JP7355733B2 - Composition containing isobornyl (meth)acrylate and method for producing the same - Google Patents

Description

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

Isobornyl (meth)acrylates are used, for example, in products such as printing inks, binders for curable paints, adhesives, and photocurable diluents. Conventionally, as a method for producing isobornyl (meth)acrylate, a method in which (meth)acrylic acid and camphene are reacted is known (Patent Documents 1 and 2). Since the reaction mixture containing isobornyl (meth)acrylate obtained by such a reaction contains unreacted (meth)acrylic acid and camphene, for example, in Patent Document 1, after distilling the reaction mixture under reduced pressure, It is disclosed that washing with water results in a composition containing isobornyl (meth)acrylate having a purity of 99.9% by gas chromatography.

Japanese Patent Application Publication No. 2006-69944 Japanese Patent Application Publication No. 2009-149559

As the quality of the above-mentioned products becomes higher, there is a demand for higher purity isobornyl (meth)acrylate as a raw material. In particular, unreacted (meth)acrylic acid contained in the reaction mixture containing isobornyl (meth)acrylate obtained by reacting (meth)acrylic acid and camphene may cause problems with the above products (e.g., coloration, storage stability). This is thought to be a factor that causes a decrease in the amount of unreacted (meth)acrylic acid, etc., and there is a strong desire in the market for products with reduced amounts of unreacted (meth)acrylic acid.

In addition, in order to reduce unreacted (meth)acrylic acid, it is considered effective to wash the reaction mixture with alkaline water as in Patent Document 1, but the production method Since a large amount of wastewater is generated, there is a problem from the viewpoint of environmental burden.

The present invention has been made in view of the above-mentioned circumstances, and is a highly pure mixture containing isobornyl (meth)acrylate obtained by reacting (meth)acrylic acid with camphene, in which unreacted acrylic acid is reduced. An object of the present invention is to provide a manufacturing method for obtaining a composition containing isobornyl (meth)acrylate.

Another object of the present invention is to provide a composition containing highly purified isobornyl (meth)acrylate in which unreacted acrylic acid is reduced.

The present invention is a method for producing a composition containing isobornyl (meth)acrylate, which comprises the steps of: obtaining a reaction mixture containing isobornyl (meth)acrylate by reacting (meth)acrylic acid and camphene; neutralizing the mixture with a solid base and distilling the mixture, the purity of the isobornyl (meth)acrylate by gas chromatography is 99.5% or more, and the amount of unreacted (meth)acrylic acid is 0.02% by weight. % or less of isobornyl (meth)acrylate.

Furthermore, the present invention is characterized in that the purity of isobornyl (meth)acrylate by gas chromatography is 99.5% or more, and the proportion of (meth)acrylic acid is more than 0% by weight and not more than 0.02% by weight. The present invention relates to a composition containing isobornyl (meth)acrylate.

According to the production method of the present invention, high purity isobornyl (meth)acrylate with reduced unreacted acrylic acid is obtained from a mixture containing isobornyl (meth)acrylate obtained by reacting (meth)acrylic acid and camphene. Therefore, the composition containing the isobornyl (meth)acrylate is useful as a raw material for products such as printing inks, binders for curable paints, adhesives, and photocuring reaction diluents. It is.

Furthermore, according to the production method of the present invention, a large amount of alkaline water is not required when neutralizing unreacted (meth)acrylic acid, so a complicated post-treatment step when treating a large amount of alkaline wastewater is eliminated. This is unnecessary and beneficial from the perspective of environmental impact.

<Method for producing a composition containing isobornyl (meth)acrylate>
The method for producing a composition containing isobornyl (meth)acrylate of the present invention includes the steps of obtaining a reaction mixture containing isobornyl (meth)acrylate by reacting (meth)acrylic acid and camphene, and converting the obtained reaction mixture into a solid. The process includes a step of neutralizing with a base and a step of distilling, and the purity of the isobornyl (meth)acrylate by gas chromatography is 99.5% or more, and the amount of unreacted (meth)acrylic acid is 0.02% by weight or less. This is a manufacturing method for obtaining a composition containing a certain isobornyl (meth)acrylate. In the present invention, isobornyl (meth)acrylate means isobornyl acrylate and/or isobornyl methacrylate. Moreover, (meth)acrylic acid means acrylic acid and/or methacrylic acid.

<Step of obtaining a reaction mixture containing isobornyl (meth)acrylate>
In the step of obtaining the reaction mixture, in the reaction between (meth)acrylic acid and camphene, the amount of (meth)acrylic acid is preferably 0.8 to 2.5 mol, preferably 0.9 to 2.5 mol, per 1 mol of camphene. More preferably, it is 2 moles. The reaction temperature is preferably 10 to 75°C, more preferably 35 to 60°C, from the viewpoint of quickly mixing camphene and (meth)acrylic acid to increase productivity. The reaction time cannot be determined unconditionally because it varies depending on the reaction temperature and the reaction conversion rate described below, but it is usually about 2 hours or more and 24 hours or less.

In the step of obtaining the reaction mixture, a solvent may be used for the reaction of (meth)acrylic acid and camphene. The solvent is not particularly limited, but is preferably an organic solvent that is inactive within the reaction system. Examples of the organic solvent include cyclohexane, hexane, toluene, ethylbenzene, methylcyclohexane, and ethylcyclohexane. The amount of the solvent used is not particularly limited, but is usually about 100 parts by weight or less based on 100 parts by weight of the total amount of camphene and (meth)acrylic acid.

The reaction between (meth)acrylic acid and camphene is preferably carried out in the presence of a polymerization inhibitor and/or an antioxidant. Examples of the polymerization inhibitor and/or antioxidant include quinone compounds such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, and p-tert-butylcatechol; 2,6-di-tert-butylphenol, and 2,4-di- Alkylphenol compounds such as tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol; alkyl Amine-based compounds such as diphenylamine, N,N'-diphenyl-p-phenylenediamine, and phenothiazine; Hindered amine-based compounds such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl; Metals Examples include copper-based compounds such as copper, copper sulfate, cuprous chloride, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate, thioether-based compounds, and phosphorus-based compounds. The polymerization inhibitor and/or antioxidant may be used alone or in combination of two or more.

The amount of polymerization inhibitor and/or antioxidant used is preferably 0.0001 to 1 part by weight, and 0.001 to 0.1 part by weight, based on 100 parts by weight of (meth)acrylic acid. It is more preferable.

It is preferable to use a catalyst for the reaction between (meth)acrylic acid and camphene. Examples of the catalyst include acidic catalysts such as p-toluenesulfonic acid, methanesulfonic acid, and sulfuric acid; solid acid catalysts, and the like.

Examples of solid acid catalysts include strongly acidic cation exchange resins, sulfuric rare earth metal salts such as zirconia sulfate, and rare earth metal complexes such as lanthanum triflate. The solid acid catalyst is preferably dried from the viewpoint of suppressing the reaction between water, camphene, and (meth)acrylic acid.

The amount of the catalyst to be used is determined depending on the catalytic activity and the desired reaction rate, but it is preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of camphene and (meth)acrylic acid. More preferably, the amount is 5 parts by weight.

In the step of obtaining the reaction mixture, the reaction method for reacting (meth)acrylic acid and camphene may be a batch method in which all raw materials are charged in a single reactor to complete the reaction, or a reaction method in which all raw materials are charged in a single reactor to complete the reaction, or A continuous type may be used, in which raw materials are continuously supplied to the reactor for continuous reaction, or a circulation type, which includes a reactor and a mixing tank and allows the raw materials to be circulated between the reactor and the mixing tank and reacted in the reactor. It may be.

The reaction equipment used for the reaction in the circulation type is, for example, equipped with a reactor filled with a catalyst such as a solid acid catalyst, and a blending tank for adding camphene to (meth)acrylic acid, and the reactor and the blending tank are A reactor can be used in which these are connected so that a mixture of (meth)acrylic acid and camphene is circulated between them. In this reactor, camphene is added dropwise to (meth)acrylic acid charged in a blending tank, and a mixture containing (meth)acrylic acid and camphene is circulated between the blending tank and the reactor. React at

In the step of obtaining the reaction mixture, the reaction conversion rate of isobornyl (meth)acrylate in the reaction between (meth)acrylic acid and camphene is checked by gas chromatography at appropriate times, and when a predetermined reaction conversion rate is reached, the reaction is stopped. Preferably, the reaction mixture is completed to obtain a reaction mixture containing isobornyl (meth)acrylate. When the reaction conversion rate increases, the reaction rate decreases, so when considering the industrial productivity of isobornyl (meth)acrylate, the predetermined reaction conversion rate is preferably 50% or more, and 80% or more. It is more preferable that there be.

<Step of neutralizing the reaction mixture with a solid base and step of distilling>
The reaction mixture containing isobornyl (meth)acrylate obtained by the reaction of (meth)acrylic acid and camphene is subjected to a step of neutralization with a solid base and a step of distillation to obtain a reaction mixture containing isobornyl (meth)acrylate by gas chromatography. A composition containing isobornyl (meth)acrylate having a purity of 99.5% or more and unreacted (meth)acrylic acid of 0.02% by weight or less is obtained.

Either of the step of neutralizing with a solid base and the step of distilling may be performed first, or each step may be performed repeatedly. From the viewpoint that unreacted (meth)acrylic acid can be efficiently removed by performing a step of distilling a reaction mixture containing isobornyl (meth)acrylate obtained by the reaction of (meth)acrylic acid and camphene, the above-mentioned distillation The step is preferably carried out before the step of neutralizing with a solid base.

Examples of solid bases include alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides, alkaline earth metal carbonates, alkaline earth metal hydrogen carbonates, alkaline earth metal hydroxides, alkaline earth Examples include metal oxides. Among these, alkali metal carbonates and alkaline earth metal carbonates are preferred. The alkali metal is preferably lithium, sodium, or potassium. As the alkaline earth metal, magnesium, calcium, and barium are preferable. The solid bases may be used alone or in combination of two or more.

When the step of distilling is performed before the step of neutralizing with a solid base, most of the unreacted (meth)acrylic acid can be distilled off, so the amount of solid base used is equal to the amount of (meth)acrylic acid used. From the viewpoint of increasing the contact probability of and efficiently promoting the neutralization reaction, the amount is preferably 0.01 to 10 parts by weight, and preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the reaction mixture containing isobornyl (meth)acrylate. More preferably, the amount is 5 parts by weight, and even more preferably 0.1 to 2 parts by weight. On the other hand, when the step of neutralizing with a solid base is performed before the step of distilling, it is difficult to make a general statement because the proportion of unreacted (meth)acrylic acid in the reaction mixture varies depending on the reaction conversion rate. Usually, the amount of the solid base used is preferably 20 to 5000 parts by weight, more preferably 50 to 2000 parts by weight, and 100 to 5000 parts by weight, more preferably 50 to 2000 parts by weight, based on 100 parts by weight of the reaction mixture containing isobornyl (meth)acrylate. More preferably, the amount is 1000 parts by weight.

In the step of neutralizing with a solid base, the treatment temperature is preferably 0 to 100°C, and preferably 10 to 80°C, from the viewpoint of promoting the neutralization reaction and considering the thermal stability of the reaction mixture. is more preferable, and even more preferably 20 to 60°C. Furthermore, the treatment time cannot be determined unconditionally since it varies depending on the treatment temperature, etc., but is usually about 30 minutes to 24 hours.

In the step of neutralizing with a solid base, the reaction method for neutralizing with a solid base may be the above-mentioned batch method, continuous method, or circulation method.

In the step of distilling, the distillation is usually preferably carried out by heating under reduced pressure. From the viewpoint of suppressing the polymerization reaction of the (meth)acrylic ester, the heating temperature is preferably 30 to 150°C, more preferably 50 to 130°C. In addition, the degree of pressure reduction cannot be determined unconditionally as it varies depending on the heating temperature, but from the viewpoint of preventing the heating temperature from exceeding 150°C, it is preferably 10 kPa or less, and 5 kPa or less. is more preferable.

In addition, in the production method of the present invention, after providing the step of neutralizing with the solid base and the step of distilling, in order to further increase the purity of the target product (composition containing isobornyl (meth)acrylate), A step of rectifying the product can be provided. Rectification is usually preferably carried out by heating under reduced pressure. Considering the boiling point of isobornyl (meth)acrylate, the heating temperature is usually about 100 to 130°C, and the degree of pressure reduction is about 0.5 to 3 kPa.

In the composition containing isobornyl (meth)acrylate obtained by the production method of the present invention, the purity of isobornyl (meth)acrylate as measured by gas chromatography is 99.5% or more. The purity of isobornyl (meth)acrylate as measured by gas chromatography is preferably 99.8% or more.

In the composition containing isobornyl (meth)acrylate obtained by the production method of the present invention, the proportion of unreacted (meth)acrylic acid is 0.02% by weight or less. The proportion of unreacted (meth)acrylic acid is preferably 0.01% by weight or less, more preferably 0.005% by weight or less, and even more preferably 0.003% by weight or less.

The composition containing isobornyl (meth)acrylate obtained by the above production method contains high purity isobornyl (meth)acrylate with reduced amount of unreacted acrylic acid, so it can be used as a binder for printing inks, curable paints, etc. It is useful as a raw material for products such as adhesives, photocuring reaction diluents, etc.

The present invention will be explained below with reference to Examples, but the present invention is not limited in any way by these Examples.

<Example 1>
<Production of reaction mixture containing isobornyl acrylate>
In a 1 L glass reactor equipped with a stirrer, a cooler, a thermometer, a sampling tube, and a 500 ml dropping funnel containing 420 g (3.08 mol) of camphene, 271 g (3.76 mol) of acrylic acid, 80 mg of hydroquinone as a polymerization inhibitor, As a catalyst, 16 g of a strongly acidic cation exchange resin (manufactured by Dow Chemical Company, trade name "AMBERLYST 15 DRY") was charged. Camphene was gradually added dropwise from the dropping funnel while controlling the temperature inside the reaction vessel to be 45 to 55°C. After the addition of camphene was completed, the reaction mixture was stirred and mixed for 15 hours while controlling the temperature at 45 to 55°C. Next, using gas chromatography (Model 6850 manufactured by Agilent), it was confirmed that the reaction conversion rate of isobornyl acrylate in the obtained reaction mixture exceeded 80%, and then the catalyst was filtered off.

The method for calculating the reaction conversion rate of isobornyl (meth)acrylate using gas chromatography is as follows.
[Method for calculating reaction conversion rate of isobornyl (meth)acrylate]
Reaction conversion rate (%) of isobornyl (meth)acrylate = Area of isobornyl (meth)acrylate/(Area of isobornyl (meth)acrylate + Area of camphene) x 100
Gas chromatography conditions are as follows. The injection port used a heater temperature of 260°C, and the detector used an FID, and the heater temperature was set to 260°C. The GC column used was HP-1 manufactured by Agilent (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). The oven was set to increase the temperature from an initial temperature of 100°C to 260°C at 8°C per minute. The split ratio was set to 50:1, and the linear velocity was set to 30 cm/min. The amount of injection was 0.2 μl.

<Production of composition containing isobornyl acrylate>
The reaction mixture from which the above catalyst has been filtered off is distilled at 85 to 125°C under reduced pressure (0.5 to 3 kPa) to remove unreacted acrylic acid and camphene, and to remove isobornyl acrylate. 495g of the composition was obtained. In the composition containing isobornyl acrylate after distillation, the purity of isobornyl acrylate by gas chromatography was 99.8%, and the acrylic acid was 0.03% by weight. Subsequently, in order to neutralize unreacted acrylic acid, 2.9 g of potassium carbonate was added to the composition containing isobornyl acrylate after distillation, and after stirring at 50°C for 6 hours, the potassium carbonate was filtered off and the isobornyl acrylate was removed. A composition containing bornyl acrylate was obtained. In the resulting composition containing isobornyl acrylate, the purity of isobornyl acrylate as determined by gas chromatography was 99.8%, and the acrylic acid content was 0.002% by weight.

The method for calculating the purity (%) of isobornyl (meth)acrylate by gas chromatography and the proportion (% by weight) of (meth)acrylic acid in a composition containing isobornyl (meth)acrylate is as follows.
[Method for calculating purity (%) of isobornyl (meth)acrylate by gas chromatography]
The purity (%) of isobornyl (meth)acrylate was analyzed under the equipment conditions used to calculate the reaction conversion rate, and was calculated from the area percentage.

[Method for calculating the proportion of (meth)acrylic acid (weight%)]
The proportion (% by weight) of (meth)acrylic acid was calculated from the free acid content (% by weight) in terms of (meth)acrylic acid below. To measure the free acid content (% by weight) in terms of (meth)acrylic acid, take approximately 50 mL of ethanol in a 100 mL Erlenmeyer flask, use phenol red as an indicator, and neutralize with 0.1 mol/L sodium hydroxide aqueous solution. Next, approximately 30 g of a sample (a composition containing isobornyl (meth)acrylate) was accurately weighed into the solution, and titrated with a 0.1 mol/L sodium hydroxide aqueous solution while stirring to uniformly dissolve the sample, until the slightly red color was approximately 30 g. The titration end point was the point that did not disappear for seconds.
Free acid content (weight%) in terms of (meth)acrylic acid = {(0.1×f×A×B)/(C×1000)}×100
A: Titration amount (mL)
f: Potency of 0.1 mol/L sodium hydroxide aqueous solution B: Molecular weight of the acid to be determined (72.06 for acrylic acid, 86.09 for methacrylic acid)
C: Weighed amount of sample (g)

<Example 2>
<Production of reaction mixture containing isobornyl methacrylate and composition containing isobornyl methacrylate>
Example 1 except that 324 g (3.76 mol) of methacrylic acid was used instead of 271 g (3.76 mol) of acrylic acid in <Production of reaction mixture containing isobornyl acrylate> in Example 1 above. The same operation as above was performed to obtain a reaction mixture containing isobornyl methacrylate. Next, the reaction mixture from which the catalyst has been filtered off is distilled at 90 to 135° C. under reduced pressure (0.5 to 3 kPa) to remove unreacted methacrylic acid and camphene, and to remove isobornyl methacrylate. 521 g of the composition was obtained. In the composition containing isobornyl methacrylate after distillation, the purity of isobornyl methacrylate by gas chromatography was 99.9%, and the methacrylic acid was 0.04% by weight. Subsequently, 3.3 g of potassium carbonate was added to the distilled composition containing isobornyl methacrylate and stirred at 30°C for 10 hours, and then the potassium carbonate was filtered off to obtain a composition containing isobornyl methacrylate. In the resulting composition containing isobornyl methacrylate, the purity of isobornyl methacrylate as determined by gas chromatography was 99.9%, and the acrylic acid content was 0.003% by weight.

<Example 3>
<Production of reaction mixture containing isobornyl acrylate and composition containing isobornyl acrylate>
The same operation as <Production of reaction mixture containing isobornyl acrylate> in Example 1 above was performed to obtain a reaction mixture containing isobornyl acrylate. Next, in <Production of a composition containing isobornyl acrylate> in Example 1, 2.9 g of potassium carbonate was added to the distilled composition containing isobornyl acrylate in order to neutralize unreacted acrylic acid. A composition containing isobornyl acrylate was prepared in the same manner as in Example 1 except that 2.1 g of calcium carbonate was added and stirred at 50°C for 24 hours instead of stirring at 50°C for 6 hours. Obtained. In the resulting composition containing isobornyl acrylate, the purity of isobornyl acrylate as determined by gas chromatography was 99.8%, and the acrylic acid content was 0.01% by weight.

<Example 4>
<Production of reaction mixture containing isobornyl acrylate and composition containing isobornyl acrylate>
The same operation as <Production of reaction mixture containing isobornyl acrylate> in Example 1 above was performed to obtain a reaction mixture containing isobornyl acrylate. Next, in <Production of a composition containing isobornyl acrylate> in Example 1, 2.9 g of potassium carbonate was added to the distilled composition containing isobornyl acrylate in order to neutralize unreacted acrylic acid. A composition containing isobornyl acrylate was prepared in the same manner as in Example 1 except that 2.2 g of sodium carbonate was added and stirred at 50°C for 24 hours instead of stirring at 50°C for 6 hours. Obtained. In the resulting composition containing isobornyl acrylate, the purity of isobornyl acrylate as determined by gas chromatography was 99.8%, and the acrylic acid content was 0.003% by weight.

<Comparative example 1>
<Production of reaction mixture containing isobornyl acrylate and composition containing isobornyl acrylate>
The same operation as <Production of reaction mixture containing isobornyl acrylate> in Example 1 above was performed to obtain a reaction mixture containing isobornyl acrylate. Next, in <Production of a composition containing isobornyl (meth)acrylate> in Example 1, the composition containing isobornyl acrylate after distillation was again subjected to the step of neutralizing unreacted acrylic acid. A composition containing isobornyl acrylate was obtained by carrying out the same operation as in Example 1, except that the distillation was carried out at 85 to 125° C. under reduced pressure (0.5 to 3 kPa). In the resulting composition containing isobornyl acrylate, the purity of isobornyl acrylate as determined by gas chromatography was 99.8%, and the acrylic acid content was 0.03% by weight.

Claims (1)

A method for producing a composition comprising isobornyl (meth)acrylate, the method comprising:
Obtaining a reaction mixture containing isobornyl (meth)acrylate by reacting (meth)acrylic acid and camphene;
neutralizing the resulting reaction mixture with a solid base and distilling it;
The solid base is one or more selected from the group consisting of alkali metal carbonates, alkali metal hydrogen carbonates, alkaline earth metal carbonates, and alkaline earth metal hydrogen carbonates,
To obtain a composition containing isobornyl (meth)acrylate, the purity of which is determined by gas chromatography is 99.5% or more, and the amount of unreacted (meth)acrylic acid is 0.02% by weight or less. A method for producing a composition containing isobornyl (meth)acrylate, characterized by: