bis (4-hydroxyphenyl) fluorenes and the solvent,
A crystallization product separation step of separating the crystal containing the inclusion compound from the crystallization product obtained in the crystallization step and washing the separated crystal;
A solvent removal step of removing the solvent from the slurry containing the clathrate compound obtained in the crystallization product separation step,
A solvent purification step for purifying at least a part of the liquid containing the solvent obtained in the solvent removal step, the mother liquor obtained in the crystallization product separation step, and the washing solution;
A phenol purification step in which at least a part of the liquid obtained in the solvent purification step is purified and supplied to the reaction step.   The 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein at least a part of the mother liquor and the washing liquid obtained in the crystallization product separation step are mixed with the concentrate obtained in the concentration step. Continuous manufacturing method.   The continuous 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein at least a part of the liquid containing the solvent obtained in the solvent removal step is mixed with the concentrated liquid obtained in the concentration step. Production method.   2. At least a part of the liquid obtained in the solvent purification step is supplied to the concentration step together with a solution containing 9,9-bis (4-hydroxyphenyl) fluorenes obtained in the dehydration step. Of 9,9-bis (4-hydroxyphenyl) fluorenes.   The method for continuously producing 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein a liquid containing phenols obtained in the concentration step is supplied to the reaction step.   The method for continuously producing 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein in the crystallization step, the inclusion compound is crystallized by evaporating the solvent under adiabatic conditions.   The continuous production method of 9,9-bis (4-hydroxyphenyl) fluorenes according to claim 1, wherein in the crystallization step, at least a part of the solvent evaporated under adiabatic conditions is cooled and refluxed to the crystallization step. .

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