TWI616431B - Continuous manufacturing method of diallyl bisphenols - Google Patents

Abstract

An object of the present invention is to provide a method for continuously producing high-quality diallyl bisphenols from bisphenols in a high yield.

Through the method of the present invention including the following steps (1) to (3), diallyl bisphenols can be continuously produced from bisphenols: (1) in the presence or absence of a basic alkali metal salt, A step of reacting a bisphenol or an alkali metal salt thereof with an allyl halide in a Sailuth solvent; (2) a step of separating an inorganic salt by-product from the reaction solution obtained in step (1); and ( 3) A step of heating the reaction solution obtained in step (2) to perform a rearrangement reaction.

Description

Continuous manufacturing method of diallyl bisphenols Field of invention

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

Background of the invention

The diallyl bisphenols are useful as a developer for a thermosensitive recording material, and various production methods have been tested. For example, bisphenol S (dihydroxydiphenylphosphonium) is reacted with allyl bromide to perform an allylation reaction. The obtained bisphenol S diallyl ether is taken out as a powder, and then the diene is heated. Propyl ether for rearrangement (Claisen rearrangement) reaction, this kind of diallyl bisphenol S (3,3'-diallyl-4,4'-dihydroxydiphenylsulfonium) The manufacturing method is well known (Patent Document 1).

However, in this manufacturing method, after the allylation reaction, the obtained bisphenol S diallyl ether is crystallized and taken out as a powder, so the yield of bisphenol S di about 6% is about 6%. Allyl ether will be lost in the filtrate, and as a result, there will be a problem that the yield of the final target product, diallyl bisphenol S, is low.

On the other hand, Patent Document 2 describes a method for producing a diallyl bisphenol S without taking out the bisphenol S diallyl ether in the middle, and discloses that an allylation reaction is performed in water and / or an organic solvent, The rearrangement reaction is performed in a solvent or without a solvent. It is described in this document that the solvents used for allylation are low For a boiling point solvent, after the solvent is distilled off, the Claisen rearrangement reaction is performed in the absence of a solvent or a solvent used for rearrangement. Specifically, the solvent used for the allylation is distilled off, and Lai Sen rearrangement reaction.

However, it is known that the Claisen rearrangement in the absence of a solvent is difficult to use industrially due to difficulty in temperature control (Patent Document 3). Furthermore, Patent Document 3 also discloses that when using ethylene glycol as a solvent in the Clesen rearrangement, a highly polar substance is generated, and therefore it is best to avoid using the solvent for the reaction as much as possible.

Therefore, in the production of diallyl bisphenols, in general, the allylation reaction is often performed in a polar solvent, and the rearrangement reaction is performed in a non-polar solvent, and there are solvent replacement operations or management of two solvents. Economical issues such as the need for separate operations and storage containers.

Advance technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open No. 61-089090

[Patent Document 2] Japanese Patent Laid-Open No. 60-169456

[Patent Document 3] Japanese Patent Laid-Open No. 62-053957

Summary of invention

The present invention has been made in view of the aforementioned problems, and its main object is to provide high-quality diallyl bisphenols in a high yield.

As a result of intensive research in order to achieve the aforementioned problems, the present inventors have found that in the production of diallyl bisphenols, it is possible to continuously perform an allylation reaction and the use of a cellosolve-based solvent and The Claisen rearrangement reaction yields diallyl bisphenols with high quality and high yield. Based on the results of continuous research on such knowledge, the present invention has been completed.

That is, this invention provides the manufacturing method of the following diallyl bisphenol.

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

Item 2. The method according to item 1, comprising the steps of: in step (2) and / or step (3), recovering a Cyrus Solvent solvent, and recovering at least A part is reused as a reaction solvent.

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

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

Item 5. The method according to any one of items 1 to 4, which includes the following step in step (2): separating an inorganic salt by-product and neutralizing the obtained reaction solution.

According to the manufacturing method of the present invention, the powdered bisphenol diallyl ether is not taken out during the manufacturing process, so the loss of bisphenol diallyl ether in the filtrate is avoided, and the diene can be obtained in high yield. Propyl bisphenols.

In addition, since the bisphenol diallyl ether is not powdered and processed in a solution state, not only does the powdering-related equipment be unnecessary, but also pumping and transportation becomes very easy to handle, so it can be manufactured. The equipment is extremely simplified.

Furthermore, since the allylation and rearrangement reactions are carried out under a common solvent, there is no need for a solvent replacement operation or an operation for managing the two solvents, and a separate storage container can be provided, which can reduce manufacturing steps or use equipment. For industrial manufacturing.

In addition, after the rearrangement reaction, when the temperature is lowered for the post-processing step, the latent heat of evaporation of the solvent can be used to recover the reaction solvent. Therefore, the recovered solvent can be reused in each step to become a reasonable and energy-saving process.

Detailed description of the preferred embodiment Forms used to implement the invention

Hereinafter, the present invention will be described in detail.

In the present invention, as the continuous production of diallyl bisphenol from bisphenols Method, which includes the following steps (1) to (3): (1) in the presence or absence of a basic alkali metal salt, bisphenols or their alkali metal salts and allyl halides A step of reacting in a Cyrus Thousand series solvent; (2) a step of separating an inorganic salt by-product from the reaction liquid obtained in step (1); and (3) heating and reacting the reaction liquid obtained in step (2) Exhaust reaction steps.

Each step is described below.

1. About step (1)

The above step (1) is performed by, for example, charging a sealed container such as an autoclave with a cyrus solvent, a bisphenol of the starting material or an alkali metal salt thereof, and a base metal compound and water as required. It is preferred that the allyl halide is added dropwise under heating and the reaction is carried out at a predetermined time.

Examples of the bisphenols as the starting material include those represented by the following general formula (1).

(In the formula, A represents a single bond, -CH _2- , -S-, -SO _2- , -C (CH ₃ ) _2- , or The benzene nucleus can be replaced again). Industrially, compounds having a hydroxyl group at the 4,4'-position are particularly important.

Specific examples include 2,2'-bis (4-hydroxyphenyl) propane (hereinafter also referred to as "bisphenol A") and 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) fluorene (hereinafter also referred to as `` bisphenol S ''), bis (3-methyl- 4-hydroxyphenyl) fluorene and the like.

Examples of the bisphenol-based alkali metal salt of the above-mentioned starting material include those in which the -OH group of H replaces an alkali metal in the general formula (1). As the alkali metal, sodium and potassium are preferred. The alkali metal salt of bisphenols may be a mono-alkali metal salt or a bis-alkali metal salt. When a double alkali metal salt of a bisphenol is used as a starting material, there may be cases where a basic alkali metal compound described below is not necessary.

The bisphenols and their alkali metal salts represented by the general formula (1) used in the present invention may be powders or wet cakes that can be produced by conventional methods, and may be in any form.

Allyl halides in the present invention include compounds in which a substituent is introduced into the α, β, and γ positions of allyl. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aromatic group, and the like. Specific examples of the allyl halide include allyl chloride, allyl bromide, allyl iodide, crotyl chloride, crotyl bromide, cinnamyl chloride, and cinnamyl bromide.

Examples of the Sailuthul-based solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Among them, ethylene glycol monobutyl ether is preferred. They can be mixed and used. It may also contain water.

Examples of the basic alkali metal compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and alkali metal carbonates such as sodium carbonate and potassium carbonate. The amount of the basic alkali metal compound used is usually 1.5 to 4 times moles, and preferably 2 to 3 times moles relative to bisphenols. In addition, when a double alkali metal salt of a bisphenol is used as a starting material, a basic alkali metal compound may not be used in some cases. These basic alkali metal compounds can be used alone or in combination of two or more.

In the reaction of the present invention, the molar ratio of bisphenols or their alkali metal salts to allyl halides is in the range of 1: 2 to 1: 5, and is preferably in the range of 1: 2 to 1: 4. .

The aforementioned reaction temperature is in a range of 50 to 150 ° C, and preferably in a range of 80 to 120 ° C.

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

2. About step (2)

The aforementioned step (2) is a step of separating an inorganic salt by-product from the reaction liquid by a conventional method. For example, it is performed by adding a sufficient amount of water or warm water to the reaction product obtained in the aforementioned step (1) to dissolve a by-product of inorganic salts (such as a halogenated alkali metal) precipitated by supersaturation. The inorganic salt by-product was dissolved, and then left to stand. The liquid was separated into a luteus-based solvent layer containing bisphenol diallyl ether and an aqueous layer containing an inorganic salt by-product. The aqueous layer was separated and removed.

Further, 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, and the inorganic salt is added. When the by-products are dissolved, the following pretreatments can be performed.

That is, by adding water to the obtained reaction solution as needed while heating and distilling, allyl halide (for example, allyl chloride) of unreacted raw materials and / or alcohols (for example, allyl) Alcohol) and the like were separated by distillation. The distillate thus obtained was further separated into an organic layer containing an allyl halide and a celestial solvent of an unreacted raw material, and an aqueous layer containing by-product alcohols and water. Therefore, the organic layer (organic layer containing an allyl halide and a celestial solvent) can be reused (reused) in the reaction system at least in part.

In this way, the allylation reaction liquid from which the by-product of the inorganic salt has been separated can be supplied to the subsequent rearrangement reaction.

In the method of the present invention, after the aqueous layer (aqueous solution layer containing an inorganic salt by-product) and the organic layer (a bisphenol diallyl ether-containing celus-based solvent layer) are separated and separated, the system is It is desirable to separate and remove a small amount of water contained in the organic layer, and then remove the inorganic salt by-products obtained by organic chromatography, and then provide the subsequent rearrangement reaction.

When separating and removing the water contained in the 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 a Cyrus Thousand series solvent, and at least a part of it can be reused (reused) in the reaction system.

After the water is separated and removed, Salt by-products can be easily removed by hot filtration (hot-time filtration), decantation, and the like.

In addition, in the method of the present invention, in order to more effectively remove the inorganic salt contained in the organic layer (a bisphenol diallyl ether-containing selenium-based solvent layer), it is also possible to separate the This organic layer is subjected to a neutralization treatment, and then the moisture in the organic layer is separated and removed in accordance with the above procedure, and the precipitated inorganic salt by-product is removed.

As the aforementioned neutralization process, 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 (Selothus solvent layer) is subjected to a neutralization treatment as necessary, and after removing water, the precipitated inorganic salt by-products such as hot filtration are removed, thereby obtaining the weight for subsequent connection. Removal of bisphenol diallyl ethers (eg, 4,4'- diallyloxydiphenylphosphonium).

3. About step (3)

The aforementioned step (3) is a rearrangement reaction step. For example, the organic layer obtained by separating the water layer in step (2) can be carried out under heating for a predetermined time.

The rearrangement reaction temperature of the present invention is in the range of 150 to 250 ° C, and preferably in the range of 190 to 220 ° C.

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

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

For the above rearrangement reaction, an amine compound or an antioxidant may be added as necessary Chemical agent.

The amine compound is not particularly limited, and examples thereof include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylaminopyridine, benzotriazole, and diethylene glycol. Triamine, N, N-dimethylbenzylamine and the like. These amine compounds may be used singly or in combination of two or more kinds.

The antioxidant is not particularly limited, and examples thereof include hydroquinone monomethyl ether, hydroquinone monoethyl ether, 3,5-di-tertiary butyl-4-hydroxytoluene, and 2,2'- Methylbis (6-tertiarybutyl-3-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tertiarybutylphenyl) butane and other phenolic antibodies Oxidant; 3,3'-thiodipropionate di (twelve) ester, 3,3'-thiodipropionate di (tetradecyl) ester, 3,3'-thiodipropionate di (eighteen) ) Sulfur-based antioxidants such as esters; phosphorus-based antioxidants such as triphenyl phosphite, diphenyl isodecyl phosphite, and tri (nonylphenyl) phosphite. These antioxidants can be used singly or in combination of two or more kinds.

After the above-mentioned bisphenol diallyl ethers are rearranged by heating, the Sailu-based solvent as a reaction solvent can be distilled off under normal pressure and / or reduced pressure, thereby recovering it. Moreover, at least a part of the recovered Celus-based solvent can be reused (reused) in the reaction system.

When the solvent is distilled off, the reaction mixture can be cooled to an appropriate temperature during the post-treatment by the latent heat of evaporation of the solvent. After cooling the reaction mixture to an appropriate temperature (about 0 to 150 ° C.) in the post-treatment step, an alkaline aqueous solution can be added to dissolve the allylized bisphenols, and distill off a small amount of the Sailusu-based solvent. In addition, a part of the distilled Silusu-based solvent can be recycled (reused) to the reaction system.

The reactant from which the azeotrope has been removed is purified by general purification operations such as solvent extraction, washing, acid precipitation, recrystallization, and activated carbon purification. This makes it possible to obtain high-quality diallyl bisphenols in a high yield.

[Example]

Hereinafter, the present invention will be described in more detail through examples, but the interpretation of the present invention is not limited to these examples.

In addition, the product contents in the examples and comparative examples were measured, analyzed, and calculated under the following conditions.

Device: LC-10 system made by Shimadzu

Column: YMC-Pack ODS-A312 (6.0φ × 150mmL)

Mobile phase: acetonitrile / distilled water = 50/50

Flow: 1.0ml / min.

Detector: UV 254nm

Dissolution time: 4,4’-diallyloxydiphenyl 碸 = 30 minutes Bis (3-allyl-4-hydroxyphenyl) 碸 = 9 minutes

However, in Example 3, the conditions are changed as follows.

Mobile phase: acetonitrile / distilled water = 80/20

Detector: UV 280nm (during rearrangement reaction)

Dissolution time: 2,2-bis (4-allyloxyphenyl) propane = 14 minutes 2,2’-bis (3-allyl-4-hydroxyphenyl) propane = 9 minutes

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

Installation: Shimadzu GC-2010

Column: TC-WAX (0.25mmφ × 30m film thickness 0.25μm)

Carrying gas: nitrogen 30ml / min

Column temperature: 90 ℃ ~ 250 ℃ 10 ℃ / min

Detector: FID 250 ℃

Dissolution 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 then 1,000 g (4.0 mol) of 4,4'-dihydroxydiphenylphosphonium (hereinafter, bisphenol S) was added sequentially. ), Sodium hydroxide 288 g (7.2 mol) and sodium carbonate 170 g (1.6 mol). Next, 670 g (8.8 mol) of allyl chloride was added to form a sealed state, and the reaction was performed by heating and stirring at 95 to 100 ° C for 5 hours.

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

After the above-mentioned distilled kettle reaction liquid was cooled to 100 ° C, 1300 g of water was added, and the inorganic salt by-products were dissolved by stirring, and the lower layer (aqueous layer) was discharged after liquid separation.

The lower layer is 1900 g, and is an aqueous solution containing about 30% by weight of inorganic salts (sodium chloride) as a main component and containing 0.3% by weight of ethylene glycol monobutyl ether. No 4,4'-diallyloxydiphenylphosphonium (hereinafter, bisphenol S diallyl ether) was detected from this lower layer.

The upper layer (organic layer) is a solution of bisphenol S diallyl ether in ethylene glycol monobutyl ether. The water content is about 5% and the Na content is about 1000 ppm. The HPLC composition ratio (area percentage) is 97.1% of bisphenol S diallyl ether, 0.2% of bisphenol S, and 4-hydroxyphenyl-4'-allyloxyphenyl hydrazone (hereinafter, bisphenol S monoallyl Ether) 0.7%.

19 g (0.2 mol) of 35% hydrochloric acid was added to this upper layer (organic layer), and after stirring for 1 hour, it was distilled under normal pressure to remove 393 g of distillate. This distillate (recovered solvent B) contained 45 g of ethylene glycol monobutyl ether.

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

The reaction solution (filtrate), 0.13 g of N, N-dimethylaniline and 0.13 g of hydroquinone monomethyl ether after the hot filtration were charged into an autoclave, and in a sealed state (0.2 MPaG) at 205 to 215 ° C. A heat rearrangement reaction was performed for 7 hours. HPLC composition ratio (area percentage) of the reaction solution after heating rearrangement reaction, based on bis (3-allyl-4-hydroxyphenyl) -4- 92.0%, monoallyl 2.9%, single rearrangement 0.9%, others 4.2%.

In this reaction solution, ethylene glycol monobutyl ether as a solvent was distilled off under normal pressure and reduced pressure to cool, and 3420 g was recovered. The recovered distillate (recovered solvent C) had a GC composition ratio (area percentage) of 99.5% as ethylene glycol monobutyl ether.

When the distilling residual reaction liquid in the kettle became about 100 ° C, 3500 g of water and 1766 g of a 13% by weight aqueous sodium hydroxide solution were added to the reaction liquid and stirred, and the remaining ethylene glycol was distilled under heating at normal pressure. Butyl ether is removed by azeotroping with water. The azeotropic distillate was 1300 g (recovered solvent D) and contained 170 g of ethylene glycol monobutyl ether.

The residual reaction liquid of the still kettle after the distillation was transferred to a four-necked flask, and after adding water, it was treated with activated carbon, and the target substance was acidified using 25% by weight sulfuric acid. The obtained crystal was filtered off, washed with water, and dried to obtain 1114 g of a purified bis (3-allyl-4-hydroxyphenyl) fluorene (yield relative to bisphenol S: 84.4%). The obtained bis (3-allyl-4-hydroxyphenyl) fluorene purified product had an HPLC composition ratio (area percentage) of 97.3% and a melting point of 154 to 155 ° C.

Example 2

145 g of ethylene glycol monobutyl ether was added to a mixture of all the recovered solvents A to C and 182 g of the recovered solvent D in Example 1, and bisphenol S, sodium hydroxide, and carbonic acid were sequentially added in the same manner as in Example 1. Sodium was subjected to the same reaction and post-treatment. As a result, 1117 g of a purified product of bis (3-allyl-4-hydroxyphenyl) fluorene was obtained (yield of p-bisphenol S: 84.5%). The obtained bis (3-allyl-4-hydroxyphenyl) fluorene purified product had an HPLC composition ratio (area percentage) of 97.1% and a melting point of 154 to 155 ° C.

Example 3

In an autoclave equipped with a stirrer, 356 g of ethylene glycol monobutyl ether and 19 g of water were added and mixed, and 150 g of 2,2'-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) was sequentially added ( 0.657 moles), sodium hydroxide 53g (1.325 moles) and sodium carbonate 14g (0.132 moles). Next, 121 g (1.581 mol) of allyl chloride was added to form a sealed state, and the mixture was heated and stirred at 100 to 105 ° C. for 8 hours to perform a reaction.

After completion of the reaction, the allyl chloride was distilled off in the same manner as in Example 1, and a water solution was added. After neutralization, heat filtration treatment was performed to obtain a solution of bisphenol A diallyl ether in ethylene glycol monobutyl ether. The Na content of this reaction liquid was about 10 ppm. The HPLC composition ratio (area percentage) is 9,2-bis (4-allyloxyphenyl) propane 95.0%, bisphenol A 0.2%, and 4-hydroxyphenyl-4'-allyloxybenzene. Propane (hereinafter, bisphenol A monoallyl ether) 2.2%. Bisphenol A diene The yield based on the propyl ether content 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 under reduced pressure at 150 ° C to obtain 2,2'-bis (3-allyl-4-hydroxyphenyl) propane (hereinafter, diallyl- Bisphenol A) 166 g (yield of para-bisphenol A: 82%). The HPLC composition ratio (area percentage) of the obtained diallyl-bisphenol A was 92.0%.

Comparative Example 1

Allylization of bisphenol S was performed, and the obtained reaction liquid (residue in the kettle) was carried out in the same manner as in Example 1 until the liquid was separated and the lower layer (aqueous layer) was discharged.

The upper layer (organic layer) was filtered hot to remove insoluble matter. In the reaction solution (filtrate) after hot filtration, the Na content was 1000 ppm. The reaction solution (filtrate) was cooled, crystallized, filtered, washed, and dried to obtain 1200 g of powdered bisphenol S diallyl ether. The yield was 90.9%.

1200 g of the obtained bisphenol S diallyl ether, 800 g of Diana Fresia W-8 (paraffin oil), 800 g of lamp oil, 0.13 g of N, N-dimethylaniline, 0.13 g of hydroquinone monomethyl ether, and 98% sulfuric acid 0.04 g was placed in a flask, and a heating rearrangement reaction was performed under a nitrogen flow at a normal pressure of 205 to 215 ° C for 7 hours. The HPLC composition ratio (area percentage) of the reactants after the heat rearrangement reaction was 93.5% of the double rearrangement, 0.8% of the monoallyl, and 1.1% of the single rearrangement.

The reaction product was cooled, and 1766 g of a 13% by weight sodium hydroxide aqueous solution was added and stirred. After standing and separated, the lower alkali aqueous solution was charged into a four-necked flask, and after adding water, it was treated with activated carbon. Acidification of target. The obtained crystal was filtered off, washed with water and dried to obtain bis (3-ene 1045 g of propyl-4-hydroxyphenyl) fluorene purified product (yield of p-bisphenol S: 79.2%). The obtained bis (3-allyl-4-hydroxyphenyl) fluorene purified product had an HPLC composition ratio (area percentage) of 97.5%.

Comparative Example 2 [Retest of Example 2 in Patent Document 2]

In a four-necked flask, 4000 g of N, N-dimethylformamide, 1,000 g (4.0 mol) of 4,4'-dihydroxydiphenylsulfonium (hereinafter, bisphenol S), and 608 g of potassium carbonate were sequentially added ( 4.4 moles) and mixed. Next, 1780 g (8.4 moles) of allyl p-toluenesulfonate was added, and the reaction was carried out by heating and stirring at 110 to 120 ° C for 8 hours.

The HPLC composition ratio (area percentage) of the reaction solution was 98.5% of bisphenol S diallyl ether, 0.1% of bisphenol S, 4-hydroxyphenyl-4'-allyloxyphenyl hydrazone (bisphenol S Monoallyl ether) 0.5%.

After completion of the reaction, the reaction solution was heated again, and unreacted allyl chloride or N, N-dimethylformamide as a solvent was distilled off, and the temperature was raised to 200 ° C. Thereafter, a heat rearrangement reaction was performed at 200 to 220 ° C for 6 hours.

The HPLC composition ratio (area percentage) of the reaction solution after the heat rearrangement reaction is bis (3-allyl-4-hydroxyphenyl) 苯基 35.3%, monoallyl 8.6%, single rearrangement 3.5%, Other ingredients 52.6%.

2400 g of 1,2,4-trichlorobenzene was added to the reaction solution, and after cooling to 30 ° C., the target substance was precipitated from the reaction solution as an uncrystallized granular solid.

Comparative Example 3 [Allylation reaction in solvent used in Comparative Example 1 rearrangement reaction]

In an autoclave equipped with a mixer, 1900g of Diana Fresia W-8 (paraffin oil), 1900g of white light oil, 500g of water, and 4,4'-dihydroxydiphenylphosphonium (hereinafter, bisphenol S) 1000g ( 4.0 moles), sodium hydroxide 288g (7.2 moles) 170 g (1.6 mol) of sodium carbonate and sodium carbonate, and then mixed with 50 g (0.18 mol) of tetrabutylammonium chloride and 670 g (8.8 mol) of allyl chloride as a phase-moving catalyst to form a closed state, The reaction was carried out by heating and stirring at 95 to 100 ° C for 5 hours.

After the reaction was terminated, the pressure was released, and the reaction solution was heated to remove unreacted allyl chloride and the like.

The reaction solution after the distillation was cooled to 100 ° C, 1300 g of water was added, and the inorganic salt by-product was dissolved by stirring. As a result, the target substance became granular and settled in the liquid separation lower layer (aqueous layer).

Therefore, after the reaction liquid was separated, the lower layer was separated by filtration to obtain a bisphenol S diallyl ether reaction product. The HPLC composition ratio (area percentage) of this reactant was 73.9% of bisphenol S diallyl ether, 3.4% of bisphenol S, and 4-hydroxyphenyl-4'-allyloxyphenyl hydrazone (bisphenol S Monoallyl ether) 10.2%, and other ingredients 12.4%, because the purity is extremely low, the subsequent step is terminated.

Claims (5)

A method for continuously producing diallyl bisphenols from bisphenols. The method comprises the following steps (1) to (3): (1) making bisphenols in the presence or absence of a basic alkali metal salt. A step of reacting a phenol or an alkali metal salt thereof with an allyl halide in a Cellosolve-based solvent; (2) a step of separating an inorganic salt by-product from the reaction solution obtained in step (1); and ( 3) A step of heating the Sailu-based solvent layer obtained in step (2) to perform a rearrangement reaction. For example, the method of claim 1 in the patent scope includes the following steps: in step (2) and / or step (3), recovering a Cyrus Solvent solvent and recovering at least one of the recovered Cyrus Solvent solvents A part is reused as a reaction solvent. For example, the method of claim 1 or 2, wherein the cyrus solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. At least one of them. For example, the method of claim 1 or 2, wherein the bisphenol is bis (4-hydroxyphenyl) fluorene. For example, the method of claim 1 or 2 in the patent application scope includes the following steps in step (2): separating the inorganic salt by-products and neutralizing the obtained celusoid solvent layer.