JP2941044B2 - Novel (Nata) acrylate compound and method for producing the same - Google Patents

Description

The present invention relates to a novel (meth) acrylate composition and a method for producing the same.

(Meth) acrylate compounds can be easily homopolymerized or copolymerized with other unsaturated group-containing compounds in the presence of heat, ultraviolet light, ion radiation, and a radical polymerization initiator.
It is also useful as an intermediate material for coating resins.

<< Conventional technology >> (Meta) having conventionally known alicyclic structure
As an acrylate compound, for example, [However, in the formula (1), R represents a hydrogen atom or a methyl group] [However, in the formula (2), R represents a hydrogen atom or a methyl group].

However, polymerized versions of these compounds generally have the disadvantage of lacking flexibility.

In addition, (1) and (2) exist as monomers and are diffused as vapor into the air, and have odor and skin irritation.

In addition, when epoxidation of a compound having a (meth) acrylate group is generally performed, there is a problem that turbidity is easily generated.

This turbidity is due to a polymer that does not dissolve in heptane used in the test called the heptane test.

<< Object of the Invention >> The present invention solves the above problems, provides a (meth) acrylate compound having excellent flexibility, low odor and low skin irritation, and a method for efficiently producing them.

In addition, the inventors have found a method for efficiently producing them without causing turbidity, and have reached the present invention.

《Means for solving the problem》 In order to achieve the above object, as a result of intensive studies,
(I) to (V) were found to be extremely effective compounds.

That is, the present invention provides the following [However, in the formula (I), R is a hydrogen atom or a methyl group, R _a and R _b are a hydrogen atom, a methyl or an ethyl group and can be simultaneously replaced with each group, c is an integer of 4 to 8, n is Is an integer of 1 to 10].

(2) The compound represented by the formula (I) (Wherein, in the formula (II), R is a hydrogen atom or a methyl group, and n is an integer of 1 to 10). The following structure characterized by reacting the compound represented by with acrylic acid or methacrylic acid in the presence of a catalyst [However, in the formulas (I) and (III), R is a hydrogen atom or a methyl group, R _a and R _b are a hydrogen atom, a methyl or an ethyl group and can be simultaneously replaced with each group.
And a method for producing a (meth) acrylate compound having the following structure: [However, R is a hydrogen atom or a methyl group, R _a and R _b are a hydrogen atom, a methyl or an ethyl group and can be simultaneously replaced with each group, c is an integer of 4 to 8, n is an integer of 1 to 10] (Meth) acrylate compounds having the formula (Meth) acrylate compound consisting of a compound having the structure [However, in the formulas (I) and (IV), R is a hydrogen atom or a methyl group, R _a and R _b are a hydrogen atom, a methyl or an ethyl group and can be simultaneously replaced with each group.
An integer of 8 and n is an integer of 1 to 10] In a reaction step for producing a (meth) acrylate compound comprising a compound having Together with the following [Group A] hydroquinone, hydroquinone monomethyl ether,
P-benzoquinone, cresol, t-butylcatechol, 2,4-dimethyl-6-t-butylphenol, 2-
t-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-P
-Cresol, 2,5-dihydroxy-P-quinone, piperidine, ethanolamine, α-nitroso-β-naphthol, diphenylamine, phenothiazine, N-nitrosophenylhydroxylamine, N, N-diethylhydroxylamine and [Group B] phosphorus Acid, potassium phosphate, sodium phosphate, ammonium hydrogen phosphate, pyrophosphate, potassium pyrophosphate, sodium pyrophosphate, 2-ethylhexyl pyrophosphate, potassium 2-ethylhexyl pyrophosphate, sodium 2-ethylhexyl pyrophosphate, A process for producing a (meth) acrylate compound, wherein at least one compound selected from the group consisting of tripolyphosphoric acid, potassium tripolyphosphate and sodium tripolyphosphate is allowed to coexist.

The (meth) acrylate compound (I), which is the first invention of the present invention, is an acrylic or (meth) acrylic ester having an alicyclic structure having an unsaturated double bond.

R in the formula (I) is a hydrogen atom or a methyl group, Ra,
Rb can be simultaneously replaced with a hydrogen atom, a methyl or ethyl group, and c is an integer of 4 to 8, and n is an integer of 1 to 10.

For example, when ring-opening polymerization of ε-caprolactone,
In the formula (I) , Ra and Rb are both hydrogen atoms and c = 5.

n is ε- for acrylic or (meth) acrylic acid
It is the number of moles of caprolactone added.

When trimethylcaprolactone is used, c = 5. n is the number of moles of trimethylcaprolactone added to acrylic or (meth) acrylic acid.

Ra and Rb have a structure in which a hydrogen atom and three methyl groups are arranged at different positions depending on each isomer.

Also, when β-methylδ valerolactone is used as the lactone compound, Ra and Rb are a hydrogen atom and a methyl group, and c is 4.

 Here, n is 1 to 10.

This is because when n is 11 or more, it tends to be too soft.

Compound (IV) is obtained by oxidizing compound (I) with an epoxidizing agent.

Compound (II) is a compound when ε-caprolactone is used as a lactone compound.

The reaction formula for synthesizing compound (I) is shown as follows.

[However, R is a hydrogen atom or a methyl group, Ra and Rb are a hydrogen atom, a methyl and an ethyl group and can be simultaneously replaced with each group, c is an integer of 4 to 8, n is an integer of 1 to 10.] Is an esterification reaction in the presence of a catalyst.

 Hereinafter, the esterification reaction will be described in detail.

The molar ratio in the esterification reaction between the lactone adduct (III) and (meth) acrylic acid is theoretically 1/1, but is actually in the range of 1/1 to 10/1 as in the present invention. , Preferably in the range of 1/1 to 1/3.

The molar ratio of the esterification reaction is lactone adduct (III) /
When (meth) acrylic acid is less than 1/10, it is preferable in terms of selectivity and conversion of the lactone adduct (III), but the loss due to polymerization of acrylic acid or methacrylic acid itself is large, and unreacted acrylic There are drawbacks, such as that the recovery of the acid or methacrylic acid is very expensive.

Conversely, the molar ratio of the esterification reaction is
When (I) / (meth) acrylic acid exceeds 10/1, the loss due to polymerization of acrylic acid or methacrylic acid decreases, but it is not preferable because a large amount of energy is required to recover the lactone adduct (III).

The catalyst used here can be arbitrarily selected from those known as commonly used esterification catalysts such as sulfuric acid, P-toluenesulfonic acid, and boron trifluoride. P-toluenesulfonic acid is particularly preferred from the viewpoints of low corrosion resistance and the like.

The amount of the catalyst used is 0.001 to 10% by weight based on the starting material,
Preferably it is 0.01 to 1.0% by weight.

When the amount of the catalyst is less than 0.001% by weight, there are disadvantages such as a slow reaction rate and a poor yield.
It is meaningless because the effect of accelerating the reaction is not improved even if it exceeds 10% by weight.

Since water is inevitably generated as the esterification reaction proceeds, it is necessary to remove this out of the system. Water produced by the reaction may be separated by distillation as it is, for example, toluene, benzene, xylene, n
It is advantageous to use an organic solvent which forms an azeotrope with water, such as hexane, methyl isobutyl ketone, and which is substantially immiscible with water, as the entrainer.

It is recommended that the entrainer be added during the initial preparation.

The amount of the entrainer used is 1 to 10 times, preferably 2 to 5 times the theoretical amount.

The entrainer distilled with water can be separated and recycled.

The reaction temperature is from 65 to 65 from the viewpoint of shortening the reaction time and preventing polymerization.
Advantageously, it is carried out at 150 ° C, preferably at 75-120 ° C.

The following polymerization inhibitors are added to prevent thermal polymerization of (meth) acrylic acid.

Examples of the polymerization inhibitor that can be used include hydroquinone, P-methoxyphenol, and the like.
2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, P-benzoquinone, 2,5-dihydroxy-P-quinone, copper salts and the like can be used. Hydroquinone and P-methoxyphenyl are preferred from the viewpoint of stability and the like.

Amines such as phenothiazine and piperidine are also effective.

Further, the effect is higher if the compounds listed in the following [Group A] and [Group B] are used in combination with the molecular oxygen-containing gas.

That is, [Group A] hydroquinone, hydroquinone monomethyl ether,
P-benzoquinone, cresol, t-butylcatechol, 2,4-dimethyl-6-t-butylphenol, 2-
t-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-P
-Cresol, 2,5-dihydroxy-P-quinone, piperidine, ethanolamine, α-nitroso-β-naphthol, diphenylamine, phenothiazine, N-nitrosophenylhydroxylamine, N, N-diethylhydroxylamine and [Group B] phosphorus Acid, potassium phosphate, sodium phosphate, ammonium hydrogen phosphate, pyrophosphate, potassium pyrophosphate, sodium pyrophosphate, 2-ethylhexyl pyrophosphate, potassium 2-ethylhexyl pyrophosphate, sodium 2-ethylhexyl pyrophosphate, Tripolyphosphoric acid, potassium tripolyphosphate and sodium tripolyphosphate.

The amount of the polymerization inhibitor as described above is 0.001 to 5.0% by weight, preferably 0.01 to 1.0% by weight, based on (meth) acrylic acid.

When the amount is less than 0.001% by weight, the effect of inhibiting the polymerization is small. Conversely, when the amount is more than 5.0% by weight, the effect is not improved, so that it is useless.

The polymerization inhibitor is dissolved in (meth) acrylic acid immediately before the esterification reaction.

The reaction is preferably carried out at normal pressure or slightly reduced pressure.

The end point of the reaction is preferably confirmed by the amount of dehydration or gas chromatography.

In order to separate the product (meth) acrylate compound from the mixed solution after the completion of the reaction, first, the mixed solution after the completion of the reaction is neutralized and washed with water, and then the low boiling components are removed with a thin film evaporator or the like. It is preferable to remove high-boiling components with a thin film evaporator or the like.

If low boiling components are removed without neutralizing the reaction crude solution, the loss due to polymerization of (meth) acrylate is large, and unreacted (meth) acrylic acid can be removed, so neutralization before removing low boiling components Is preferred.

As an aqueous alkaline solution used for neutralization, for example, NaO
Solutions such as H, KOH, K ₂ CO ₃ , Na ₂ CO ₃ , NaHCO ₃ , KHCO ₃ , NH _{3 and} the like can be used, the concentration of which can be freely selected within a wide range.

In some cases, by adjusting the pH, the polymerization inhibitor present in the reaction crude liquid can be removed.

For example, when PH12 is used when hydroquinone is used as a polymerization inhibitor and an aqueous solution of sodium hydroxide is used as an alkaline aqueous solution, most of hydroquinone can be transferred from an organic layer to an aqueous layer. It is desirable to further wash with water in order to remove salts formed by the neutralization.

Neutralization and rinsing can be carried out within a temperature range of 10-90 ° C, with temperatures of 10-50 ° C being advantageous.

Since the reaction is carried out at normal pressure or slightly reduced pressure, a pressure-resistant container is not required, but it is preferable to use a corrosion-resistant material such as stainless steel or glass-lined steel plate.

Further, the compound (I) can be produced not only from the esterification reaction as described above but also from the (meth) acrylate ester by a transesterification reaction.

In this case, as the (meth) acrylate used, known (meth) acrylates such as methyl, ethyl, n-propyl, i-propyl and butyl can be used. Taking into account the ease of removal of the alcohol generated as a result of the transesterification reaction, methyl methacrylate, methyl acrylate and the like are preferred.

The epoxidized (meth) acrylate compound (IV) in the composition according to another invention of the present invention is obtained by epoxidizing the double bond of the cyclohexenyl moiety in the formula (I).

Therefore, R, Ra, Rb, c and n are the same as those in the formula (I).

As the epoxidizing agent for epoxidation, a peracid or various hydroperoxides can be used.

For example, the peracids include formic acid, peracid, perpropionic acid, perbenzoic acid, trifluoroperacetic acid and the like.

Of these, peracetic acid is a preferred epoxy epoxidizing agent because it is industrially manufactured in large quantities, is available at low cost, and has high stability.

Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide, metachloroperbenzoic acid and the like. At the time of epoxidation, a catalyst can be used in combination as needed.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.

In the case of hydroperoxides, a catalyst effect is obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. Can be.

The epoxidation reaction is performed by adjusting the presence or absence of a solvent and the reaction temperature in accordance with the apparatus and the physical properties of the raw materials.

The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used.

Regarding peracetic acid, which is a preferred epoxidizing agent, 0
A range of -70 ° C is preferred.

If the temperature is lower than 0 ° C., the reaction is slow, and if the temperature is higher than 70 ° C., decomposition of peracetic acid occurs.

In the case of tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate, which is an example of hydroperoxide, the temperature is 20 ° C. to 150 ° C. for the same reason.
Is preferred.

The solvent can be used for the purpose of lowering the viscosity of the raw material, stabilizing the epoxidizing agent by dilution, and the like.

In the case of peracetic acid, an aromatic compound, an ether compound, an ester compound or the like can be used.

In particular, ethyl acetate or xylene is a preferred solvent.

For example, in the case of a peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid may be used as a catalyst.

Although the reaction molar ratio of the oxidizing agent to the composition comprising the compound represented by the formula (I) is theoretically 1/1, in the method of the present invention, it is in the range of 0.1 to 10, preferably 0.5 to 10 And more preferably in the range of 0.8 to 1.5.

When the molar ratio of the oxidizing agent to the composition comprising the compound represented by the formula (I) exceeds 10, it is preferable in terms of the conversion rate, the reaction time, and the loss due to polymerization. There are drawbacks such as that the reaction and the selectivity of the oxidizing agent and the cost of collecting and recovering the unreacted oxidizing agent are large.

Conversely, when the molar ratio of the reaction between the oxidizing agent and the composition comprising the compound represented by the formula (I) is 0.1 or less, the selectivity of the oxidizing agent, the conversion, and the suppression of the side reaction due to the oxidizing agent are suppressed. Although preferred, there are drawbacks such as loss due to polymerization, and high cost in recovering the unreacted composition comprising the compound represented by formula (I).

The reaction temperature is lower than the upper limit such that the epoxidation reaction takes precedence over the decomposition reaction of the oxidizing agent.For example, when peracetic acid is used, the reaction temperature is 70 ° C or lower, and when tertiary butyl hydroperoxide is used, the temperature is 150 ° C or lower. preferable.

If the reaction temperature is low, it takes a long time to complete the reaction. Therefore, when peracetic acid is used, the reaction is preferably performed at a lower limit of 0 ° C. or tertiary butyl hydroperoxide at 20 ° C. or more.

In addition, during the epoxidation reaction, an organic acid due to a by-product from the oxidizing agent, an alcohol, and a side reaction in which the epoxy group is opened with water occurs. Select from the appropriate temperature range.

The reaction pressure is generally operated under normal pressure, but it can also be carried out under elevated or low pressure.

 The reaction can also be performed in the presence of a solvent.

The reaction in the presence of a solvent is preferred because it has the effects of lowering the viscosity of the reaction crude liquid and stabilizing the oxidizing agent by diluting it.

Examples of the solvent used include aromatic compounds such as benzene, toluene and xylene, halides such as chloroform, dimethyl chloride, carbon tetrachloride, and chlorobenzene; esterified compounds such as ethyl acetate and butyl acetate; ketone compounds such as acetone and methyl ethyl ketone. 1,
An ether compound such as 2-dimethoxyethane can be used.

The amount of the solvent used is preferably 0.5 to 5 times the amount of cyclohexenyl (meth) acrylate.

When the amount is less than 0.5 times, the effect of stabilization by diluting the oxidizing agent is small. Conversely, when the amount is more than 5 times, the stabilizing effect does not increase so much and a large cost is required for solvent recovery. So it's wasted.

One of the points of the present invention resides in that a specific polymerization inhibitor is used together with a molecular oxygen-containing gas when performing an epoxidation reaction.

It is the same as that described for the esterification reaction.

In general, when the reaction is carried out in a system to which no inhibitor is added, a polymer is produced in the purification step of obtaining the product, or the product becomes cloudy.

Also, opacity occurs when the product is added to heptane.
This is because a small amount of the polymer becomes insoluble in heptane and precipitates (abbreviated as HT).

In particular, when used in a combination of three or more compounds specified in the present invention, the effect of the compound of each group alone or in combination with only two compounds from each group is far superior, and the synergistic effect is extremely large. That is remarkable.

In the present invention, air is usually used as molecular oxygen, and charged into a reactor.

A predetermined effect can be obtained by blowing directly into the liquid or into the gas phase.

The blowing amount can be arbitrarily selected, but if it is too large, solvent loss is not preferred.

In addition, nitrogen is usually blown into the system together with air to avoid the formation of an explosive mixture in the system. In this case, the oxygen concentration in the blown gas is 0.01% (by volume) or more, preferably 3%. (Capacity) or more. The higher the oxygen concentration, the better the effect, but the upper limit is the lower limit oxygen concentration under explosion in the system, and the value varies depending on the solvent used.

Nitrogen injection is not always required to be at the same position as air, but it is important for safety to take measures on equipment so that explosive air-fuel mixture is not locally formed in the system.

After the reaction is completed, the crude epoxidation reaction solution can be purified by removing a solvent, a low-boiling substance, unreacted raw materials, a catalyst, etc., neutralizing, treating with an adsorbent or an ion exchange resin, or the like.

In particular, when an organic peracid is used as the oxidizing agent, it is preferable that the reaction crude liquid is washed with neutralized water.

This is because polymerization is extremely easy if low boiling components such as a solvent are removed without neutralization.

As an aqueous alkaline solution used for neutralization, for example, NaOH,
An aqueous solution of an alkaline substance such as KOH, K ₂ CO ₃ , Na ₂ CO ₃ , NaHCO ₃ , KHCO ₃ , NH ₃ and the like can be used.

The concentration at the time of use can be freely selected within a wide range.

From the viewpoint of liquid separation, it is preferable to use an aqueous solution of NaOH, an aqueous solution of Na ₂ CO _{3, or an} aqueous solution of NaHCO ₃ .

The neutralization and washing with water are preferably performed at a temperature in the range of 10 to 90 ° C, preferably 10 to 50 ° C.

For example, it is known that a combination of hydroquinone, hydroquinone monomethyl ether and molecular oxygen gas is effective in preventing the polymerization of so-called acrylic acid or acrylic acid ester. The ban effect is compared below.

The reason that the method of the present invention adds at least one compound of [Group B] as an essential component is considered to be effective in suppressing the generation of a radical source due to decomposition of a small amount of oxidizing agent even though the amount is small. That is because

Next, the amount of the polymerization inhibitor used is the type of the target compound,
It can be arbitrarily changed according to the conditions in the manufacturing process.
The compound of group [B] is 0.005 to 5% by weight, more preferably 0.001 to 0.1% by weight, based on the composition comprising the compound represented by the formula (I), which is a reaction raw material. 1% by weight, more preferably 0.01 to 0.2% by weight.

The addition method may be a powder as it is, or may be added after being dissolved in a solvent.

The reaction is carried out continuously or batchwise. In the case of continuous reaction, a piston flow type is preferred.

At this time, the polymerization inhibitor used in the method of the present invention may be charged alone, but in the case of a powder, it is preferable to charge it after dissolving it in a solvent.

 Moreover, you may melt | dissolve in raw material ester and may charge.

The same applies to the case of the batch system, but the semi-batch system in which the oxidizing agent is charged sequentially is desirable.

The point of the present invention is to prevent polymerization in the reaction step in order to obtain a product in which polymerization is minimized, but the present invention can be effectively used as it is in the purification step.

After the reaction is completed, the crude epoxidation reaction solution can be purified by removing a solvent, a low-boiling substance, unreacted raw materials, a catalyst, etc., neutralizing, treating with an adsorbent or an ion exchange resin, or the like.

In particular, when an organic peracid is used as the oxidizing agent, it is preferable that the reaction crude liquid is washed with neutralized water.

This is because polymerization is extremely easy if low boiling components such as a solvent are removed without neutralization.

As an aqueous alkaline solution used for neutralization, for example, NaOH,
An aqueous solution of an alkaline substance such as KOH, K ₂ CO ₃ , Na ₂ CO ₃ , NaHCO ₃ , KHCO ₃ , NH ₃ and the like can be used.

The concentration at the time of use can be freely selected within a wide range.

From the viewpoint of liquid separation, it is preferable to use an aqueous solution of NaOH, an aqueous solution of Na ₂ CO _{3, or an} aqueous solution of NaHCO ₃ .

The neutralization and washing with water are preferably performed at a temperature in the range of 10 to 90 ° C, preferably 10 to 50 ° C.

In order to remove low boiling components from the neutralized or washed crude reaction liquid, it is preferable to use a thin film evaporator or the like after adding a polymerization inhibitor.

In particular, the compound selected from the [Groups A and B] contained in the crude reaction solution may be extracted into the lower layer water and the content in the neutralized upper layer solution may be reduced. It is preferable to replenish the compound of the formula (1) in an appropriate amount. It is also desirable to blow molecular oxygen into the system during the neutralized water washing.

In the neutralized water washing step, it is important to remove the residual organic peracid while neutralizing and removing the organic acid.

In order to operate the following low boiling point component removing step stably,
It is necessary to repeatedly wash with neutralized water until the residual organic peracid content in the neutralized upper layer solution becomes 0.1% or less, preferably 0.01% or less.

Therefore, when washing with neutralized water in a continuous manner, it becomes a multi-stage type,
Usually, if the number of stages is 3 to 5, the concentration of the organic peracid can be reduced to a specified value or less.

In the case of a multi-stage system, it is preferable that the final stage be completely washed with water or an alkaline aqueous solution of at most about 1%.

This is because when the bottom liquid after removing the low-boiling components is converted into a product as it is, an alkali metal is mixed into the product to affect the quality.

The same applies to the case where the neutralization is repeated in batches. When the neutralized water is washed in a continuous manner, it is not problematic to use the lower layer water for pre-neutralization in a countercurrent manner, and it is more economical.

The amount of alkali used in the neutralized water washing is 0.5 to 3 times, preferably 1.1 to 1.5 times, the equivalent ratio to the total amount of the organic peracid and the organic acid in the reaction crude liquid. Increasing the amount is not economical.

In addition, if the equivalent ratio is reduced more than necessary, a large amount of water is required to remove the organic peracid or the organic acid, so it is not advisable, and the loss of dissolution in lower water such as a solvent increases.

 After the neutralizing washing step, the solvent is removed.

(De-boiling step) A thin-film evaporator is usually used for de-boiling, but the heating temperature is preferably from 50 to 180 ° C, and more preferably from 60 to 100 ° C, from the viewpoint of preventing polymerization.

The pressure can be arbitrarily selected depending on the physical properties of the low-boiling components, but it is generally operated at reduced pressure in relation to the heating temperature.

The place where the molecular oxygen is introduced into the evaporator can be arbitrarily selected, but is usually blown from the line from which the bottom liquid distills.

The injection amount can be selected arbitrarily, but the upper limit is naturally determined from the viewpoint of the vacuum system capacity, whether the bottom liquid flows down stably, or the recovery loss when collecting the distilled low-boiling components with a condenser. Limited. The bottom liquid obtained in the deboiling step has a purity of only 94 to 96%, but as a result of the present invention, the HT is of such a quality that HT is transparent or slightly clouded.

Therefore, it can be used as a product in ordinary applications.

Next, in order to obtain a product with higher purity, a commercialization process is performed. The commercialization process is a process for completely removing the remaining low-boiling components, and is performed in the same manner as the low-boiling process, but is generally performed under a high vacuum with an increased degree of reduced pressure.

<< Effect of the Invention >> According to the present invention, an epoxy compound having an acrylic group and having low skin irritation was able to be obtained.

At the same time, a means for efficiently synthesizing new epoxy compounds was established.

Synthesis Example-1 994.0 gr of 3-cyclohexenemethanol and ε were placed in a separable flask equipped with a stirrer, an N ₂ introduction tube, and a cooling tube.
1007 gr of caprolactone and 2.34 gr of 1% tin chloride (ε-caprolactone solution) were added.

This was heated to 170 ° C. and reacted for 10 hours. After completion of the reaction, the amount of ε-caprolactone was analyzed by gas chromatography and found to be 30.11%. As a result of examining the properties after cooling, it was confirmed that the compound had the following structure.

 The IR chart of the obtained compound is shown in FIG.

Example -1 The compound 680 gr obtained in Synthesis Example 1, methacrylic acid 324 gr, paramethoxyphenol 0.91 gr, sulfuric acid 6.9 gr, heptane 400 were placed in a two reactor equipped with a dehydration tube, a gas introduction tube and a stirrer.
I put gr.

Next, air was charged from the gas introduction tube using a 10 ml / Min rotor meter.

The temperature was gradually increased, and heptane and water were continuously removed by azeotropic distillation. After heptane and water were separated, heptane was returned to the reaction system.

 After the dehydration reaction was performed for 10 hours, it was cooled.

 After cooling, 300 ml of a 10% aqueous NaOH solution was added, and the mixture was stirred for 10 minutes.

After standing for 30 minutes, the upper layer and the lower layer were separated. After removing the lower layer, 300 ml of purified water was added, and the mixture was stirred for 10 minutes and left standing for 60 minutes to separate into an upper layer and a lower layer.

The lower layer was removed, 300 ml of purified water was added again, and the mixture was stirred for 10 minutes, allowed to stand for 60 minutes, and separated into an upper layer and a lower layer. The lower layer was removed, and 0.9 g of paramethoxyphenol was added to the upper layer and uniformly dissolved.

Next, the upper layer solution was transferred to a 1 eggplant flask and set on a rotary evaporator.

Deboiling was performed while air was leaked at 100 mmHg to 10 mmHg and 80-100 ° C for about 3 hours.

H-nmr, IR and GPC of the obtained compound are shown in FIG. 1 and FIG.
FIG. 3 and FIG.

In Fig. 1 δppm 7.3 ~ 5.3 4H Ha Hb Hk 4.4 ~ 3.9 4H H _D H _I 2.7 ~ 1.2 18H H _H H _J H _E H _F H _{G From} Fig. 2 ν _co 1709 1718cm ^-1 Compare with Fig. 4 Then, the absorption of the OH value of 3418 cm ^-1 has disappeared, indicating that esterification has progressed.

From the above, the structure of this compound is It is clear that

FIG. 3 shows that the composition has a distribution of n = 1, 2, 3, 4, 5,.

Example 2 296.1 gr of the compound (A) obtained in Example 1, 600 gr of ethyl acetate and hydroquinone methyl ether were placed in a two-jacketed reactor equipped with a stirrer, a cooling pipe, a thermometer, a gas introduction pipe, and a dropping funnel. , 0.15 gr, and the mixture was heated to 30 ° C. and stirred uniformly.

Next, 304.0 gr of peracetic acid (concentration 30%, ethyl acetate solvent) and 1.4 gr of sodium 2-ethylhexyltetrapolyphosphate (concentration 20%, acetic acid solution) were added to the dropping funnel.

Peracetic acid was added dropwise over about 2 hours while blowing 1 / h of air from the gas inlet tube.

Since the reaction temperature was exothermic, the temperature of the reaction system gradually increased to about 40 ° C.

After this, the reaction system controls the temperature of the circulating water to 40 ° C.
It was fixed.

 After the addition of peracetic acid was completed, the mixture was left at 40 ° C. for 1 hour.

Next, 750 gr of a 10% aqueous NaOH solution was added thereto, and the mixture was stirred for 10 minutes and allowed to stand for 30 minutes.

 After standing, the separated lower layer was extracted.

Next, 750 gr of water was added, and the mixture was stirred at 40 ° C. for 10 minutes and left standing for 60 minutes.

 After standing, the separated lower layer was removed.

 Similarly, it was washed once more with water.

Next, 0.014 gr of hydroquinone monomethyl ether was added to the washed upper layer solution.

Next, the upper layer liquid was placed in a two eggplant-shaped flask and subjected to deboiling with a glass Smith thin film evaporator equipped with a gas inlet tube.

Operating conditions are air 100 / h, heating temperature 100 ° C, pressure 150mmHg.
Was performed.

 The properties of the obtained product were as follows.

APHA 50 Oxirane oxygen 5.05% Viscosity (cp / 25 ° C) 40 FIG. 5 is an NMR measurement chart of this compound, and FIG.
It is a PC measurement chart.

From the above results, it was confirmed that this compound had the following structural formula.

Example 3 Synthesis was performed in the same manner as in Example 1, except that acrylic acid 227.0 gr was used instead of methacrylic acid 324 gr.

 FIG. 7 is an NMR measurement chart of this compound.

From the above results, it was confirmed that this compound had the following structural formula.

Example 4 The same procedure was performed as in Example 2 except that 280.6 gr of compound (B) was added instead of compound (A) in Example 2.

 The properties of the obtained product were as follows.

APHA 40 Oxirane oxygen 5.20% Viscosity (cp / 25 ° C) 50 Fig. 8 is NMR measurement chart of this compound, Fig. 9 is G
It is a PC measurement chart.

From the above results, it was confirmed that this compound had the following structural formula.

Comparative Example 1 In Example 2, the glass was subjected to deboiling by a glass Smith thin film evaporator without blowing air and without adding hydroquinone monomethyl ether.

The operation was performed at a heating temperature of 100 ° C. and a pressure of 150 mmHG, but the operation was interrupted because a polymer adhered to the evaporator surface.

[Brief description of the drawings]

FIG. 1 is a chart of H-NMR of the compound obtained in Example 1, FIG. 2 is a chart of IR, and FIG. 3 is a chart of GPC. FIG. 4 is an IR chart of the compound obtained in Synthesis Example-1. FIG. 5 is an NMR measurement chart of the compound obtained in Example-2, and FIG. 6 is a GPC measurement chart thereof. FIG. 7 is an NMR measurement chart of the compound obtained in Example-3. FIG. 8 is an NMR measurement chart of the compound obtained in Example 4, and FIG. 9 is a GPC measurement chart thereof.

Claims (6)

(57) [Claims] 1. The following structure [However, in the formula (I), R is a hydrogen atom or a methyl group, R _a and R _b are a hydrogen atom, a methyl or an ethyl group and can be simultaneously replaced with each group, c is an integer of 4 to 8, n is Is an integer of 1 to 10]. 2. The compound represented by the formula (I) (Wherein, in the formula (II), R is a hydrogen atom or a methyl group, and n is an integer of 1 to 10). The (meth) acrylate compound according to claim 1, wherein 3. The following formula (III) The following structure characterized by reacting the compound represented by with acrylic acid or methacrylic acid in the presence of a catalyst [However, in the formulas (I) and (III), R is a hydrogen atom or a methyl group, R _a and R _b are a hydrogen atom, a methyl or an ethyl group and can be simultaneously replaced with each group.
An integer of from 1 to 8 and n is an integer of from 1 to 10]. 4. The following structure [However, R is a hydrogen atom or a methyl group, R _a and R _b are a hydrogen atom, a methyl or an ethyl group and can be simultaneously replaced with each group. C is an integer of 4 to 8, n is an integer of 1 to 10. (Meth) acrylate compounds having the formula: 5. The formula (IV) (Wherein, R is a hydrogen atom or a methyl group, and n is an integer of 1 to 10).
Acrylate compounds. 6. The following structure (Meth) acrylate compound comprising a compound having [However, in the formulas (I) and (IV), R is a hydrogen atom or a methyl group, R _a and R _b are a hydrogen atom, a methyl or an ethyl group and can be simultaneously replaced with each group.
An integer of 8 and n is an integer of 1 to 10] In a reaction step for producing a (meth) acrylate compound comprising a compound having Together with the following [Group A] hydroquinone, hydroquinone monomethyl ether,
P-benzoquinone, cresol, t-butylcatechol, 2,4-dimethyl-6-t-butylphenol, 2-
t-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-P
-Cresol, 2,5-dihydroxy-P-quinone, piperidine, ethanolamine, α-nitroso-β-naphthol, diphenylamine, phenothiazine, N-nitrosophenylhydroxylamine, N, N-diethylhydroxylamine and [Group B] phosphorus Acid, potassium phosphate, sodium phosphate, ammonium hydrogen phosphate, pyrophosphate, potassium pyrophosphate, sodium pyrophosphate, 2-ethylhexyl pyrophosphate, potassium 2-ethylhexyl pyrophosphate, sodium 2-ethylhexyl pyrophosphate, A method for producing a (meth) acrylate compound, wherein at least one compound selected from the group consisting of tripolyphosphoric acid, potassium tripolyphosphate and sodium tripolyphosphate is allowed to coexist.