JP2014240377A - Method for producing polyvalent glycidyl compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of efficiently producing a polyvalent glycidyl compound by oxidation of a 2-alkenyl ether group and a 2-alkenyl group of a compound having a 2-alkenyl ether group and a 2-alkenyl group in the molecule by using a hydrogen peroxide aqueous solution as an oxidant.SOLUTION: There is provided a method for producing a polyvalent glycidyl compound by controlling a pH of a reaction solution containing a glycidyl ether compound having two or more substituted or unsubstituted 2-alkenyl groups and one or more substituted or unsubstituted 2-alkenyl ether groups in the molecule to 1.0 to 4.0 in the presence of a tungsten compound as a catalyst, a quaternary ammonium salt and two or more acids containing at least phosphoric acid using a hydrogen peroxide aqueous solution as an oxidant, adding a hydrogen peroxide aqueous solution to the reaction solution over 0.1 to 2 hours, and after the completion of addition of the hydrogen peroxide aqueous solution, terminating the reaction for 2 to 6 hours.

Description

  The present invention relates to a method for producing a polyvalent glycidyl (epoxy) compound. More specifically, the present invention relates to a method for producing a polyvalent glycidyl compound which is excellent in hardness, strength and heat resistance, and which is a raw material for a curable resin composition particularly suitable for the field of electronic materials.

  Glycidyl (epoxy) compounds are excellent in electrical properties, adhesiveness, heat resistance, and the like, and thus are used in many applications such as the paint field, civil engineering field, and electrical field. In particular, aromatic glycidyl (epoxy) compounds such as bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolac type epoxy resin, cresol novolac type epoxy resin are water resistant, adhesive, mechanical properties, heat resistant, It is widely used in combination with various curing agents because of its excellent electrical insulation and economy.

  In order to improve the physical properties of the resin containing the glycidyl compound and the curing agent, the glycidyl compound is molecularly designed to meet the target physical properties. For example, in bisphenol A type diglycidyl ether, the aromatic ring of the phenol moiety of the basic skeleton is hydrogenated and induced to an aliphatic cyclohexane skeleton, thereby improving the optical properties (transparency) of the cured product, or at the time of curing. It is known that fluidity is improved. In phenol novolac type epoxy resin, by adjusting the polymerization degree, molecular weight distribution, etc. of glycidyl compound, it is possible to change the fluidity at the time of curing or to control the heat resistance, adhesiveness, etc. of the cured product. .

  Multifunctionalization of a glycidyl compound is known as a technique for improving the heat resistance and adhesion of a cured product of a resin containing a glycidyl compound and a curing agent. Increasing the density of reactive functional groups in the resin (the amount of functional groups contained per molecule) can increase the reactive crosslinking point between the glycidyl compound and the curing agent. Since the crosslink density per unit volume of the cured product is increased, the micro-motion of the molecule is controlled, and the resistance to the external influence of the cured product is increased. As a result, it becomes possible to improve the heat resistance of the cured product, and to impart rigidity, adhesion, etc. to the cured product.

  As one technique for polyfunctionalization of a glycidyl compound, a method is known in which two or more glycidyl groups are introduced into the aromatic ring skeleton of the glycidyl compound having an aromatic ring skeleton to improve the crosslinking density. For example, Patent Document 1 (Japanese Patent Laid-Open No. 63-142019) discloses a polyvalent glycidyl group having a glycidyl group at the ortho-position or para-position with respect to the glycidyl ether group bonded to the phenol moiety of a compound having bisphenol as a basic skeleton. It is disclosed that the compounds have good adhesion to metals, low hygroscopicity, and good mechanical properties. These compounds are obtained by starting from phenols such as bisphenol-F, 2-alkenylation of the phenol hydroxy group, and 2-alkenylation of the ortho or para position by Claisen rearrangement of the resulting 2-alkenyl ether group, It is synthesized by subsequent glycidyl etherification using epichlorohydrin and oxidation of the side chain 2-alkenyl group (glycidylation).

  However, in the oxidation (glycidylation) reaction performed in the final stage, an organic peroxide such as peracetic acid, performic acid, m-chloroperbenzoic acid, peroxophthalic acid, etc., with respect to the 2-alkenyl group that is the reaction point, Or, since an inorganic peroxide such as permolybdic acid, pervanadic acid, pertungstic acid or the like is required in a chemical equivalent or more, it is difficult to remove these oxidant residues from the target product, or the cost of the oxidant is low. In some cases, it is expensive and industrially unfeasible. In addition, since epichlorohydrin is used in the synthesis process, when a compound having a large number of functional groups is produced, the content of the organic chlorine compound in the product increases as the amount of epichlorohydrin used increases.

  In order to avoid contamination with organic chlorine compounds, it is effective to use a method that does not use epichlorohydrin for the synthesis of glycidyl (epoxy) compounds. For example, as a method for synthesizing a polyvalent glycidyl compound having an aromatic ring skeleton, 2-alkenylation of ortho- or para-position by Claisen rearrangement of 2-alkenylphenyl ether, 2-alkenyl etherification of the generated phenolic hydroxy group, 2 A method involving simultaneous oxidation (glycidylation) of an alkenyl ether group and its ortho- or para-alkenyl group is conceivable. According to this method, since no epichlorohydrin is used, in principle, the amount of chlorine in the glycidyl compound can be greatly reduced. However, simultaneous oxidation of a 2-alkenyl ether group and a 2-alkenyl group in the ortho-position or para-position thereof is generally difficult to control because of the reactivity of these groups, and has not been known so far.

Japanese Patent Laid-Open No. 63-142019

  The present invention relates to a polyvalent glycidyl compound by oxidizing a 2-alkenyl ether group and a 2-alkenyl group of a compound having a 2-alkenyl ether group and a 2-alkenyl group in the molecule using an aqueous hydrogen peroxide solution as an oxidizing agent. The present invention provides a method for efficiently producing the above.

  As a result of intensive studies and experiments conducted in order to solve the above-mentioned problems, the present inventors have found a compound having two or more 2-alkenyl groups and one or more 2-alkenyl ether groups in the molecule as a substrate. In the presence of two or more kinds of acids including a tungsten compound as a catalyst, a quaternary ammonium salt, and at least phosphoric acid, an aqueous hydrogen peroxide solution is used as an oxidizing agent, the pH of the reaction solution, hydrogen peroxide into the reaction solution It was found that a polyvalent glycidyl compound having three or more glycidyl groups in the molecule can be obtained with high efficiency and high purity by controlling the addition time of the aqueous solution and the subsequent reaction time within a predetermined range. It came to complete.

（式中、Ｒ^１及びＲ^２は、各々独立して、下記式（２）で表される基であり、Ｑは、各々独立して、式：−ＣＲ^３Ｒ^４−で表されるアルキレン基、炭素数３〜１２のシクロアルキレン基、炭素数６〜１０の単独芳香環からなるアリーレン基若しくは２〜３の炭素数６〜１０の芳香環が結合してなるアリーレン基、炭素数７〜１２の二価の脂環式縮合環、又はこれらを組み合わせた二価基であり、Ｒ^３及びＲ^４は各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数３〜１２のシクロアルキル基、又は炭素数６〜１０のアリール基であり、ｎは０〜５０の整数を表す。式（２）中のＲ^５、Ｒ^６及びＲ^７は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１２のシクロアルキル基又は炭素数６〜１０のアリール基を表す。）で表される化合物である［１］又は［２］のいずれかに記載の多価グリシジル化合物の製造方法。

［４］前記２−アルケニルエーテル化合物が、ビスフェノール−Ａ、ビスフェノール−Ｆ、フェノールノボラック、トリフェニルメタンフェノール、ビフェニルアラルキル型フェノール、フェニルアラルキル型フェノール、又は無置換のテトラヒドロジシクロペンタジエン骨格のフェノール若しくは両端にＣＨ_２が結合した無置換のテトラヒドロジシクロペンタジエン骨格のフェノールのいずれかの基本骨格を有し、ＯＲ^１に対してＲ^２がオルト位又はパラ位に位置する２−アルケニルエーテル化合物である［３］に記載の多価グリシジル化合物の製造方法。
［５］前記タングステン化合物が、タングステン酸ナトリウムとタングステン酸の混合物、タングステン酸ナトリウムと鉱酸の混合物、又はタングステン酸とアルカリ化合物の混合物である［１］〜［４］のいずれかに記載の多価グリシジル化合物の製造方法。
［６］前記第四級アンモニウム塩の窒素原子に結合した置換基の炭素数の合計が６以上５０以下である［１］〜［５］のいずれかに記載の多価グリシジル化合物の製造方法。
［７］リン酸以外の前記酸が、ポリリン酸、ピロリン酸、スルホン酸、硝酸、硫酸、塩酸、及びホウ酸からなる群から選択される少なくとも一種の鉱酸又はベンゼンスルホン酸、ｐ−トルエンスルホン酸、メタンスルホン酸、トリフルオロメタンスルホン酸、及びトリフルオロ酢酸からなる群から選択される少なくとも一種の有機酸である［１］〜［６］のいずれかに記載の多価グリシジル化合物の製造方法。 That is, the present invention is as follows.
[1] A 2-alkenyl ether compound having two or more substituted or unsubstituted 2-alkenyl groups and one or more substituted or unsubstituted 2-alkenyl ether groups in a molecule, an aqueous hydrogen peroxide solution as an oxidizing agent In the presence of two or more acids including a tungsten compound, a quaternary ammonium salt, and at least phosphoric acid as a catalyst, the pH of the reaction solution containing the 2-alkenyl ether compound is set to 1.0 to 4.0. And a hydrogen peroxide aqueous solution is added to the reaction solution over a period of 0.1 to 2 hours, and the reaction is stopped in 2 to 6 hours after the addition of the hydrogen peroxide aqueous solution is completed. Compound production method.
[2] The 2-alkenyl ether compound contains an aromatic ring in the molecule, and one or more substituted or unsubstituted 2-alkenyl ether groups directly bonded to the aromatic ring and two or more substituted or directly bonded to the aromatic ring A compound having an unsubstituted 2-alkenyl group and having a substituted or unsubstituted 2-alkenyl group positioned in the ortho-position or para-position relative to the substituted or unsubstituted 2-alkenyl ether group [1] A method for producing the polyvalent glycidyl compound described in 1.
[3] The 2-alkenyl ether compound is represented by the general formula (1):

Wherein R ¹ and R ² are each independently a group represented by the following formula (2), and Q are each independently an alkylene represented by the formula: —CR ³ R ⁴ —. Group, a C3-C12 cycloalkylene group, an arylene group composed of a single aromatic ring having 6 to 10 carbon atoms, or an arylene group formed by bonding 2-3 aromatic rings having 6 to 10 carbon atoms, C7- 12 divalent alicyclic condensed rings, or a divalent group obtained by combining these, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 to 10 carbon atoms. An alkenyl group, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and n represents an integer of 0 to 50. R ⁵ , R ⁶ and R ^{7 in} formula (2) Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloaryl having 3 to 12 carbon atoms. Method for producing a polyglycidyl compound according to any one of the representative Kill group or an aryl group having 6 to 10 carbon atoms.) Is a compound represented by [1] or [2].

[4] The 2-alkenyl ether compound is bisphenol-A, bisphenol-F, phenol novolak, triphenylmethanephenol, biphenyl aralkyl type phenol, phenyl aralkyl type phenol, or phenol of an unsubstituted tetrahydrodicyclopentadiene skeleton or both ends. It is a 2-alkenyl ether compound having a basic skeleton of any of the phenols of an unsubstituted tetrahydrodicyclopentadiene skeleton in which CH ₂ is bonded to R ¹ and R ² is located in the ortho or para position with respect to OR ¹ [ [3] The method for producing a polyvalent glycidyl compound according to [3].
[5] The multiple tungsten according to any one of [1] to [4], wherein the tungsten compound is a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or a mixture of tungstic acid and an alkali compound. For producing a monovalent glycidyl compound.
[6] The method for producing a polyvalent glycidyl compound according to any one of [1] to [5], wherein the total number of carbon atoms of the substituents bonded to the nitrogen atom of the quaternary ammonium salt is 6 or more and 50 or less.
[7] The acid other than phosphoric acid is at least one mineral acid selected from the group consisting of polyphosphoric acid, pyrophosphoric acid, sulfonic acid, nitric acid, sulfuric acid, hydrochloric acid, and boric acid, benzenesulfonic acid, p-toluenesulfone The method for producing a polyvalent glycidyl compound according to any one of [1] to [6], which is at least one organic acid selected from the group consisting of an acid, methanesulfonic acid, trifluoromethanesulfonic acid, and trifluoroacetic acid.

  According to the method for producing a polyvalent glycidyl compound of the present invention, removal of an oxidant-derived residue from a target product can be simplified, and an inexpensive aqueous hydrogen peroxide solution is used as an oxidant, so that the production cost can be reduced. In addition, by controlling the pH of the reaction solution and controlling the contact time between the acidic aqueous solution that contributes to hydrolysis of the glycidyl group generated during the reaction and the product, the amount of hydrolyzate produced as a by-product is reduced. The polyvalent glycidyl compound can be obtained with high purity. Therefore, an industrially useful polyvalent glycidyl compound can be efficiently produced by the present invention. In addition, since an organic chlorine compound is not used in the reaction process, it can be applied to electronic devices that require high electrical reliability.

1 is a ¹ H-NMR spectrum of the product obtained in Example 1. 2 is a ¹ H-NMR spectrum of the product obtained in Example 2. 2 is a ¹ H-NMR spectrum of the product obtained in Example 3. It is the ¹ H-NMR spectrum (lower part) of the product obtained in Comparative Example 4 and the ¹ H-NMR spectrum (upper part) of the target product (formula (5)).

  Hereinafter, the present invention will be described in detail. The method for producing a polyvalent glycidyl compound of the present invention comprises a 2-alkenyl ether compound having two or more substituted or unsubstituted 2-alkenyl groups and one or more substituted or unsubstituted 2-alkenyl ether groups in the molecule. Of the reaction solution containing the 2-alkenyl ether compound in the presence of two or more acids including a tungsten compound, a quaternary ammonium salt, and at least phosphoric acid, using an aqueous hydrogen peroxide solution as an oxidizing agent. The pH is controlled to 1.0 to 4.0, and an aqueous hydrogen peroxide solution is added to the reaction solution over 0.1 to 2 hours. After the addition of the aqueous hydrogen peroxide solution is completed, the reaction is stopped in 2 to 6 hours. It is characterized by doing. Although details will be described later, in the present invention, a polyalkenyl group having three or more glycidyl groups by oxidizing (glycidylation) the carbon-carbon double bond in the 2-alkenyl group and 2-alkenyl ether group present in the molecule. A monovalent glycidyl compound is produced. In the present specification, the “glycidyl group” includes a substituted or unsubstituted glycidyl ether group having a glycidyl skeleton in addition to a substituted or unsubstituted glycidyl group. That is, “three or more glycidyl groups” means that the total number of substituted or unsubstituted glycidyl groups and substituted or unsubstituted glycidyl ether groups is three or more. In the present specification, the “2-alkenyl ether group” means a 2-alkenyloxy group.

式中、Ｒ^１及びＲ^２は、各々独立して、下記式（２）で表される基であり、Ｑは、各々独立して、式：−ＣＲ^３Ｒ^４−で表されるアルキレン基、炭素数３〜１２のシクロアルキレン基、炭素数６〜１０の単独芳香環からなるアリーレン基若しくは２〜３の炭素数６〜１０の芳香環が結合してなるアリーレン基（例えば、２つの芳香環が結合してなるアリーレン基としてビフェニル骨格を有するアリーレン基が、３つの芳香環が結合してなるアリーレン基としてトリフェニル骨格を有するアリーレン基が挙げられる）、炭素数７〜１２の二価の脂環式縮合環、又はこれらを組み合わせた二価基であり、Ｒ^３及びＲ^４は各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数３〜１２のシクロアルキル基、又は炭素数６〜１０のアリール基であり、ｎは０〜５０の整数を表す。式（２）中のＲ^５、Ｒ^６及びＲ^７は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１２のシクロアルキル基又は炭素数６〜１０のアリール基を表す。なお、式（２）及び式（３）中の＊は、酸素原子又は芳香環を構成する炭素原子との結合部であることを意味する。

The reaction substrate used for the oxidation reaction in the present invention is a 2-alkenyl ether compound having two or more substituted or unsubstituted 2-alkenyl groups and one or more substituted or unsubstituted 2-alkenyl ether groups in the molecule. If there is no particular limitation, there is an aromatic ring in the molecule, and one or more substituted or unsubstituted 2-alkenyl ether groups directly connected to the aromatic ring and two or more substituted or unsubstituted directly connected to the aromatic ring And a compound in which a substituted or unsubstituted 2-alkenyl group is located at the ortho-position or para-position relative to a substituted or unsubstituted 2-alkenyl ether group is relatively easily available Is preferable. For example, a suitable 2-alkenyl ether compound includes a compound represented by the following general formula (1).

In the formula, R ¹ and R ² are each independently a group represented by the following formula (2), and Q are each independently an alkylene group represented by the formula: —CR ³ R ⁴ —. A cycloalkylene group having 3 to 12 carbon atoms, an arylene group consisting of a single aromatic ring having 6 to 10 carbon atoms, or an arylene group formed by bonding an aromatic ring having 2 to 3 carbon atoms and 6 to 10 carbon atoms (for example, two aromatic An arylene group having a biphenyl skeleton as an arylene group formed by bonding of rings includes an arylene group having a triphenyl skeleton as an arylene group formed by bonding three aromatic rings), and a divalent divalent having 7 to 12 carbon atoms. An alicyclic condensed ring, or a divalent group obtained by combining these, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, carbon Cycloal of the number 3-12 Group, or an aryl group having a carbon number of 6 to 10, n is an integer of 0 to 50. R ⁵ , R ⁶ and R ^{7 in} formula (2) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl having 6 to 10 carbon atoms. Represents a group. In addition, * in Formula (2) and Formula (3) means that it is a coupling | bond part with the carbon atom which comprises an oxygen atom or an aromatic ring.

As a specific 2-alkenyl ether compound represented by the general formula (1), R ¹ and R ² are preferably R ^{5 to} R ¹⁰ in the hydrogen atom formula (2) or the formula (3). And the group represented. As preferable examples of Q, as an alkylene group represented by the formula: —CR ³ R ⁴ —, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or The thing which is a naphthyl group is mentioned. Preferred examples of the cycloalkylene group having 3 to 12 carbon atoms include a cyclohexylidene group, an arylene group consisting of a single aromatic ring having 6 to 10 carbon atoms, or an aromatic ring having 2 to 3 carbon atoms and 6 to 10 carbon atoms. Preferable examples of the arylene group include a phenylene group and a biphenyldiyl group. Preferable examples of the divalent alicyclic condensed ring having 7 to 12 carbon atoms include a divalent tetrahydrodicyclopentadiene ring. Preferred examples of the divalent group in which these are combined include a —CH ₂ —Ph—Ph—CH ₂ — group (in this specification, Ph means an unsubstituted benzene ring), and —CH ₂ —Ph—CH. ₂ -groups are mentioned. Preferred specific compounds, bisphenol -A, bisphenol -F, phenol novolac, triphenylmethane _phenol, the CH ₂ -Ph-Ph-CH 2 backbone biphenyl aralkyl type _phenol, CH ₂ -Ph-CH 2 backbone phenyl It has a basic skeleton of either aralkyl type phenol, phenol of unsubstituted tetrahydrodicyclopentadiene skeleton or phenol of unsubstituted tetrahydrodicyclopentadiene skeleton having CH ₂ bonded to both ends, and R ^{2 with} respect to OR ¹ 2-alkenyl ether compounds in which is located in the ortho or para position. Examples of the 2-alkenyl ether compound other than the 2-alkenyl ether compound represented by the general formula (1) include a compound having a naphthalene skeleton instead of the phenol skeleton of the general formula (1), for example, naphthalene novolak.

  As an example, bisphenol compounds such as 4,4′-dihydroxydiphenyldimethylmethane (bisphenol-A) and 4,4′-dihydroxydiphenylmethane (bisphenol-F), and known polyphenols such as novolak based on phenol and formaldehyde are used. Then, after converting this to the corresponding 2-alkenyl ether compound, it is derivatized to a phenol compound through a Claisen rearrangement to obtain a compound in which the 2-alkenyl group is located at the ortho-position or para-position of the phenolic hydroxyl group. be able to. The compound represented by the general formula (1) can be obtained by converting this phenol compound into the corresponding 2-alkenyl ether compound again.

  The reaction up to the Claisen rearrangement step is carried out using a commercially available phenol compound as a starting material, and converted by 2-alkenyl etherification, followed by rearrangement under heating conditions, followed by a conversion step to a 2-alkenyl ether compound, For example, a method using a metal catalyst using allyl carboxylate described in US Pat. No. 5,578,740 as an allylating agent is known. In this case, phenol in which the ortho position is 2-alkenylated is converted to an allyl ether compound having two or more 2-alkenyl groups in the molecule by an allyl etherification reaction.

  In 2-alkenyl etherification, it is preferable to avoid the use of 2-alkenyl chloride as a 2-alkenylating agent in order to reduce the chlorine content in the product 2-alkenyl ether compound. Examples of the 2-alkenylating agent include allyl acetate, allyl alcohol, allyl carbonate, allyl carbamate and the like, and industrially inexpensive allyl acetate and allyl alcohol are preferable. Examples of 2-alkenylation of phenolic hydroxyl groups include, for example, J. Org. Muzart et al., J. MoI. Organomet. Chem. , 326, pp. C23-C28 (1987) and the like disclose a method for converting to an allyl ether form using a metal catalyst.

  In the method for producing a polyvalent glycidyl compound of the present invention, the carbon-carbon double bond of the 2-alkenyl group of the 2-alkenyl ether compound, which is a reaction substrate, is oxidized (glycidyl) using an aqueous hydrogen peroxide solution as an oxidizing agent. ). The concentration of the aqueous hydrogen peroxide solution is not particularly limited, but is generally selected from the range of about 1 to about 80% by mass, preferably about 20 to about 60% by mass. From the viewpoint of industrial productivity and operability and cost during separation, a high concentration of the aqueous hydrogen peroxide solution is preferable, but an excessively high concentration and / or an excessive amount of hydrogen peroxide is preferable. It is preferable not to use an aqueous solution from the viewpoints of economy and safety.

  There is no restriction | limiting in particular in the usage-amount of hydrogen peroxide aqueous solution. The hydrogen peroxide concentration in the reaction solution decreases as the reaction proceeds. It is preferable to keep the hydrogen peroxide concentration in the reaction solution within the range of about 0.1 to about 30% by mass, more preferably about 5 to about 10% by mass by supplementing and supplementing this decrease. When the amount is less than 0.1% by mass, the productivity is deteriorated. On the other hand, when the amount is more than 30% by mass, the explosive property in the mixed composition of the solvent and water may be increased and may be dangerous.

  Addition of the aqueous hydrogen peroxide solution to the reaction solution is carried out little by little in succession or continuously in the range of 0.1 to 2 hours from the start of addition. The addition is preferably performed in the range of 0.5 to 1.5 hours. If the addition time of the aqueous hydrogen peroxide solution is long (addition rate is slow), the concentration of hydrogen peroxide in the system is lowered, the efficiency of the oxidation reaction is lowered, and hydrolysis may occur in competition. In addition, if a large amount of aqueous hydrogen peroxide solution is added to the reaction solution at the beginning of the reaction at a time, the reaction may suddenly proceed and may be dangerous. It is preferable to add by adding dropwise while confirming that it is consumed in the reaction.

  The reaction is continued after the addition of the aqueous hydrogen peroxide solution. The reaction is preferably continued while stirring the reaction solution, and it is preferable to use a stirrer having a magnetic stirring bar or stirring blade for stirring. The stirring speed is generally in the range of 100 to 2000 rpm, and preferably in the range of 300 to 1500 rpm. The reaction liquid is a two-phase system of a 2-alkenyl ether compound alone, which is a reaction substrate, or an organic layer containing a 2-alkenyl ether compound dissolved in an organic solvent, and an aqueous layer containing hydrogen peroxide. It is desirable to stir so that it becomes emulsion-like. As the oxidation (glycidylation) reaction of the carbon-carbon double bond of the 2-alkenyl group proceeds, a glycidyl compound is generated, and the viscosity of the reaction solution increases. In order to prevent hydrolysis of the glycidyl group of the glycidyl compound, which is the intermediate product or the final product, and by-product formation of a gel-like product resulting therefrom, the reaction is continued for 2 to 6 hours after the addition of the hydrogen peroxide solution. After that, stirring and heating are stopped to complete the oxidation reaction. When the reaction is stopped in less than 2 hours, a large amount of 2-alkenyl ether compound as a reaction substrate is contained, and the yield of the target product is low. When the reaction is continued for longer than 6 hours, the hydrolyzate becomes the main product, and in some cases, a gel-like product is formed. Therefore, the post-treatment step of the reaction solution becomes complicated, and the yield of the target product is reduced.

  Oxidation (glycidylation) using an aqueous hydrogen peroxide solution can be performed in the presence of a tungsten compound, a quaternary ammonium salt and a catalyst containing at least two acids including at least phosphoric acid. Since these compounds are relatively inexpensive, the oxidation of the carbon-carbon double bond of the 2-alkenyl ether compound using hydrogen peroxide as an oxidizing agent can be performed at low cost.

  As the tungsten compound used as a catalyst, a compound that generates a tungstate anion in water is suitable. For example, tungstic acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, phosphotungstic acid, ammonium tungstate, potassium tungstate Examples thereof include dihydrate and sodium tungstate dihydrate, but tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate dihydrate and the like are preferable. These tungsten compounds may be used alone or in combination of two or more.

  The catalytic activity of these compounds that produce tungstate anions in water is higher when about 0.2 to about 0.8 mole of counter cation is present per mole of tungstate anion. As a method for preparing such a tungsten composition, for example, an alkali metal salt of tungstic acid and tungstic acid may be mixed so that the tungstate anion and counter cation are in the above ratio, or tungstic acid may be mixed with an alkali compound ( Mixed with alkali metal or alkaline earth metal hydroxides, carbonates, etc.) or combined with alkali metal or alkaline earth metal salts of tungstic acid and acidic compounds such as mineral acids such as phosphoric acid and sulfuric acid Also good. Specific examples of these include a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or a mixture of tungstic acid and an alkali compound.

  The amount of the tungsten compound used as a catalyst is about 0.0001 to about 20 mol%, preferably as a tungsten atom, with respect to the carbon-carbon double bond of the 2-alkenyl group of the 2-alkenyl ether compound as the reaction substrate. Is selected from the range of about 0.01 to about 20 mol%.

  As the quaternary ammonium salt used as a catalyst, a quaternary organic ammonium salt having a total of 6 to 50, preferably 10 to 40, carbon atoms of the substituents bonded to the nitrogen atom is oxidized (glycidylated). The reaction activity is high and preferable.

  Quaternary ammonium salts include trioctylmethylammonium chloride, trioctylethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, tricaprylmethylammonium chloride, dichloride chloride. Chlorides such as decyldimethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride; trioctylmethylammonium bromide, trioctylethylammonium bromide, dilauryldimethylammonium bromide, lauryltrimethylammonium bromide, Stearyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium bromide, bromide Bromides such as licaprylmethylammonium, didecyldimethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide; trioctylmethylammonium iodide, trioctylethylammonium iodide, diiodide iodide Lauryldimethylammonium, lauryltrimethylammonium iodide, stearyltrimethylammonium iodide, lauryldimethylbenzylammonium iodide, tricaprylmethylammonium iodide, didecyldimethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium iodide, iodine Iodides such as benzyltriethylammonium iodide; trioctylmethylammonium hydrogen phosphate, hydrogen phosphate Trioctylethylammonium phosphate, dilauryldimethylammonium phosphate, lauryltrimethylammonium phosphate, stearyltrimethylammonium phosphate, lauryldimethylbenzylammonium phosphate, tricaprylmethylammonium phosphate, phosphoric acid Hydrogenated didecyldimethylammonium phosphate, tetrabutylammonium phosphate hydrogenated, benzyltrimethylammonium phosphate, benzyltriethylammonium phosphate hydrogenated phosphates; trioctylmethylammonium sulfate, trioctyl hydrogenate sulfate Ethyl ammonium, dilauryl dimethyl ammonium hydrogen sulfate, lauryl trimethyl ammonium hydrogen sulfate, stearyl trimethyl ammonium hydrogen sulfate, aqueous sulfuric acid Hydrogenated sulfates such as lauryl dimethylbenzylammonium sulfate, tricaprylmethylammonium sulfate, didecyldimethylammonium sulfate, tetrabutylammonium sulfate, benzyltrimethylammonium sulfate, benzyltriethylammonium sulfate, etc. Can be mentioned.

  These quaternary ammonium salts may be used alone or in combination of two or more. The amount used is preferably about 0.0001 to about 10 mol%, more preferably about 0.01 to about 10 mol, based on the carbon-carbon double bond of the 2-alkenyl group of the 2-alkenyl ether compound of the reaction substrate. % Range.

  When a phase transfer catalyst having a chloride ion, bromide ion or iodide ion as a counter anion is used as the quaternary ammonium salt, the halide content in the product increases. In order to reduce impurities derived from halogen in the product, a quaternary ammonium salt remover disclosed in JP 2010-70480 A can be used. Although it is possible to carry out the oxidation reaction using a halogen-based quaternary ammonium salt, a step of removing the quaternary ammonium salt is required, and the operation becomes complicated.

  In the method for producing a polyvalent glycidyl compound of the present invention, phosphoric acid is used as a promoter. Phosphoric acid generates an active species by coordinating an oxygen atom to a tungsten metal center that is a catalytic metal. Moreover, pH of a reaction liquid is controlled to 1.0-4.0 by using acids other than phosphoric acid together. The pH of the reaction solution is preferably 1.2 to 3.8, and more preferably 1.4 to 3.7. When the pH of the reaction solution is higher than 4.0, the reaction rate is lowered and thus the productivity is lowered. On the other hand, when the pH is lower than 1.0, hydrolysis of the glycidyl group proceeds and the yield tends to be lowered. The amount of phosphoric acid used is preferably from about 0.01 to about 10 mol%, more preferably from about 0.1 to about 10 mol%, based on the carbon-carbon double bond of the 2-alkenyl group of the 2-alkenyl ether compound of the reaction substrate. It is selected from the range of 10 mol%.

  As the acid other than phosphoric acid, either a mineral acid or an organic acid can be used. Examples of mineral acids include polyphosphoric acid, pyrophosphoric acid, sulfonic acid, nitric acid, sulfuric acid, hydrochloric acid, and boric acid. Examples of organic acids include benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and trifluoroacetic acid. The amount used is preferably about 0.001 to about 10 mol%, more preferably about 0.01 to about 10 mol, based on the carbon-carbon double bond of the 2-alkenyl group of the 2-alkenyl ether compound of the reaction substrate. % Range. Among these acids, sulfuric acid is preferable because of its large buffering effect and easy pH retention in the range of 1.0 to 4.0.

  In the glycidylation reaction, an organic solvent is not used or an organic solvent is used as necessary, and the aqueous hydrogen peroxide solution and the above-mentioned catalyst are mixed to proceed with the glycidylation reaction of the 2-alkenyl ether compound as the reaction substrate. Can do. When a solvent is used, the reaction rate becomes slow, and depending on the solvent, an undesirable reaction such as a hydrolysis reaction may easily proceed, so it is necessary to select appropriately. When the viscosity of the 2-alkenyl ether compound as the reaction substrate is too high or is a solid, a minimum necessary organic solvent may be used. The organic solvent that can be used is preferably an aromatic hydrocarbon, an aliphatic hydrocarbon, or an alicyclic hydrocarbon, and examples thereof include toluene, xylene, hexane, octane, and cyclohexane. Regarding the concentration, it is advantageous in terms of production cost to keep the minimum necessary use, and the amount of the organic solvent used is preferably about 300 parts by mass or less, more preferably 100 parts by mass or less with respect to 100 parts by mass of the 2-alkenyl ether compound. Is about 100 parts by mass or less.

  In addition, considering that industrial production is stable in the oxidation (glycidylation) reaction, the catalyst and the substrate are charged into the reactor first, and the reaction temperature is kept as constant as possible while the hydrogen peroxide solution is reacted. It is better to add gradually while confirming that it is consumed. 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.

  If the reaction temperature is too high, there will be many side reactions, and if it is too low, the consumption rate of hydrogen peroxide will slow down and may accumulate in the reaction solution, so the reaction temperature is preferably about 40 to about 100 ° C. More preferably, the temperature is controlled in the range of about 50 ° C to about 80 ° C. It is preferable to perform both the addition of the aqueous hydrogen peroxide solution and the reaction after the end of the addition within the above temperature range. For example, during the addition of the aqueous hydrogen peroxide solution, the reaction temperature is set low (about 50 ° C. to 60 ° C.), the dropping time is shortened by increasing the addition rate, and the reaction temperature is lowered after the addition of the aqueous hydrogen peroxide solution. The efficiency of oxidation can also be improved by controlling the temperature within a high range (about 70 ° C. to 80 ° C.) and advancing the reaction.

  After completion of the reaction, there may be almost no difference in specific gravity between the aqueous layer and the organic layer. In that case, an organic extraction solvent is prepared by mixing the aqueous layer with a saturated aqueous solution of an inorganic compound and making a difference in specific gravity with the organic layer. Two-layer separation can be carried out without using. In particular, since the specific gravity of the tungsten compound is heavy, in order to bring the aqueous layer to the lower layer, a tungsten compound exceeding the above-mentioned usage amount that is originally necessary as a catalyst may be used. In this case, it is desirable to increase the utilization efficiency of the tungsten compound by reusing the tungsten compound from the aqueous layer.

  Conversely, depending on the substrate, the specific gravity of the organic layer may be close to 1.2. In such a case, water is added to bring the specific gravity of the aqueous layer closer to 1, so that It is also possible to bring an organic layer under the layer. The extraction of the reaction solution can also be carried out using an organic solvent such as toluene, cyclohexane, hexane, methylene chloride, etc., and an optimal separation method can be selected according to the situation.

  After concentrating the organic layer separated from the aqueous layer in this way, the obtained polyvalent glycidyl compound can be taken out by ordinary methods such as distillation, chromatographic separation, recrystallization and sublimation.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited to a following example.

Synthesis Example 1: Synthesis of Substrate (4,4 ′-(Dimethylmethylene) bis [2- (2-propenyl) phenyldiallyl ether]) In a 500 mL three-necked round bottom flask, 138 g of potassium carbonate (manufactured by Nippon Soda Co., Ltd.) .00 mol) in 125 g of pure water, 80.6 g of 4,4 ′-(dimethylmethylene) bis [2- (2-propenyl) phenol] (manufactured by Daiwa Kasei Co., Ltd.) represented by the formula (3) (262 mmol) and 52.0 g (0.500 mol, as solid) of sodium carbonate (manufactured by Kanto Chemical Co., Inc.) were charged, and the reactor was purged with nitrogen and heated to 85 ° C. Under nitrogen flow, allyl acetate (made by Showa Denko KK) 220 g (2.19 mol), triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 2.62 g (10.0 mmol), and 50% water content 5% -Pd / C -84.6 mg (0.0200 mmol) of STD type (manufactured by N.E. Chemcat Co., Ltd.) was added, heated to 105 ° C in a nitrogen atmosphere and reacted for 4 hours, and then 22.0 g (0.219 mol) of allyl acetate. ) Was added and heating was continued for 12 hours. After completion of the reaction, the reaction system was cooled to room temperature, and pure water was added until all the precipitated salts were dissolved, followed by liquid separation treatment. The organic layer was separated and the organic solvent (70 ° C., 50 mmHg, 2 hours) was distilled off. After adding pure water (200 g), 200 g of toluene was added, and the temperature was kept at 80 ° C. or higher and it was confirmed that no white precipitate was deposited. Then, Pd / C was filtered (1 micron membrane filter (Advantech)). This was recovered by pressurization (0.3 MPa) using KST-142-JA, Inc. The filter cake was washed with 100 g of toluene and the aqueous layer was separated, and the organic layer was washed with 200 g of pure water at 50 ° C. or higher. After washing twice, it was confirmed that the aqueous layer was neutral.After separating the organic layer, the organic layer was concentrated under reduced pressure, and 4,4 ′-(dimethylmethylene) bis [2- (2-propenyl) brown liquid whose main component is phenyl diallyl ether] (93.6 g, 241 mmol, 92.0% yield). the brown liquid the ¹ H-NMR measurement result, equation (4) Represented by Measurement data attributable to the compound represented by the object was confirmed to contain as a main component. Equation (4) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 1.66 (6H, s, CH ₃ ), δ 3.39 (4H, d, PhC H ₂ CH═CH ₂ ), δ 4.95-5.55 _{(4H, m, PhCH 2 CH} = C H 2), δ5.25 (2H, d, PhOCH 2 CH = C H H), δ5.42 (2H, d, PhOCH 2 CH = CH H), δ5.25 _{(4H, m, PhOCH 2 C} H = CH 2, PhCH 2 C H = CH 2), δ6.73 (d, 2H, aromatic), δ6.90-7.08 (m, 2H, aromatic), δ7. 13-7.40 (2H, m, aromatic).

Example 1: Synthesis of 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane Into a 200 mL three-necked round bottom flask, 4,4 '-(dimethylmethylene) bis [2 obtained in Synthesis Example 1 above was added. -(2-propenyl) phenyl diallyl ether] 18.1 g (46.5 mmol), sodium tungstate dihydrate (manufactured by Nippon Inorganic Chemical Co., Ltd.) 1.53 g (4.70 mmol), phosphoric acid (Wako Pure Chemical Industries, Ltd.) Industrial Co., Ltd.) 0.231 g (2.35 mmol), sulfuric acid (Wako Pure Chemical Industries, Ltd.) 0.230 g (2.35 mmol), and trioctylmethylammonium hydrogen sulfate (MTOAHS, manufactured by Asahi Chemical Industry Co., Ltd.) ) 2.17 g (4.70 mmol) was added and dissolved in 18 g of toluene (manufactured by Junsei Chemical Co., Ltd.). After the temperature was raised to 65 ° C., 51.1 g (0.465 mol) of a 35% by mass hydrogen peroxide aqueous solution (manufactured by Hishie Kasei Co., Ltd.) was added dropwise over 1 hour with stirring, and the mixture was further stirred at 70 ° C. for 2 hours (stirring). Speed 400 rpm). At the beginning of the reaction, the pH of the reaction solution was 1.5, and the pH of the reaction solution after 2 hours of reaction was 3.7. After completion of the reaction, the reaction solution was cooled to room temperature, and then 20 g of pure water was added to carry out a liquid separation treatment. The organic layer was separated, and the remaining hydrogen peroxide was reduced by adding and washing 15 g of an aqueous sodium sulfite solution (10% by mass, manufactured by Wako Pure Chemical Industries, Ltd.). The aqueous layer was removed, and 20 g of pure water was added and washed again. By isolating the organic layer and distilling off the organic solvent (toluene), 18.6 g (41) of a product having an epoxy equivalent ratio (E / Er = measured epoxy equivalent / theoretical epoxy equivalent) of the epoxy compound of 1.16 0.0 mmol, epoxy equivalent 131, yield 88.2%). The yield was calculated as (acquired amount of the mixture containing the target epoxy compound after the post-treatment / substance amount obtained when the oxidation reaction proceeded at a reaction rate of 100%) × 100). The epoxy equivalent of the product is close to the theoretical epoxy equivalent of the compound represented by the formula (5), which suggests that the product contains almost no hydrolyzate of glycidyl group. As a result of ¹ H-NMR measurement of this product, it was confirmed that the compound represented by the formula (5) was contained as a main component. The measurement data belonging to the compound represented by the formula (5) is as follows. The ¹ H-NMR spectrum of the product is shown in FIG.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 1.64 (6H, s, CH ₃ ), δ 2.54 (2H, m, PhCH ₂ CHC H HO), δ 2.7-2.8 (6H) , M, PhC H ₂ CHCHHO, PhCH ₂ CHCH H ₂ O), δ 2.90 (4H, m, PhOC H ₂ CHCH ₂ O), δ 3.17 (2H, m, PhOCH ₂ CHC H HO), δ 3.35 ( _{2H, m, PhOCH 2 CHCH H} O), δ3.95 (2H, m, PhCH 2 C H CH 2 O), δ4.24 (2H, dd, PhOCH 2 C H CH 2 O), δ6.74 (d , 2H, aromatic), δ 7.02-7.05 (m, 4H, aromatic).

Synthesis Example 2 Synthesis of Substrate (Phenol Novolak-type Allyl Ether (Alleviated as BRG-556-AL2) having an Allyl Group at Ortho- or Para-Position) A solution prepared by dissolving 171.1 g (1.24 mol) in 155.6 g of pure water, phenol novolak represented by formula (6) (Shonol (registered trademark) BRG-556, o = 2 to 7, average value: 5 .1) 500.0 g (manufactured by Showa Denko KK) and 65.61 g (0.619 mol, solid) of sodium carbonate (manufactured by Kanto Chemical Co., Ltd.) were charged, and the reactor was purged with nitrogen and heated to 85 ° C. Under a nitrogen stream, allyl acetate (made by Showa Denko KK) 272.7 g (2.72 mol), triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 3.247 g (12.4 mmol) and 50% water content 5% -Pd / C-STD type (manufactured by N.E. Chemcat Co., Ltd.) 0.105 g (0.0248 mmol) were added, and the temperature was raised to 105 ° C. in a nitrogen atmosphere. The reaction was continued for 4 hours, 27.3 g (0.273 mol) of allyl acetate was added, and the heating was continued for 12 hours, after which stirring was stopped and the mixture was allowed to stand to form two layers, an organic layer and an aqueous layer. After adding pure water (200 g) until the precipitated salt is dissolved, 200 g of toluene is added, and the temperature is kept at 80 ° C. or higher, and it is confirmed that no white precipitate is deposited. Pd / C was recovered by filtration (1 micron membrane filter (pressure (0.3 MPa) using KST-142-JA manufactured by Advantech)). The filter cake was washed with 100 g of toluene. The aqueous layer was separated, and the organic layer was washed twice with 200 g of pure water at 50 ° C. or higher to confirm that the aqueous layer was neutral, and the organic layer was separated and concentrated under reduced pressure to give a brown oily substance. As a result of ¹ H-NMR measurement of this brown oily substance, a phenol novolak allyl ether represented by formula (7) (hereinafter abbreviated as BRG-556-AL) was used as a main component. The measurement data belonging to the compound represented by formula (7) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.6-4.0 (4H, m, PhCH ₂ Ph), δ 4.4-4.8 (2H, m, C H ₂ CH═CH ₂ ), Δ 5.1-5.3 (1H, m, CH ₂ CH═CH H ), δ 5.3-5.5 (1H, m, CH ₂ CH═C H H), δ 5.8-6.2. _{(1H, m, CH 2 C} H = CH 2), δ6.6-7.3 (12H, m, aromatic).

A magnetic stirring bar and 500 g of the phenol novolak allyl ether obtained in the above synthesis were placed in a 1000 mL eggplant flask and heated at 190 ° C. in a nitrogen atmosphere. After 3 hours, it was cooled to give a black solid (550 g, quantitative). As a result of ¹ H-NMR measurement of this black solid, it was confirmed that it contained a phenol novolac allyl substitute represented by formula (8) (hereinafter abbreviated as BRG-556-CL) as a main component. The measurement data belonging to the compound represented by formula (8) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.2-3.4 (2H, m, C H ₂ CH═CH ₂ ), δ 3.6-4.0 (5H, m, PhCH ₂ Ph _{, OH), δ4.6-5.0 (1H,} m, CH 2 CH = CH H), δ5.0-5.3 (1H, m, CH 2 CH = C H H), δ5.8-6 _{.1 (1H, m, CH 2} C H = CH 2), δ6.6-7.2 (12H, m, aromatic).

Synthesis Example except that 4,4 ′-(dimethylmethylene) bis [2- (2-propenyl) phenol] in Synthesis Example 1 was changed to the phenol novolak allyl substitute (BRG-556-CL) obtained in the above synthesis. The phenol novolac type allyl ether having an allyl group at the ortho-position or para-position was synthesized using allyl acetate in the same manner as in 1 to obtain a brown oil (yield 92%). As a result of ¹ H-NMR measurement of the brown oily substance, a phenol novolak type allyl ether (hereinafter abbreviated as BRG-556-AL2) having an allyl group at the ortho or para position represented by the formula (9) is a main component. Confirmed as including. Measurement data belonging to the compound represented by the formula (9) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.4-4.0 (4H, m, PhOC H ₂ CH═CH ₂ , PhC H ₂ CH═CH ₂ ), δ 4.3-4.9. (4H, m, PhCH ₂ Ph), δ 5.2-5.3 (4H, m, PhOCH ₂ CHC = H H, PhCH ₂ CH = C H H), δ 5.3-5.5 (2H, m, _{PhOCH 2 CHC = H H, PhCH} 2 CH = CH H), δ5.8-6.2 (1H, m, PhOCH 2 C H C = H 2, PhCH 2 C H = CH 2), δ6.5-7 .3 (12H, m, aromatic).

Example 2: Synthesis of a phenol novolac type polyvalent glycidyl compound A phenol novolac type allyl ether (BRG-556-AL2) having an allyl group at the ortho or para position obtained in Synthesis Example 2 above in a 200 mL three-necked round bottom flask. 20 g (about 106 mmol), sodium tungstate dihydrate 3.48 g (10.6 mmol), phosphoric acid 0.52 g (5.27 mmol), sulfuric acid 0.51 g (5.27 mmol), and MTOAHS 4.94 g (10. 6 mmol) was added and dissolved in 20 g of toluene. After heating up to 70 degreeC, 61.7 g (0.63 mol) of 35 mass% hydrogen peroxide aqueous solution was dripped over 1 hour, stirring, and also it stirred at 70 degreeC for 2 hours (stirring speed 400rpm). At the beginning of the reaction, the pH of the reaction solution was 1.4, and the pH of the reaction solution after 2 hours of reaction was 3.4. After completion of the reaction, the reaction solution was cooled to room temperature, and then 20 g of pure water was added to carry out a liquid separation treatment. The organic layer was separated, and 20 g of an aqueous sodium sulfite solution (10% by mass) was added and washed to reduce the remaining hydrogen peroxide. The aqueous layer was removed, and 20 g of pure water was added and washed again. The organic layer was isolated and the organic solvent (toluene) was distilled off. 15.3 g (81.4 mmol, yield 76.5%) of a brown high-viscosity oil having an epoxy equivalent of 182 and an epoxy equivalent ratio (E / Er = measured epoxy equivalent / theoretical epoxy equivalent) of 1.54 was obtained. It was. As a result of ¹ H-NMR measurement of this brown highly viscous oily substance, it was confirmed that it contained a phenol novolac type polyvalent glycidyl compound represented by the formula (10) as a main component. The measurement data belonging to the compound represented by formula (10) is as follows. The ¹ H-NMR spectrum of the product is shown in FIG.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 2.5-2.8 (2H, m, PhOC H ₂ CHCH ₂ O), δ 2.8-3.0 (4H, m, PhC H ₂ CHCH ₂ O, PhCH ₂ CHC H ₂ O), δ 3.1-3.4 (2H, m, PhOCH ₂ CHC H ₂ O), δ 3.6-4.0 (6H, m, PhCH ₂ Ph, PhOCH ₂ C) _{H CH 2 O, PhCH 2 C} H CH 2 O), δ6.6-7.2 (12H, m, aromatic).

Synthesis Example 3: Synthesis of substrate (triphenylmethane novolak (polycondensation product of phenol and benzaldehyde) allyl ether (abbreviated as TRI-220-AL2) having an allyl group at ortho- or para-position) Shonol (registered trademark) as a raw material Triphenylmethane novolak represented by formula (11) instead of BRG-556 (Shonol (registered trademark) TRI-220, p = 2 to 7, average value: 3.1) (manufactured by Showa Denko KK) 500 Except for using 0.0 g, the substrate was synthesized in three steps in the same manner as BRG-556-AL2 in Synthesis Example 2. First, in the first step, triphenylmethane novolak allyl ether (hereinafter referred to as TRI-220-AL) was synthesized. represented by synthesizing the abbreviated) and to give a brown oil (94% yield). the brown oil was the ¹ H-NMR measurement result, equation (12) That measurement data attributable to the compound represented by the triphenylmethane novolac allyl ether member was confirmed to contain as a main component. Equation (12) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.2-3.4 (2H, m, PhCHPh), δ 4.5-4.6 (2H, m, C H ₂ CH═CH ₂ ), δ5.2-5.3 (1H, m, CH ₂ CH═CH H ), δ 5.3-5.5 (1H, m, CH ₂ CH═C H H), δ 6.0-6.1 (1H _{, m, CH 2 C H =} CH 2), δ6.6-7.3 (17H, m, aromatic).

Similar to the synthesis of BRG-556-AL2, the triphenylmethane novolak allyl substitute (hereinafter abbreviated as TRI-220-CL) was synthesized in the second step to obtain a brown oil (yield 98%). . As a result of ¹ H-NMR measurement of the brown oily substance, it was confirmed that the compound represented by the formula (13) was contained as a main component. Measurement data belonging to the compound represented by the formula (13) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.2-3.4 (2H, m, PhCHPh), δ 4.8-4.9 (1H, m, CH H CH═CH ₂ ), δ5 0.0-5.2 (3H, m, C H HCH═CH ₂ , CH ₂ CH═CH H , CH ₂ CH═C H H), δ5.8-6.1 (1H, m, CH ₂ C H _{= CH 2), δ6.6-7.4 (17H} , m, aromatic).

Similar to BRG-556-AL2, the triphenylmethane novolak type allyl ether (hereinafter abbreviated as TRI-220-AL2) was synthesized in the third step to obtain a brown oil (yield 98%). As a result of ¹ H-NMR measurement of this brown oily substance, it was confirmed that the compound represented by the formula (14) was contained as a main component. The measurement data belonging to the compound represented by formula (14) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 2.6-2.9 (2H, m, PhOC H ₂ CH═CH ₂ ), δ 3.1-3.3 (2H, m, PhCHPh), δ4.5-4.9 (2H, m, PhCH H CH═CH ₂ , PhOCH H CH═CH ₂ ), δ 5.0-5.4 (3H, m, PhC H HCH═CH ₂ , PhOC H HCH = _{CH 2, PhCH 2 CH = C} H 2, PhOCH 2 CH = C H 2), δ5.8-6.1 (2H, m, PhCH 2 C H = CH 2, PhOCH 2 C H = CH 2), δ6 6-7.3 (17H, m, aromatic).

Example 3: Synthesis of triphenylmethane novolak type polyvalent glycidyl compound Triphenylmethane novolak type allyl ether (TRI-) having an allyl group at the ortho-position or para-position obtained in Synthesis Example 3 above in a 200 mL three-neck round bottom flask. 220-AL2) 15 g (about 48 mmol), sodium tungstate dihydrate 3.48 g (10.6 mmol), phosphoric acid 0.52 g (5.27 mmol), sulfuric acid 0.51 g (5.27 mmol), and MTOAHS4. 94 g (10.6 mmol) was added and dissolved in 20 g of toluene. After heating up to 70 degreeC, 61.7 g (0.63 mol) of 35 mass% hydrogen peroxide aqueous solution was dripped over 1 hour, stirring, and also it stirred at 70 degreeC for 2 hours (stirring speed 400rpm). At the beginning of the reaction, the pH of the reaction solution was 1.4, and the pH of the reaction solution after 2 hours of reaction was 3.4. After completion of the reaction, the reaction solution was cooled to room temperature, and then 20 g of pure water was added to carry out a liquid separation treatment. The organic layer was separated, and 20 g of an aqueous sodium sulfite solution (10% by mass) was added and washed to reduce the remaining hydrogen peroxide. The aqueous layer was removed, and 20 g of pure water was added and washed again. The organic layer was isolated, the organic solvent (toluene) was distilled off, and a brown highly viscous oily product having an epoxy equivalent of 192 and an epoxy equivalent ratio (E / Er = measured epoxy equivalent / theoretical epoxy equivalent) of 1.34 11.4 g (36 mmol, yield 75.7%) was obtained. As a result of ¹ H-NMR measurement of this brown highly viscous oily substance, it was confirmed that it contained a triphenylmethane novolak type polyvalent glycidyl compound represented by the formula (15) as a main component. Measurement data belonging to the compound represented by the formula (15) is as follows. The ¹ H-NMR spectrum of the product is shown in FIG.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 2.4-2.6 (2H, m, PhOC H ₂ CHCH ₂ O), δ 2.6-2.8 (4H, m, PhC H ₂ CHCH ₂ O, PhCH ₂ CHC H ₂ O), δ 2.8-3.0 (2H, m, PhOCH ₂ CHC H ₂ O), δ 3.0-3.3 (2H, m, PhCHPh), δ 3.8- _{4.0 (2H, m, PhOCH 2} C H CH 2 O), δ4.1-4.3 (2H, m, PhCH 2 C H CH 2 O), δ6.6-7.3 (12H, m, aromatic).

Comparative Example 1
The glycidylation reaction was performed in the same manner as in Example 1 except that the reaction time after the addition of the aqueous hydrogen peroxide solution was 9 hours, and the epoxy equivalent was 209, the epoxy equivalent ratio (E / Er = epoxy equivalent by measurement / theoretical epoxy) 12 g (yield 66.3%) of product with an equivalent weight of 1.85 was obtained. Since the reaction was carried out for a long time, a gel-like product was generated, the yield of the target product was decreased, and the epoxy equivalent ratio was also increased.

Comparative Example 2
A glycidylation reaction was carried out in the same manner as in Example 1 except that the dropping time of the aqueous hydrogen peroxide solution was 3 hours and the reaction time after the addition of the aqueous hydrogen peroxide solution was 1 hour, and the epoxy equivalent was 337, the epoxy equivalent ratio ( 17.2 g (yield 95.0%) of a product having an E / Er = measured epoxy equivalent / theoretical epoxy equivalent) of 1.85 was obtained. If the dropwise addition is performed for a long time and the reaction time after completion of the addition of the aqueous hydrogen peroxide solution is shortened, the epoxy equivalent ratio increases. ¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.} analysis confirmed that the allyl content, which is a reaction intermediate, was about 50% higher than that in Example 1. The reason for the increase in the epoxy equivalent ratio is presumed to be the low reaction efficiency.

Comparative Example 3
The glycidylation reaction was carried out in the same manner as in Example 1 except that the amount of phosphoric acid was doubled (0.462 g (4.7 mmol)) and sulfuric acid was not allowed to coexist. 18.2 g (yield: 86.3%) of a product having an epoxy equivalent of 179 and an epoxy equivalent ratio (E / Er = measured epoxy equivalent / theoretical epoxy equivalent) of 1.58 was obtained. When only phosphoric acid is used as the acid, the epoxy equivalent ratio increases. ¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.} analysis confirmed that the allyl content, which is a reaction intermediate, was about 40% higher than that in Example 1. The reason for the increase in the epoxy equivalent ratio is presumed to be the low reaction efficiency.

Comparative Example 4
A glycidylation reaction was performed in the same manner as in Example 1 except that the amount of phosphoric acid was increased to 10 times and the pH of the reaction solution was adjusted to about 0.5. A large amount of a gel-like product that was considered to be a hydrolyzate was precipitated (53 g, hydrated), and it was difficult to extract the target product from the reaction solution. The gel was collected by filtration, washed successively with ethyl acetate (50 mL) and methanol (50 mL), and dried under reduced pressure to give a brown solid. A ¹ H-NMR spectrum of the obtained product is shown in FIG. Lower is ¹ H-NMR spectrum of the product is a ¹ H-NMR spectrum of the upper is the desired product (formula (5)). The content of the signal attributed to the target product in the product is 10% or less, and 90% or more is attributed to the hydrolyzate and its associated product (gel-like product). The signal data that can be inferred to be attributed to the hydrolyzate are as follows.
^{1 H-NMR {400MHz, DMSO} -d 6, 27 ℃} δ1.60 (6H, s, CH 3), δ3.3-3.5 (2H, brm, PhCH 2 CH (O H) CH 2 (O _{H), PhOCH 2 CH (O} H) CH 2 (O H)), δ3.6 (2H, brm, PhCH 2 CH (OH) C H 2 (OH)), δ3.8 (2H, m, PhOCH 2 _{CH (OH) C H 2 (} OH)), δ3.9 (2H, brm, PhOCH 2 C H (OH) CH 2 (OH)), δ4.4 (2H, brm, PhCH 2 C H (OH) CH _{2 (OH)), δ4.6 (} 2H, brm, PhOC H 2 CH (OH) CH 2 (OH)), δ4.9 (2H, brm, PhC H 2 CH (OH) CH 2 (OH)), δ6.8 (brm, 2H, aromatic), δ6.9-7 .1 (m, 4H, aromatic).

Comparative Example 5
A glycidylation reaction was conducted in the same manner as in Example 1 except that the amounts of phosphoric acid and sulfuric acid were each 0.5 times and the pH of the reaction solution was adjusted to 5.0. The epoxy equivalent was 321 and the epoxy equivalent ratio (E / 19.2 g (yield 91.1%) of a product having an Er = actually measured epoxy equivalent / theoretical epoxy equivalent) of 2.84 was obtained. When the pH of the reaction solution is higher than 4.0, the epoxy equivalent ratio increases. ¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.} analysis confirmed that the allyl content, which is a reaction intermediate, was about 60% higher than that in Example 1. The reason for the increase in the epoxy equivalent ratio is presumed to be the low reaction efficiency.

Comparative Example 6
Instead of using phosphoric acid, a glycidylation reaction was carried out in the same manner as in Example 1 except that sulfuric acid was used in an amount twice as much and the pH of the reaction solution was adjusted to about 0.5. There was obtained 9.2 g (yield 43.6%) of product having an epoxy equivalent of 182 and an epoxy equivalent ratio (E / Er = measured epoxy equivalent / theoretical epoxy equivalent) of 1.61. The cause of the decrease in yield is estimated to be due to hydrolysis as in Comparative Example 4.

  According to the method for producing a polyvalent glycidyl compound of the present invention, from the reaction between a substituted or unsubstituted 2-alkenyl ether compound having two or more substituted or unsubstituted 2-alkenyl groups in the molecule and an aqueous hydrogen peroxide solution. It is industrially useful because a substituted or unsubstituted polyvalent glycidyl compound can be produced safely with a simple operation, in a high yield (suppressing hydrolysis of the glycidyl ether group) and at a low cost.

Claims (7)

  A 2-alkenyl ether compound having two or more substituted or unsubstituted 2-alkenyl groups and one or more substituted or unsubstituted 2-alkenyl ether groups in the molecule, using an aqueous hydrogen peroxide solution as an oxidizing agent In the presence of two or more kinds of acids including a tungsten compound, a quaternary ammonium salt, and at least phosphoric acid as a catalyst, the pH of the reaction solution containing the 2-alkenyl ether compound is controlled to 1.0 to 4.0. A hydrogen peroxide aqueous solution is added to the reaction solution over 0.1 to 2 hours, and the reaction is stopped in 2 to 6 hours after the addition of the hydrogen peroxide aqueous solution is completed. Method.   The 2-alkenyl ether compound contains an aromatic ring in the molecule, and one or more substituted or unsubstituted 2-alkenyl ether groups directly connected to the aromatic ring and two or more substituted or unsubstituted direct bonds to the aromatic ring. 2. The compound according to claim 1, wherein the compound has a 2-alkenyl group and a substituted or unsubstituted 2-alkenyl group is located in the ortho-position or para-position with respect to the substituted or unsubstituted 2-alkenyl ether group. A method for producing a polyvalent glycidyl compound. The 2-alkenyl ether compound is represented by the general formula (1):

Wherein R ¹ and R ² are each independently a group represented by the following formula (2), and Q are each independently an alkylene represented by the formula: —CR ³ R ⁴ —. Group, a C3-C12 cycloalkylene group, an arylene group composed of a single aromatic ring having 6 to 10 carbon atoms, or an arylene group formed by bonding 2-3 aromatic rings having 6 to 10 carbon atoms, C7- 12 divalent alicyclic condensed rings, or a divalent group obtained by combining these, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 to 10 carbon atoms. An alkenyl group, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and n represents an integer of 0 to 50. R ⁵ , R ⁶ and R ^{7 in} formula (2) Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloaryl having 3 to 12 carbon atoms. Method for producing a polyglycidyl compound according to claim 1 or 2 which is a compound represented by.) Representing a kill or aryl group having 6 to 10 carbon atoms.

The 2-alkenyl ether compound is bisphenol-A, bisphenol-F, phenol novolac, triphenylmethanephenol, biphenylaralkyl type phenol, phenylaralkyl type phenol, phenol of an unsubstituted tetrahydrodicyclopentadiene skeleton, or CH _{2 at} both ends. An unsubstituted tetrahydrodicyclopentadiene skeleton phenol to which is bonded is a 2-alkenyl ether compound having any basic skeleton of R ² in the ortho or para position with respect to OR ¹ . The manufacturing method of the polyvalent glycidyl compound of description.   The polyvalent glycidyl compound according to any one of claims 1 to 4, wherein the tungsten compound is a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or a mixture of tungstic acid and an alkali compound. Manufacturing method.   The method for producing a polyvalent glycidyl compound according to any one of claims 1 to 5, wherein the total number of carbon atoms of the substituents bonded to the nitrogen atom of the quaternary ammonium salt is 6 or more and 50 or less.   The acid other than phosphoric acid is at least one mineral acid selected from the group consisting of polyphosphoric acid, pyrophosphoric acid, sulfonic acid, nitric acid, sulfuric acid, hydrochloric acid, and boric acid, benzenesulfonic acid, p-toluenesulfonic acid, methane The method for producing a polyvalent glycidyl compound according to any one of claims 1 to 6, which is at least one organic acid selected from the group consisting of sulfonic acid, trifluoromethanesulfonic acid, and trifluoroacetic acid.

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