JPWO2013114987A1 - Integrated production method of diallyl bisphenols - Google Patents

Abstract

The object of the present invention is to provide a process for consistently producing high quality diallyl bisphenols from bisphenols in high yield. By adopting a method comprising the following steps (1) to (3), diallyl bisphenols can be produced consistently from bisphenols. (1) a step of reacting a bisphenol or an alkali metal salt thereof and an allyl halide in a cellosolve solvent in the presence or absence of a basic alkali metal salt, (2) obtained in step (1) (2) a step of separating the by-product inorganic salt from the reaction solution, and (3) a step of heating the reaction solution obtained in step (2) to perform a rearrangement reaction.

Description

  The present invention relates to a method for producing diallyl bisphenols.

  Diallyl bisphenols are useful substances as color developers for heat-sensitive recording materials, and various production methods have been attempted. For example, bisphenol S (dihydroxydiphenyl sulfone) and allyl bromide are reacted to carry out an allylation reaction. After the obtained bisphenol S diallyl ether is taken out as a powder, the diallyl ether is heated to undergo rearrangement (Claisen rearrangement). The production method of diallylated bisphenol S (3,3′-diallyl-4,4′-dihydroxydiphenylsulfone), which is reacted, is well known (Patent Document 1).

  However, in this production method, after the allylation reaction, the obtained bisphenol S diallyl ether is crystallized and taken out as a powder, so that about 6% of bisphenol S diallyl ether is obtained in the filtrate. As a result, there is a problem that the yield of diallylated bisphenol S, which is the final target product, decreases.

  On the other hand, Patent Document 2 describes a method for producing diallylated bisphenol S without taking out bisphenol S diallyl ether in the middle. The allylation reaction is carried out in water and / or an organic solvent, and the rearrangement reaction is carried out. It is disclosed to carry out in a solvent or without a solvent. In this document, when the solvent used for the allylation is a low boiling point solvent, after the solvent is distilled off, it is described that the Claisen rearrangement reaction is carried out by replacing with no solvent or the solvent used for rearrangement. In this method, after the solvent used for allylation is distilled off, the Claisen rearrangement reaction is carried out without solvent.

  However, it is known that the Claisen rearrangement without solvent is difficult to use industrially because temperature control is difficult (Patent Document 3). Furthermore, Patent Document 3 also discloses that, in the Claisen rearrangement, when ethylene glycol is used as a solvent, a highly polar substance is generated, so that the reaction using the solvent is avoided as much as possible.

  As described above, in the production of diallyl bisphenols, in general, the allylation reaction is often carried out in a polar solvent and the rearrangement reaction is carried out in a nonpolar solvent. There were economic problems, such as the work to manage and the need to install storage containers separately.

JP 61-089090 A JP-A-60-169456 JP 62-053957 A

  This invention is made | formed in view of the said problem, and makes it a main objective to provide high quality diallyl bisphenol by a high yield.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have consistently conducted an allylation reaction and a Claisen rearrangement reaction using a cellosolve solvent in the production of diallyl bisphenols. It was also found that diallyl bisphenols can be obtained in high yield. As a result of further research based on this knowledge, the present invention has been completed.

  That is, the present invention provides the following method for producing diallyl bisphenols.

Item 1. A method for consistently producing diallyl bisphenols from bisphenols, comprising the following steps (1) to (3).
(1) reacting a bisphenol or an alkali metal salt thereof with an allyl halide in a cellosolve solvent in the presence or absence of a basic alkali metal salt;
(2) a step of separating a by-product inorganic salt from the reaction solution obtained in step (1),
(3) A step of heating the reaction liquid obtained in step (2) to perform a rearrangement reaction.

  Item 2. Item 2. The method according to Item 1, comprising a step of recovering the cellosolve solvent in step (2) and / or step (3) and reusing at least a part of the recovered cellosolve solvent as a reaction solvent.

  Item 3. Item 3. The method according to Item 1 or 2, wherein the cellosolve solvent is at least one selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

  Item 4. Item 4. The method according to any one of Items 1 to 3, wherein the bisphenol is bis (4-hydroxyphenyl) sulfone.

  Item 5. Item 5. The method according to any one of Items 1 to 4, comprising a step of separating the by-product inorganic salt and neutralizing the obtained reaction solution in the step (2).

  According to the production method of the present invention, since powder bisphenol diallyl ether is not taken out during production, loss of bisphenol diallyl ether into the filtrate can be prevented, and diallyl bisphenols can be obtained in high yield. .

  In addition, handling bisphenol diallyl ether in a solution state without powdering eliminates the need for equipment related to powdering and makes it easy to handle, such as being transportable by a pump, making the production equipment very It becomes possible to simplify.

  Furthermore, by carrying out the allylation and rearrangement reaction with a common solvent, there is no need to switch solvents, manage both solvents, or install separate storage containers, reducing the number of manufacturing processes and equipment used. Therefore, it is suitable for industrial production.

  In addition, after the rearrangement reaction, when the temperature is lowered for the post-treatment process, the reaction solvent can be recovered using the latent heat of vaporization of the solvent, so the solvent recovered in each process can be reused. It can be a rational and energy-saving manufacturing process.

  Hereinafter, the present invention will be described in detail.

In the present invention, the method for consistently producing diallyl bisphenols from bisphenols is a method including the following steps (1) to (3).
(1) reacting a bisphenol or an alkali metal salt thereof with an allyl halide in a cellosolve solvent in the presence or absence of a basic alkali metal salt;
(2) a step of separating a by-product inorganic salt from the reaction solution obtained in step (1),
(3) A step of heating the reaction liquid obtained in step (2) to perform a rearrangement reaction.

Hereinafter, each step will be described.
1. Step (1) The above step (1) is preferably carried out by charging a cellosolve solvent, a starting bisphenol or its alkali metal salt, and if necessary, a basic metal compound and water in a closed container such as an autoclave. Is carried out by adding dropwise allyl halide under heating and reacting for a predetermined time.

  Examples of the starting bisphenols include the following general formula (1):

（式中、Aは単結合、−CH₂−、−S−、−SO₂−、−C(CH₃)₂−、または

(Wherein, A is a single bond, —CH ₂ —, —S—, —SO ₂ —, —C (CH ₃ ) ₂ —, or

を示す。ベンゼン核はさらに置換されていてもよい。）
で表される化合物が挙げられる。工業的には、４，４’−位に水酸基を有する化合物が特に重要である。

Indicates. The benzene nucleus may be further substituted. )
The compound represented by these is mentioned. Industrially, a compound having a hydroxyl group at the 4,4′-position is particularly important.

  Specifically, 2,2′-bis (4-hydroxyphenyl) propane (hereinafter also referred to as “bisphenol A”), bis (4-hydroxyphenyl) cyclohexane (hereinafter also referred to as “bisphenol C”), bis ( 4-hydroxyphenyl) methane (hereinafter also referred to as “bisphenol F”), bis (4-hydroxyphenyl) sulfone (hereinafter also referred to as “bisphenol S”), bis (3-methyl-4-hydroxyphenyl) sulfone, etc. Can be mentioned.

  Examples of the alkali metal salt of the bisphenol as the starting material include those in which H in the —OH group is substituted with an alkali metal in the general formula (1). As the alkali metal, sodium, potassium and the like are preferable. The alkali metal salt of bisphenols may be a monoalkali metal salt or a dialkali metal salt. When a dialkali metal salt of bisphenol is used as a starting material, a basic alkali metal compound described later may be unnecessary.

  The bisphenols represented by the general formula (1) and the alkali metal salts thereof used in the present invention may be in any form of powder or wet cake produced by a known method.

  The allyl halide in the present invention includes compounds in which substituents are introduced at the α, β and γ positions of the allyl group. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an aromatic group. Specific examples of the allyl halide include allyl chloride, allyl bromide, allyl iodide, crotyl chloride, crotyl bromide, cinnamilk bromide, cinnamyl bromide and the like.

  Examples of the cellosolve solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Of these, ethylene glycol monobutyl ether is preferred. These can also be mixed and used. Moreover, it may contain water.

  Examples of the basic alkali metal compound include alkali metal hydroxide compounds such as sodium hydroxide and potassium hydroxide, and alkali metal carbonate compounds such as sodium carbonate and potassium carbonate. The usage-amount of a basic alkali metal compound is 1.5-4 times mole normally with respect to bisphenols, Preferably it is 2-3 times mole. When a dialkali metal salt of bisphenol is used as a starting material, a basic alkali metal compound may not be used. This basic alkali metal compound is used alone or in combination of two or more.

  In the reaction of the present invention, the molar ratio of the bisphenol or its alkali metal salt to the allyl halide is in the range of 1: 2 to 1: 5, preferably in the range of 1: 2 to 1: 4.

  The said reaction temperature is the range of 50-150 degreeC, Preferably it is the range of 80-120 degreeC.

  The reaction time is in the range of 1 to 20 hours, preferably in the range of 2 to 10 hours. The pressure is in the range of 0 to 1 MPaG (G represents the gauge pressure), and preferably in the range of 0 to 0.3 MPaG.

2. Step (2) The step (2) is a step of separating the by-product inorganic salt from the reaction solution by a known method. For example, to the reaction product obtained in the step (1), an amount of water or warm water sufficient to dissolve a by-product inorganic salt (for example, alkali metal halide) that is supersaturated and precipitated is added. This is carried out by dissolving the raw inorganic salt and then allowing to stand, separating the cellosolve solvent layer containing bisphenol diallyl ether and the aqueous layer containing the by-product inorganic salt, and separating and removing the aqueous layer.

  In the method of the present invention, water or warm water is added to a reaction solution (reaction system) containing a reaction product obtained by reacting a bisphenol or an alkali metal salt thereof with an allyl halide to produce a by-product inorganic substance. When the salt is dissolved, the following pretreatment can be performed.

  That is, by heating and distilling the obtained reaction liquid while adding water as necessary, allyl halide (for example, allyl chloride) which is an unreacted raw material and / or alcohol which is a by-product from the reaction liquid. (Eg, allyl alcohol) and the like can be distilled off and separated. The distillate obtained here is further separated into an organic layer containing allyl halide and cellosolve solvent as unreacted raw materials, and an aqueous layer containing alcohols and water as by-products. The organic layer (an organic layer containing an allyl halide and a cellosolve solvent) can be recycled (reused) at least partially in the reaction system.

  Thus, the allylation reaction liquid from which the by-product inorganic salt is separated can be used for the next rearrangement reaction.

  In the method of the present invention, after separation of the aqueous layer (aqueous solution layer containing by-product inorganic salt) and the organic layer (cellosolve solvent layer containing bisphenol diallyl ether), a small amount is contained in the organic layer. It is preferable to separate and remove the water, and then remove by-product inorganic salts precipitated in the organic layer before subjecting to the next rearrangement reaction.

  In order to separate and remove the water contained in this organic layer, various methods such as adding a desiccant and filtering can be considered, but a method of separating and removing water by distillation is preferred. The separated and removed water contains a small amount of cellosolve solvent, and at least a part of this water can be recycled (reused) as it is to the reaction system.

  The by-product inorganic salt precipitated in the organic layer after the water is separated and removed can be easily removed by hot filtration (hot filtration), decantation, or the like.

  Furthermore, in the method of the present invention, in order to remove inorganic salts contained in the organic layer (cellosolve solvent layer containing bisphenol diallyl ethers) more reliably, the aqueous layer and the separated organic layer are After performing the sum treatment, water contained in the organic layer may be separated and removed, and precipitated by-product inorganic salts may be removed according to the above procedure.

  As the neutralization treatment, a conventionally known method can be used. For example, a method of adding a neutralizing agent such as hydrochloric acid or dilute sulfuric acid to the organic layer and stirring at 0 to 100 ° C. for about 0.1 to 20 hours can be mentioned.

  In this way, the obtained organic layer (cellosolve solvent layer) is neutralized as necessary, and after removing water, by-product inorganic salts precipitated by hot filtration or the like are removed, Bisphenol diallyl ethers (for example, 4,4′-diallyloxydiphenyl sulfone) subjected to the rearrangement reaction of can be obtained.

3. Step (3) The step (3) is a rearrangement reaction step, and is performed, for example, by reacting the organic layer obtained by separating the aqueous layer in the step (2) for a predetermined time under heating. .

  The rearrangement reaction temperature of this invention is the range of 150-250 degreeC, Preferably, it is the range of 190-220 degreeC.

  The reaction time is in the range of 0.1 to 100 hours, and preferably in the range of 1 to 20 hours.

  The rearrangement reaction can be carried out at normal pressure or under pressure.

  The rearrangement reaction can be carried out by adding an amine compound or an antioxidant as necessary.

  The amine compound is not particularly limited, and examples thereof include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylaminopyridine, benzotriazole, diethylenetriamine, and N, N-dimethylbenzylamine. be able to. These amine compounds may be used individually by 1 type, or may be used in combination of 2 or more type.

  The antioxidant is not particularly limited, and examples thereof include hydroquinone monomethyl ether, hydroquinone monoethyl ether, 3,5-di-t-butyl-4-hydroxytoluene, 2,2′-methylenebis (6-t-butyl). -3-methylphenol), phenolic antioxidants such as 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 3,3′-thiodipropionate didodecyl, Sulfur-based antioxidants such as ditetradecyl 3,3′-thiodipropionate, dioctadecyl 3,3′-thiodipropionate, triphenyl phosphite, diphenylisodecyl phosphite, tris phosphite (nonylphenyl) ) And the like. These antioxidants can be used alone or in combination of two or more.

  After the thermal rearrangement reaction of the bisphenol diallyl ethers, the cellosolve solvent as a reaction solvent can be recovered by distilling off under normal pressure and / or reduced pressure. The recovered cellosolve solvent can be recycled (reused) as it is to at least a part of it in the reaction system.

  When the solvent is distilled off, the reaction mixture can be cooled to a temperature suitable for post-treatment by the latent heat of vaporization of the solvent. The reaction mixture cooled to a temperature suitable for the post-treatment step (about 0 to 150 ° C.) is added with an alkaline aqueous solution to dissolve allylated bisphenols, and a small amount of cellosolve solvent is stored. Can be left. The distilled cellosolve solvent can be recycled (reused) as it is at least in part to the reaction system.

  The reaction product from which the azeotrope has been removed is further purified by ordinary purification operations such as solvent extraction, washing, acid precipitation, recrystallization, and activated carbon purification. Thereby, high quality diallyl bisphenols can be obtained with a high yield.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not construed as being limited to these examples.

  In addition, content of the product in an Example and a comparative example was measured and analyzed on the following conditions, and computed.

Apparatus: LC-10 system manufactured by Shimadzu Corporation Column: YMC-Pack ODS-A312 (6.0φ × 150mmL)
Mobile phase: acetonitrile / distilled water = 50/50
Flow rate: 1.0ml / min.
Detector: UV 254nm
Elution time: 4,4'-diallyloxydiphenylsulfone = 30 minutes
Bis (3-allyl-4-hydroxyphenyl) sulfone = 9 minutes

  However, about Example 3, the conditions were changed as follows.

Mobile phase: acetonitrile / distilled water = 80/20
Detector: UV 280nm (during rearrangement reaction)
Elution time: 2,2-bis (4-allyloxyphenyl) propane = 14 minutes
2,2'-bis (3-allyl-4-hydroxyphenyl) propane = 9 minutes

  Further, ethylene glycol monobutyl ether was measured, analyzed and calculated under the following conditions.

Device: GC-2010 manufactured by Shimadzu Corporation
Column: TC-WAX (0.25 mmφ × 30 m film thickness 0.25 μm)
Carrier gas: Nitrogen 30ml / min
Column temperature: 90 ° C. to 250 ° C. 10 ° C./min
Detector: FID 250 ° C
Elution time: ethylene glycol monobutyl ether = 9 minutes

Example 1
In an autoclave equipped with a stirrer, 3800 g of ethylene glycol monobutyl ether and 500 g of water were added and mixed, and 1000 g (4.0 mol) of 4,4′-dihydroxydiphenylsulfone (hereinafter referred to as bisphenol S) and 288 g of sodium hydroxide (7. 2 mol) and 170 g (1.6 mol) of sodium carbonate were added successively. Next, 670 g (8.8 mol) of allyl chloride was added to form a sealed state, and the reaction was carried out by stirring with heating at 95 to 100 ° C. for 5 hours.

  After completion of the reaction, the pressure was released, and the reaction solution was further heated to distill off unreacted allyl chloride and the like. The distillate was separated into an upper layer and a lower layer. The upper layer (recovered solvent A) contained 165 g of ethylene glycol monobutyl ether.

  After cooling the residual reaction liquid after distillation to 100 ° C., 1300 g of water was added and stirred to dissolve the by-product inorganic salt, followed by liquid separation to extract the lower layer (aqueous layer).

  The lower layer was 1900 g, and was an aqueous solution containing about 30% by weight of inorganic salts (sodium chloride) as main components and 0.3% by weight of ethylene glycol monobutyl ether. 4,4'-diallyloxydiphenyl sulfone (hereinafter referred to as bisphenol S diallyl ether) was not detected from the lower layer.

  The upper layer (organic layer) was an ethylene glycol monobutyl ether solution of bisphenol S diallyl ether, having a water content of about 5% and a Na content of about 1000 ppm. The HPLC composition ratio (area percentage) was as follows: bisphenol S diallyl ether 97.1%, bisphenol S 0.2%, 4-hydroxyphenyl-4′-allyloxyphenyl sulfone (hereinafter referred to as bisphenol S monoallyl ether) 0. 7%.

  To the upper layer (organic layer), 19 g (0.2 mol) of 35% hydrochloric acid was added and stirred for 1 hour, followed by distillation under normal pressure to remove 393 g of distillate. This distillate (recovered solvent B) contained 45 g of ethylene glycol monobutyl ether.

  The kettle residue reaction liquid after the distillation was subjected to hot filtration to remove insoluble matters. The reaction solution (filtrate) after hot filtration contained 30 ppm of Na, and the yield calculated from the content of bisphenol S diallyl ether was 97%.

  The reaction solution (filtrate) after hot filtration, 0.13 g of N, N-dimethylaniline, and 0.13 g of hydroquinone monomethyl ether were charged into an autoclave and sealed at 205 to 215 ° C. in a sealed state (0.2 MPaG). The heat rearrangement reaction was performed for a time. The HPLC composition ratio (area percentage) of the reaction solution after the heat rearrangement reaction was 92.0% bis (3-allyl-4-hydroxyphenyl) sulfone, 2.9% monoallyl, 0.9% monorearrange, and others. It was 4.2%.

  Ethylene glycol monobutyl ether, which is a solvent in this reaction solution, was cooled by distillation under normal pressure and reduced pressure, and 3420 g was recovered. The recovered distillate (recovered solvent C) had a GC composition ratio (area percentage) of 99.5% ethylene glycol monobutyl ether.

  When the residual reaction solution after distillation has reached about 100 ° C., 3500 g of water and 1766 g of 13 wt% sodium hydroxide aqueous solution are added to the reaction solution and stirred. The ethylene glycol monobutyl ether was removed by azeotropy with water. The azeotropic distillate was 1300 g (recovered solvent D), and contained 170 g of ethylene glycol monobutyl ether.

  After the distillation, the remaining reaction liquid in the kettle was transferred to a four-necked flask, water was further added thereto, activated carbon treatment was performed, and the target product was acidified using 25% by weight sulfuric acid. The obtained crystals were separated by filtration, washed with water, and dried to obtain 1114 g of a bis (3-allyl-4-hydroxyphenyl) sulfone purified product (yield based on bisphenol S: 84.4%). The purified bis (3-allyl-4-hydroxyphenyl) sulfone purified product had an HPLC composition ratio (area percentage) of 97.3% and a melting point of 154-155 ° C.

Example 2
145 g of ethylene glycol monobutyl ether was added to the mixture of the total amount of the recovery solvents A to C in Example 1 and 182 g of the recovery solvent D, and bisphenol S, sodium hydroxide and sodium carbonate were sequentially added in the same manner as in Example 1, When the reaction and the post-treatment were performed in the same manner, 1117 g of bis (3-allyl-4-hydroxyphenyl) sulfone purified product (yield based on bisphenol S: 84.5%) was obtained. The purified bis (3-allyl-4-hydroxyphenyl) sulfone purified product had an HPLC composition ratio (area percentage) of 97.1% and a melting point of 154-155 ° C.

Example 3
In an autoclave equipped with a stirrer, 356 g of ethylene glycol monobutyl ether and 19 g of water were mixed and mixed, 150 g (0.657 mol) of 2,2′-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), hydroxylated Sodium 53 g (1.325 mol) and sodium carbonate 14 g (0.132 mol) were added sequentially. Subsequently, 121 g (1.581 mol) of allyl chloride was added to form a sealed state, and the reaction was carried out by stirring with heating at 100 to 105 ° C. for 8 hours.

  After completion of the reaction, allyl chloride was distilled off in the same manner as in Example 1, a water solution was added, neutralized, and then subjected to a hot filtration treatment to obtain an ethylene glycol monobutyl ether solution of bisphenol A diallyl ether. This reaction solution had a Na content of about 10 ppm. The HPLC composition ratio (area percentage) was 2,2-bis (4-allyloxyphenyl) propane 95.0%, bisphenol A 0.2%, 4-hydroxyphenyl-4′-allyloxyphenylpropane (hereinafter, Bisphenol A monoallyl ether) 2.2%. The yield calculated from the content of bisphenol A diallyl ether was 95%.

  The reaction solution (filtrate) after the hot filtration was charged into an autoclave, and a heat rearrangement reaction was performed at 195 to 200 ° C. for 7 hours in a sealed state (0.1 MPaG). Thereafter, ethylene glycol monobutyl ether was distilled off at 150 ° C. under reduced pressure to obtain 166 g of 2,2′-bis (3-allyl-4-hydroxyphenyl) propane (hereinafter referred to as diallyl-bisphenol A) (relative to bisphenol A). Yield: 82%). The HPLC composition ratio (area percentage) of the obtained diallyl-bisphenol A was 92.0%.

Comparative Example 1
Allylation of bisphenol S was carried out, and the reaction solution (bottle residue) thus obtained was separated in the same manner as in Example 1 until the lower layer (aqueous layer) was extracted.

  The upper layer (organic layer) was filtered hot to remove insolubles. The reaction liquid (filtrate) after hot filtration contained 1000 ppm of Na. This reaction liquid (filtrate) was cooled, crystallized, filtered and washed, and then dried to obtain 1200 g of bisphenol S diallyl ether as a powder. The yield was 90.9%.

  A flask containing 1200 g of the obtained bisphenol S diallyl ether, 800 g of Diana Fresia W-8 (paraffin oil), 800 g of kerosene, 0.13 g of N, N-dimethylaniline, 0.13 g of hydroquinone monomethyl ether and 0.04 g of 98% sulfuric acid. And a heat rearrangement reaction was carried out at 205 to 215 ° C. under normal pressure for 7 hours under a nitrogen stream. The HPLC composition ratio (area percentage) of the reaction product after the thermal rearrangement reaction was 93.5% di-rearranged, 0.8% monoallyl, and 1.1% mono-rearranged.

  The reaction product was cooled, added with 1766 g of a 13 wt% aqueous sodium hydroxide solution, stirred and allowed to stand and separated. Then, the lower layer alkaline aqueous solution was charged into a four-necked flask and water was added, followed by activated carbon treatment. The target product was acidified using 25% by weight sulfuric acid. The obtained crystals were separated by filtration, washed with water, and then dried to obtain 1045 g of bis (3-allyl-4-hydroxyphenyl) sulfone purified product (yield based on bisphenol S: 79.2%). It was. The HPLC composition ratio (area percentage) of the purified bis (3-allyl-4-hydroxyphenyl) sulfone product was 97.5%.

Comparative Example 2 [Additional Examination of Example 2 in Patent Document 2]
To a four-necked flask, 4000 g of N, N-dimethylformamide, 1000 g (4.0 mol) of 4,4′-dihydroxydiphenylsulfone (hereinafter referred to as bisphenol S) and 608 g (4.4 mol) of potassium carbonate are sequentially added and mixed. did. Subsequently, 1780 g (8.4 mol) of p-toluenesulfonic acid allyl ester was added, and the mixture was reacted by heating and stirring at 110 to 120 ° C. for 8 hours.

  The HPLC composition ratio (area percentage) of this reaction solution was as follows: bisphenol S diallyl ether 98.5%, bisphenol S 0.1%, 4-hydroxyphenyl-4'-allyloxyphenyl sulfone (bisphenol S monoallyl ether) 0. 5%.

  After completion of the reaction, the reaction solution was further heated, and the temperature was raised to 200 ° C. while unreacted allyl chloride, the solvent N, N-dimethylformamide and the like were distilled off. Then, the heat rearrangement reaction was performed at 200-220 degreeC for 6 hours.

  The HPLC composition ratio (area percentage) of the reaction solution after the heat rearrangement reaction was 35.3% bis (3-allyl-4-hydroxyphenyl) sulfone, 8.6% monoallyl, 3.5% monorearrange, and others. The component was 52.6%.

  To this reaction solution, 2,400 g of 1,2,4-trichlorobenzene was added and cooled to 30 ° C., but the target product did not crystallize from the reaction solution, and a granular solid precipitated.

Comparative Example 3 [Allylation Reaction with Solvent Used in Rearrangement Reaction of Comparative Example 1]
In an autoclave equipped with a stirrer, 1900 g of Diana Fresia W-8 (paraffin oil), 1900 g of white kerosene, 500 g of water, 1000 g (4.0 mol) of 4,4′-dihydroxydiphenyl sulfone (hereinafter referred to as bisphenol S), sodium hydroxide 288 g (7.2 mol) and 170 g (1.6 mol) of sodium carbonate were sequentially added and mixed. Then, 50 g (0.18 mol) of tetrabutylammonium chloride and 670 g (8.8 mol) of allyl chloride were used as a phase transfer catalyst. Was added to form a sealed state, and the reaction was carried out by stirring with heating at 95 to 100 ° C. for 5 hours.

  After completion of the reaction, the pressure was released, and the reaction solution was further heated to distill off unreacted allyl chloride and the like.

  After cooling the reaction liquid after distillation to 100 ° C., 1300 g of water was added and stirred to dissolve the by-product inorganic salt. As a result, the target product became granular and settled to the lower liquid separation layer (water layer). It was.

  Therefore, after separating the reaction solution, the lower layer of the separated solution was filtered to obtain a bisphenol S diallyl ether reaction product. The HPLC composition ratio (area percentage) of the reaction product was 73.9% bisphenol S diallyl ether, 3.4% bisphenol S, 4-hydroxyphenyl-4′-allyloxyphenyl sulfone (bisphenol S monoallyl ether) 10. Since the purity was as low as 2% and other components were 12.4%, the post-process was stopped.

Claims (5)

A method for consistently producing diallyl bisphenols from bisphenols, comprising the following steps (1) to (3).
(1) reacting a bisphenol or an alkali metal salt thereof with an allyl halide in a cellosolve solvent in the presence or absence of a basic alkali metal salt;
(2) a step of separating a by-product inorganic salt from the reaction solution obtained in step (1),
(3) A step of heating the reaction liquid obtained in step (2) to perform a rearrangement reaction. The method according to claim 1, comprising a step of recovering the cellosolve solvent in step (2) and / or step (3) and reusing at least a part of the recovered cellosolve solvent as a reaction solvent. The method according to claim 1 or 2, wherein the cellosolve solvent is at least one selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. The method according to claim 1, wherein the bisphenol is bis (4-hydroxyphenyl) sulfone. The method of any one of Claims 1-4 including the process of isolate | separating a byproduct inorganic salt and neutralizing the obtained reaction liquid in a process (2).