KR20140022432A - Method for producing aromatic diol mono(meth)acrylate - Google Patents

Abstract

An object of the present invention is to obtain a highly purified aromatic diol mono (meth) acrylate with little coloring and solvent insoluble content, and to provide an economically advantageous production method. In order to achieve this object, the present invention is a method for producing aromatic diol mono (meth) acrylate by esterifying an aromatic diol and (meth) acrylic acid in the presence of a strong acid, and the method is solventless or aprotic. It provides at the 100-140 degreeC in presence of an organic solvent, and provides the method of manufacturing aromatic diol mono (meth) acrylate including the process of esterifying reaction, removing water in a reaction system by heat reduction.

Description

Method for producing aromatic diol mono (meth) acrylate {Method for producing aromatic diol mono (meth) acrylate}

TECHNICAL FIELD This invention is a method of obtaining highly pure aromatic diol mono (meth) acrylate with little coloring and a solvent insoluble content, and relates to the manufacturing method which is economically advantageous.

As a method of manufacturing aromatic diol mono (meth) acrylate, the method of making aromatic diol, (meth) acrylic anhydride, or (meth) acrylic acid chloride react is known (for example, refer patent document 1).

Moreover, as a method of obtaining an aromatic diol mono (meth) acrylate of high purity, an aromatic diol and (meth) acrylic anhydride are made to react, and the aromatic diol mono (meth) acrylate and the aromatic diol di (meth) acrylate which are a by-product are obtained. A process for producing a reaction solution containing, a process for removing unreacted aromatic diol in the reaction solution by washing with water to produce a crude crystal, a process for dissolving the crude crystal in a solvent to produce a solution, and the solution A method for obtaining a high-purity aromatic diol mono (meth) acrylate, including a step of removing the aromatic diol di (meth) acrylate in the solution by contacting with a poor solvent, has been reported ( Patent document 2).

The aromatic diol is further heated and refluxed with (meth) acrylic acid in the presence of a strong acid catalyst in a hydrophobic solvent to remove the effluent and terminate when the amount of the removed water reaches 40 to 100% of the number of moles of the aromatic diol. The manufacturing method of (meth) acrylate is reported (patent document 3).

However, when (meth) acrylic acid chloride is used in the method of the said patent document 1, it is not industrially advantageous because there exists a problem which corrodes a reaction container, and waste liquid containing a halide generate | occur | produces in large quantities. However, since the halide is used, the resulting aromatic diol mono (meth) acrylate composition is not suitable for electrical and electronic applications. Moreover, both of the two phenolic hydroxyl groups which aromatic diol has reacted, and there exists a problem that a large amount of aromatic diol di (meth) acrylate is easy to produce | generate. On the other hand, when (meth) acrylic acid anhydride is used in the method of the said patent document 1, although the problem with the said halide does not arise, the purity containing comparatively many aromatic diol di (meth) acrylate by-products is low Only aromatic diol mono (meth) acrylate compositions can be obtained. This aromatic diol di (meth) acrylate has a problem that the solvent solubility of the polymer, which becomes a crosslinking component at the time of polymerization, may be lowered, and in some cases, gelation may be caused at the time of polymerization.

Although this problem is solved by the method of patent document 2, since expensive (meth) acrylic anhydride is used, it cannot be said to be an economically advantageous method when production on an industrial level is considered.

As an economically advantageous method, the method of patent document 3 is reported. In this method, the aromatic diol is heated and refluxed with (meth) acrylic acid in the presence of a strong acid in a hydrophobic solvent, and reacted while separating and removing the water which has flowed out at reflux temperature of 110 to 160 ° C. It is succeeded to dehydrate esterification of aromatic diol and (meth) acrylic acid directly, without using this. In addition, by measuring the amount of water removed and terminating heating reflux when the amount of water removed reaches an amount corresponding to 40 to 100% of the number of moles of the aromatic diol, the aromatic diol (meth) acrylate is converted into an aromatic diol. It is obtained at a much higher ratio compared to di (meth) acrylate. However, with this method, the by-product amount of aromatic diol di (meth) acrylate is large, and it is insufficient as an economically advantageous method. In addition, the aromatic diol mono (meth) acrylate obtainable by this method is colored in comparison with the material obtainable by the method described in Patent Document 2, and solvent insoluble tends to occur, which can be satisfied in terms of purity. It is not there. In particular, when the synthesized aromatic diol mono (meth) acrylate is polymerized and used in a photoresist or the like, it is fatal to generate a solvent insoluble fraction.

Patent Document 1: Publication No. 49-34667 Patent Document 2: Japanese Patent Application Laid-Open No. 2007-204448 Patent Document 3: Japanese Patent Application Laid-Open No. 2007-106749

Therefore, this invention obtains aromatic diol (meth) acrylate in much higher ratio compared with aromatic diol di (meth) acrylate, without using (meth) acrylic acid chloride, and it is economical and coloring and solvent insoluble It is an object to provide a high-purity aromatic diol mono (meth) acrylate with little powder.

Thus, the present inventors have conducted a thorough research and development, and as a result of esterifying the aromatic diol and (meth) acrylic acid in the presence of a strong acid, in the preparation of the aromatic diol mono (meth) acrylate, there is no solvent or aprotic It was found that the above-described problems can be solved by reacting the reaction at 100 ° C to 140 ° C in the presence of an organic solvent, and performing esterification while removing moisture in the reaction system by heating and pressure reduction.

Economically, the present invention,

(1) A method of producing an aromatic diol mono (meth) acrylate by esterifying an aromatic diol and (meth) acrylic acid in the presence of a strong acid, wherein the method is 100 to 140 in the presence of a solvent-free or aprotic organic solvent. A process for producing an aromatic diol mono (meth) acrylate, which is carried out at ° C. and includes a step of esterifying while removing moisture in the reaction system by heating and decompression.

(2) the method for producing the aromatic diol mono (meth) acrylate of (1), wherein the strong acid is a liquid in the reaction system;

(3) The method for producing the aromatic diol mono (meth) acrylate of (2), wherein the strong acid is selected from p-toluenesulfonic acid, sulfuric acid, or methanesulfonic acid,

(4) In any one of Claims (1)-(3) whose molar ratio at the time of esterifying an aromatic diol and (meth) acrylic acid is 3.0-4.0 mol of (meth) acrylic acid with respect to 1.0 mol of aromatic diols. Process for producing the aromatic diol mono (meth) acrylates described,

(5) The method according to any one of (1) to (4), wherein the esterification reaction is terminated when the production rate of the aromatic diol mono (meth) acrylate with respect to the aromatic diol to be introduced is 40 to 70 mol%. A process for producing an aromatic diol mono (meth) acrylate,

(6) Said heating pressure reduction is aromatic diol mono of any one of (1)-(5) which starts after the said esterification reaction and the hydrolysis reaction of water and esterified water of a reaction system become parallel state. Method for producing (meth) acrylate,

(7) It is a manufacturing method of the aromatic diol mono (meth) acrylate in any one of (1)-(6) which makes esterification-react while inhaling air.

According to this invention, coloring and solvent insoluble content are few, and high-purity aromatic diol mono (meth) acrylate can be manufactured economically advantageously. Thereby, the problem which corrodes a reaction container and the waste liquid process containing a halide which generate | occur | produce when using (meth) acrylic acid chloride are used can be solved. Moreover, when (meth) acrylic acid chloride and (meth) acrylic anhydride are used, generation | occurrence | production of the aromatic diol di (meth) acrylate which by-produces many can be suppressed. Aromatic diol di (meth) acrylate as an impurity becomes a problem of causing the solvent solubility of a polymer to fall, and in some cases, gelatinization at the time of superposition | polymerization. Moreover, this invention can obtain aromatic diol mono (meth) acrylate, even if it does not use expensive (meth) acrylic anhydride, and is an economically advantageous manufacturing method.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the transmittance | permeability of the polymer (reference example 1, comparative reference example 2) using the hydroxyphenyl methacrylate obtained by refine | purifying the product of Example 1 and the comparative example 3.

Carrying out the invention  Form for

Hereinafter, embodiments of the present invention will be described in detail.

In the method for producing an aromatic diol mono (meth) acrylate according to the present invention, the aromatic diol and (meth) acrylic acid are reacted in the presence of a strong acid at 100 ° C. to 140 ° C. in the presence of a solvent-free or aprotic organic solvent. Then, it is characterized in that the esterification reaction while removing the water in the reaction system by heating and decompression.

"Aromatic diol" used in the method of the present invention refers to a compound having two hydroxyl groups in one benzene ring. Specifically, they are hydroquinone, resorcin, and catechol. Moreover, about these compounds, you may have substituents, such as a C1-C4 alkyl group and an alkoxy group. Specifically, 2-methylhydroquinone, 2-ethylhydroquinone, 2-n-propylhydroquinone, 2-isopropylhydroquinone, 2-n-butylhydroquinone, 2-sec-butylhydroquinone, 2-tert-butylhydroquinone, 2- Methylresorcin, 2-ethylresorcin, 2-n-propylresorcin, 2-isopropylresorcin, 2-n-butylresorcin, 2-sec-butylresorcin, 2-tert-butylresorcin, 4 -Methylresorcin, 4-ethylresorcin, 4-n-propylresorcin, 4-isopropylresorcin, 4-n-butylresorcin, 4-sec-butylresorcin, 4-tert-butylresorcin, 5-methylresorcin, 5-ethylresorcin, 5-n-propylresorcin, 5-isopropylresorcin, 5-n-butylresorcin, 5-sec-butylresorcin, 5-tert-butylresorcin , 3-methylcatechol, 3-ethylcatechol, 3-n-propylcatechol, 3-isopropylcatechol, 3-n-butylcatechol, 3-sec-butylcatechol, 3-tert-butylcatecate Cole, 4-methylcatechol, 4-ethylcatechol, 4-n-propylcatechol, 4-isopropylcatete Cole, 4-n-butylcatechol, 4-tert-butylcatechol, methoxycatechol, methoxyresorcin, methoxyhydroquinone and the like are exemplified.

The (meth) acrylic acid used in the present invention is acrylic acid or methacrylic acid.

In this invention, the molar ratio at the time of making aromatic diol and (meth) acrylic acid react is 1.0-10.0 mol (meth) acrylic acid with respect to 1.0 mol of aromatic diols, Preferably it is 2.0-5.5 mol. More preferably, it is 3.0-4.0 mol. When (meth) acrylic acid is less than 1.0 mol with respect to 1.0 mol of aromatic diols, the solubility of the aromatic diol which is a raw material will run short, and it is unpreferable in order to perform stirring uniformly. Moreover, when reaction is performed in the state which the solubility of aromatic diol is insufficient, there exists a tendency for the generation amount of the aromatic diol di (meth) acrylate of a by-product to increase, and the quantity after removing an impurity falls, and it is unpreferable. Conversely, when (meth) acrylic acid exceeds 10.0 mol, the ratio of the quantity of water with respect to preparation amount falls, and production efficiency is not good. From these viewpoints, it is optimal to make it react at 3.0-4.0 mol.

At the time of reaction, an aprotic polar organic solvent, such as dioxane and tetrahydrofuran, can be used. It is better to avoid using water as a solvent. The amount of the solvent used may be added in an amount of about 0 to 500 parts by mass with respect to 100 parts by mass of the aromatic diol, for the purpose of improving the solubility of the aromatic diol as a raw material, or for the purpose of facilitating control of the reaction temperature. However, hydrophobic solvents, such as toluene and xylene, are not used. Although hydrophobic solvents are advantageous for the purpose of removing condensed water, the solubility of aromatic diols is lowered, and as a result, there is a tendency to increase the generation of aromatic diol di (meth) acrylate as a by-product. Moreover, there exists a tendency for a solvent insoluble content to form in the aromatic diol mono (meth) acrylate finally obtained. Solvent-insoluble fraction is a component with relatively large molecular weight, and is a polymer.

Examples of the strong acid used in the present invention include ion exchange resins such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and styrene-divinylbenzene copolymers having a sulfonic acid group as a functional group. As for the usage-amount of strong acid, 1-10 mass parts is preferable with respect to 100 mass parts of (meth) acrylic acid. If the amount of the strong acid used is less than 1 part by mass, the progress of the reaction is delayed, which is not preferable. If it exceeds 10 parts by mass, a large amount of the basic substance required for neutralization is required, which is not preferable.

Solid strong acids, such as strong acidic ion exchange resins, such as styrene-divinylbenzene copolymers, need to be removed by filtration from within the reaction system before carrying out the purification step after the completion of the reaction. not. Depending on the composition at the end of the reaction, when cooled to about 90 ° C., the reaction liquid aromatic diol or aromatic diol mono (meth) acrylate precipitates, making it difficult to remove the solid strong acid from the reaction system by filtration. In view of this, a strong acid that does not require a filtration step, that is, a strong acid that is liquid in the reaction system is preferable. Examples of this strong acid include sulfuric acid, p-toluenesulfonic acid, and methanesulfonic acid.

It is preferable to perform reaction at 100-140 degreeC in presence of a strong acid, Preferably it is 110 to 130 degreeC about 1 to 24 hours. If reaction temperature is less than 100 degreeC, progress of reaction will be delayed and it is unpreferable. Moreover, when reaction temperature exceeds 140 degreeC, there exists a problem which the reaction liquid colors extremely. This is presumed to be accelerated when the by-product of impurities resulting from coloring exceeds 140 ° C.

When esterification of the aromatic diol and (meth) acrylic acid in the presence of a strong acid, condensation water is generated, and the esterification reaction and the hydrolysis reaction are in parallel. In order to prioritize the esterification reaction, that is, to improve the yield of the aromatic diol mono (meth) acrylate, it is necessary to remove the condensed water generated in the reaction. For that purpose, it is necessary to remove the condensed water by depressurizing the inside of the reaction system. For example, when the temperature is 120 ° C, the condensed water can be removed at -75 kPa to -85 kPa. If the pressure is higher than -75 kPa, the condensation water removal efficiency is poor and the esterification reaction is delayed. If the pressure is lower than -85 kPa, solvent insoluble fraction may be generated. Moreover, although the method of removing a condensed water out of the system by azeotropic with condensed water using hydrophobic solvent, such as toluene, is generally known, In addition to the problem that a solvent-insoluble matter arises, the aromatic diol di (meth) of a by-product is produced. Since there is a tendency to increase the generation of acrylate, a method of removing the condensed water by heating and decompression is preferable. The moisture in the reaction system varies depending on the reaction rate of the esterification, but, for example, when the esterification proceeds by 30%, the hydrolysis takes precedence when it exceeds 1.3% by mass. It is preferable to keep the moisture in the reaction system at 0.5 mass% or less. In this case, the concentration of water is the concentration relative to the total mass of the substance present in the reaction system at the time of measurement, and when the aprotic polar organic solvent is used for the reaction, the mass of the solvent is not considered.

The timing for starting the removal of the condensed water by heating and depressurization is not particularly limited. However, when the heating and depressurizing distillation is performed with the start of the esterification reaction, the main component of the effluent is (meth) acrylic acid as a raw material and is not economical. In that respect, it is preferable to start after the esterification reaches the initial parallelism.

In the initial stage of the esterification reaction, a large amount of unreacted aromatic diol is present, and if the esterification reaction is continued, the amount of generation of aromatic diol di (meth) acrylate as a by-product increases. Unreacted aromatic diols and aromatic diol di (meth) acrylates of the by-products need to be finally removed by purification. From this viewpoint, it is preferable to complete | finish reaction at the time when the production | generation rate of aromatic diol mono (meth) acrylate became 30-70 mol% with respect to the injected aromatic diol, More preferably, it is 40-70 mol%.

During the esterification reaction, for the purpose of preventing polymerization, it is preferable to inhale a gas containing oxygen such as air or to use a polymerization inhibitor as appropriate. A polymerization inhibitor is generally used and it is good to select what does not inhibit reaction. As a method of inhaling the gas having a polymerization inhibiting action, a method of inhaling the gaseous phase of the reactor or a method of directly inhaling the liquid phase may be mentioned. The flow rate to be sucked is not particularly limited as long as it can stop the polymerization. For example, in the case of air, an amount of 50 mL / min or less per 1 L of reaction liquid is sufficient.

After completion of the esterification reaction, it is preferable to neutralize the strong acid with a basic substance. For neutralization, for example, triethylamine, tributylamine, triethanolamine and the like can be used. The neutralized reaction solution contains unreacted aromatic diol, aromatic diol mono (meth) acrylate, and aromatic diol di (meth) acrylate as a byproduct. By washing this reaction solution with water, the content of unreacted aromatic diol can be reduced. When sufficiently washed with water to remove unreacted aromatic diol, crude crystals are precipitated in water. Here, with respect to a total of 100 mol% of unreacted aromatic diol, aromatic diol mono (meth) acrylate and aromatic diol di (meth) acrylate, water washing is repeated until unreacted aromatic diol is 1.0 mol% or less. It is preferable. When unreacted aromatic diol exceeds 1.0 mol%, the purity of the finally obtained aromatic diol mono (meth) acrylate is lowered, and when the polymerization is carried out using this as a raw material, the aromatic diol acts as a polymerization inhibitor. Because it is not desirable.

In addition, the aromatic diol di (meth) acrylate can be removed by washing the reaction solution with a hydrophobic solvent. Specifically as a hydrophobic solvent used for washing | cleaning, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, etc. are mentioned, These at least 1 sort (s) can be used. A hydrophobic solvent is a solvent with respect to aromatic diol di (meth) acrylate here, and becomes a poor solvent with respect to aromatic diol mono (meth) acrylate. Therefore, by adding a hydrophobic solvent, aromatic diol mono (meth) acrylate precipitates as a crude crystal, and this is employ | adopted. In addition, with respect to a total of 100 mol% of unreacted aromatic diols, aromatic diol mono (meth) acrylates and aromatic diol di (meth) acrylates, the hydrophobic solvent until the aromatic diol di (meth) acrylate is 1.0 mol% or less. It is preferable to repeat washing with. When the aromatic diol di (meth) acrylate is more than 1.0 mol% remaining, the purity of the finally obtained aromatic diol mono (meth) acrylate is lowered and polymerization is carried out using this as a raw material to produce an aromatic diol di (meth) acryl. Since the rate is a crosslinking component, the molecular weight of the polymer is unusually large, and in some cases, gelation or solvent solubility may be deteriorated, which is not preferable.

The washing procedure may be performed either by washing with water or by washing with a hydrophobic solvent, but an optimal method can be selected according to the composition at the end of the reaction. In the case where water washing is first generated, it is preferable to dissolve the crude crystal precipitated in water after completion of washing with water in a solvent. Toluene, xylene, or a mixture thereof is mentioned as a solvent used for melt | dissolution. These are poor solvents for the aromatic diol which is a raw material, but are solvents for the crude crystals after the completion of water washing. By using such a solvent, the yield of the aromatic diol mono (meth) acrylate composition finally obtained improves. When dissolving the crude crystal in a solvent, it is preferable to dissolve it by heating, if necessary, using 50 to 300 parts by mass of the solvent, more preferably 100 to 200 parts by mass with respect to 100 parts by mass of the crude crystal. In that case, it is preferable to separate and remove the water contained in a crude crystal from the solvent layer containing a crude crystal. Thereafter, the solvent layer is washed with the hydrophobic solvent. As a specific method, the method of inject | pouring the solvent layer which the crude crystal melt | dissolved in the said hydrophobic solvent, or the method of adding the said hydrophobic solvent to the solvent layer which the crude crystal melt | dissolved is mentioned. Thus, the crystal of an aromatic diol mono (meth) acrylate is precipitated by dissolving a crude crystal with a solvent and making a hydrophobic solvent contact the solvent which this crude crystal melt | dissolved. By this method, the purity of the aromatic diol mono (meth) acrylate finally obtained improves.

In addition, when washing with a hydrophobic solvent is performed first, the reaction solution and the hydrophobic solvent are brought into contact with each other to produce a coarse crystal containing an aromatic diol mono (meth) acrylate and an unreacted aromatic diol. By washing, the crystal | crystallization of aromatic diol mono (meth) acrylate is obtained.

After completion of washing with water and washing with a hydrophobic solvent, dehydration and drying can provide aromatic diol mono (meth) acrylates with little coloration and solvent insoluble content and high purity.

The aromatic diol mono (meth) acrylate obtained by the manufacturing method of this invention is a solid at normal temperature, is comparatively stable with respect to heat | fever and light, and has a characteristic that polymerizability is equivalent to general (meth) acrylic acid ester.

When the polymer is synthesized using the aromatic diol mono (meth) acrylate obtained in the production method of the present invention, it is excellent in solvent solubility, alkali solubility, transparency, heat discoloration resistance, and the like, and has a high Tg, high thermal decomposition temperature, and high refractive index. Can be obtained. Therefore, it can be applied to alkali developing photoresists used in semiconductor manufacturing, display members, printing plate materials and the like, protective films requiring transparency and heat discoloration resistance. Moreover, it is useful also as hardening | curing agents, such as an epoxy resin.

Moreover, the aromatic diol mono (meth) acrylate obtained by the manufacturing method of this invention has favorable copolymerizability with not only a homopolymer but other unsaturated group containing polymeric compound. Specific examples of such an unsaturated group-containing polymerizable compound include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride, fumaric anhydride, citraconic anhydride, and mesa anhydride. Cholic acid, itaconic anhydride, vinyl benzoic acid, o-carboxyphenyl (meth) acrylate, m-carboxyphenyl (meth) acrylate, p-carboxyphenyl (meth) acrylate, o-carboxyphenyl (meth) acrylamide, m -Carboxyphenyl (meth) acrylamide, p-carboxyphenyl (meth) acrylamide, monosuccinate mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω -Carboxypolycaprolactone mono (meth) acrylate, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-carboxy -5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethyl Cyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2- Yen, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride, tricyclo [5.2.1.02,6] decane-8-yl (meth) acrylate, tricyclo [5.2.1.02,6 ] Decane-8-yloxyethyl (meth) acrylate,

Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (Meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl glycoside,

Phenyl (meth) acrylate, benzyl (meth) acrylate, o-methoxyphenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) acrylate,

Diethyl maleate, diethyl fumarate, diethyl itaconic acid, bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2. 1] hepto-2-ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.2 .1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-t-butoxycarbonyl bicyclo [2.2.1] hepto-2-ene, 5 -Cyclohexyl oxycarbonyl bicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonyl bicyclo [2.2.1] hepto-2-ene, 5,6-di (t-butoxycarbonyl ) Bicyclo [2.2.1] hepto-2-ene, 5,6-di (cyclohexyl oxycarbonyl) bicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) ratio Cyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto 2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5- Hydroxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methyl ratio Cyclo [2.2.1] hepto-2-ene,

Styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 1,2-butadiene, isoprene, 2, 3-dimethyl-1,3-butadiene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, o-hydroxyphenyl (meth) acrylamide, m-hydride Hydroxyphenyl (meth) acrylamide, p-hydroxyphenyl (meth) acrylamide, 3,5-dimethyl-4-hydroxybenzyl (meth) acrylamide, phenyl maleimide, hydroxyphenyl maleimide, cyclohexyl maleimide Benzyl maleimide, trifluoromethyl (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3, 4-Epoxybutyl, α-ethylacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxyheptyl, meta Acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, vinylglycidyl ether, allyl glycidyl ether, isopropenyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, vinylcyclohexene monooxide, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and the like. have.

The polymerization was carried out using methanol, ethanol, 1-propanol, isopropyl alcohol, butanol, ethylene glycol, acetone, methyl using an azo initiator representing azobisisobutyronitrile, an organic peroxide represented by benzoyl peroxide, or the like. Ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, toluene, xylene, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethylether acetate, ethylene glycol mono Ethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 3-methoxy Butanol, di can be carried out in ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, an organic solvent such as ethyl lactate.

Example

Although an Example, a comparative example, a reference example, and a comparative reference example are shown below and this invention is demonstrated further more concretely, this invention is not limited to the following examples. In addition, the composition ratio, color, and turbidity in an Example, a comparative example, and a reference example were measured with the following method.

(Composition ratio)

^{By 1} H-NMR measurement, the sum total of aromatic diol, aromatic diol mono (meth) acrylate, and aromatic diol di (meth) acrylate was 100 mol%, and each component was computed.

(color)

The coloring state at the end of reaction was visually observed.

○: slightly colored, ×: fairly colored

(Turbidity)

The reaction liquid at the end of the reaction was diluted to 4 parts by mass with a reaction liquid propylene glycol monomethyl ether acetate and observed visually.

○: transparent, ×: turbidity

[Example 1]

Synthesis of 4-hydroxyphenyl methacrylate

100 mass parts of hydroquinone, 235 mass parts of methacrylic acid, and 4 mass parts of p-toluenesulfonic acid were thrown into the 1 L separate flask with a cooler, a thermometer, and a stirrer impeller, and reaction was started at 120 degreeC, taking in air. When the reaction reached equilibrium and the composition of the product became constant, the reaction was continued while distilling off under reduced pressure at -80 kPa so that the moisture in the system was kept at 0.2 mass% or less. When the ratio of 4-hydroxyphenyl methacrylate became 49.9% of the number-of-moles which hydroquinone was thrown in, the system was returned to normal pressure, it cooled, and the esterification reaction was complete | finished. Composition ratio, color, and turbidity are as shown in Table 1.

[Example 2]

Synthesis of 4-hydroxyphenyl methacrylate

100 parts by mass of hydroquinone, 235 parts by mass of methacrylic acid, and a strong acid ion exchange resin Amberlyst manufactured by Organo Co., Ltd. 15.DRY 10 parts by mass were charged in a 1L separate flask equipped with a cooler, a thermometer and a stirrer impeller. The reaction was initiated at. When the reaction reached equilibrium and the composition of the product became constant, the reaction was continued while distilling under reduced pressure at -80 kPa so that the moisture in the system was kept at 0.2 mass% or less. The ratio of 4-hydroxyphenyl methacrylate became 56.8% of the number of moles added with hydroquinone, and then the system was returned to normal pressure, cooled to terminate the esterification reaction. Composition ratio, color, and turbidity are as shown in Table 1.

[Example 3]

Synthesis of 4-hydroxyphenyl methacrylate

100 mass parts of hydroquinone, 86 mass parts of methacrylic acid, and 4 mass parts of p-toluenesulfonic acid were thrown into the 1 L separate flask with a cooler, a thermometer, and a stirrer impeller, and reaction was started at 125 degreeC. When the reaction reached equilibrium and the composition of the product became constant, the reaction was continued while distilling off under reduced pressure at -80 kPa. When the ratio of 4-hydroxyphenyl methacrylate became 34.4% of the number-of-moles which added hydroquinone, the system was returned to normal pressure, it cooled, and the esterification reaction was complete | finished. Composition ratio, color, and turbidity are as shown in Table 1.

[Comparative Example 1]

Synthesis of 4-hydroxyphenyl methacrylate

100 parts by mass of hydroquinone, 86 parts by mass of methacrylic acid, 4 parts by mass of p-toluenesulfonic acid, and 100 parts by mass of toluene were added to a 1 L separate flask equipped with a reflux condenser, a water separator, a thermometer, and a stirrer impeller, followed by reflux for reaction. It was done. The azeotrope of toluene and water started to flow out at 120 degreeC, and it reacted at 120 degreeC for 5 hours, removing the water isolate | separated with the water separator out of the system. When the ratio of 4-hydroxyphenyl methacrylate became 37.0% of the number-of-moles which hydroquinone was thrown in, the system was returned to normal pressure, it cooled, and the esterification reaction was complete | finished. Composition ratio, color, and turbidity are as shown in Table 1.

[Comparative Example 2]

Synthesis of 4-hydroxyphenyl methacrylate

100 parts by mass of hydroquinone, 86 parts by mass of methacrylic acid, and a strongly acidic ion-exchange resin amber List manufactured by Organo Co., Ltd. 15. DRY 10 parts by mass , 100 parts by mass of toluene was added and refluxed to react. Outflow of the azeotropic mixture of toluene and water started at 120 degreeC, and it reacted at 120 degreeC for 16 hours, removing the water isolate | separated with the water separator out of the system. When the ratio of 4-hydroxyphenyl methacrylate became 51.3% of the number of moles which added hydroquinone, it cooled and complete | finished esterification reaction. Composition ratio, color, and turbidity are as shown in Table 1. When toluene which is a hydrophobic solvent is used, the ratio of hydroquinone dimethacrylate increases, which is not economical because a large amount of washing solvent is required in the purification step.

[Comparative Example 3]

Synthesis of 4-hydroxyphenyl methacrylate

100 parts by mass of hydroquinone, 86 parts by mass of methacrylic acid, and 4 parts by mass of p-toluenesulfonic acid were added to a 1 L separate flask equipped with a cooler, a thermometer, and a stirrer impeller, and the reaction product ratio was 1.5 hours. As it became constant, the water in the system was removed by distillation under reduced pressure at -80 kPa. Again, when the reaction product was constant at 145 ° C for 1.5 hours under normal pressure, the proportion of the reaction product was constant, so that the water in the system was removed by distillation under reduced pressure at -80 kPa. At this time, the moisture in the system was changed at 0.5 to 1.0% by mass. This operation was repeated and the esterification reaction was complete | finished when the ratio of 4-hydroxyphenyl methacrylate became 35.1% of the number-of-moles which hydroquinone was thrown in. Composition ratio, color, and turbidity are as shown in Table 1.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 catalyst PTS 15DRY PTS PTS 15DRY PTS Input molar ratio 3.0 3.0 1.1 1.1 1.1 1.1 menstruum none none none toluene toluene none Dehydration method Heating Heating Heating Public expense Public expense Heating Reaction temperature 120 DEG C 120 DEG C 125 ℃ 120 DEG C 120 DEG C 145 ° C Composition ratio, mol% Divalent phenol 47.4 38.1 64.5 62.2 28.1 63.9 Monoester 49.9 56.8 34.4 37.0 51.3 35.1 Diester 2.7 5.2 1.2 0.8 20.6 1.0 color ○ ○ ○ X ○ X Turbidity ○ ○ ○ X ○ ○

PTS: p-toluenesulfonic acid

15dry: organo strong acid ion exchange resin

Input molar ratio: Input molar ratio of (meth) acrylic acid to dihydric phenol

Reference Example 1

Purification of 4-hydroxyphenyl methacrylate

The reaction solution obtained in Example 1 was neutralized with triethylamine and washed repeatedly with methylcyclohexane to terminate the washing with methylcyclohexane when the mole fraction of p-phenylene dimethacrylate became 0.1%. It was. Here, the crude crystal from which p-phenylene dimethacrylate was removed can be obtained. Subsequently, washing this crude crystal with water was repeated, and water washing was complete | finished when the mole fraction of unreacted aromatic diol became 0.2%. Subsequently, 52.6 mass parts (yield: 32.5%) of white crystals were obtained by deaeration and drying.

The mole fraction of hydroquinone: 4-hydroxyphenyl methacrylate: p-phenylene dimethacrylate was 0.2: 99.7: 0.1.

Polymerization of 4-hydroxyphenyl Methacrylate

100 mass parts of white crystal | crystallization obtained, 300 mass parts of propylene glycol monoethyl ether acetates, and 4.0 mass parts of azobisisobutyronitrile were put into the 1 L separate flask with a cooler, a thermometer, and a stirrer impeller, and it reacts at 70 degreeC for 6 hours. And the polymer solution was obtained.

Measurement of the transmittance of the polymer

The resulting polymer solution was filtered through a 0.1 μm Teflon® filter. It applied to the glass plate by the 50 micrometer applicator, and it dried for 90 second on the 110 degreeC hotplate, and obtained the coating film of 3 micrometers in film thickness. Moreover, the transmittance | permeability in wavelength 400nm when heat-processing for 0, 1, 2, 3 hours in 230 degreeC oven was measured with the ultraviolet-visible spectrophotometer, respectively. The results are shown in Fig. The polymer which uses the hydroxyphenyl methacrylate without coloring as a raw material is favorable because there is little change of a transmittance | permeability even if it heats.

Comparative Reference Example 1

The reaction solution obtained in Comparative Example 1 was treated in a similar manner to Reference Example 1 to purify to obtain a brown powder. Polymerization was carried out similarly to Reference Example 1 using the obtained brown powder, to obtain a polymer solution. The resulting polymer solution was then tested for filtration with a 0.1 μm Teflon® filter, but could not be filtered due to clogging. This is considered to be because turbidity is high.

Comparative Reference Example 2

The reaction liquid obtained in the comparative example 3 was processed similarly to the reference example 1, and refine | purified, and the brown powder was obtained. Polymerization was carried out similarly to Reference Example 1 using the obtained brown powder, to obtain a polymer solution. Subsequently, the transmittance of the coating film was measured similarly to Reference Example 1 using the obtained polymer solution. The results are shown in Fig. The polymer using colored hydroxyphenyl methacrylate as a raw material has a large change in transmittance when heated, and cannot be applied to a use requiring transparency.

Claims (7)

A method of producing an aromatic diol mono (meth) acrylate by esterifying an aromatic diol and (meth) acrylic acid in the presence of a strong acid, wherein the method is performed at 100 to 140 ° C. in the presence of a solvent-free or aprotic organic solvent. And a step of esterifying while removing moisture in the reaction system by heating and decompression. The method of claim 1, wherein the strong acid is a liquid in the reaction system. The process of claim 2, wherein the strong acid is selected from p-toluenesulfonic acid, sulfuric acid, or methanesulfonic acid. The aromatic diol mono (any one of Claims 1-3 whose molar ratio at the time of esterifying an aromatic diol and (meth) acrylic acid is 3.0-4.0 mol of (meth) acrylic acid with respect to 1.0 mol of aromatic diols. Method for producing methacrylate. The aromatic diol mono according to any one of claims 1 to 4, wherein the esterification reaction is terminated when the production rate of the aromatic diol mono (meth) acrylate with respect to the aromatic diol to be introduced is 40 to 70 mol%. Method for producing methacrylate. The aromatic diol mono (meth) acrylic according to any one of claims 1 to 5, wherein the heating and decompression is started after the esterification reaction and the hydrolysis reaction between the water and the esterified product in the reaction system are in an equilibrium state. Method of producing a rate. The process for producing an aromatic diol mono (meth) acrylate according to any one of claims 1 to 6, wherein the esterification reaction is carried out while inhaling air.

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