JP2001172226A - Method for producing alicyclic skeleton acrylic compound - Google Patents

Abstract

(57) [Problem] To produce an alicyclic skeleton acrylic compound by an esterification reaction of an alicyclic skeleton diol and (meth) acrylic acid, and to wash a reaction product solution with an aqueous detergent. Prevents the emulsification of
And a method for improving the yield. SOLUTION: When an alicyclic skeleton diol and (meth) acrylic acid are reacted in the presence of a solvent to produce an alicyclic skeleton acrylic compound, after removing a solvent-insoluble matter from a reaction product solution, Perform water-based cleaning.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an alicyclic skeleton acrylic compound. Specifically, the present invention relates to an improvement in a method for producing an alicyclic skeleton acrylic compound by reacting an alicyclic skeleton diol with (meth) acrylic acid. The alicyclic skeleton acrylic compound obtained by the present invention is used as a raw material of a resin useful as an optical transparent material such as a lens and a substrate.

[0002]

2. Description of the Related Art There have been known various methods for producing an alicyclic skeleton acrylic compound which is a raw material of a transparent and tough molded product. For example, Japanese Patent Application Laid-Open
JP-A-225508 discloses an alicyclic skeleton diol and (meth)
A method of esterifying acrylic acid with a catalyst in the presence of a solvent is disclosed.

[0003]

However, when an alicyclic skeleton acrylic compound is produced by the above method, when the reaction product solution is washed with an aqueous detergent, an intermediate between the reaction product solution and the aqueous detergent is used. In addition, a large amount of emulsion layer is generated, and the separation of the emulsion layer is poor, so that a long production time is required.In some cases, the emulsion layer is not dissolved and the emulsion layer containing the reaction product solution is discarded. For this reason, there is a problem that the yield is greatly reduced. The present invention overcomes the problems of the conventional method, improves the separability between the reaction product solution and the aqueous detergent when the reaction product solution is washed with the aqueous detergent, shortens the production time, and reduces the reaction yield. It is an object of the present invention to provide a method for producing an alicyclic skeleton acrylic compound which can improve the above.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above circumstances. As a result, the present inventors have surprisingly removed the solvent insolubles from the reaction product solution and then carried out an aqueous washing treatment to obtain an emulsion. Have been found, and it has been found that the separation of the reaction product liquid and the aqueous detergent proceeds rapidly, and the present invention has been completed. That is, the gist of the present invention is to react an alicyclic skeleton diol with (meth) acrylic acid in the presence of a solvent to produce an alicyclic skeleton acrylic compound, and to remove a solvent-insoluble substance from a reaction product solution. A method of producing an alicyclic acryl compound, which comprises performing an aqueous washing treatment after the removal.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Esterification Reaction) The esterification reaction between the alicyclic diol and (meth) acrylic acid in the present invention is not particularly limited, and may be carried out by a known method, for example, a method described in JP-A-62-225508. It can be performed according to the method. The alicyclic skeleton diol used in the present invention is not particularly limited, but for example, it is preferable to use a compound of the formula (1).

[0006]

Embedded image

(Wherein m is 1 or 2 and n is 0 or 1) As a specific example of the compound of the formula (1), for example, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, bis (hydroxymethyl) pentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane. Of these, bis (hydroxymethyl)
Tricyclodecane is commercially available as "TCD alcohol DM (trade name of Hoechst)".

As (meth) acrylic acid, a commercially available one can be used as it is. The amount of (meth) acrylic acid to be used is generally 2.0 to 2.6 mol per 1 mol of the alicyclic skeleton diol. As the esterification catalyst, a usual esterification catalyst is used. Specific examples thereof include, for example, sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, p-
Examples thereof include toluenesulfonic acid, benzenesulfonic acid, and a cation-type ion exchange resin. Of these, p-toluenesulfonic acid and benzenesulfonic acid are preferred.

The amount of the catalyst used is usually 0.1 to 10 parts by weight based on 100 parts by weight of the alicyclic skeleton diol. Examples of the polymerization inhibitor include phenols such as hydroquinone and hydroquinone monomethyl ether, quinones such as benzoquinone and diphenylbenzoquinone, phenothiazine, and copper salts. The amount of the polymerization inhibitor to be used is generally 0.001 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of (meth) acrylic acid.

In the present esterification reaction, it is preferable to use a solvent. As the solvent, a saturated aliphatic hydrocarbon having 6 to 8 carbon atoms is used. Specific examples thereof include, for example, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4 -Dimethylpentane, octane, 2,2
3-trimethylpentane, isooctane and the like can be mentioned.

The solvent is used so that the reaction temperature becomes close to its boiling point in order to remove water generated by the reaction out of the system. When the solvent used is a saturated aliphatic hydrocarbon having 5 or less carbon atoms, the reaction temperature decreases, and the reaction time becomes longer. When the solvent is a saturated aliphatic hydrocarbon having 9 or more carbon atoms, the reaction temperature becomes lower. Since the reaction product is gelled or colored due to the rise, both are not preferred.

The saturated aliphatic hydrocarbon having 6 to 8 carbon atoms used is mixed with other solvents, for example, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. The saturated aliphatic hydrocarbon having 6 to 8 carbon atoms in the mixed solvent is 10 to 99% by weight, preferably 30 to 99% by weight.

[0013] The amount of the solvent used is 10 g of the alicyclic skeleton diol.
It is usually 50 to 100 parts by weight, preferably 100 to 300 parts by weight, based on 0 parts by weight. For the esterification reaction, for example, an alicyclic skeleton diol, (meth) acrylic acid, a solvent, an esterification catalyst, and a polymerization inhibitor are charged into a reactor, preferably under stirring, and preferably under an inert gas atmosphere such as nitrogen. This is carried out while removing water generated under heating out of the system by azeotropic distillation. The reaction temperature is usually 50 to 200
° C, preferably 80-150 ° C, the pressure is usually at normal pressure,
The reaction time is usually 3 to 30 hours, preferably 5 to 15 hours.

(Washing Treatment) In the present invention, when the obtained reaction product solution is subjected to an aqueous washing treatment, impurities insoluble in the solvent are removed from the reaction product solution before the washing treatment is performed. It is characterized by the following. In this case, the concentration of the reaction product in the reaction product solution is 50 to 500 parts by weight of the solvent with respect to 100 parts by weight of the alicyclic skeleton acrylic compound,
The concentration is preferably 100 to 300 parts by weight, and when the concentration is too high, it is preferable to dilute the reaction product solution by appropriately adding a solvent.

The method of removing the solvent-insoluble matter is not particularly limited, but a method of filtering the reaction product solution using a filter material is convenient and preferable. As the filter material, filter paper, felt, filter cloth such as pure silk feather, asbestos, glass wool, glass filter, unglazed filter, porous aluminum oxide filter, and the like can be used. At this time, a filter aid such as diatomaceous earth and acid clay may be used.

The temperature for the filtration treatment is from room temperature to 80 ° C., preferably from room temperature to 40 ° C. The reaction product solution from which impurities unnecessary for the solvent have been removed by filtration is then washed with an aqueous treating agent such as acid, alkali or water to remove the esterification catalyst, the polymerization inhibitor and the like. In this case, usually, 10 to 100 parts by volume of a 3 to 30% aqueous solution of caustic soda is added to 100 parts by volume of the reaction product solution for washing,
Then, it is washed 1 to 3 times with almost the same volume of water until it becomes neutral. Next, a polymerization inhibitor is added as necessary to the reaction product solution after washing, and the solvent is distilled off under reduced pressure.
An intended alicyclic skeleton acrylic compound is obtained.

[0017]

The present invention will be described in more detail with reference to examples and comparative examples below, but the present invention is not limited to these examples unless it exceeds the gist of the present invention. Example 1 (Esterification reaction step) Bis (hydroxymethyl) tricyclo [5.2.1.0 was placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a condenser, and a water separator.
^2,6 ] decane 150 parts by weight, methacrylic acid 160 parts by weight, hydroquinone monomethyl ether 0.25 parts by weight, copper powder 0.07 parts by weight, p-toluenesulfonic acid 2.
7 parts by weight and 200 parts by weight of n-heptane were charged at a rate of 4 per minute.
While flowing cc of air into the system, the reaction was carried out while extracting water generated at 90 to 130 ° C. for 6 hours. After completion of the reaction, the mixture was cooled and bis (oxymethyl) tricyclo [5.
2.1.0 ^2,6 ] decane dimethacrylate solution was obtained. Bis (oxymethyl) tricyclo [5.2.1.0
^2,6 ] decane dimethacrylate solution was cloudy.

(Filtration Step) The bis (oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate solution obtained in the preceding step was filtered using a filter paper having 4 μm retention particles. . Filtration was rapid and the filtrate obtained was clear.

(Post-treatment step) Solvent insoluble obtained in the previous step
Bis (oxymethyl) tricyclo from which various impurities have been removed
[5.2.1.0^2,6] Decane dimethacrylate solution
500 parts by weight of 5% sodium hydroxide aqueous solution 200 parts by weight
Parts, then with 200 parts by weight of water, wash twice until neutral
Was cleaned. Bis (oxymethyl) tricyclo during washing
[5.2.1.0^{2, 6}] Decane dimethacrylate solution
And 5% aqueous solution of sodium hydroxide and water
C. and no emulsion layer was formed. That
After that, hydroquinone monomethyl ether 0.05 parts by weight
At 60 ° C. under a reduced pressure of 5 Torr for 30 minutes.
The butane is distilled off and 250 parts by weight of bis (oxymethyl)
Tricyclo [5.2.1.0^2,6] Decane = dimethacry
Got the rate. Purity was about 95%.

Example 2 The procedure of Example 1 was repeated, except that 130 parts by weight of acrylic acid was used instead of methacrylic acid. Bis (oxymethyl) tricyclo [5.2.1.0 obtained in the reaction step
^{The 2,6} ] decane-diacrylate solution was cloudy. Filtration in the filtration step was performed quickly and the resulting filtrate was clear. Next, a post-treatment step was performed to obtain 240 parts by weight of bis (oxymethyl) tricyclo [5.2.1.0.
^2,6 ] decane diacrylate was obtained. Purity is about 95%
Met.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the filtration step was not carried out. When washing in the post-treatment step, bis (oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane was added. = Separation of the dimethacrylate solution and the 5% aqueous sodium hydroxide solution was not performed quickly, an emulsion layer was formed in the middle, and the emulsion layer was not eliminated even after standing for 24 hours. Inevitably, the emulsion layer was discarded, and then washed with water. Then, bis (oxymethyl) tricyclo [5.2.
[1.0 ^2,6 ] decane = dimethacrylate solution and water were washed seven times until an emulsion layer was formed between the solution and the solution became neutral. The emulsion layer was not dissolved even after standing for one day and night, and was discarded to obtain 200 parts by weight of bis (oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane dimethacrylate.

COMPARATIVE EXAMPLE 2 The same procedure as in Example 2 was carried out except that the filtration step was not carried out. When washing in the post-treatment step, bis (oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane was used. = Separation of the diacrylate solution and the 5% aqueous sodium hydroxide solution was not performed quickly, an emulsion layer was formed in the middle, and the emulsion layer was not eliminated even after standing for 24 hours. Inevitably, the emulsion layer was discarded, and then washed with water. Then, bis (oxymethyl) tricyclo [5.2.
[1.0 ^2,6 ] decane-diacrylate solution was washed with water six times until an emulsion layer was formed between the solution and water and became neutral. The emulsion layer was not dissolved even after standing for one day and night, and was discarded to obtain 190 parts by weight of bis (oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane diacrylate.

Reference Example 1 In Example 1, the solvent-insoluble impurities remaining on the filter paper in the filtration step were taken out, put into a mixture of n-heptane and a 5% sodium hydroxide solution, and stirred to obtain n-heptane. A large amount of emulsion layer formed between the 5% sodium hydroxide solution.

[0024]

According to the present invention, when an alicyclic skeleton acrylic compound is produced by reacting an alicyclic skeleton diol with (meth) acrylic acid, emulsification during washing with an aqueous detergent is prevented, and the production time is greatly reduced. It is possible to shorten the time and improve the production yield.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yoshiharu Kanazaki 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Within the Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (72) Inventor Aytaro Sakuno Chuohachi, Ami-cho, Inashiki-gun, Ibaraki Prefecture Chome No.3-1 F-term in Mitsubishi Chemical Corporation Tsukuba Research Laboratory (reference) 4H006 AA02 AC48 AD17 BB11 BB31 BB44 BB45 BB47 BJ30 KA06

Claims (3)

[Claims] 1. An alicyclic skeleton diol and (meth) acrylic acid are reacted in the presence of a solvent to remove an insoluble solvent from a reaction product solution when producing an alicyclic skeleton acrylic compound. And a water-based washing treatment. 2. The method for producing an alicyclic acryl compound according to claim 1, wherein the solvent is a saturated aliphatic hydrocarbon having 6 to 8 carbon atoms. 3. The method for producing an alicyclic acryl compound according to claim 1, wherein the alicyclic diol is a compound represented by the following general formula (1). Embedded image (Where m is 1 or 2 and n is 0 or 1)