JP2015209410A - Monoglycidyl ether compound and monoallyl ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a monoglycidyl ether compound useful as a diluent for epoxy resins, and to provide a monoallyl ether compound useful as a synthetic intermediate of a monoglycidyl ether compound and also useful as a raw material for an active energy ray curable or heat curable ink, a paint/coating agent and the like.SOLUTION: A monoglycidyl ether compound and a monoallyl ether compound are represented by general formula (1). (in the general formula (1), R-Reach independently represents a hydrogen atom or a hydrocarbon group having 1-3 carbon atoms; Xand Xeach independently represents a hydrocarbon group which may have a branch having 1-3 carbon atoms; Y represents an allyl or glycidyl group; and n and m each independently represents 0-10.)

Description

  The present invention relates to a novel monoglycidyl ether compound and a monoallyl ether compound.

Epoxy resins have excellent adhesiveness to various materials, heat resistance, chemical resistance, electric resistance, electrical insulation, and low cure shrinkage, so paints, adhesives, semiconductor encapsulants, etc. It is used for various purposes. Since many epoxy resins have high viscosity and poor workability, it is known to use a diluent in the epoxy resin to improve this.
Glycidyl ether compounds are known as diluents. Specific examples thereof include monoglycidyl ethers such as n-butanol, 2-ethylhexanol, and glycidyl ethers of higher alcohols having 12 to 13 carbon atoms; 1,6-hexane Diglycidyl ethers such as diol, 2-butyl-2-ethyl-1,3-propanediol, and glycidyl ether of neopentyl glycol are known (see Non-Patent Document 1).

“Review Epoxy Resin Basics II”, Epoxy Resin Technology Association, November 19, 2003, p. 45-54

As described above, by using a known glycidyl ether compound as a diluent, the workability of the epoxy resin is improved, but there is a problem of deterioration in physical properties such as a decrease in strength of the cured product and an increase in water absorption. . Therefore, development of a compound capable of obtaining a cured product having excellent mechanical properties and low water absorption when used as a diluent for an epoxy resin is desired.
As a result of detailed studies, the present inventor has found that when a compound represented by the general formula (1) is used as a diluent, a cured product having excellent mechanical properties and low water absorption can be obtained. It came to do.
An object of this invention is to provide a useful compound in order to solve the said subject.

That is, the present invention provides the following [1].
[1] A compound represented by the following general formula (1).

(In General Formula (1), R ^{1 to} R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and X ¹ and X ² each independently represent 1 to 1 carbon atoms. 3 represents a hydrocarbon group which may have 3 branches, Y represents an allyl group or a glycidyl group, and n and m each independently represent 0 to 10.)
In the present specification, a compound in which Y in the general formula (1) represents a glycidyl group is referred to as a monoglycidyl ether compound, and a compound in which Y in the general formula (1) represents an allyl group is referred to as a monoallyl ether compound.

  According to the present invention, novel monoglycidyl ether compounds and monoallyl ether compounds useful as diluents are provided. The monoglycidyl ether compound of the present invention is useful as a diluent for epoxy resins. Monoallyl ether compounds are useful as intermediates for the synthesis of monoglycidyl ether compounds. Furthermore, monoallyl ether compounds are useful as raw materials for active energy ray-curable or thermosetting inks, paints and coating agents.

Hereinafter, the present invention will be described in detail.
According to the present invention, a compound represented by the general formula (1) is provided.

(In General Formula (1), R ^{1 to} R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and X ¹ and X ² each independently represent 1 to 1 carbon atoms. 3 represents a hydrocarbon group which may have 3 branches, Y represents an allyl group or a glycidyl group, and n and m each independently represent 0 to 10.)

Examples of the hydrocarbon group having 1 to 3 carbon atoms represented by R ^{1 to} R ³ each independently include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a vinyl group, an allyl group, and a cyclopropyl group. . R ^{1 to} R ³ are each independently preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.

The hydrocarbon group which may have 1 to 3 carbon atoms represented by X ¹ and X ² may be a chain or a ring, and each independently represents a methylene group, an ethylene group, And a propylene group, a 1-methylethylene group and a 2-methylethylene group, preferably a methylene group, an ethylene group, a 1-methylethylene group and a 2-methylethylene group, more preferably an ethylene group and 1-methyl. An ethylene group and a 2-methylethylene group.
n and m each independently represent 0 to 10, preferably 0 to 5, and more preferably 0 to 3.

  Specific examples of the compound represented by the general formula (1) are illustrated below, but the present invention is not limited thereto.

  There is no restriction | limiting in particular in the manufacturing method of the compound represented by General formula (1). For example, in the presence of a basic substance, a diol compound represented by the following general formula (2) (hereinafter abbreviated as diol compound (2))

(In the general formula (2), R ^{1 to} R ³ , X ¹ , X ² , n, and m are as defined above.)
A monoallyl ether compound can be produced by reacting a halogenated allyl halide. Furthermore, a monoallyl ether compound can be epoxidized to produce a monoglycidyl ether compound.

  The diol compound (2) is a diol compound represented by the following general formula (3) (hereinafter abbreviated as diol compound (3)) when n = m = 0, otherwise diol It can be produced by reacting compound (3) with alkylene oxide or haloalcohol.

(In general formula (3), R ^{1 to} R ³ are as defined above.)

  Examples of the alkylene oxide used include ethylene oxide and propylene oxide. An alkylene oxide may be used individually by 1 type, and 2 or more types may be mixed and used for it. There is no restriction | limiting in particular in the mixing amount ratio of the alkylene oxide in the case of using 2 or more types. Although there is no restriction | limiting in particular in the usage-amount of alkylene oxide, Usually, the range of 1-10 mol times is preferable with respect to a diol compound (3), and the range of 1-6 mol times is more preferable.

  Examples of the haloalcohol used include 3-chloropropan-1-ol, 3-bromopropan-1-ol, 3-iodopropan-1-ol, 2-chloropropan-1-ol, 2-bromopropan-1-ol, 2-iodopropan-1-ol is mentioned. A haloalcohol may be used individually by 1 type, and 2 or more types may be mixed and used for it. There is no restriction | limiting in particular in the mixing amount ratio of the halo alcohol in the case of using 2 or more types. Although there is no restriction | limiting in particular in the usage-amount of a halo alcohol, Usually, the range of 1-10 mol times is preferable with respect to a diol compound (3), and the range of 1-6 mol times is more preferable.

The reaction between the diol compound (3) and the alkylene oxide can be carried out in the presence of a catalyst.
Examples of the catalyst to be used include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium methoxide; aromatics such as pyridine, picoline and 2-methylimidazole. Basic substances such as group amines; or acidic substances such as Lewis acids such as boron trifluoride and tin tetrachloride. Among these, sodium hydroxide, potassium hydroxide, sodium methoxide, and potassium methoxide are preferable. The amount of the catalyst is preferably in the range of 0.001 to 2 mol%, more preferably in the range of 0.05 to 1 mol% with respect to the diol compound (3).

The reaction of the diol compound (3) and the haloalcohol can be carried out in the presence of a basic substance.
Examples of basic substances to be used include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride; metal lithium and metal Examples thereof include alkali metals such as sodium and potassium metal. Although there is no restriction | limiting in the usage-amount of a basic compound, The range of 1-10 mol times is preferable with respect to the hydroxyl group of a diol compound (3), and the range of 1-6 mol times is more preferable.

  The reaction between the diol compound (3) and the alkylene oxide or haloalcohol can be carried out in the presence or absence of a solvent. Examples of the solvent include ethers such as diethyl ether and dioxane; aromatic hydrocarbons such as toluene, benzene and xylene. When a solvent is used, the amount used is not particularly limited, but a range of 0.1 to 5 times by mass is usually preferable with respect to the total amount of the diol compound (3) and the alkylene oxide or haloalcohol. A range of 1 to 2 times by mass is more preferable.

The reaction temperature in the reaction between the diol compound (3) and the alkylene oxide or haloalcohol is usually preferably in the range of 20 to 200 ° C, more preferably in the range of 50 to 150 ° C. There is no restriction | limiting in particular in reaction pressure, It can implement even under atmospheric pressure or pressurization. Although there is no restriction | limiting in particular in reaction time, Usually, the range for 1 to 30 hours is preferable. The reaction of the diol compound (3) with the alkylene oxide or haloalcohol can be carried out in an air atmosphere or an inert gas atmosphere such as nitrogen and argon.
For example, a basic substance or an acidic substance and a diol compound (3) are charged into an agitation-type reactor in an air atmosphere, set to a predetermined temperature and a predetermined pressure, alkylene oxide or haloalcohol is added thereto, and the mixture is stirred for a predetermined time. Can be implemented.

  After completion of the reaction, the obtained reaction mixture is washed with an aqueous solution of an acidic substance such as hydrochloric acid, an aqueous solution of a basic substance such as sodium hydroxide, or water as necessary, and then appropriately concentrated, distilled, etc. The diol compound (2) can be separated and obtained by performing a normal purification operation.

  Hereinafter, a method for producing a monoallyl ether compound by reacting the diol compound (2) with an allyl halide in the presence of a basic substance will be described.

  Examples of the allyl halide include allyl chloride, allyl bromide, allyl iodide, and the like. Although there is no restriction | limiting in particular in the usage-amount of an allyl halide, Usually, the range of 0.5-20 mol times is preferable with respect to a diol compound (2), and from the viewpoint of reaction rate and volumetric efficiency, 1.2- The range of 10 mole times is more preferable.

  Examples of the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal hydrides such as sodium hydride and potassium hydride. The amount of the basic substance used is usually preferably in the range of 0.5 to 30 mol times, more preferably in the range of 2 to 15 mol times with respect to the diol compound (2).

  The reaction can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not adversely influence the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; saturated aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl ether, Examples include ethers such as diethylene glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; dimethylformamide, N-methylpyrrolidone and sulfolane. It is done. These may be used individually by 1 type, and may use 2 or more types together. There is no restriction | limiting in particular in the usage-amount of using a solvent, Usually, the range of 0.01-20 mass times is preferable with respect to a diol compound (2), and the range of 0.1-10 mass times is more preferable. In the case of this reaction, the compound represented by the general formula (1) can be efficiently produced without using any solvent.

  In particular, when a basic substance is used in the reaction as an aqueous solution, it is extremely preferable to use a phase transfer catalyst in order to accelerate the reaction. There is no particular limitation on the phase transfer catalyst, for example, quaternary ammonium salts such as trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide; phosphonium salts such as tetrabutylphosphonium chloride; 15-crown-5, 18- And crown ethers such as crown-6. When using a phase transfer catalyst, the amount used is usually preferably in the range of 0.001 to 0.5 mol times, and in the range of 0.01 to 0.2 mol times with respect to the diol compound (2). More preferred.

  The reaction temperature is usually preferably in the range of −30 to 150 ° C., more preferably in the range of −10 to 120 ° C. Below -30 ° C, the reaction rate tends to be extremely small. On the other hand, when it exceeds 150 ° C., for example, side reactions such as polymerization tend to occur, and the yield tends to decrease. In addition, the reaction time is preferably in the range of 10 minutes to 15 hours, and from the viewpoint of suppressing side reactions, it is preferably in the range of 10 minutes to 10 hours.

The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Further, the reaction can be carried out under atmospheric pressure or under pressure, but it is preferably carried out under atmospheric pressure from the viewpoint of production equipment.
The reaction is performed, for example, by adding an aqueous solution of a basic substance, a diol compound (2), an allyl halide and, if necessary, a solvent and a phase transfer catalyst to a stirring type reaction apparatus at a time or in a divided manner and reacting at a predetermined temperature for a predetermined time. This can be done.

  After completion of the reaction, the basic substance contained in the obtained reaction mixture is neutralized, washed with water, saturated saline, etc. as necessary, and concentrated, and further distilled, column chromatography, etc. A highly pure monoallyl ether compound can be obtained by carrying out a purification operation usually used in the purification of organic compounds.

  Such monoallyl ether compounds can be used as raw materials for active energy ray-curable or thermosetting inks, paints, coating agents such as ultraviolet rays and electron beams.

  Hereinafter, a method for producing a monoglycidyl ether compound by epoxidizing the monoallyl ether compound will be described.

  The monoglycidyl ether compound of the general formula (1) uses, for example, organic peroxides such as performic acid, peracetic acid, metachloroperbenzoic acid and t-butyl hydroperoxide, and oxidizing agents such as hydrogen peroxide and molecular oxygen. The monoallyl ether compound can be produced by a known epoxidation method. Moreover, it can manufacture also by reaction of a diol compound (2) and epihalohydrin. Hereinafter, a method using peracetic acid will be described in detail.

  The peracetic acid used as an epoxidizing agent in the present invention is preferably substantially free of water. Specifically, the use of peracetic acid having a water content of 0.8% by mass or less, preferably 0.6% by mass or less provides the desired monoglycidyl ether compound with high selectivity and conversion. More preferred. “Peracetic acid substantially free of water” is produced by air or oxygen oxidation of aldehydes such as acetaldehyde, and is described in German Patent Publication No. 1418465 and Japanese Patent Application Laid-Open No. 54-30006. Manufactured by the above method. According to these methods, peracetic acid is synthesized from hydrogen peroxide and acetic acid, and a high concentration of peracetic acid can be synthesized in a large amount continuously compared to a method in which peracetic acid is extracted with a solvent.

  From the viewpoint of synthesizing the monoglycidyl ether compound with high selectivity and conversion, the amount of peracetic acid used is preferably 1 to 3 times by mole, more preferably 1.05 to 1.5 times by mole with respect to the monoallyl ether compound. preferable. If it exceeds 3 mole times, it is usually disadvantageous due to problems of economy and side reaction.

In the epoxidation reaction, a solvent may coexist depending on the apparatus and reaction conditions.
The solvent can be used for the purpose of stabilization by diluting peracetic acid, and by increasing the solvent ratio, the concentration of acetic acid generated from peracetic acid during the epoxidation reaction can be lowered. It becomes easy to prevent. When the solvent is allowed to coexist, the amount is usually preferably 20 to 500 parts by mass with respect to 100 parts by mass of peracetic acid. When the amount of the solvent is more than 500 parts by mass, the epoxidation reaction rate tends to decrease. Conversely, when the amount is less than 20 parts by mass, the significance of coexistence tends to decrease.
As the solvent, esters, aliphatic or aromatic hydrocarbons, ethers and the like can be used. Of these, ethyl acetate, hexane, cyclohexane, toluene, benzene and the like are preferable, and ethyl acetate is more preferable.

  The epoxidation reaction temperature is determined by the reactivity of peracetic acid to the monoallyl ether compound. The reaction temperature is preferably in the range of 20 to 100 ° C, more preferably in the range of 30 to 70 ° C, and still more preferably in the range of 45 to 55 ° C. If it is less than 20 ° C., the reaction rate decreases, and if it exceeds 100 ° C., decomposition accompanied by heat generation of peracetic acid tends to occur.

The epoxidation reaction is preferably carried out by sequentially adding a monoallyl ether compound and, if necessary, a solvent to the reactor and adding peracetic acid dropwise while maintaining the temperature within a predetermined temperature range. The epoxidation reaction may be performed continuously.
In the present invention, for example, after the dropwise addition of peracetic acid, the reaction solution may be reacted by stirring for 1 to 10 hours.

  The monoglycidyl ether compound from the obtained reaction solution is obtained by, for example, extracting unreacted peracetic acid and acetic acid produced from peracetic acid contained in the reaction solution with water, and distilling the organic layer separated from the aqueous layer. Can be isolated by distilling off the solvent. Furthermore, since the unreacted monoallyl ether compound has a lower boiling point than the target monoglycidyl ether compound, it can be recovered by distillation in the same manner as the solvent.

  After completion of the reaction, it is preferable to first neutralize and wash the reaction solution with a base such as a high concentration sodium hydroxide aqueous solution. That is, when an aqueous sodium hydroxide solution is used, sodium acetate is produced by a neutralization reaction with acetic acid generated from peracetic acid, so that sodium acetate acts as a buffer and the specific gravity of the sodium acetate aqueous solution layer increases. There is a secondary effect that the specific gravity difference between the organic layer of the glycidyl ether compound is increased and the liquid separation property is improved. After this neutralization washing and liquid separation, sodium acetate remaining in the organic layer containing the monoglycidyl ether compound is preferably removed by washing with water, and then the solvent is distilled off. Furthermore, a side reaction in which acetic acid generated from peracetic acid is added to the epoxy group of the resulting monoglycidyl ether compound may produce acetoxyhydroxy alcohols, which are removed by distillation because they have a higher boiling point than the monoglycidyl ether compound. it can.

  Such monoglycidyl ether compounds are useful, for example, as a diluent for epoxy resins. Furthermore, it can be used for various synthetic intermediates.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited at all by this Example.

<Example 1>
Production of cyclohexane-1,1-dimethanol monoallyl ether Into an eggplant flask having an internal volume of 500 ml, 73.7 g of cyclohexane-1,1-dimethanol and 234.6 g of allyl chloride were charged, and the internal temperature was increased to 45 ° C. while stirring. The temperature rose. To this, 26.6 g of powdered sodium hydroxide was added in three portions, and reacted for 4.5 hours while continuing to stir. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered, and the filtrate obtained was washed twice with 100 g of distilled water. The organic layer was concentrated to obtain 75.7 g of cyclohexane-1,1-dimethanol monoallyl ether (colorless transparent liquid; yield 80.4%, purity 95.5%). Physical property values are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 1.32-1.43 (m, 10H), 2.93 (t, 1H), 3.39 (s, 2H), 3.56 (d , 2H), 3.97 (dt, 2H), 5.18 (ddt, 1H), 5.26 (ddt, 1H), 5.88 (ddt, 1H)

<Example 2>
Preparation of cyclohexane-1,1-dimethanol monoglycidyl ether Into a reactor, 50 g of cyclohexane-1,1-dimethanol monoallyl ether obtained by the method of Example 1 and 50 g of ethyl acetate were charged, and the internal temperature was stirred. The temperature was raised to 50 ° C. While maintaining the internal temperature at 50 ° C. and blowing nitrogen into the gas phase, 94.9 g of an ethyl acetate solution containing 30% by mass of peracetic acid was added dropwise over about 2 hours. After the peracetic acid solution was dropped, the reaction was carried out at 50 ° C. for 7 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, washed twice with 100 g of 10% aqueous sodium hydroxide solution and then twice with 100 g of distilled water, and the organic layer was concentrated to concentrate cyclohexane-1,1-dimethanol monoglycidyl. 48.3 g of ether (colorless transparent liquid; yield 69.6%, purity 94.3%) was obtained. Physical property values are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 1.32-1.43 (m, 10H), 2.62 (dd, 1H), 2.66 (t, 1H), 2.78-2 .81 (m, 1H), 3.11-3.15 (m, 1H), 3.36-3.56 (m, 5H), 3.76 (dd, 1H)

Claims (1)

A compound represented by the following general formula (1).

(In General Formula (1), R ^{1 to} R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and X ¹ and X ² each independently represent 1 to 1 carbon atoms. 3 represents a hydrocarbon group which may have 3 branches, Y represents an allyl group or a glycidyl group, and n and m each independently represent 0 to 10.)