JP6351487B2 - Method for producing polyvalent glycidyl compound - Google Patents

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.

  On the other hand, as a method for oxidizing a 2-alkenyl group, a method using an aqueous hydrogen peroxide solution as an oxidizing agent is known (Patent Document 2: Japanese Patent Laid-Open No. 60-60123). According to this method, a phenylallyl ether compound can be efficiently oxidized in the presence of a trace amount of a metal catalyst. A polyvalent glycidyl compound having a glycidyl group in the ortho position or para position relative to the glycidyl ether group bonded to the phenol moiety of a compound having bisphenol as a basic skeleton is 2-alkenyl in the ortho position or para position relative to the glycidyl ether group. It can be obtained by oxidizing a corresponding substrate having a group, but when an aqueous hydrogen peroxide solution is used as an oxidizing agent, there is a problem that a glycidyl ether group originally present in the substrate is hydrolyzed. In addition, a diol compound is generated as a by-product by the hydrolysis reaction of the glycidyl ether group, but the diol compound has a hydroxyl group (hydrophilic portion) bonded to a hydrophobic main skeleton (aromatic ring). Among them, molecules tend to aggregate and form a gel-like substance. These gel-like substances complicate the post-treatment after the reaction and become a factor of reducing the yield and purity of the target product. In this way, when an aqueous hydrogen peroxide solution is used as an oxidizing agent to glycidylate a 2-alkenyl group of a substrate having a 2-alkenyl group at the ortho-position or para-position relative to the glycidyl ether group, hydrolysis of the glycidyl ether group It is necessary to control side reactions such as gelation and gelation accompanying hydrolysis.

Japanese Patent Laid-Open No. 63-142019 Japanese Patent Application Laid-Open No. 60-60123

  When oxidizing the 2-alkenyl group of a glycidyl ether compound having a 2-alkenyl group using an aqueous hydrogen peroxide solution as an oxidizing agent, the present invention involves side reactions such as hydrolysis of the glycidyl ether group originally present in the compound, The present invention provides a method capable of producing a polyvalent glycidyl compound safely, with high yield and high purity, in which gelation associated with hydrolysis is suppressed.

  As a result of intensive studies and experiments conducted in order to solve the above-mentioned problems, the present inventors have obtained a catalyst for a glycidyl ether compound having one or more glycidyl ether groups and two or more 2-alkenyl groups in the molecule. As a tungsten compound, a quaternary ammonium salt, and in the presence of phosphoric acid as a co-catalyst, oxidation (glycidylation) using an aqueous hydrogen peroxide solution as an oxidizing agent while controlling the pH of the reaction solution using an acid other than phosphoric acid ), The addition of an aqueous hydrogen peroxide solution to the reaction solution and the addition of an acid other than phosphoric acid to adjust the pH of the reaction solution are repeated several times at alternate intervals to ensure high yields. It has been found that a polyvalent glycidyl compound having three or more glycidyl groups in the molecule can be obtained with high efficiency and high purity, and the present invention has been completed.

（式中、Ｒ^１及びＲ^２は、各々独立して、下記式（２）又は（３）で表され、Ｑは、各々独立して、式：−ＣＲ^３Ｒ^４−で表されるアルキレン基、炭素原子数３〜１２のシクロアルキレン基、炭素原子数６〜１０の単独芳香環からなるアリーレン基若しくは２〜３の炭素原子数６〜１０の芳香環が結合してなるアリーレン基、炭素原子数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、炭素原子数１〜１０のアルキル基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１２のシクロアルキル基、又は炭素原子数６〜１０のアリール基であり、ｎは０〜５０の整数を表す。式（２）及び（３）中のＲ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、各々独立して、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数３〜１２のシクロアルキル基又は炭素原子数６〜１０のアリール基を表す。但し、複数のＲ^１の内少なくとも１つは式（２）で表され、複数のＲ^２の内少なくとも２つは式（３）で表される。）で表される化合物、又は上記一般式（１）のベンゼン骨格の代わりにナフタレン骨格を有する化合物である［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］前記グリシジ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グリシジルエーテル化合物である［６］に記載の多価グリシジル化合物の製造方法。
［８］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のいずれかである［１］〜［７］のいずれかに記載の多価グリシジル化合物の製造方法。
［９］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原子数の合計が６以上５０以下である［１］〜［８］のいずれかに記載の多価グリシジル化合物の製造方法。
［１０］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］〜［９］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 glycidyl ether compound having one or more substituted or unsubstituted glycidyl ether groups and two or more substituted or unsubstituted 2-alkenyl groups in the molecule, using an aqueous hydrogen peroxide solution as an oxidizing agent, Polyhydric glycidyl which is oxidized in the presence of phosphoric acid as a catalyst and a tungsten compound as a catalyst and an acid other than phosphoric acid while controlling the pH of the reaction liquid at 1.0 to 4.0. In the method for producing a compound, the step of adding a hydrogen peroxide aqueous solution to the reaction solution and the step of adding an acid other than phosphoric acid are alternately repeated a plurality of times with a time interval, and the polyvalent glycidyl compound is characterized in that Manufacturing method.
[2] The hydrogen peroxide aqueous solution addition step and the acid addition step other than phosphoric acid in the repetition step are repeated 2 to 20 times during the reaction with 0.1 to 1 hour between each step. [1] A method for producing a polyvalent glycidyl compound according to [1].
[3] Until the total amount of hydrogen peroxide aqueous solution added to the reaction solution reaches 0.5 equivalents relative to the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound, The method for producing a polyvalent glycidyl compound according to any one of [1] and [2], wherein the step of adding an aqueous hydrogen peroxide solution and the step of adding an acid other than phosphoric acid are repeated at least twice.
[4] The hydrogen peroxide aqueous solution adding step and the acid adding step other than phosphoric acid to the reaction solution are performed in a range where the temperature of the reaction solution does not exceed 50 ° C. [1] to [3] The manufacturing method of the polyvalent glycidyl compound of description.
[5] The glycidyl ether compound contains an aromatic ring in the molecule, and one or more substituted or unsubstituted glycidyl ether groups directly bonded to the aromatic ring and two or more substituted or unsubstituted 2 bonded directly to the aromatic ring Any of [1] to [4], which is a compound having an alkenyl group and having a substituted or unsubstituted 2-alkenyl group located in the ortho or para position with respect to the substituted or unsubstituted glycidyl ether group A method for producing the polyvalent glycidyl compound according to claim 1.
[6] The glycidyl ether compound is represented by the general formula (1):

(In the formula, R ¹ and R ² are each independently represented by the following formula (2) or (3), and Q are each independently an alkylene represented by the formula: —CR ³ R ⁴ —. group, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group in which an aromatic ring is bonded having 6 to 10 carbon atoms in the arylene group or 2-3 consisting solely an aromatic ring having 6 to 10 carbon atoms, carbon A divalent alicyclic condensed ring having 7 to 12 atoms , 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, 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. Formulas (2) and ( 3) ^R 5 ^{in, R 6, R 7, R} 8, R 9 and ^{R 10} are each independently A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group having 6 to 10 carbon atoms of 3 to 12 carbon atoms. However, at least one formula of a plurality of ^{R 1} (2), and at least ^two of the plurality of R ² are represented by the formula (3)) or a naphthalene skeleton instead of the benzene skeleton of the general formula (1). method for producing a polyglycidyl compound according to any one of compound [1] to [5].

[7] The glycidyl ether compound is bisphenol-A, bisphenol-F, phenol novolak, triphenylmethanephenol, biphenylaralkyl type phenol, phenylaralkyl type phenol, or phenol of an unsubstituted tetrahydrodicyclopentadiene skeleton or It is a glycidyl ether compound having any basic skeleton of phenol having an unsubstituted tetrahydrodicyclopentadiene skeleton to which CH ₂ — is bonded, and R ² is located in the ortho or para position with respect to OR ¹ [6]. A method for producing the polyvalent glycidyl compound described in 1.
[8] Any one of [1] to [7], wherein the tungsten compound is any one of 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 manufacturing method of the polyvalent glycidyl compound of description.
[9] The method for producing a polyvalent glycidyl compound according to any one of [1] to [8], 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. .
[10] 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 [9], 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, while controlling the pH of the reaction solution to 1.0 to 4.0, the addition of an aqueous hydrogen peroxide solution and the addition of an acid other than phosphoric acid added to control the pH are repeated a plurality of times at alternate intervals. By controlling the temperature of the reaction solution, the amount of by-product hydrolyzate produced can be reduced, and a polyvalent glycidyl compound can be obtained safely in high yield and high purity.

  Hereinafter, the present invention will be described in detail. The method for producing a polyvalent glycidyl compound of the present invention is a method for peroxidizing a glycidyl ether compound having one or more substituted or unsubstituted glycidyl ether groups and two or more substituted or unsubstituted 2-alkenyl groups in the molecule. Using an aqueous hydrogen solution as an oxidizing agent, a tungsten compound, a quaternary ammonium salt as a catalyst, and an acid other than phosphoric acid in the presence of phosphoric acid as a promoter, the pH of the reaction solution is adjusted to 1.0 to 4.0. Oxidize while controlling. At this time, the step of adding the hydrogen peroxide aqueous solution to the reaction solution and the step of adding an acid other than phosphoric acid are alternately repeated a plurality of times at intervals. Although details will be described later, in the present invention, the hydrolysis of the glycidyl ether group originally present in the molecule is suppressed to a minimum, and the carbon-carbon double bond of the 2-alkenyl group is oxidized (glycidylation). 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. For example, “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 “glycidyl ether group” means a glycidyloxy group.

式中、Ｒ^１及びＲ^２は、各々独立して、下記式（２）又は（３）で表され、Ｑは、各々独立して、式：−ＣＲ^３Ｒ^４−で表されるアルキレン基、炭素原子数３〜１２のシクロアルキレン基、炭素原子数６〜１０の単独芳香環からなるアリーレン基若しくは２〜３の炭素原子数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）、炭素原子数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、炭素原子数１〜１０のアルキル基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１２のシクロアルキル基、又は炭素原子数６〜１０のアリール基であり、ｎは０〜５０の整数を表す。式（２）及び（３）中のＲ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、各々独立して、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数３〜１２のシクロアルキル基又は炭素原子数６〜１０のアリール基を表す。但し、複数のＲ^１の内少なくとも１つは式（２）で表され、複数のＲ^２の内少なくとも２つは式（３）で表される。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 particularly a glycidyl ether compound having one or more substituted or unsubstituted glycidyl ether groups and two or more substituted or unsubstituted 2-alkenyl groups in the molecule. Although there is no limitation, one or more substituted or unsubstituted glycidyl ether groups directly containing an aromatic ring in the molecule and two or more substituted or unsubstituted 2-alkenyl groups directly connected to the aromatic ring. And a compound in which a substituted or unsubstituted 2-alkenyl group is located in the ortho or para position with respect to the substituted or unsubstituted glycidyl ether group is preferable in that it is relatively easily available. For example, the compound represented by the following general formula (1) is mentioned as a suitable glycidyl ether compound.

In the formula, R ¹ and R ² are each independently represented by the following formula (2) or (3), 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, alone aromatic consist ring arylene group or 2-3 aromatic rings bonded to become an arylene group having 6 to 10 carbon atoms of 6 to 10 carbon atoms (e.g., an arylene group having a biphenyl skeleton arylene group two aromatic rings formed by bonding is an arylene group having a triphenyl skeleton arylene group three aromatic rings formed by bonding), carbon atoms 7-12 divalent alicyclic fused, or a divalent group comprising a combination thereof, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 2 carbon atoms 10 alkenyl groups, charcoal Atoms 3-12 cycloalkyl 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, R 7} , R 8, R 9 and ^{R 10} in the formula (2) and (3) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, carbon atoms It represents a 3-12 cycloalkyl group or an aryl group having 6 to 10 carbon atoms. However, at least ^one of the plurality of R ¹ is represented by the formula (2), and at least two of the plurality of R ² are represented by the formula (3). * In Formula (2) and Formula (3) means that it is a bond part with the carbon atom which comprises an oxygen atom or an aromatic ring.

As a specific glycidyl ether compound represented by the general formula (1), R ¹ and R ² are preferably represented by the formula (2) or the formula (3) in which R ^{5 to} R ¹⁰ are all hydrogen atoms. Group. 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 what is a naphthyl group is mentioned. Preferred as the cyclohexylidene group cycloalkylene group having 3 to 12 carbon atoms, an aromatic ring bonded to an arylene group or 2-3 carbon atoms 6 to 10 consists of a single aromatic ring having 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 include bisphenol-A, bisphenol-F, phenol novolac, triphenylmethanephenol, such as a biphenylaralkyl type phenol having a —CH ₂ —Ph—Ph—CH ₂ — skeleton, such as —CH ₂ —Ph. A basic skeleton of either a phenylaralkyl-type phenol having a —CH ₂ — skeleton, a phenol having an unsubstituted tetrahydrodicyclopentadiene skeleton, or a phenol having an unsubstituted tetrahydrodicyclopentadiene skeleton having —CH ₂ — bonded to both ends. And a glycidyl ether compound in which R ² is located at the ortho position or the para position with respect to OR ¹ . Further, examples of the glycidyl ether compound other than the glycidyl ether compound represented by the general formula (1) include a compound having a naphthalene skeleton instead of the benzene skeleton of the general formula (1), for example, naphthalene novolak.

  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 glycidyl ether compound as a reaction substrate is oxidized (glycidylation) using an aqueous hydrogen peroxide solution as an oxidizing agent. To do. 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 the operability and / or cost of separation, a high concentration of the aqueous hydrogen peroxide solution is preferable, but on the other hand, an excessively high concentration and / or an excessive amount of hydrogen peroxide is required. It is preferable not to use an aqueous hydrogen oxide solution from the viewpoints of economy and safety.

  When an aqueous hydrogen peroxide solution is added to the reaction solution, the pH of the reaction solution changes. The present inventors pay attention to the fact that the control of the pH of the reaction solution is extremely important for solving the problems of the present invention, and in the embodiment of the present invention, a step of adding an aqueous hydrogen peroxide solution to the reaction solution (hereinafter referred to as the following step). , "First step") and a step of adding an acid other than phosphoric acid for controlling pH (hereinafter referred to as "second step") alternately with multiple intervals. It has been found that it is extremely effective to contain. Specifically, when the number of iterations is n and attention is paid to an arbitrary k (2 ≦ k ≦ n) step, an interval T1 after the completion of the (k−1) th first step is set (k -1) The second step is carried out, and the k-th first step is carried out at an interval T2 after the completion of the (k-1) second step. The period from the (k-1) th first step to the kth first step is defined as one series of steps, and this is repeated n times. Each first step, T1, second step and T2 in the n repetitive steps can be the same conditions, or different conditions.

  This reaction system is a two-phase system of an organic phase based on the organic solvent or the glycidyl ether compound itself and an aqueous phase based on the added aqueous hydrogen peroxide solution, and usually becomes emulsion-like as the reaction solution is stirred. When an aqueous solution of hydrogen peroxide or an acid other than phosphoric acid is added to the reaction solution, the relative proportion of the aqueous phase in the reaction solution is low at the beginning of the reaction, and a true pH value is observed with a pH analyzer that uses the measurement target as an aqueous solution. Can not. Therefore, it is possible to estimate the pH value of the reaction solution from an observation value obtained by sampling a part of the solution and diluting it about 2 to 10 times with water to increase the water ratio. . According to the present invention, it is possible to prevent the pH in the reaction system from rapidly decreasing by keeping an interval between the addition of an aqueous hydrogen peroxide solution (oxidizing agent) and the addition of an acid other than phosphoric acid (pH adjusting agent). Can do. In this way, the pH of the reaction solution can be accurately controlled even in the early stage of the reaction when it is difficult to directly observe the pH of the reaction solution. For example, the pH of the reaction solution after the first addition of an aqueous hydrogen peroxide solution and the addition of an acid other than phosphoric acid is apparently observed to be about 5 but is obtained by measuring the emulsion diluted 10 times. The true pH value is estimated to be about 4 from the measured values.

  In the embodiment of the present invention, an aqueous hydrogen peroxide solution is first added to a reaction solution charged with a substrate, a catalyst, etc., but since the reaction solution contains phosphoric acid as a co-catalyst, the pH of the reaction solution is 1 at this stage. It will not be outside the range of .0 to 4.0. Actually, before adding an acid other than phosphoric acid, a part of the solution is taken and diluted with water, and then the pH of the aqueous layer is measured. The estimated pH value calculated from the actual measurement value is 4. 0 or less. The pH is gradually lowered by adding an acid other than phosphoric acid, but the addition amount is adjusted so that the pH does not become lower than 1.0.

  When the pH of the reaction solution can be measured directly with a pH analyzer, buffering action is achieved by the coexistence of hydrogen peroxide, phosphoric acid, acids other than phosphoric acid (preferably sulfuric acid), and tungsten compounds in the reaction solution. Will come to show. At such a stage, even if the remaining hydrogen peroxide aqueous solution and an acid other than phosphoric acid are added all at once, a large pH change of the reaction solution does not occur.

  In a preferred embodiment of the present invention, the first step and the second step are repeated a plurality of times, for example, 2 to 20 times during the reaction with 0.1 to 1 hour between each step. As a more specific example, the amount of hydrogen peroxide aqueous solution added to the reaction solution is 0.05 to 0.3 equivalents relative to the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound. After adding hydrogen peroxide aqueous solution for the first time in the range (first step) and continuing the reaction for 0.1 to 1 hour (corresponding to T1) after the addition, other than phosphoric acid as the first second step The acid is added within a range where the pH of the reaction solution is maintained within the range of 1.0 to 4.0 (for example, within the range of 5 to 30% by mass of the total addition amount), and 0.1 to 1 hour after the addition is completed. The reaction is continued (corresponding to T2 above). That is, 0.1 to 1 hour is left from the end of the first first step to the start of the second step, and 0.1 to 1 hour is left from the end of the first second step to the start of the second first step. By setting it as such a process, it can prevent that the pH of a reaction liquid falls rapidly, and can also adjust the residual accumulation amount of hydrogen peroxide. In the first step and the second step, it is preferable to add little by little intermittently or continuously while stirring the reaction solution, and more preferably 0.1 to 1.5 hours. It is preferable to continue stirring of the reaction solution between both steps (T1 and T2). Subsequently, the total amount of hydrogen peroxide aqueous solution added to the reaction solution (total amount in the first and second times) is 0.1 to the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound. After the addition of the second aqueous hydrogen peroxide solution (first step) within the range of 0.5 equivalents, the reaction was continued for 0.1 to 1 hour (corresponding to T1) after the addition was completed. In the second step, an acid other than phosphoric acid is added within a range where the pH of the reaction solution is maintained within the range of 1.0 to 4.0 (for example, within a range of 5 to 30% by mass of the total addition amount), and added. The reaction is continued for 0.1 to 1 hour (corresponding to T2) after completion.

  The number of repetitions n may be 2 or more, but considering reaction time, reaction efficiency, labor, etc., n is preferably 3-20, more preferably 4-15, and n is 5 More preferably, it is 10-10.

  In a preferred embodiment of the present invention, at least until the total amount of hydrogen peroxide aqueous solution added to the reaction solution reaches 0.5 equivalent to the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound, at least Two repeated steps are performed. At this time, n is preferably 3 to 20. In another preferred embodiment, the total amount of hydrogen peroxide aqueous solution added to the reaction solution reaches at least 2 before reaching 0.4 equivalents relative to the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound. Repeat the process once. At this time, n is preferably 4-15. In still another preferred embodiment, the total amount of the aqueous hydrogen peroxide solution added to the reaction solution is at least 2 before reaching 0.3 equivalent to the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound. Repeat the process once. At this time, n is preferably 5 to 10. The first step and the second step are alternately repeated several times, and the amount added per time is suppressed to a small amount, thereby controlling the pH of the reaction solution during the reaction compared to the case where both steps are performed simultaneously. (Ie, the fluctuation in pH can be reduced), the rapid progress of the reaction and the accompanying temperature rise are suppressed, and the oxidation reaction can proceed safely and efficiently.

  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. If a large amount of aqueous hydrogen peroxide solution is added all at once to the reaction solution at the beginning of the reaction, the reaction may proceed rapidly, which may be dangerous. It is preferable to add continuously or intermittently while confirming that the hydrogen concentration is consumed in the reaction. The total amount of hydrogen peroxide aqueous solution added is 1.0 to 5.0 equivalents, preferably 1.1 to 3.0 equivalents, based on the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound. More preferably, it is 1.2-2.0 equivalent. If it is less than 1.0 equivalent, all the carbon-carbon double bonds of the 2-alkenyl group cannot theoretically be oxidized. When the amount is more than 5.0 equivalents, a large amount of a reducing agent is required to quench the excess oxidizing agent, and the post-treatment process becomes complicated.

  It is preferable to continue the reaction after completion of the above repeating process. The amount of the remaining aqueous hydrogen peroxide solution obtained by subtracting the amount of the aqueous hydrogen peroxide solution added in the repetition process from the amount of the aqueous hydrogen peroxide solution that is 1.0 equivalent of the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound. It is preferable to continue the addition of the hydrogen peroxide aqueous solution in the same amount or more and the subsequent reaction while stirring the reaction solution. In this stage, an acid other than phosphoric acid can be added to adjust the pH of the reaction solution as necessary. The addition of an acid other than phosphoric acid may not be performed after an interval after the addition of the aqueous hydrogen peroxide solution, or may be performed simultaneously with the addition of the aqueous hydrogen peroxide solution.

  It is preferable to use a stirrer having a magnetic stirrer or a stirring blade for stirring including the above-described repeating steps. 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 glycidyl ether compound alone as a reaction substrate or an organic phase containing a glycidyl ether compound dissolved in an organic solvent, and an aqueous phase containing hydrogen peroxide. It is desirable to stir. As the oxidation (glycidylation) reaction of the carbon-carbon double bond of the 2-alkenyl group proceeds, the viscosity of the reaction solution increases. In order to prevent hydrolysis of the glycidyl group of the glycidyl ether compound as the reaction substrate and / or the polyvalent glycidyl compound as the product and by-product formation of the gel-like product, a range of 2 to 30 hours after the addition of the aqueous hydrogen peroxide solution is completed After the reaction is continued, stirring and heating are stopped to complete the oxidation reaction. When the reaction is stopped in less than 2 hours, the reaction substrate contains a large amount of glycidyl ether compound, and the yield of the target product is low. If the reaction is continued for longer than 30 hours, the hydrolyzate becomes the main product and, in some cases, a gel-like product is formed, so that the post-treatment process of the reaction solution becomes complicated, and the yield of the target product is greatly reduced. .

  Oxidation (glycidylation) using an aqueous hydrogen peroxide solution controls the pH of the reaction solution using an acid other than phosphoric acid in the presence of a tungsten compound, a quaternary ammonium salt as a catalyst, and phosphoric acid as a promoter. Can be implemented. Since these compounds are relatively inexpensive, oxidation of the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound using hydrogen peroxide as an oxidizing agent can be performed at low cost.

  As the tungsten compound used as the 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 the catalyst is about 0.0001 to about 20 mol%, preferably about about 0.0001 to about 20 mol%, based on the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound as the reaction substrate, as a tungsten atom. It is selected from the range of 0.01 to about 20 mol%.

As a quaternary ammonium salt used as a catalyst, a quaternary organic ammonium salt having a total number of carbon atoms of substituents bonded to nitrogen atoms of 6 to 50, preferably 10 to 40 is oxidized (glycidylated). ) High reaction activity is 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 glycidyl ether compound of the reaction substrate. Selected from a range.

  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 3.5. 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. Furthermore, when the pH of the reaction solution is lower than 1.0, the generation of reaction heat, which is considered to be caused by the rapid generation of catalytically active species, becomes remarkable, and the reaction heat gradually increases the reaction solution without heating. The temperature rises and can cause thermal runaway. The amount of phosphoric acid used is preferably about 0.01 to about 10 mol%, more preferably about 0.1 to about 10 mol, based on the carbon-carbon double bond of the 2-alkenyl group of the glycidyl ether compound of the reaction substrate. % Range.

  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 glycidyl ether compound of the reaction substrate. Selected from a 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-described catalyst are mixed to advance the glycidylation reaction of the glycidyl ether compound as a reaction substrate. it can. 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 glycidyl 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 necessary minimum amount. The amount of the organic solvent used is preferably about 300 parts by mass or less, more preferably about 300 parts by mass with respect to 100 parts by mass of the glycidyl ether compound. 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 20 ° C. or higher, about It is controlled in the range of 70 ° C. or lower, more preferably about 25 ° C. or higher, about 60 ° C. or lower, more preferably about 30 ° C. or higher and about 50 ° C. or lower. It is preferable to perform both the repetition process of a 1st process and a 2nd process, and reaction after completion | finish of a repetition process in the said temperature range. If the reaction temperature is set higher than about 70 ° C., thermal runaway tends to occur, and the thermal decomposition reaction of the added hydrogen peroxide itself may compete to generate flammable oxygen gas. In a preferred embodiment, the first step and the second step are carried out in such a range that the temperature of the reaction solution does not exceed 50 ° C.

  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 manner, the obtained polyvalent glycidyl compound can be taken out by ordinary methods such as distillation, chromatographic separation, recrystallization, sublimation and the like.

  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) phenyldiglycidyl ether]) In a 5 L three-necked round bottom flask, 4,4 represented by the formula (4) '-(Dimethylmethylene) bis [2- (2-propenyl) phenol] (manufactured by Daiwa Kasei Co., Ltd.) 1000 g (3.25 mol), epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.) 2700 g (20.9 mol), And 156 g (4.87 mol) of methanol (manufactured by Junsei Co., Ltd.) were added and dissolved. After the temperature was raised to 70 ° C., 312 g (7.80 mol) of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added in a granular form over 3 hours, and after completion of addition, the mixture was stirred at 80 ° C. for 3 hours (stirring speed 400 rpm). )did. After completion of the reaction, the reaction solution was cooled to room temperature, and then pure water was added until the precipitated salt was completely dissolved, followed by liquid separation treatment. The organic layer was separated and the organic solvent was distilled off (70 ° C., 50 mmHg, 2 hours). The obtained crude product was dissolved in 2700 g of methyl ethyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.), heated to 70 ° C., and then 389 g (9.73 mol) of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was granulated. The mixture was added as it was and stirred for 1 hour (stirring speed: 400 rpm). After completion of the reaction, the reaction solution was cooled to room temperature, and then pure water was added until the precipitated salt was completely dissolved, followed by liquid separation treatment. The organic layer was separated, the organic solvent was distilled off (70 ° C., 50 mmHg, 2 hours), and 4,4 ′-(dimethylmethylene) bis [2- (2-propenyl) phenyldibenzene represented by formula (5) Glycidyl ether] (1300 g, 3.09 mol, 95% yield) was obtained as a brown liquid. The epoxy equivalent (based on JIS-K7236 standard) of this brown liquid was 220, and as a result of ¹ H-NMR measurement, 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.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 1.64 (6H, s, CH ₃ ), δ 2.75 (2H, dd, PhOCH ₂ CHC H HO), δ 2.89 (2H, dd, PhOCH _{2 CHCH H O), δ3.35 (} 6H, m, PhOCH 2 C H CH 2 O, PhC H 2 CH = CH 2), δ3.95 (2H, dd, PhOC H HCHCH 2 O), δ4.19 ( _{2H, dd, PhOCH H CHCH 2} O), δ5.05 (4H, m, PhCH 2 CH = C H 2), δ5.97 (2H, m, PhCH 2 C H = CH 2), δ6.71 (d , 2H, aromatic), δ 6.90-7.08 (m, 2H, aromatic), δ 7.12-7.30 (2H, m, aromatic).

Example 1 Synthesis of 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane Into a 5 L three-necked round bottom flask, 4,4 ′-(dimethylmethylene) bis [2 obtained in Synthesis Example 1 above was added. -(2-propenyl) phenyldiglycidyl ether] 811 g (1.93 mol), sodium tungstate dihydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) 25.5 g (77.1 mmol), phosphoric acid (Wako Pure Chemical Industries, Ltd.) 30.3 g (309 mmol) manufactured by Co., Ltd., and 81.4 g (174 mmol) trioctylmethylammonium hydrogen sulfate (MTOAHS, manufactured by Asahi Chemical Industry Co., Ltd.) are dissolved in 120 g of toluene (manufactured by Junsei Chemical Co., Ltd.). It was. After heating up to 40 ° C., 81 g (835 mmol) of 35% by mass aqueous hydrogen peroxide solution (manufactured by Hishie Kasei Co., Ltd.) was added with stirring over 0.1 hour, and then stirred and held for 0.1 hour. 35% by weight of dilute sulfuric acid (concentrated sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) diluted with pure water, adjusted to 35% by weight and used) 8.1 g (29 mmol) was added over 0.1 hour, and then 0.1%. Stir and hold for 1 hour. The hydrogen peroxide aqueous solution adding step and the sulfuric acid adding step were alternately carried out 5 times each for 2 hours in total. After confirming that the pH reached 1.8, an aqueous hydrogen peroxide solution was added dropwise over 2 hours so that the total addition amount was 563 g (5.8 mol). After completion of dropping, stirring was continued at 40 ° C. for 16 hours (stirring speed: 400 rpm). The pH of the reaction solution at the time of 1 hour after the completion of the addition is 1.1, the pH of the reaction solution after the reaction for 6 hours is 2.4, and the pH at the end of the reaction (after 16 hours) is 2 .5. Stirring was performed at a stirring speed of 400 rpm from the start to the end of the reaction. After completion of the reaction, the reaction solution was cooled to room temperature, and then 1200 g of toluene was added for liquid separation treatment. The organic layer was separated, and the remaining hydrogen peroxide was reduced by adding 2000 g of a 10% by mass aqueous sodium sulfite solution prepared by dissolving sodium sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) in pure water. The aqueous layer was removed, and 750 g of pure water was added and washed again. By isolating the organic layer and distilling off the organic solvent (toluene), the relative content of the epoxy compound (EP ratio (%) = (theoretical epoxy equivalent / epoxy equivalent by actual measurement) × 100) was 95.6%. 783 g (1.73 mol, 89.9% yield) of some product was obtained. 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 (6), 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 (6) was contained as a main component. The measurement data belonging to the compound represented by the formula (6) is as follows.
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 novolac glycidyl ether having an allyl group at ortho- or para-position (abbreviated as BRG-556-ALEP)) Into a 2 L three-necked reaction vessel, 428 g of potassium carbonate (manufactured by Nippon Soda Co., Ltd.) 3.1 mol) dissolved in 389 g of pure water, phenol novolak represented by formula (7) (Shonol (registered trademark) BRG-556, o = 2 to 7, average value: 5.1) (Showa Denko) 250 g and sodium carbonate (manufactured by Kanto Chemical Co., Inc.) 164 g (1.55 mol, as solid) were charged, and the reaction vessel was purged with nitrogen gas and heated to 85 ° C. Allyl acetate ( Showa Denko K.K.) 421 g (4.2 mol), triphenylphosphine (Hokuko Chemical Co., Ltd.) 12.3 g (45.8 mmol), And 50% water content 5% -Pd / C-STD type (manufactured by NP Chemcat Co., Ltd.) 3.98 g (0.94 mmol as Pd atoms) was added, and the temperature was raised to 105 ° C. in a nitrogen gas atmosphere for 4 hours. After the reaction, 42.1 g (0.42 mol) of allyl acetate was added, and heating was continued for 12 hours, after which stirring was stopped and the mixture was allowed to stand to separate into two layers, an organic layer and an aqueous layer. After adding pure water (500 g) until the precipitated salt is dissolved, 500 g of toluene is added, and the temperature is kept at 80 ° C. or higher and it is confirmed that no white precipitate is precipitated, and then 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 250 g of toluene and the aqueous layer was separated. The organic layer was washed twice with 500 g of pure water at 50 ° C. or higher, and the aqueous layer was confirmed to be neutral, and the organic layer was separated and concentrated under reduced pressure to obtain a brown oil (343 g, As a result of ¹ H-NMR measurement of this brown oily substance, it was confirmed that it contained a phenol novolak allyl ether represented by the formula (8) (hereinafter abbreviated as BRG-556-AL) as a main component. The measurement data belonging to the compound represented by the formula (8) 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 100 g of the phenol novolak allyl ether obtained by the above synthesis were placed in a 300 mL eggplant flask and heated at 190 ° C. in a nitrogen gas atmosphere. After 3 hours, it was cooled to give a black solid (98 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 (9) (hereinafter abbreviated as BRG-556-CL) as a main component. Measurement data belonging to the compound represented by the formula (9) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.2-3.4 (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. 1 A phenol novolac glycidyl ether having an allyl group at the ortho or para position was synthesized using epichlorohydrin in the same manner as described above to obtain a brown oily substance (yield 96%). As a result of ¹ H-NMR measurement of this brown oily substance, a phenol novolak glycidyl ether having an allyl group at the ortho-position or para-position represented by the formula (10) (hereinafter abbreviated as BRG-556-ALEP) is a main component. Confirmed as including. The measurement data belonging to the compound represented by formula (10) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 2.5-3.0 (2H, m, PhOC H ₂ CHCH ₂ O), δ 3.2-3.4 (2H, m, C H ₂ CH _{= CH 2), δ3.4-3.6 (2H} , m, PhOCH 2 CHC H 2 O), δ3.6-4.0 (5H, m, PhCH 2 Ph, PhOCH 2 C H CH 2 O), δ 4.9-5.1 (2H, m, CH ₂ CH═C HH ), δ 5.8-6.1 (1 H, m, CH ₂ C H = CH ₂ ), δ 6.6-7.2 (12H , M, aromatic).

Example 2: Synthesis of a phenol novolac type polyvalent glycidyl compound A phenol novolac type glycidyl ether (BRG-556-ALEP) having an allyl group at the ortho-position or para-position obtained in Synthesis Example 2 above in a 5 L three-necked round bottom flask. 750 g (containing about 3.7 mol of carbon-carbon double bond of 2-alkenyl group (calculated based on the molecular weight of the repeating unit of formula (10)), sodium tungstate dihydrate 24.4 g (73.8 mmol), 14.5 g (148 mmol) of phosphoric acid and 77.9 g (166 mmol) of MTOAHS were added and dissolved in 1120 g of toluene (manufactured by Junsei Chemical Co., Ltd.). After the temperature was raised to 40 ° C., 35 g (360 mmol) of 35 mass% aqueous hydrogen peroxide was added with stirring over 0.1 hour, stirred and held for 0.1 hour, and then 7.5 g of 35% dilute sulfuric acid ( 26.8 mmol) was added over 0.1 hour, followed by stirring and holding for 0.1 hour. The hydrogen peroxide aqueous solution adding step and the sulfuric acid adding step were alternately carried out 5 times each for 2 hours in total. After confirming that the pH was 1.2, an aqueous hydrogen peroxide solution was added over 2 hours so that the total addition amount was 538 g (5.55 mol). After completion of the addition, stirring was continued at 40 ° C. for 16 hours. Stirring was performed at a stirring speed of 400 rpm from the start to the end of the reaction. After completion of the addition, the pH of the reaction solution at 1 hour was 1.0, and the pH of the reaction solution after 2 hours of reaction was 1.7. After completion of the reaction, the reaction solution was cooled to room temperature, and then 1000 g of toluene was added for liquid separation treatment. The organic layer was separated, and 2000 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 1000 g of pure water was added and washed again. The organic layer was isolated and the organic solvent (toluene) was distilled off. 702 g (1.6 mol, yield 86.8%) of a brown highly viscous oily product having an epoxy equivalent of 131 and an EP ratio of 83.6% was obtained. As a result of ¹ H-NMR measurement of this product, it was confirmed that a phenol novolac type polyvalent glycidyl compound represented by the formula (11) was contained as a main component. The measurement data belonging to the compound represented by the formula (11) is as follows.
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).

Comparative Example 1
Addition of hydrogen peroxide aqueous solution and acid other than phosphoric acid are not performed alternately, but at the start of the reaction, hydrogen peroxide aqueous solution addition amount: 563 g (5.8 mol), sulfuric acid addition amount: 40.5 g (145 mmol) ), Reaction time: 18 hours), and a glycidylation reaction was carried out in the same manner as in Example 1 to obtain 327 g (yield: 40.4%) of a product having an epoxy equivalent of 199 and an EP ratio of 55.1%. Obtained. Immediately after the start of the reaction, the temperature of the reaction solution rose, eventually exceeding 100 ° C., and bumping occurred. A gel was formed and colored brown. The acquisition yield of the target product decreased and the EP ratio also decreased .

Comparative Example 2
The glycidylation reaction was carried out in the same manner as in Example 1 except that the addition amount of sulfuric acid in the sulfuric acid addition step was doubled (16.2 g (58 mmol)) in all steps. It was confirmed that the pH of the reaction solution when adding all the sulfuric acid was 0.8. After the completion of the reaction, 401 g (yield 49.6%) of a product having an epoxy equivalent of 159 and an EP ratio of 69.2% was obtained. Immediately after the start of the reaction, the temperature of the reaction solution rose, eventually exceeding 100 ° C., and bumping occurred. A gel-like product was formed and the color changed to brown. The acquisition yield of the target product decreased and the EP ratio also decreased . A large amount of a brown gel-like product, which is considered to be a hydrolyzate, was precipitated (800 g, containing water), and it was difficult to extract the target product from the reaction solution. The entire reaction solution gelled and became a viscous sponge. The gel-like material was collected by filtration, washed successively with ethyl acetate (500 mL) and methanol (500 mL), then sandwiched with filter paper to absorb the solvent, and the solid was dried under reduced pressure to obtain a brown solid. 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).

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

Claims (10)

  A glycidyl ether compound having one or more substituted or unsubstituted glycidyl ether groups and two or more substituted or unsubstituted 2-alkenyl groups in the molecule, an aqueous hydrogen peroxide solution as an oxidizing agent, and tungsten as a catalyst. Production of a polyvalent glycidyl compound that oxidizes in the presence of phosphoric acid as a co-catalyst with the compound, a quaternary ammonium salt, and using an acid other than phosphoric acid while controlling the pH of the reaction solution to 1.0 to 4.0 A method for producing a polyvalent glycidyl compound, comprising a step of alternately repeating a step of adding an aqueous hydrogen peroxide solution and a step of adding an acid other than phosphoric acid to the reaction solution a plurality of times at intervals. .   2. The hydrogen peroxide aqueous solution addition step and the acid addition step other than phosphoric acid in the repetition step are repeated 2 to 20 times during the reaction with 0.1 to 1 hour between each step. The manufacturing method of the polyvalent glycidyl compound of description. The total amount of aqueous hydrogen peroxide solution to the reaction solution carbon of 2-alkenyl group having the said glycidyl ether compound - to reach 0.5 equivalents to carbon double bond, hydrogen peroxide in the iteration The method for producing a polyvalent glycidyl compound according to claim 1, wherein the step of adding an aqueous solution and the step of adding an acid other than phosphoric acid are repeated at least twice.   The process according to any one of claims 1 to 3, wherein the step of adding an aqueous hydrogen peroxide solution and the step of adding an acid other than phosphoric acid to the reaction solution are performed within a range where the temperature of the reaction solution does not exceed 50 ° C. For producing a monovalent glycidyl compound.   The glycidyl ether compound contains an aromatic ring in the molecule, and one or more substituted or unsubstituted glycidyl ether groups directly bonded to the aromatic ring and two or more substituted or unsubstituted 2-alkenyl groups directly bonded to the aromatic ring And a substituted or unsubstituted 2-alkenyl group is located at the ortho-position or para-position relative to the substituted or unsubstituted glycidyl ether group. A method for producing a polyvalent glycidyl compound. The glycidyl ether compound has the general formula (1):

(In the formula, R ¹ and R ² are each independently represented by the following formula (2) or (3), and Q are each independently an alkylene represented by the formula: —CR ³ R ⁴ —. group, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group in which an aromatic ring is bonded having 6 to 10 carbon atoms in the arylene group or 2-3 consisting solely an aromatic ring having 6 to 10 carbon atoms, carbon A divalent alicyclic condensed ring having 7 to 12 atoms , 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, 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. Formulas (2) and ( 3) ^R 5 ^{in, R 6, R 7, R} 8, R 9 and ^{R 10} are each independently A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group having 6 to 10 carbon atoms of 3 to 12 carbon atoms. However, at least one formula of a plurality of ^{R 1} (2), and at least ^two of the plurality of R ² are represented by the formula (3)) or a naphthalene skeleton instead of the benzene skeleton of the general formula (1). method for producing a polyglycidyl compound according to any one of claims 1 to 5 compounds.

The glycidyl ether compound is bisphenol-A, bisphenol-F, phenol novolac, triphenylmethanephenol, biphenylaralkyl type phenol, phenylaralkyl type phenol, or phenol of an unsubstituted tetrahydrodicyclopentadiene skeleton, or —CH ₂ — at both ends. The glycidyl ether compound according to claim 6, which is a glycidyl ether compound having any basic skeleton of phenol of an unsubstituted tetrahydrodicyclopentadiene skeleton to which is bonded, wherein R ² is located in the ortho position or the para position with respect to OR ¹ . A method for producing a polyvalent glycidyl compound. The tungsten compound is any one of 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. The method for producing a polyvalent glycidyl compound according to any one of claims 1 to 8, 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 9, which is at least one organic acid selected from the group consisting of sulfonic acid, trifluoromethanesulfonic acid, and trifluoroacetic acid.