JPH0625203A - Production of epoxidized (meth)acrylate compound and purified and epoxidized (meth)acrylate compound - Google Patents

Abstract

PURPOSE:To produce the subject compound having satisfactory qualities in an industrial scale by washing reaction crude liquid obtained by epoxidizing using an organic peracid with water for a short contact time and then lowering heating temperature and remov ing low-boiling opint components with 2 stages. CONSTITUTION:(a) A reaction crude liquid containing 3, 4-epoxycyclohexylmethyl (meth)acrylate of formula II obtained by epoxidizing a cyclohexylmethyl (meth)acrylate of formula I (R<1> and R<2> are H or 1-5C alkyl; R<3> is H or mathacryl) is washed with water using an apparatus (e.g. centrifugal extraction apparatus) for a short contact time and (b) the liquid is treated with an aqueous solution of an alkali to remove an organic acid and an organic peracid both of whose main chains exist in the crude liquid washed with water. Then, (c) the liquid is subjected to low-boiling point component-removing treatment at <=100 deg.C heating temperature under reduced pressure to afford a liquid having 3-50wt.% content of low-boiling point component and (d) further, the washed liquid is subjected to low-boiling point component-removing treatment at <=100%oC heating temperature and under reduced pressure of <=1/2 of the step (c). Thereby, a liquid having <1wt.% content of low-boiling point component is obtained to provide the objective purified compound of formula II.

Description

Detailed Description of the Invention

[0001]

The present invention relates to epoxidized (meth) acrylates with or without substituents.
And a purified epoxidized (meth) acrylate compound.

(Meth) acrylate compounds can be easily homopolymerized or copolymerized with other unsaturated group-containing compounds in the presence of heat, ultraviolet rays, ionizing radiation or radical polymerization initiators, and also for paints. It is also useful as an intermediate raw material for resins.

[0003]

2. Description of the Related Art Heretofore, as a purification method of a reaction crude liquid obtained by epoxidation using an organic peracid, (1) purification method by distillation The product is relatively stable against heat. In this case, a method of purifying by distillation is generally used.

(2) Purification method by washing with water Since organic acids and organic peracids are present in the reaction crude liquid, distillation of the reaction crude liquid often causes the epoxy compound to polymerize or cause a side reaction. In such a case, the organic acid or organic peracid that induces the polymerization or side reaction is removed by washing with water, and then the product is usually purified by distillation.

(3) Purification Method by Neutralization If the organic acid or organic peracid cannot be removed by washing with water, or if the aqueous solution of the organic acid and the epoxy compound easily react, the purification method by neutralization is used. If the substance that induces the polymerization or side reaction cannot be removed by merely adjusting the pH of the liquid to the neutralization point, the substance that induces the polymerization or side reaction may be removed with an alkaline aqueous solution. A substance that induces polymerization or a side reaction by neutralization is washed and removed, and then purified by distillation.

Methods such as the above are known.

However, since the organic acid and the epoxy group are likely to react with each other, the above-mentioned prior art (1) cannot be used in many cases because the polymerization reaction or ring-opening reaction of the epoxy group occurs during distillation.

The above-mentioned conventional techniques (2) and (3), which are used when the above-mentioned conventional technique (1) cannot be used, also have a problem. In the case where the reaction rate between the organic acid or water and the epoxy group is high, Cannot use the prior art (2).

Further, the above-mentioned prior art (3) not only causes the loss of valuables when manufacturing on an industrial scale, but also increases the drainage load.

[0010]

As described above, when the reaction crude liquid cannot be purified by distillation due to polymerization or side reaction, and in the case of an epoxy compound having a high reaction rate with an organic acid or water, Could not be produced on an industrial scale with the prior art.

On the other hand, as a method for improving the above-mentioned prior art (2), the present inventors removed the organic acid and the organic peracid by washing with water from the reaction crude liquid which was epoxidized with the organic peracid. In this method, it was found that valuable materials are lost by the following mechanism. That is, the loss of valuables is that the valuables dissolved in the water layer react with the organic acid of the water in the water layer, the concentration of valuables in the water layer decreases, and It was confirmed to occur in the form of a reactive extraction that promotes dissolution.

By using an apparatus in which the contact time between the organic layer and the water layer is short so that this mechanism does not occur, the reaction between the organic acid or water and the epoxy compound can be made extremely small.

The epoxidized (meth) acrylic acid ester [hereinafter, in the present invention, in order to simplify the explanation, R ₁
AETHB when both R ₂ are hydrogen and R ₃ is hydrogen,
When R ₁ and R ₂ are both hydrogen and R ₃ is a methacryl group, M
It is known that ETHB is representatively referred to as ETHB] and is often polymerized by heat, light and other factors during the manufacturing process, storage and transportation.

The product obtained when the solvent was removed from the crude liquid washed with water using the above-mentioned apparatus having a short contact time to obtain a product had a low purity (purity 90%) and had a high polymerizability. Such low purity and high polymerizability AETHB
In (METHB), a polymer precipitates as a sticky insoluble substance, which causes various problems in the process and significantly reduces the commercial value.

This is because the organic acid having a main chain formed in the reaction step cannot be sufficiently removed only by washing with water for a short period of time, so that they are carried over to the product, and therefore the polymerizability becomes high. Seem. Against such a phenomenon, the inventors of the present invention washed the reaction crude liquid with water for a short period of time and then treated it with an alkaline aqueous solution to wash the organic acid and organic peroxide having a main chain present in the crude water washed. It was found that by removing the acid, a product with a purity of 94-97% was obtained.

Furthermore, AETHB (ME
THB) has various restrictions, and these must be cleared. That is, AETHB (METH
B) The low boiling point component contained in the product must be within 2-3% to 1%, and for that purpose, the heating temperature must be raised or the residence time must be prolonged in the deboiling step. However, in such a case, a trace amount of polymer is contained in the product. With respect to this point, it has been clarified that there is a problem if the development progresses after that and the product contains a trace amount of the polymer.

These minute amounts of polymers cause various problems when synthesizing an intermediate raw material for a paint resin, for example, and significantly reduce the commercial value of the paint.

The trace amount of the polymer contained in the product AETHB (METHB) is considered to be the low molecular weight polymer of AETHB (METHB) itself. These polymers are
Product 10 in 100 cc of n-hexane or n-heptane
The slurry formed when g is dissolved can be expressed by the weight% of the polymer contained in the product by filtering the slurry and measuring the weight (such solubility test using n-heptane will be referred to as heptane hereinafter). Test = call HT).

AETHB (METH that can be used as a product
It has been found that B) must have an HT of 0.1% or less. That is, in order to industrially produce AETHB (METHB), it was necessary to establish a more effective polymerization suppressing method.

[0020] By conducting intensive studies on such problems, and finding that the heating temperature is lowered and the solvent is deboiling in two steps to achieve low boiling point, the above object is extremely met, and finally AETHB which is satisfactory in quality is found. The method for producing (METHB) on an industrial scale was established, and the present invention was completed.

[0021]

That is, the present invention relates to "whether it has an alkyl substituent obtained by epoxidizing cyclohexylmethyl (meth) acrylate having an alkyl substituent or having no alkyl substituent with an organic peracid. Alternatively, a reaction crude liquid containing 3,4-epoxycyclohexylmethyl (meth) acrylate having no alkyl substituent is washed with water using a device having a short contact time as follows (b) alkali neutralization treatment Step (c) A step of obtaining a liquid having a low boiling point component content of 3 to 50 wt% by deboiling under reduced pressure at a heating temperature of 100 ° C. or lower (d) Heating temperature of 100 ° C. or lower, (c) Step 1 Having a purified alkyl substituent or having an alkyl substituent, which is characterized by treatment in a step of obtaining a liquid having a low boiling point content of less than 1% by weight by deboiling under a reduced pressure of / 2 or less. For producing 3,4-epoxycyclohexylmethyl (meth) acrylate "and" 3,4-epoxy with or without alkyl substituent having a heptane test value of less than 0.15% by weight And cyclohexylmethyl (meth) acrylate ".

In the present invention, cyclohexylmethyl (meth) acrylate represented by the above chemical formula 1 with or without an alkyl substituent before epoxidation uses 1,3-butadiene as one raw material. ,
As the other raw material, acrolein, methacrolein,
Crotonaldehyde, 3 ethylacrolein or 2,
Using at least one compound selected from 3 dimethyl acrolein, a tetrahydrobenzaldehyde having an alkyl substituent or no alkyl substituent is first synthesized by a Diels-Alder reaction, which is selectively hydrogenated to give a corresponding compound. Get an alcohol. The compound represented by Chemical formula 1 can be obtained by reacting this with acrylic acid or methacrylic acid for esterification, or by reacting with acrylic acid ester or methacrylic acid ester for transesterification. When 1,3-butadiene and acrolein are used as the starting materials, R ₁ and R ₂ in the above chemical formula ₁ are both hydrogen, and the most commonly known one is obtained.

A typical method of manufacturing AETHB (METHB) will be described below in detail. First, the epoxidation reaction step will be described.

That is, R ₁ and R in the above chemical formula ₁
Cyclohexenyl (meth) acrylate in which ₂ is hydrogen is epoxidized with an organic peracid. Specific organic peracids include performic acid, peracetic acid, perpropionic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, and perbenzoic acid. These may be used in combination with a catalyst,
An alkali such as sodium carbonate or an acid such as sulfuric acid may be used together as a catalyst.

When the reaction is carried out in a batch, first, a predetermined amount of cyclohexenylmethyl (meth) acrylate is charged in a reactor, and a catalyst and a stabilizer are dissolved therein, if necessary. Perform by adding peracid dropwise.

The reaction molar ratio between the organic peracid and cyclohexenylmethyl (meth) acrylate is theoretically 1/1, but in the method of the present invention, it is in the range of 0.1 to 10, preferably 0. .5 to 10, more preferably 0.8 to
A range of 1.5 is good.

When the molar ratio of the organic peracid to cyclohexenylmethyl (meth) acrylate exceeds 10, the conversion rate of cyclohexenylmethyl (meth) acrylate and the reaction time are shortened, and (meth) acrylate Although it is preferable from the viewpoint of reduction of loss due to polymerization, it has drawbacks such as side reaction due to excess organic peracid, selectivity of organic peracid, and great expense in recovering unreacted oxidizing agent.

On the contrary, when the molar ratio of the reaction between the organic peracid and cyclohexenylmethyl (meth) acrylate is 0.1 or less, the selectivity of the organic peracid, the conversion rate, and the side reaction due to the organic peracid are suppressed. However, there are drawbacks such as a loss due to polymerization of the (meth) acrylate and a large amount of cost for recovering unreacted cyclohexenylmethyl (meth) acrylate.

The reaction temperature is lower than the upper limit value so that the epoxidation reaction has priority over the decomposition reaction of the organic peracid. Specifically, 70 ° C. or lower is preferable.

When the reaction temperature is low, it takes a long time to complete the reaction. Therefore, when peracetic acid, which is a typical organic peracid, is used, it is preferable to perform the reaction at a lower limit of 0 ° C. or higher.

In addition, during the epoxidation reaction, a side reaction occurs in which the epoxy group is ring-opened by the corresponding organic acid generated from the organic peracid and other by-produced organic acids, alcohol and water. The temperature at which the amount of side reaction is reduced is selected from the above-mentioned temperature range and the operation is performed.

The reaction pressure is generally operated under normal pressure, but it can be carried out under pressure or under low pressure. The reaction can also be carried out in the presence of a solvent.

The reaction in the presence of a solvent lowers the viscosity of the reaction crude liquid, stabilizes the organic peracid by diluting it, and slows the reaction rate between the organic acid and the epoxidized cyclohexenylmethyl (meth) acrylate. It is preferable because it has the effect of

Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene and p-cymene, and fats such as cyclohexane, n-hexane, heptane, octane, nonane, decane and decalin. Group hydrocarbons,
Cyclohexanol, hexanole, heptanol, octanole, nonanol, furfuryl alcohol and other alcohols, chloroform, dimethyl chloride, carbon tetrachloride, chlorobenzene and other halides, ethyl acetate , Butyl acetate, n-amyl acetate, cyclohexyl acetate, isoamyl propionate, esterified products such as methyl benzoate, ketone compounds such as methyl ethyl ketone,
Etc. can be used.

The amount of the solvent used is 0.5 to 5 times, more preferably 1.5 to 3 times the amount of cyclohexenylmethyl (meth) acrylate.

When the amount is less than 0.5 times, the stabilizing effect by diluting the organic peracid is small. On the contrary, when the amount is more than 5 times, the stabilizing effect is not so improved and the solvent is recovered. It costs a lot of money and is wasted.

When carrying out the epoxidation reaction as described above, hydroquinone, hydroquinone monomethyl ether, P-benzoquinone, cresol and t-butyl catechol are used as polymerization inhibitors together with a molecular oxygen-containing gas as a polymerization inhibitor. 2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol,
3-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-P-cresol, 2,5-dihydroxy-P-quinone, piperidine, ethanolamine, α-nitroso-β -Naphthol, diphenylamine, phenothiazine, N-nitrosophenylhydroxylamine,
N, N-diethylhydroxylamine or the like is used.

Ammonium hydrogen phosphate, potassium pyrophosphate, pyrophosphoric acid-2-ethylhexyl ester, potassium pyrophosphate-2-ethylhexyl ester, sodium pyrophosphate-2-ethylhexyl ester tripolyphosphoric acid, tripolyphosphoric acid as stabilizers of organic peracids. Potassium, sodium tripolyphosphate, tripolyphosphate-
2-ethylhexyl ester, potassium tripolyphosphate-2-ethylhexyl ester, tetrapolyphosphoric acid, potassium tetrapolyphosphate, sodium tetrapolyphosphate, tetrapolyphosphoric acid-2-ethylhexyl ester,
Tetrapolyphosphate potassium-2-ethylhexyl ester, sodium tetrapolyphosphate-2-ethylhexyl ester, potassium hexametaphosphate, sodium hexametaphosphate and the like can be used. These may be used alone or in combination.

Air is usually used as the molecular oxygen and is blown into the reactor.

The blowing position may be directly blowing into the liquid or blowing into the gas phase to obtain a predetermined effect. The blowing amount can be arbitrarily selected, but if it is too large, solvent loss occurs, which is not preferable. Further, in order to avoid the formation of an explosive mixture in the system, it is usual to blow nitrogen into the system together with air. In that case, the oxygen concentration in the blown gas is preferably 0.01% (volume) or more. It is 3% (volume) or more.

The higher the oxygen concentration is, the more effective it is, but the upper limit value is the lower limit oxygen concentration for explosion in the system, and the value depends on the solvent used. The blowing of nitrogen does not necessarily have to be at the same position as air, but it is important for safety to devise a facility so as not to locally form an explosive mixture in the system.

The amount of the polymerization inhibitor to be used can be optionally changed depending on the kind of the compound to be treated and the conditions in the manufacturing process, but it is 0.005 with respect to the reaction starting material cyclohexenylmethyl (meth) acrylate. To 5% by weight, more preferably 0.001 to 0.1% by weight, 0.001 to 1% by weight as a stabilizer of organic peracid, and more preferably 0.01 to 0.1% by weight.
It is preferable to add it in the range of 0.2% by weight. The powder may be added as it is, or may be dissolved in a solvent and added.

The reaction is carried out continuously or batchwise. In the case of continuous reaction, the piston flow type is preferred. Further, in the case of the batch system, a semi-batch system in which organic peracids are sequentially charged is desirable. In that case, first, a predetermined amount of cyclohexenylmethyl (meth) acrylate and a solvent are charged into a reaction vessel, and if necessary, a catalyst and a stabilizer are dissolved therein, and the organic peracid is dropped therein. Then do.

The completion of the reaction may be confirmed by the residual organic peracid concentration or gas chromatographic analysis. After the completion of the reaction, water is first washed to remove the organic acid and the organic peracid from the crude liquid for the epoxidation reaction.

The conditions of the apparatus used for washing with water include that the contact time between the organic layer and the aqueous layer is short. To what extent the residence time is required is determined by the amount of loss allowed in the washing step and the reaction rate between the epoxidized cyclohexenylmethyl (meth) acrylate and the aqueous organic acid solution.

A typical example of such a device having a short residence time is a centrifugal extractor, and a device such as a mixer-settler type or an extraction tower which is generally used in a water washing step is used as a residence time. You may add ingenuity to shorten. For example, in the case of a mixer-settler type, a line mixer or the like may be used in the mixer part, and a tank as small as possible may be used in the settler part. Good. Further, in the case of the extraction tower, which of the organic layer and the aqueous layer is the continuous layer also affects the residence time.

However, in any of the mixer-settler type and the extraction column, the longer the liquid separation time is, the longer the mixing degree of the organic layer and the water layer is. Therefore, how long can the retention time be shortened? Is greatly affected by the liquid separation properties of each system.

In this respect, the centrifugal extractor is advantageous because it can perform the liquid separation in a short time by utilizing the centrifugal force even when the difference in specific gravity is small and the liquid separation property is poor.

By the way, the residence time in the centrifugal extractor is several seconds to several tens of seconds, and at most about 1 minute. The operating temperature of the water washing step is preferably lower as the reaction rate between the epoxidized cyclohexenylmethyl (meth) acrylate and the organic acid aqueous solution becomes smaller. However, care must be taken because if the temperature is too low, the liquid separation property may deteriorate. The charging ratio of the reaction crude liquid in the water washing step and water as the extraction agent is arbitrary, but usually S / F = 0.5 to 3.0.
(Wt ratio, S is water, F is reaction crude liquid). In the water washing step, it is important to remove the residual organic peracid together with the extraction and removal of the organic acid. In order to remove the organic acid and organic peracid having a sufficient main chain in the subsequent alkali treatment step, the residual organic acid content in the crude water washed with water is 0.1% or less, preferably 0.05% or less, and It is necessary to adjust the S / F so that the residual organic peracid content is 0.1% or less, preferably 0.05% or less.

The point of the present invention is that the reaction crude liquid after epoxidation is washed with water for a short time as described above, then treated with an alkaline aqueous solution, and further treated with a two-step de-low boiling step to purify. This is to obtain the epoxidized cyclohexenylmethyl (meth) acrylate.

By the way, Japanese Patent Application No. 1-320 without treating the crude liquid after washing with water for a short time with an alkaline aqueous solution.
The product purity is 9 when the product is produced by deboiling by the method described in Japanese Patent Application No. 956 and Japanese Patent Application No. 2-276099.
It was 0% or less.

This is because washing with water for a short time only
It is considered that the organic acids and organic peracids having a main chain formed in the reaction step cannot be removed sufficiently, and they are present in the product, which increases the polymerizability.

Against such a phenomenon, the inventors of the present invention washed the reaction crude liquid with water for a short period of time and then treated it with an alkaline aqueous solution to remove the organic acid having a main chain present in the crude water washed and Purity 9 by removing organic peracid
It was found that 4-97% product was obtained.

Examples of the alkaline aqueous solution used for the alkaline treatment include NaOH, KOH, K ₂ CO ₃ and Na ₂ C.
O ₃ , NaHCO ₃ , KHCO ₃ , NH _{3 and the} like can be used. From the viewpoint of liquid separation, NaOH, NaC
It is preferable to use an aqueous solution of O ₃ and NaHCO ₃ .

The concentration of the alkaline aqueous solution is 0.1 to 10
%, More preferably 0.5 to 2% concentration range. When the concentration of the alkaline aqueous solution is set to 0.1% or less, the high-boiling organic acid and the high-boiling organic peracid present in the washing solution cannot be sufficiently removed, which is not good. Further, when the concentration of the alkaline aqueous solution is 10% or more, there are problems that the drainage load at the time of treatment becomes large and it is not economical.

In the alkali treatment step, the ratio of the raw water for washing and the aqueous alkaline solution which is the extractant may be arbitrary, but S /
F = 0.1-5, more preferably 0.3-2 (Wt ratio,
It is preferable that S is an alkaline aqueous solution, and F is a water washing crude liquid. If the S / F is set to 0.1 or less, the high-boiling organic acid and the high-boiling organic peracid present in the washing solution cannot be sufficiently removed, which is not good. Further, if the S / F is set to 5 or more, the treatment tank becomes large and the drainage load at the time of treatment becomes large.

The pH of the alkali-treated heavy liquid must be 9 or more. If it is less than this, there is a problem because the organic acid or organic peracid cannot be removed.

The processing temperature is preferably in the range of 0 to 50 ° C. If the temperature is lower than 0 ° C, the liquid separation property will be deteriorated. If it is carried out at 50 ° C. or higher, the amount of organic substances dissolved in the alkaline aqueous solution increases, which causes a problem of drainage load.

The treatment method is continuous or batch,
When continuous, the mixer-settler type is preferred.

In the alkali treatment step, it is important to remove the organic acid having a main chain as well as the residual organic peracid. In order to stably operate the subsequent low boiling point component removing step, the residual organic peracid content in the crude liquid must be 0.01% or less.

When the low boiling point component is removed from the crude liquid which has been washed with water and treated with an alkali, it is preferable to add a polymerization inhibitor.

In particular, hydroquinone, hydroquinone monomethyl ether, P-benzoquinone, cresol, t-butyl catechol, 2,4-dimethyl-6-t-butylphenol as a polymerization inhibitor contained in the reaction crude liquid. Le,
2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-P-cresol, 2,5-dihydroxy-P- Quinone, piperidine, ethanolamine, α-nitroso-β
-Naphthol, diphenylamine, phenothiazine, N
-Nitrosophenylhydroxylamine, N, N-diethylhydroxylamine, etc., or ammonium hydrogenphosphate as a stabilizer of organic peracid, potassium pyrophosphate, pyrophosphate-2-ethylhexyl ester, potassium pyrophosphate-2-ethylhexyl ester, Sodium pyrophosphate-2-ethylhexyl ester tripolyphosphate, potassium tripolyphosphate, sodium tripolyphosphate, tripolyphosphate-2-ethylhexyl ester,
Potassium tripolyphosphate-2-ethylhexyl ester, tetrapolyphosphoric acid, potassium tetrapolyphosphate, sodium tetrapolyphosphate, tetrapolyphosphoric acid-2-ethylhexyl ester, potassium tetrapolyphosphate-2
-Ethylhexyl ester, sodium tetrapolyphosphate-2-ethylhexyl ester, potassium hexametaphosphate, compounds such as sodium hexametaphosphate may be extracted during water washing or alkali treatment and the content in the water rinse crude solution may decrease, but in that case, It is preferable to replenish the above-mentioned compound in an appropriate amount after the completion of the alkali treatment.

<De-low boiling step> For the low-boiling point, a thin film evaporator is usually used, and it is preferable to treat it in two stages as described in Japanese Patent Application No. 2-276099.

Since the solvent is desolvated to 1% by weight or less in one stage, when a high vacuum is applied, the volume of the solvent vapor becomes enormous and a large evaporator is required to realize a sufficient evaporation capacity. . On the contrary, if the heating is carried out in a low vacuum, the heating temperature must be raised, so that the polymerization is accelerated. In addition, even when the heating temperature is lowered, AETHB (ME
The residence time of THB) becomes longer and the polymerization is accelerated.

That is, when the solvent is removed up to 1% by weight in one step, HT having a quality of 0.1% or less cannot be obtained. Therefore, low boiling point removal by two steps is performed.

In the first step of removing the low boiling point liquid obtained by the alkali treatment, the heating temperature is 50 to 100 ° C., preferably 50.
It is good to carry out in the range of up to 70 ° C. The pressure at that time can be arbitrarily selected depending on the physical properties of the solvent, but it is common to operate under reduced pressure in relation to the heating temperature.

The solvent concentration in the bottom liquid of the thin film evaporator thus obtained is 3 to 50 wt%, more preferably 10%.
Must be in the range of ~ 20 wt%. When the solvent concentration is 3 wt% or less, high vacuum must be applied,
When collecting the distilled solvent with a condenser, the recovery loss becomes large, which is not preferable.

On the contrary, when the solvent concentration is set to 50 wt% or more, the solvent to be distilled out cannot be repaired by the condenser because the second step of removing low boiling point is performed in a high vacuum, and the recovery loss becomes large, which is not preferable.

In the second step of removing low boiling point, the heating temperature is 50 to 1
It may be carried out at 00 ° C, preferably in the range of 50 to 70 ° C. The pressure at that time varies depending on the physical properties of the solvent, but can be arbitrarily selected in relation to the heating temperature.

The position where molecular oxygen having a polymerization preventing effect is introduced into the evaporator can be arbitrarily selected, but it is usually blown from a line through which the bottom liquid is distilled.

The blowing amount can be arbitrarily selected, but the upper limit amount is the capacity of the vacuum system or whether or not the bottom liquid stably flows down.
Alternatively, it is naturally limited from the viewpoint of recovery loss when the distilled solvent is collected by the condenser.

The bottom liquid obtained in the deboiling step is 94 to 97 wt% in terms of purity, but as a result of the present invention, the solvent concentration is 1 wt% or less, and HT is 0.1 wt%. The quality is as follows.

[0073]

The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 In a reactor made of SUS316 having an internal capacity of 20 liter, equipped with a stirrer and a cooling jacket, 3000 g of cyclohexenyl methyl acrylate (hereinafter abbreviated as CHAA), 11100 g of ethyl acetate, and hydroquinone monomethyl ether.
Tellurium 0.9 gr, sodium tripolyphosphate 9.0 g, and oxygen / nitrogen (10/9
0% by volume) of the mixed gas was blown at 32 Nl / Hr.

Then, the reaction temperature was kept at 40 ° C., and 5623 g of a 30% peracetic acid solution was charged by a metering pump over 4 hours. After the completion of the charging, the reaction was terminated after aging for 5 hours. Thus, 19723 g of a reaction crude liquid containing 3,4-epoxycyclohexylmethyl acrylate (hereinafter abbreviated as AETHB) was obtained.

Rotor outer diameter 46 cm, rotor inner diameter 25 mm
By charging the reaction crude liquid containing AETHB from the light liquid inlet at a rate of 2108 g / min into the centrifugal extractor rotating the rotor of No. 4 at a rate of 2108 g / min, and simultaneously charging water from the heavy liquid inlet at a rate of 3590 g / min. , 166 light liquid from the light liquid outlet
Heavy liquid was obtained from the heavy liquid outlet at a rate of 434 g / min at a rate of 40 g / min.

The obtained light liquid is again placed in the same centrifugal extractor.
At the same time as charging at a rate of 08 g / min, by charging water from the heavy liquid inlet at a rate of 3590 g / min, the light liquid is discharged from the light liquid outlet at a rate of 1877 g / min and the heavy liquid is discharged from the heavy liquid outlet at 3821 g / min. Got at the speed of. The acetic acid and peracetic acid concentrations in the light liquid were 400 ppm and 150 ppm, respectively.
The light liquid thus obtained was charged into a SUS316 treatment tank having a stirrer and a cooling jacket and having an internal capacity of 15 liters (3000 g), and 1 g NaOH aqueous solution (3000 g) was charged therein, and the temperature was kept at 10 ° C. for 1 hour. It was stirred.

The residual peracetic acid concentration in the obtained crude liquid was 100.
It was below ppm.

Next, 0.16 g of hydroquinone monomethyl ether was added to 2790 g of this light liquid, and the first stage deboiling was carried out with a Smith type thin film evaporator made of SUS. The operating conditions were a heating temperature of 60 ° C. and a pressure of 150 mmHg, and a mixed gas of oxygen / nitrogen was blown at a rate of 32 L / Hr from the bottom liquid distillation line.

This bottom liquid is heated at a temperature of 60 ° C. and a pressure of 40 m.
The second stage deboiling was performed under the condition of mHg, and a mixed gas of oxygen / nitrogen (10/90% by volume) was mixed with 3 from the bottom liquid distillation line.
Blow at 2 Nl / Hr. The bottom liquid was 538 g.

When the composition was examined by gas chromatography analysis, it was found that AETHB was 96.4%.

As a result of HT, the polymer content was 0.
It was 01%.

Example 2 3000 g of the centrifugally extracted light liquid obtained in Example 1 was charged into a SUS316-made treatment tank having an internal volume of 15 liters equipped with a stirrer and a cooling jacket, and 3000 g of 0.5% NaOH aqueous solution was charged therein. The mixture was stirred for 1 hour while keeping the temperature at 10 ° C. The residual peracetic acid concentration in the obtained crude liquid was 10
It was 0 ppm or less.

Next, 0.21 g of hydroquinone monomethyl ether was added to 2790 g of this light liquid, and the first stage deboiling was carried out with a Smith type thin film evaporator made of SUS. The operating conditions were a heating temperature of 60 ° C. and a pressure of 150 mmHg, and a mixed gas of oxygen / nitrogen was blown at a rate of 32 L / Hr from the bottom liquid distillation line.

This bottom liquid is heated at a temperature of 60 ° C. and a pressure of 40 m.
The second stage deboiling was performed under the condition of mHg, and a mixed gas of oxygen / nitrogen (10/90% by volume) was mixed with 3 from the bottom liquid distillation line.
Blow at 2 Nl / Hr. The bottom liquid was 538 g.

When the composition was examined by gas chromatography analysis, it was found that AETHB was 95.7%.

As a result of HT, the polymer content was 0.
It was 02%.

Example 3 3000 g of the centrifugally extracted light liquid obtained in Example 1 was charged into a SUS316-made treatment tank having an internal volume of 15 liter equipped with a stirrer and a cooling jacket, and 3000 g of 0.1% NaOH aqueous solution was charged therein. The mixture was stirred for 1 hour while keeping the temperature at 10 ° C. The residual peracetic acid concentration in the obtained crude liquid was 10
It was 0 ppm or less.

Next, 0.16 g of hydroquinone monomethyl ether was added to 2790 g of this light liquid, and the first stage deboiling was carried out with a Smith type thin film evaporator made of SUS. The operating conditions were a heating temperature of 60 ° C. and a pressure of 150 mmHg, and a mixed gas of oxygen / nitrogen was blown at a rate of 32 L / Hr from the bottom liquid distillation line.

This bottom liquid is heated at a temperature of 60 ° C. and a pressure of 40 m.
The second stage deboiling was performed under the condition of mHg, and a mixed gas of oxygen / nitrogen (10/90% by volume) was mixed with 3 from the bottom liquid distillation line.
Blow at 2 Nl / Hr. The bottom liquid was 538 g.

When the composition was examined by gas chromatography analysis, it was found to be 92.3% AETHB.

Comparative Example 1 3000 g of the centrifugally extracted light liquid obtained in Example 1 was charged into a SUS316-made treatment tank having an internal volume of 15 liters equipped with a stirrer and a cooling jacket, and 3000 g of distilled water was charged therein, and the temperature was adjusted to 10 ° C. The mixture was stirred for 1 hour while maintaining the above.

Next, 0.16 g of hydroquinone monomethyl ether was added to 2790 g of this light liquid, and the first stage deboiling was carried out with a Smith type thin film evaporator made of SUS. The operating conditions were a heating temperature of 60 ° C. and a pressure of 150 mmHg, and a mixed gas of oxygen / nitrogen was blown at a rate of 32 L / Hr from the bottom liquid distillation line.

This bottom liquid is heated at a temperature of 60 ° C. and a pressure of 40 m.
The second stage deboiling was performed under the condition of mHg, and a mixed gas of oxygen / nitrogen (10/90% by volume) was mixed with 3 from the bottom liquid distillation line.
Blow at 2 Nl / Hr. The bottom liquid was 538 g.

When the composition was examined by gas chromatography analysis, it was found to be 86.5% AETHB.

Example 4 3000 g of the centrifugally extracted light liquid obtained in Example 1 was placed in a SUS316-made treatment tank having an internal volume of 15 liter, equipped with a stirrer and a cooling jacket, and 300 g of a 1% NaOH aqueous solution was placed therein, and the temperature was raised. The mixture was stirred for 1 hour while maintaining the temperature at 10 ° C.

The residual peracetic acid concentration in the obtained crude liquid was 100.
It was below ppm.

Next, 0.21 g of hydroquinone monomethyl ether was added to 2790 g of this light liquid, and the first stage deboiling was carried out in a Smith type thin film evaporator made of SUS. The operating conditions were a heating temperature of 60 ° C. and a pressure of 150 mmHg, and a mixed gas of oxygen / nitrogen was blown at a rate of 32 L / Hr from the bottom liquid distillation line.

This bottom liquid is heated at a temperature of 60 ° C. and a pressure of 40 m.
The second stage deboiling was performed under the condition of mHg, and a mixed gas of oxygen / nitrogen (10/90% by volume) was mixed with 3 from the bottom liquid distillation line.
Blow at 2 Nl / Hr. Moreover, when the composition was examined by gas chromatography analysis, AETHB was 92.4%.
Met.

(Hereinafter, margin)

[Brief description of drawings]

FIG. 1 is a flow chart showing a combination of steps for producing a “purified epoxidized (meth) acrylate compound” of the present invention.

[Explanation of symbols]

(a) a step of washing with water using a device having a short contact time (b) a step of neutralizing with an alkali (c) a heating temperature of 100 ° C. or lower, and a low boiling point component content of 3 to 50 by deboiling under reduced pressure Step of obtaining a liquid by weight% (d) Step of obtaining a liquid having a low boiling point component content of less than 1% by weight by deboiling under a heating temperature of 100 ° C. or lower and (c) a reduced pressure of 1/2 or less of the step

Claims (5)

[Claims] 1. The following general formula: Embedded image The following general formula obtained by epoxidizing cyclohexylmethyl (meth) acrylate having an alkyl substituent or having no alkyl substituent with an organic peracid: << However, in the above general formulas 1 and 2, R ₁ ,
R ₂ is hydrogen or an alkyl group having C _{1 to} C ₅ , R ₃
Has an alkyl substituent represented by hydrogen or a methacryl group or does not have an alkyl substituent 3,4-
The reaction crude liquid containing epoxycyclohexylmethyl (meth) acrylate is washed with (a) a device having a short contact time with water (b) an alkali neutralization process (c) a heating temperature of 100 ° C or lower, a reduced pressure The step of obtaining a liquid having a low boiling point content of 3 to 50% by weight by deboiling under low temperature (d) Heating temperature of 100 ° C or lower, (c) Low boiling point under reduced pressure of 1/2 or less of the step Purified alkyl-substituted or non-alkyl-substituted 3,4-epoxycyclohexylmethyl (meth), characterized in that it is treated in a step to obtain a liquid having a low boiling point content of less than 1% by weight.
Acrylate manufacturing method. 2. A 3,4-epoxycyclohexylmethyl (meth) acrylate with or without alkyl substituents having a heptane test value of less than 0.15% by weight. 3. The method for producing a compound according to claim 1, wherein the organic peracid is peracetic acid. 4. The method for producing a compound according to claim 1, wherein the device having a short contact time is a centrifugal extraction device. 5. The method for producing a compound according to claim 1, wherein R ₁ and R ₂ in the general formulas, 1 and ₂ are hydrogen.