WO2011019061A1

WO2011019061A1 - Method for producing polyglycidyl ether compound

Info

Publication number: WO2011019061A1
Application number: PCT/JP2010/063658
Authority: WO
Inventors: 博内田
Original assignee: 昭和電工株式会社
Priority date: 2009-08-13
Filing date: 2010-08-11
Publication date: 2011-02-17
Also published as: JPWO2011019061A1

Abstract

In order to provide a method for converting a carbon-carbon double bond in an aryl group of a polyaryl ether compound that is a polyaryl-etherized compound having a plurality of phenolic hydroxyl groups into an efficiently-responding polyglycidyl ether by means of epoxidation using hydrogen peroxide as a catalyst under mild conditions, the disclosed method for producing a polyglycidyl ether compound includes a step for epoxidizing a carbon-carbon double bond in an aryl group of a polyaryl ether compound of a compound having a plurality of phenolic hydroxyl groups that is the starting material, said epoxidizing using hydrogen peroxide as an oxidizing agent under the presence of a quaternary ammonium salt, a phosphorus compound, and a tungsten compound.

Description

Method for producing polyglycidyl ether compound

The present invention relates to a polyglycidyl ether compound in which a carbon-carbon double bond of an allyl group of a compound having a plurality of phenolic hydroxyl groups is epoxidized using hydrogen peroxide as an oxidizing agent in the presence of a tungsten catalyst. It relates to the manufacturing method.

Polyglycidyl ether known as an epoxy resin is widely used in various fields, and is industrially produced on a large scale. As a method for producing polyglycidyl ether, there is a method of obtaining glycidyl ether by reacting bisphenol-A or phenol novolac resin with epichlorohydrin in the presence or absence of a catalyst under basic conditions. The glycidyl ether produced by this production method has a high content of organochlorine compounds that are considered undesirable for electronics applications. Therefore, attempts have been made for a long time to epoxidize the corresponding double bond after allyl etherification of the starting phenolic compound using peracetic acid or hydrogen peroxide.

Patent Document 1 below discloses a method of performing epoxidation in the presence of molybdenum or a tungsten compound, a quaternary ammonium salt, and phosphoric acid, but the reaction rate, yield, and selectivity are not sufficient. .

The following Patent Document 2 discloses an example in which epoxidation of allyl ether, which is subject to conformational restrictions, is successful, but there are restrictions on allyl ether that can be used, and it is not a method that can be universally adopted industrially. .

Further, Patent Document 3 below discloses a method using peracid without using hydrogen peroxide. However, it is necessary to use organic peracid which is frequently used in accidents such as explosions. Since the produced carboxylic acid easily reacts with the epoxy resin, there is a problem that it is difficult to isolate the product with a high yield.

Other than that, the starting material is not polyphenol polyallyl ether, but the following Patent Document 4 discloses a method of epoxidation using methanol or acetonitrile solvent in the presence of potassium carbonate. However, since polyallyl ether of polyphenol is difficult to dissolve in the reaction system of this method, the reaction cannot be carried out. Patent Document 5 discloses a method for producing an epoxy compound in which an olefin is reacted with a hydrogen peroxide solution using α-aminomethylphosphonic acid having a specific structure. However, the olefins described in Patent Document 5 are mainly low molecular weight olefins, and there is no description or suggestion that they can be similarly applied to polyphenol ethers of polyphenols.

Therefore, there is still a need to develop a polyallyl ether epoxidation reaction after allyl etherification of a phenol compound, which can achieve a high conversion rate in a short period of time, and which is satisfactory in yield and selectivity. The

Japanese Unexamined Patent Publication No. 60-60123 JP-T-2002-517287 JP 7-145221 A JP 2006-28057 A JP-A-8-27136

The problem to be solved by the present invention is that an allyl group carbon-carbon double bond of a polyallyl ether compound having a plurality of phenolic hydroxyl groups is bonded to an epoxy using hydrogen peroxide as an oxidizing agent under mild conditions. It is an object to provide a method for efficiently converting to a corresponding polyglycidyl ether with less residual organochlorine compound.

As a result of intensive studies and experiments to solve the above problems, the present inventors have found that a polyglycidyl ether compound can be efficiently obtained by carrying out the reaction in the presence of a specific catalyst system. The invention has been completed.
That is, the present invention includes the following [1] to [12].

[1] A carbon-carbon double bond of an allyl group of a polyallyl ether compound of a compound having a plurality of phenolic hydroxyl groups as a starting material is used as an oxidizing agent in the presence of a tungsten compound, a phosphorus compound and a quaternary ammonium salt. A method for producing a polyglycidyl ether compound, comprising a step of epoxidation using hydrogen peroxide.
[2] The method for producing a polyglycidyl ether compound according to [1], wherein the compound having a plurality of the phenolic hydroxyl groups is polyphenol.

[3] The polyallyl ether compound of polyphenol is catechol, resorcinol, hydroquinone, bisphenol A (p, p′-isopropylidenediphenol), bisphenol F (p, p′-methylenediphenol), bisphenol K (p, p'-diphenolcarbonyl), dihydroxymethylstilbene, dihydroxybiphenyl, tetramethyldihydroxybiphenyl, dihydroxynaphthalene, bis (hydroxyphenyl) fluorene, methane type trisphenols, trisphenols, phenol-aldehyde novolac resin, alkyl-substituted phenol- At least one phenol selected from the group consisting of aldehyde novolac resin, polycyclopentadiene-modified phenolic resin, and polyvinylphenol The method for producing a polyglycidyl ether compound according to [2] above, wherein a part or all of the rutile hydroxyl group is allyl etherified.

[4] The polyallyl ether compound of polyphenol is a methane type trisphenol obtained by condensing an aromatic hydrocarbon having a phenolic hydroxyl group and an aldehyde compound, a phenol-aldehyde novolak resin, and an alkyl-substituted phenol-aldehyde novolak resin. The method for producing a polyglycidyl ether compound according to [3] above, wherein all or part of at least one phenolic hydroxyl group selected from the group is allyl etherified.

[5] The polyallyl ether compound of polyphenol is composed of a polycyclopentadiene-modified phenol resin obtained by condensing an aromatic hydrocarbon having a phenolic hydroxyl group and dicyclopentadiene, and polyvinyl phenol obtained by polymerizing vinyl phenol. The method for producing a polyglycidyl ether compound according to the above [3], wherein a part or all of at least one selected phenolic hydroxyl group is allyl etherified.

[6] The phosphorus compound is phosphoric acid, aminomethylphosphonic acid, α-aminoethylphosphonic acid, α-aminopropylphosphonic acid, α-aminobutylphosphonic acid, α-aminopentylphosphonic acid, α-aminohexylphosphonic acid, α -At least one selected from the group consisting of aminoheptylphosphonic acid, α-aminooctylphosphonic acid, α-aminononylphosphonic acid, α-amino-α-phenylmethylphosphonic acid, and nitrilotris (methylene) trisphosphonic acid A method for producing a polyglycidyl ether compound according to any one of [1] to [5].

[7] The method for producing a polyglycidyl ether compound according to [6], wherein the phosphorus compound is nitrilotris (methylene) trisphosphonic acid.

[8] Any of the above [1] to [7], wherein the tungsten compound is at least one selected from the group consisting of tungstic acid, alkali tungstate, ammonium tungstate, phosphotungstic acid, and silicotungstic acid. A process for producing the polyglycidyl ether compound according to claim 1.

[9] The above [1] to [8], wherein the quaternary ammonium salt is at least one selected from the group consisting of quaternary ammonium sulfate, hydrogen sulfate, and nitrate. The manufacturing method of the polyglycidyl ether compound of description.

[10] The polyglycidyl ether compound according to any one of [1] to [9], wherein the molar ratio of the tungsten atom to the phosphorus compound in the tungsten compound is in the range of 1: 0.1 to 1:10. Manufacturing method.

[11] The molar ratio of the allyl group carbon-carbon double bond to hydrogen peroxide of the polyallyl ether compound of the compound having a plurality of phenolic hydroxyl groups is in the range of 1: 0.5 to 1: 4. The method for producing a polyglycidyl ether compound according to any one of [1] to [10].

[12] The method for producing a polyglycidyl ether compound according to any one of [1] to [11], wherein hydrogen peroxide and, if necessary, a phosphorus compound are additionally added in the epoxidation step.

According to the method for producing a polyglycidyl ether compound of the present invention, it is not necessary to use epichlorohydrin as a raw material, so there is almost no organic chlorine compound mixed in the obtained epoxy compound, and particularly an electronic material (especially an encapsulant or solder). -Glycidyl ether, which is a useful substance widely used in various industrial fields including chemical industry as a raw material for resist materials) and as a raw material for various polymers such as intermediates for agricultural chemicals and pharmaceuticals, plasticizers, adhesives and paint resins. Type epoxy resin can be produced safely, with good yield and at low cost by a simple operation from the reaction of the corresponding polyallyl ether and hydrogen peroxide solution. Therefore, the present invention has a great industrial effect.

It is the schematic explaining an example of the preferable manufacturing flow in the manufacturing method of the polyglycidyl ether compound of this invention. It is the schematic explaining another example of the preferable manufacturing flow in the manufacturing method of the polyglycidyl ether compound of this invention.

The present invention will be described in detail below.
The method for producing a polyglycidyl ether compound of the present invention comprises a polyallyl ether compound of a compound having a plurality of phenolic hydroxyl groups using hydrogen peroxide as an oxidizing agent in the presence of a tungsten compound, a phosphorus compound and a quaternary ammonium salt. The carbon-carbon double bond of the allyl group is epoxidized.

There is no particular limitation on the concentration of the hydrogen peroxide aqueous solution that is a supply source of hydrogen peroxide used as the oxidizing agent in the production method of the present invention, but it is generally 1 to 80% by mass, preferably 20 to 65% by mass. Selected from a range. Of course, from the viewpoint of industrial productivity, hydrogen peroxide is preferably a high concentration, but it is needless to say that it is preferable not to use a high concentration of hydrogen peroxide for safety.

Also, the amount of aqueous hydrogen peroxide used is not particularly limited, but at least the molar equivalent of hydrogen peroxide used cannot epoxidize the allyl group. Therefore, when all the carbon-carbon double bonds of the allyl group of the polyallyl ether compound of the compound having a plurality of phenolic hydroxyl groups are epoxidized, the peroxidation is more than equimolar with respect to the carbon-carbon double bond. Although hydrogen is required, when partially epoxidizing, the amount of hydrogen peroxide used may be less than an equimolar amount. In addition, because the reaction system is acidic, the hydrolysis of the epoxy group tends to proceed easily. Therefore, when the purpose is to increase the yield of epoxidation, excessive amounts of hydrogen peroxide are entrained. An increase in volume should be avoided. In addition, if hydrogen peroxide is used in an excessive amount, the treatment of unreacted hydrogen peroxide after the reaction also becomes a problem. Therefore, the amount of hydrogen peroxide depends on the number of phenolic hydroxyl groups that are substrates to be epoxidized. The number of carbon-carbon double bonds of the allyl group of the polyallyl ether compound of the compound is preferably in the range of 0.5 to 10 molar equivalents, more preferably in the range of 0.5 to 4 molar equivalents. And even more preferably in the range of 1 to 4 molar equivalents.

Tungsten compounds used as catalysts include compounds that generate tungstate anions in water, such as tungstic acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, silicotungstic acid, phosphotungstic acid, ammonium tungstate, and alkali tungstate. Examples include potassium tungstate dihydrate, sodium tungstate dihydrate, etc., but tungstic acid, alkali tungstate (for example, sodium tungstate dihydrate), ammonium tungstate, phosphotungstic acid, silica Tungstic acid or the like is preferable. These tungsten compounds may be used alone or in combination of two or more. The amount used is 0.001 to 20 mol% of tungsten atoms based on the number of carbon-carbon double bonds of the allyl group of the polyallyl ether compound of the compound having a plurality of phenolic hydroxyl groups as the substrate, preferably 0.8. The range is 1 to 20 mol%.

As a method for adding the tungsten compound to the reaction solution, the tungsten compound is previously dissolved in pure water, and then added in a form mixed with a hydrogen peroxide aqueous solution in a range of 0.5 to 10 times moles of the tungsten compound. It is desirable. If this treatment is not performed, the tungsten compound exists in a solid state depending on the pH of the reaction solution, and the reaction does not proceed immediately after the dropwise addition of the aqueous hydrogen peroxide solution. After the addition, the tungsten compound dissolves and the reaction proceeds suddenly, so that the selectivity may deteriorate.

Specific examples of the phosphorus compound include phosphoric acid, aminomethylphosphonic acid, α-aminoethylphosphonic acid, α-aminopropylphosphonic acid, α-aminobutylphosphonic acid, α-aminopentylphosphonic acid, α-aminohexylphosphonic acid, α -Aminoheptylphosphonic acid, α-aminooctylphosphonic acid, α-aminononylphosphonic acid, α-amino-α-phenylmethylphosphonic acid, nitrilotris (methylene) trisphosphonic acid and the like. Among these, phosphoric acid, aminomethylphosphonic acid and nitrilotris (methylene) trisphosphonic acid are preferable, aminomethylphosphonic acid and nitrilotris (methylene) trisphosphonic acid are more preferable, and nitrilotris (methylene) trisphosphonic acid is even more preferable. . These phosphorus compounds may be used alone or in combination of two or more. If the amount used is small, the effect as an epoxidation catalyst is low, and if it is large, the remaining in the product becomes a problem. Therefore, the carbon-carbon double of the allyl group of the polyallyl ether of the compound having a plurality of phenolic hydroxyl groups of the substrate. A range of 0.001 to 10 mol% is preferable based on the number of bonds, and a range of 0.1 to 5 mol% is more preferable.

The ratio of the amount of the tungsten compound and the phosphorus compound used is such that the molar ratio of the tungsten atom to the phosphorus compound in the tungsten compound is in the range of 1: 0.01 to 1: 100, and 1: 0.1 to 1 The range of 10 is more preferable.

In the present invention, the quaternary ammonium salt acts as a phase transfer catalyst. Of the quaternary ammonium salts, sulfate, hydrogen sulfate, and nitrate are preferable. Examples of the quaternary ammonium ion include tetrahexyl ammonium ion, tetraoctyl ammonium ion, methyl trioctyl ammonium ion, tetrabutyl ammonium ion, ethyl trioctyl ammonium ion, cetyl pyridinium ion, and the like. As the quaternary ammonium salt, tetrahexylammonium hydrogen sulfate, tetraoctylammonium hydrogensulfate, methyltrioctylammonium hydrogensulfate and the like are preferable. These quaternary ammonium hydrogen sulfates may be used alone or in combination of two or more. If the amount used is small, the effect as a phase transfer catalyst is low, and if it is large, the remaining in the product becomes a problem. Therefore, the allyl group carbon-carbon two-carbon compound of the compound having a plurality of phenolic hydroxyl groups of the substrate is used. A range of 0.001 to 10 mol% is preferable based on the number of heavy bonds, and a range of 0.1 to 5 mol% is more preferable.

The substrate to be epoxidized, that is, the starting material of the method of the present invention is a polyallyl ether compound of a compound having a plurality of phenolic hydroxyl groups, preferably a polyallyl ether compound of polyphenol, specifically catechol, resorcinol, Hydroquinone, bisphenol A (p, p'-isopropylidenediphenol), bisphenol F (p, p'-methylenediphenol), bisphenol K (p, p'-diphenolcarbonyl), dihydroxymethylstilbene, dihydroxybiphenyl, tetra Methyldihydroxybiphenyl, dihydroxynaphthalene, bis (hydroxyphenyl) fluorene, methane type trisphenols, trisphenols, phenol-aldehyde novolac resin, alkyl-substituted phenol- Aldehyde novolak resins, polycyclopentadiene modified phenol resin, and is obtained by allyl etherifying a part or all of at least one phenolic hydroxyl group is selected from the group consisting of polyvinyl phenol.

Among these, polyphenol polyallyl ether compounds having 3 or more phenolic hydroxyl groups are preferable. Examples of such compounds include methane type trisphenols, trisphenols, phenol-aldehyde novolak resins, alkyl-substituted phenol-aldehyde novolak resins, Examples thereof include allyl etherified part or all of phenolic hydroxyl groups such as polycyclopentadiene-modified phenol resin and polyvinylphenol.

(Methane-type) trisphenols and (alkyl-substituted) phenol-aldehyde novolak resins can be synthesized by, for example, condensing an aromatic hydrocarbon having a phenolic hydroxyl group with an aldehyde compound or a ketone compound, Widely manufactured industrially.

Synthetic reaction formula of (methane type) trisphenols

Synthetic reaction formula of (alkyl-substituted) phenol-aldehyde novolak resin

Polycyclopentadiene-modified phenolic resin and polyvinylphenol can also be synthesized according to the following reaction formula and are industrially produced.

Synthetic reaction formula of polycyclopentadiene modified phenolic resin

Synthetic reaction formula of polyvinylphenol

The polyallyl ether compound of polyphenol can be obtained by allyl etherification of the polyphenol by a known method using allyl chloride, allyl alcohol, and allyl acetate. However, allyl alcohol, Preference is given to using allyl acetate.

These polyphenol polyallyl ether compounds are very viscous liquids or solids and cannot be epoxidized without solvent. Therefore, it is necessary to use a solvent. Preferred solvents include aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbon solvents, among which toluene, o-xylene, m-xylene, p-xylene, hexane, octane, cyclohexane, methylcyclohexane Is preferred. Regarding the concentration to be used, if it is used excessively, the substrate concentration becomes dilute and the productivity is low, and the reaction rate is also slowed. On the other hand, if the amount is too small, the effect of reducing the viscosity is low. Although the optimum concentration varies depending on the substrate, it is preferably in the range of 5 to 800 parts by weight, more preferably in the range of 30 to 300 parts by weight, based on 100 parts by weight of the polyphenol polyallyl ether compound used.

In the method for producing a polyglycidyl ether compound of the present invention, when the reaction temperature is low, the reaction rate becomes slow, the viscosity of the reaction system becomes high, and in severe cases, the raw material may precipitate, and it is high In some cases, side reactions are likely to occur, which is not preferable. Therefore, the reaction temperature is usually in the range of 0 to 180 ° C., preferably in the range of 50 to 120 ° C.

As a method for charging hydrogen peroxide, it is desirable to add it little by little while confirming that epoxidation is proceeding in the reaction system rather than charging a predetermined amount first. By adopting such a method, even if hydrogen peroxide is abnormally decomposed in the reactor and oxygen gas is generated, the amount of hydrogen peroxide accumulated is small and the pressure rise can be minimized. Therefore, in the epoxidation in the method of the present invention, preferably, hydrogen peroxide and, if necessary, a phosphorus compound are added.
The addition time of the hydrogen peroxide and the phosphorus compound added as needed varies depending on the reaction scale, but in the case of a 1 liter glass scale, it takes 30 minutes to 2 hours and is 1 in the case of an industrial scale of 10 m ^3. It is desirable to perform the addition over a period of 20 hours.
After completion of the addition, the reaction is usually terminated by stirring for 1 to 4 hours.

During the reaction, the aqueous layer and the organic layer of the reaction solution are separated, and an unused tungsten compound-phosphorus compound aqueous solution obtained as an aqueous layer or a concentrated tungsten compound catalyst aqueous solution used for epoxidation is reused. Therefore, it is desirable to perform an epoxidation reaction. FIG. 1 is an example thereof, which can be implemented by the following procedure.
(1) The reaction solution is allowed to stand after the epoxidation reaction. The container to be allowed to stand may be a reactor or another container. (2) After standing, the upper organic layer and the aqueous layer are separated. (3) Readjust the catalyst concentration. For example, the separated aqueous layer is concentrated to increase the tungsten catalyst concentration and / or a new catalyst is added. When a catalyst is newly added, a phosphorus compound and / or a quaternary ammonium salt and further a tungsten compound are added to the separated aqueous layer as necessary. In addition, an aqueous layer containing a newly prepared catalyst can be used instead of the separated aqueous layer. (4) The catalyst (water layer) whose catalyst concentration has been readjusted as described above is mixed with the separated organic layer and epoxidized again. Thereafter, the operations (1) to (4) are repeated until a desired conversion rate is obtained.
The reason why it is preferable to separate the reaction solution into two layers during the reaction as described above, and to mix the separated organic layer and the aqueous layer with the catalyst concentration readjusted to repeat the reaction is that hydrogen peroxide is removed during the epoxidation reaction. This is because the aqueous layer containing a catalyst such as tungsten is diluted with water contained in the aqueous hydrogen peroxide solution when dropped as an aqueous solution, and the catalytic activity decreases. In order to effectively use the catalyst, it is preferable to recycle after concentrating the aqueous layer to increase the tungsten concentration. In particular, when α-aminoalkylphosphonic acids are used, they are consumed and decomposed during the reaction, so it is desirable to add them during recycling.
FIG. 1 is an example of a method of intermittently separating the aqueous layer and the organic layer of the reaction solution, but the operation can also be carried out continuously using a continuous reactor as shown in FIG.
As the continuous reactor, a tubular reactor can generally be used, and it is more preferable if the organic layer-water layer such as a microreactor is designed to be mixed well. Moreover, it can implement similarly by extracting continuously, even in a stirring tank, supplying a reaction liquid continuously.
After continuously extracting the reaction solution in this way, the organic layer and the aqueous layer are separated into two layers, and then the organic layer is recycled while adding new raw materials and solvents as necessary, and the aqueous layer is necessary. Depending on the concentration, the catalyst components are added and hydrogen peroxide is added and recycled.
In this case, a part of the reaction solution is extracted and sent to the next step (reaction tank for increasing the conversion rate to the target value, purification step).

After the epoxidation reaction, an organic solvent such as ethyl acetate, toluene, cyclohexane and hexane is further added as necessary, and the organic layer is treated with a reducing agent such as sodium bisulfite, sodium sulfite and sodium thiosulfate, After decomposing hydrogen peroxide, after washing, extraction, and purification as necessary, the solution is left as it is or in a solution with another solvent by exchanging the solvent, or without solvent. As a polyglycidyl ether compound, it can be used for a desired use.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples.

(Synthesis Example 1) Synthesis of polyallyl cresol novolak resin In a 2000 ml eggplant-shaped flask, 200.0 g of cresol novolak resin CRG-951 (hydroxyl equivalent 118 produced by Showa Polymer Co., Ltd.), 50% water content 5% -Pd / C- STD type (manufactured by N.E. Chemcat Co., Ltd.) 3.61 g (0.847 mmol), triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd.) 2.22 g (8.47 mmol), potassium carbonate (manufactured by Asahi Glass Co., Ltd.) 234 g (1.69 mol) ), Allyl acetate (produced by Showa Denko KK) 187 g (1.86 mol), and isopropanol 200 g were added and reacted at 85 ° C. for 8 hours in a nitrogen atmosphere. After the reaction, a part is sampled, diluted with ethyl acetate, washed with pure water until the washing solution becomes neutral, then isopropanol and ethyl acetate are distilled off, and the hydroxyl value is measured according to JIS K0070. It was confirmed that it was almost consumed.

Thereafter, 400 g of toluene was added to the reaction solution, Pd / C and the precipitated solid were removed by filtration, and isopropanol and toluene were distilled off by an evaporator to obtain 260 g of polyallyl ether of cresol novolac resin. As a result of measuring the iodine value of this polyallyl ether in accordance with JIS K0070, it was 157.

(Synthesis Example 2) Synthesis of polyallylmethane type trisphenol resin In a 2000 ml eggplant type flask, 200 g of methane type trisphenol resin NCR-231 (manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 106), 50% water content 5%- Pd / C-STD type (NEC Chemcat Co., Ltd.) 4.02 g (0.943 mmol), triphenylphosphine (Hokuko Chemical Co., Ltd.) 2.47 g (9.43 mmol), potassium carbonate (Asahi Glass Co., Ltd.) 261 g (1.89 mol), 208 g (2.08 mol) of allyl acetate (manufactured by Showa Denko KK) and 200 g of isopropanol were added and reacted at 85 ° C. for 8 hours in a nitrogen atmosphere. After the reaction, a part is sampled, diluted with ethyl acetate, washed with pure water until the washing solution becomes neutral, then isopropanol and ethyl acetate are distilled off, and the hydroxyl value is measured according to JIS K0070. It was confirmed that it was almost consumed.

Thereafter, 400 g of toluene was added to the reaction solution, Pd / C and the precipitated solid were removed by filtration, and isopropanol and toluene were distilled off by an evaporator to obtain 271 g of polyallyl ether of methane type trisphenol resin. As a result of measuring iodine value of this polyallyl ether in accordance with JIS K0070, it was 168.

(Synthesis Example 3) Synthesis of diallyl ether of bisphenol-F In a 2000 ml eggplant type flask, 200 g (0.999 mol) of bisphenol-F-ST (manufactured by Mitsui Chemicals), 50% water content 5% -Pd / C-STD Type (made by N.E. Chemcat Co., Ltd.) 2.13 g (0.499 mmol), triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 2.62 g (9.99 mmol), potassium carbonate (made by Asahi Glass Co., Ltd.) 276 g (2.00 mol) Then, 220 g (2.20 mol) of allyl acetate (manufactured by Showa Denko KK) and 200 g of isopropanol were added and reacted at 85 ° C. for 8 hours in a nitrogen atmosphere. After the reaction, a part was sampled, diluted with ethyl acetate, and analyzed by gas chromatography, and it was confirmed that the ratio of bisphenol-F diallyl ether to monoallyl ether was 99: 1.

Thereafter, 400 g of toluene was added to the reaction solution, Pd / C and the precipitated solid were removed by filtration, and isopropanol and toluene were distilled off by an evaporator. After performing this reaction and the post-treatment operation four times, all the reaction products were combined and applied to a molecular distillation apparatus (manufactured by Daishin Kogyo Co., Ltd.), so that 748 g of distillate (isolation yield 66%, bisphenol) -F diallyl ether 98.7% the remainder was monoallyl ether), and 368 g of non-distilled product (bisphenol-F diallyl ether 88%) was obtained.

Example 1
A solution prepared by previously dissolving 0.409 g (1.24 mmol) of sodium tungstate in 0.409 g of pure water and 0.241 g (2.48 mmol) of 35% aqueous hydrogen peroxide was prepared.
In a 100 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 10 g of the polyallyl cresol novolak resin obtained in Synthesis Example 1 (0.062 mol as the allyl group), 10 g of toluene, 0.290 g (0.620 mmol) of methyl trioctylammonium hydrogen sulfate Then, 0.0688 g (0.620 mmol) of aminomethylphosphonic acid and a tungstic acid solution prepared in advance were added, and the bath temperature was heated to 80 ° C. When the bath temperature reached 80 ° C, 12.1 g (0.124 mol) of an aqueous hydrogen peroxide solution was added dropwise over 30 minutes, and then the reaction was continued at a bath temperature of 80 ° C for 4 hours.
After completion of the reaction, a part of the reaction solution was sampled, and after toluene was distilled off, the epoxy equivalent was measured and found to be 288. In addition, the epoxy equivalent when all double bonds calculated from the iodine value are epoxidized is 177.

(Examples 2-6, Comparative Examples 1-2)
The reaction was performed in the same manner as in Example 1 except that the catalysts shown in Table 1 below were used. The results are shown in Table 1 below.

(Example 7)
A solution prepared by previously dissolving 0.438 g (1.33 mmol) of sodium tungstate in 0.438 g of pure water and 0.258 g (2.66 mmol) of 35% aqueous hydrogen peroxide solution was prepared.
To a 100 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 10 g of the polyallylmethane type trisphenol resin obtained in Synthesis Example 2 (0.0664 mol as the allyl group), 10 g of toluene, 0.310 g of methyl trioctylammonium hydrogen sulfate (0.664 mmol), 0.0737 g (0.664 mmol) of aminomethylphosphonic acid, and a tungstic acid solution prepared in advance, and the bath temperature was heated to 80 ° C. When the bath temperature reached 80 ° C., 12.9 g (0.133 mol) of an aqueous hydrogen peroxide solution was added dropwise over 30 minutes, and then the reaction was continued at a bath temperature of 80 ° C. for 4 hours.
After completion of the reaction, a part of the reaction solution was sampled, and after toluene was distilled off, the epoxy equivalent was measured and found to be 264. In addition, the epoxy equivalent when all the double bonds calculated from the iodine value are epoxidized is 167.

(Example 8)
A solution prepared by previously dissolving 0.409 g (1.24 mmol) of sodium tungstate in 0.409 g of pure water and 0.241 g (2.48 mmol) of 35% aqueous hydrogen peroxide was prepared.
Into a 100 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 10 g of the polyallyl cresol novolak resin obtained in Synthesis Example 1, 10 g of toluene, 0.290 g (0.620 mmol) of methyl trioctylammonium hydrogen sulfate, 0.0344 g of aminomethylphosphonic acid ( 0.310 mmol) and one portion of the previously prepared tungstic acid solution divided into two, and the bath temperature was heated to 80 ° C. When the bath temperature reached 80 ° C, 12.1 g (0.124 mol) of an aqueous hydrogen peroxide solution was added dropwise over 30 minutes, and then the reaction was continued at a bath temperature of 80 ° C for 4 hours.

After 4 hours, the reaction solution was cooled to room temperature, transferred to a separatory funnel, the aqueous layer was separated, the toluene layer was returned to the reaction flask, 0.0344 g (0.310 mmol) of aminomethylphosphonic acid, The remaining one of the two parts was placed and the bath temperature was reheated to 80 ° C. When the bath temperature reached 90 ° C, 12.1 g (0.124 mol) of an aqueous hydrogen peroxide solution was added dropwise over 30 minutes, and then the reaction was continued at a bath temperature of 80 ° C for 4 hours. A part of the reaction solution was sampled, toluene was distilled off, and then the epoxy equivalent was measured. Example 5 shows that epoxidation has progressed.

Example 9
A solution prepared by previously dissolving 0.235 g (0.713 mmol) of sodium tungstate in 0.235 g of pure water and 0.139 g (1.43 mmol) of 35% aqueous hydrogen peroxide solution was prepared.
In a 100 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 10 g (0.0357 mol) of the diallyl ether distillate of bisphenol-F obtained in Synthesis Example 3, 10 g of toluene, 0.167 g (0.357 mmol) of methyltrioctylammonium hydrogensulfate ), 0.0396 g (0.357 mmol) of aminomethylphosphonic acid, and a previously prepared tungstic acid solution were added, and the bath temperature was heated to 80 ° C. When the bath temperature reached 80 ° C., 8.32 g (0.0856 mol) of an aqueous hydrogen peroxide solution was added dropwise over 30 minutes, and then the reaction was continued at a bath temperature of 80 ° C. for 4 hours.
When a part of the reaction solution was sampled and analyzed by gas chromatography, the conversion rate of the diaryl ether of bisphenol-F was 95%, the yield of monoepoxide was 33%, and the yield of diepoxide was 58. %Met.

(Example 10)
A solution prepared by previously dissolving 0.214 g (0.648 mmol) of sodium tungstate in 0.214 g of pure water and 0.126 g (1.30 mmol) of 35% aqueous hydrogen peroxide was prepared.
In a 100 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 10 g (0.0324 mol) of bisphenol-A diallyl ether (China: Natama Chemical Co., Ltd.), 10 g of toluene, 0.151 g (0.324 mmol) of methyl trioctylammonium hydrogen sulfate ), 0.0360 g (0.324 mmol) of aminomethylphosphonic acid, and a previously prepared tungstic acid solution were added, and the bath temperature was heated to 80 ° C. When the bath temperature reached 80 ° C, 7.56 g (0.0778 mol) of an aqueous hydrogen peroxide solution was added dropwise over 30 minutes, and then the reaction was continued at a bath temperature of 80 ° C for 4 hours.
When a part of the reaction solution was sampled and analyzed by gas chromatography, the conversion rate of bisphenol-A diallyl ether was 93%, the yield of monoepoxide was 36%, and the yield of diepoxide was 55%.

(Example 11)
A solution prepared by previously dissolving 0.214 g (0.648 mmol) of sodium tungstate in 0.214 g of pure water and 0.126 g (1.30 mmol) of 35% aqueous hydrogen peroxide was prepared.
In a 100 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 10 g (0.0324 mol) of bisphenol-A diallyl ether (China: Natama Chemical Co., Ltd.), 10 g of toluene, 0.151 g (0.324 mmol) of methyl trioctylammonium hydrogen sulfate ), 0.0180 g (0.162 mmol) of aminomethylphosphonic acid, and half of the tungstic acid solution prepared in advance, and the bath temperature was heated to 80 ° C. When the bath temperature reached 80 ° C, 3.78 g (0.0389 mol) of an aqueous hydrogen peroxide solution was added dropwise over 15 minutes, and then the reaction was continued at a bath temperature of 80 ° C for 4 hours.
When a part of the reaction solution was sampled and analyzed by gas chromatography, the conversion of bisphenol-A diallyl ether was 82%, the yield of monoepoxide was 61%, and the yield of diepoxide was 19%.
After completion of the reaction, the reaction solution was transferred to a separating funnel, the catalyst solution (aqueous layer) was separated from the lower layer, and the upper organic layer was returned to the reaction flask.
The remaining half of the tungstic acid solution and 0.0180 g (0.162 mmol) of aminomethylphosphonic acid were added, and the bath temperature was heated to 80 ° C. When the bath temperature reached 80 ° C, 3.78 g (0.0389 mol) of an aqueous hydrogen peroxide solution was added dropwise over 15 minutes, and then the reaction was continued at a bath temperature of 80 ° C for 4 hours.
When a part of the reaction solution was sampled and analyzed by gas chromatography, the conversion of bisphenol-A diallyl ether was 99%, the yield of monoepoxide was 6%, and the yield of diepoxide was 89%.

(Example 12)
A solution prepared by previously dissolving 0.214 g (0.648 mmol) of sodium tungstate in 0.214 g of pure water and 0.126 g (1.30 mmol) of 35% aqueous hydrogen peroxide was prepared.
In a 100 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 10 g (0.0324 mol) of bisphenol-A diallyl ether (China: Natama Chemical Co., Ltd.), 10 g of toluene, 0.151 g (0.324 mmol) of methyl trioctylammonium hydrogen sulfate ), 0.0360 g (0.324 mmol) of aminomethylphosphonic acid, and a previously prepared tungstic acid solution were added, and the bath temperature was heated to 80 ° C. When the bath temperature reached 80 ° C., 3.78 g (0.0389 mol) of an aqueous hydrogen peroxide solution was added dropwise over 30 minutes, and then the reaction was continued at a bath temperature of 80 ° C. for 4 hours.
When a part of the reaction solution was sampled and analyzed by gas chromatography, the conversion rate of bisphenol-A diallyl ether was 87%, the yield of monoepoxide was 56%, and the yield of diepoxide was 29%.
After completion of the reaction, the reaction solution was transferred to a separating funnel, the catalyst solution (aqueous layer) was separated from the lower layer, and the upper organic layer was returned to the reaction flask.
An evaporator was used to distill off 2.3 g of water from the aqueous layer, and the mixture was returned to the reaction flask and the bath temperature was heated to 80 ° C. When the bath temperature reached 80 ° C, 3.78 g (0.0389 mol) of an aqueous hydrogen peroxide solution was added dropwise over 15 minutes, and then the reaction was continued at a bath temperature of 80 ° C for 4 hours.
When a part of the reaction solution was sampled and analyzed by gas chromatography, the conversion rate of bisphenol-A diallyl ether was 94%, the yield of monoepoxide was 33%, and the yield of diepoxide was 54%.

(Examples 13 to 15)
The reaction was carried out in the same manner as in Example 6 except that allyl compounds shown in Table 2 below were used. The results are shown in Table 2 below.

Claims

The carbon-carbon double bond of the allyl group of the polyallyl ether compound of the compound having a plurality of phenolic hydroxyl groups as a starting material is hydrogen peroxide as an oxidizing agent in the presence of a tungsten compound, a phosphorus compound and a quaternary ammonium salt. The manufacturing method of a polyglycidyl ether compound including the process of epoxidizing using.
The method for producing a polyglycidyl ether compound according to claim 1, wherein the compound having a plurality of phenolic hydroxyl groups is polyphenol.
The polyallyl ether compound of polyphenol is catechol, resorcinol, hydroquinone, bisphenol A (p, p'-isopropylidenediphenol), bisphenol F (p, p'-methylenediphenol), bisphenol K (p, p'- Diphenolcarbonyl), dihydroxymethylstilbene, dihydroxybiphenyl, tetramethyldihydroxybiphenyl, dihydroxynaphthalene, bis (hydroxyphenyl) fluorene, methane type trisphenols, trisphenols, phenol-aldehyde novolak resin, alkyl-substituted phenol-aldehyde novolak resin , Polycyclopentadiene modified phenolic resin, and at least one phenolic water selected from the group consisting of polyvinylphenol The method for producing a polyglycidyl ether compound according to claim 2, wherein a part or all of the acid groups are allyl etherified.
The polyallyl ether compound of polyphenol is selected from the group consisting of methane-type trisphenols obtained by condensing an aromatic hydrocarbon having a phenolic hydroxyl group and an aldehyde compound, a phenol-aldehyde novolak resin, and an alkyl-substituted phenol-aldehyde novolak resin. The method for producing a polyglycidyl ether compound according to claim 3, wherein a part or all of at least one selected phenolic hydroxyl group is allyl etherified.
The polyallyl ether compound of the polyphenol is selected from the group consisting of a polycyclopentadiene-modified phenol resin obtained by condensing an aromatic hydrocarbon having a phenolic hydroxyl group and dicyclopentadiene, and a polyvinyl phenol obtained by polymerizing vinyl phenol. The method for producing a polyglycidyl ether compound according to claim 3, wherein all or at least one phenolic hydroxyl group is allyl etherified.
The phosphorus compound is phosphoric acid, aminomethylphosphonic acid, α-aminoethylphosphonic acid, α-aminopropylphosphonic acid, α-aminobutylphosphonic acid, α-aminopentylphosphonic acid, α-aminohexylphosphonic acid, α-aminoheptyl The phosphonic acid, α-aminooctylphosphonic acid, α-aminononylphosphonic acid, α-amino-α-phenylmethylphosphonic acid, and at least one selected from the group consisting of nitrilotris (methylene) trisphosphonic acid, Item 6. The method for producing a polyglycidyl ether compound according to any one of Items 1 to 5.
The method for producing a polyglycidyl ether compound according to claim 6, wherein the phosphorus compound is nitrilotris (methylene) trisphosphonic acid.
The tungsten compound according to any one of claims 1 to 7, wherein the tungsten compound is at least one selected from the group consisting of tungstic acid, alkali tungstate, ammonium tungstate, phosphotungstic acid, and silicotungstic acid. A method for producing a polyglycidyl ether compound.
The polyglycidyl according to any one of claims 1 to 8, wherein the quaternary ammonium salt is at least one selected from the group consisting of quaternary ammonium sulfate, hydrogen sulfate, and nitrate. A method for producing an ether compound.
The method for producing a polyglycidyl ether compound according to any one of claims 1 to 9, wherein the molar ratio of the tungsten atom to the phosphorus compound in the tungsten compound is in the range of 1: 0.1 to 1:10.
The molar ratio of the carbon-carbon double bond of the allyl group to hydrogen peroxide in the polyallyl ether compound of the compound having a plurality of phenolic hydroxyl groups is in the range of 1: 0.5 to 1: 4. 11. A process for producing a polyglycidyl ether compound according to any one of 1 to 10.
The method for producing a polyglycidyl ether compound according to any one of claims 1 to 11, wherein hydrogen peroxide and, if necessary, a phosphorus compound are additionally added in the epoxidation step.