JP2001354619A - Method for producing highly pure adamantyl (meth) acrylates - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing highly pure adamantyl (meth) acrylate useful as a raw material for a highly functional polymer, a synthetic lubricant oil, a plasticizer, an electronic part or the like. SOLUTION: Adamantanols are reacted with a (meth)acrylic acid (ester), and the reaction liquid is subjected to an alkali cleaning and an acid cleaning to produce the objective highly pure adamantyl (meth)acrylates.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing high-purity adamantyl (meth) acrylates useful as raw materials for high-performance polymers, synthetic lubricating oils, plasticizers, electronic components and the like.

[0002]

2. Description of the Related Art As a method for producing adamantyl (meth) acrylates, a method of reacting (meth) acrylic acid with 1-adamantanol using cresol sulfonic acid or the like as a catalyst and a polymerization inhibitor (JP-A-8-310995) Publication), a method of producing adamantyl mono (meth) acrylates by reacting adamantanol with (meth) acrylic acid in a toluene solvent in the presence of a p-toluenesulfonic acid catalyst (Japanese Patent Publication No. 7-61980), and A method has been proposed in which an adamantanol is reacted with a (meth) acrylic acid ester in the presence of a catalyst composed of a Group 3 element compound of the periodic table (JP-A-11-35522).
However, it has been difficult to produce high-purity adamantyl (meth) acrylates.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing adamantyl (meth) acrylate having high purity.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, in the presence of an esterification catalyst,
After reacting adamantanols with (meth) acrylic acid (ester) in an organic solvent, the reaction solution is washed in the order of alkali washing, water washing, acid washing, and water washing, and then concentrated and crystallized to remove metal impurities. Of 100 ppb or less and high-purity adamantyl (meth) acrylates having a halogen ion of 1000 ppb or less, and reached the present invention.

That is, the present invention provides an adamantyl (Adamanthin) comprising reacting an adamantanol with a (meth) acrylic acid (ester) in the presence of an esterification catalyst, and then washing the reaction solution with an alkali and an acid. The present invention relates to a method for producing (meth) acrylates.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The adamantanols of the present invention are represented by the following general formula.

[0007]

Embedded image (Wherein, R ^{1 to} R ³ are the same or different and are each a hydrogen atom,
A hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group, a cycloalkyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group, an acyloxy group having 2 to 6 carbon atoms, and a halogen group. )

Here, the aryl group includes a phenyl group, a naphthyl group and the like, the cycloalkyl group includes a cyclohexyl and cyclooctyl group, and the aryloxy group includes a phenoxy group.

The organic solvent used in the present invention has low compatibility with water, high solubility of adamantane (meth) acrylates, and is inert to the reaction. In order to remove water produced as a by-product during the reaction, it is preferable to use a solvent azeotropic with water. As specific examples, hexane, heptane, octane, aliphatic hydrocarbons having 6 to 10 carbon atoms such as nonane, cyclohexane, methylcyclohexane, dimethylcyclohexane, alicyclic hydrocarbons having 6 to 10 carbon atoms such as ethylcyclohexane, benzene, And aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more. The amount of the solvent is based on 1 part by weight of adamantanol used as a raw material.
The proportion is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight.

[0010] Esterification catalysts include mineral acids such as sulfuric acid and hydrochloric acid;
A compound selected from the group consisting of organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and compounds of Group 3 to 8 metal elements such as Sc, Ti, V, and W;
Preferably, sulfuric acid is used. When sulfuric acid is used, 0.005 to 1 mol of adamantanol as a raw material is used.
It is used in a ratio of 1.0 mol, preferably 0.01 to 0.1 mol. If the amount used is less than this range, the reaction rate decreases, and if it is too large, the selectivity for adamantane (meth) acrylates decreases.

The (meth) acrylic acid is used in an amount of 1.0 to 10 equivalents, preferably 1.2 to 5 equivalents, per equivalent of the hydroxyl group in the adamantanols. If the amount is less than this range, unreacted adamantanol remains, and if it is too large, the kettle efficiency decreases.

In order to suppress the polymerization of (meth) acrylic acid during the reaction, a polymerization inhibitor is used. As the polymerization inhibitor, those generally commercially available can be used, and examples thereof include p-methoxyphenol and methylhydroquinone. The polymerization inhibitor is used in an amount of 0.005 to 1.5 mol%, preferably 0.01 to 1.5 mol% per 1 mol of the (meth) acrylic acid.
Use 0.5 mol%. If the amount is less than this range, polymerization occurs during the reaction, while if it is too large, the selectivity for adamantane (meth) acrylates is reduced by a by-product derived from the polymerization inhibitor.

[0013] The reaction temperature is in the range of 50 to 180 ° C, preferably 60 to 150 ° C. When the reaction temperature is lower than this range, the reaction rate is significantly reduced, and when the reaction temperature is higher, the selectivity of adamantane (meth) acrylates is reduced.

The adamantyl (meth) acrylates of the present invention include adamantyl mono (meth) acrylate, adamantyl di (meth) acrylate, adamantyl tri (meth) acrylate, adamantyl tetra (meth) acrylate and the like.

In the present invention, after reacting adamantanols with (meth) acrylic acid (ester), the reaction solution is washed in the order of alkali washing, water washing, acid washing and water washing to remove metal impurities and halogen ions. Remove.

[0016] The alkali washing is carried out with an aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonium hydroxide. The amount of alkali is used in an amount sufficient to neutralize and remove unreacted (meth) acrylic acid. The excess amount is 0 to 100 parts by weight, preferably 0.01 to 100 parts by weight, based on 1 part by weight of unreacted (meth) acrylic acid.
Used in a proportion of 10 parts by weight. If the amount is less than this, halogen ions in the organic layer cannot be removed, and if it is more than that, adamantyl (meth) acrylates are hydrolyzed.

In the acid washing, the acid washing is performed with an aqueous solution selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, oxalic acid and methanesulfonic acid. Preferably, sulfuric acid is used. The amount of the acid is 0.01 to 10 parts by weight based on 1 part by weight of the organic layer.
0 parts by weight, preferably 0.1 to 5 parts by weight. Washing is performed 1 to 20 times, preferably 2 to 10 times.

For the water washing, pure water is preferable. Pure water is used in an amount of 0.01 to 100 parts by weight, preferably 0.1 to 5 parts by weight, based on 1 part by weight of the organic layer. The washing frequency is 1
This is performed 20 times, preferably 2 to 10 times.

The temperature of the alkali washing, acid washing and pure water washing is 0 ° C. to 95 ° C., preferably 10 ° C. to 60 ° C. If the temperature is lower than this, the washing effect is reduced, and if the temperature is higher, adamantyl (meth) acrylate is hydrolyzed.

The determination of the cleaning effect is performed by analyzing the organic layer after washing and the washing water by an analytical method such as a colorimetric method or an atomic absorption method to control the concentrations of metal impurities and halogen ions. As a simple method, when the electric conductivity of the washing wastewater becomes 10 mS / m or less, metal impurities including adamantyl (meth) acrylates are 100 ppb or less and halogen ions are 1
000 ppb or less. After washing, the resulting organic layer is concentrated and crystallized to obtain high-purity adamantyl (meth) acrylates.

According to the present invention, materials that do not elute impurities, such as glass lining, titanium, Hastelloy,
It is preferable to use one made of synthetic quartz or Teflon (registered trademark). It is preferable that these devices and the like also remove metal impurities and halogen ions on the surface by washing. As a simple method, washing may be performed until the electric conductivity of the washing wastewater of these devices and the like becomes 5 mS / m or less.

[0022]

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited by these examples.

Example 1 In a 2000 ml glass four-necked flask equipped with a stirrer, thermometer, Dean-Stark water separator, Dimroth condenser and air inlet tube, 84 g of 1,3-adamantanediol, n-octane 400 ml, toluene 400
ml, 129 g of methacrylic acid, 1.2 g of concentrated sulfuric acid, and 0.37 g of p-methoxyphenol. The used glassware was washed with a 1% by weight aqueous hydrochloric acid solution, and further washed with pure water until the electrical conductivity of the washing wastewater became 5 mS / m.
Then, while blowing a small amount of air, the reflux state (115
C) for 5 hours. During this time, by-product water was removed from the drain tube. After cooling the reaction solution to room temperature, 840 g of a 5% by weight aqueous sodium hydroxide solution was added thereto for washing. Thereafter, 800 ml of pure water was added to wash twice. The reaction solution was transferred to a well-washed glass flask, washed twice with 400 g of a 5% by weight aqueous sulfuric acid solution, and further washed twice with 800 ml of pure water. The organic layer was concentrated, and the precipitated solid was collected by filtration with a glass filter and dried to obtain 90 g of 3-hydroxy-1-adamantyl monomethacrylate.

The metal impurities in the raw material 1,3-adamantanediol are Na: 355 ppb and Ca: 236 ppb.
b, Mg: 98 ppb and Fe: 1800 ppb, but the metal impurities in 3-hydroxy-1-adamantyl monomethacrylate were Na: 34 ppb and Ca: 18
ppb, Mg: 6 ppb, Fe: 94 ppb, Zn: 1
It was 2 ppb, K, Al, Cr, Cu, Ni and Pb were 20 ppb or less and free chlorine was 112 ppb.

Example 2 The same operation as in Example 1 was carried out except that 108 g of acrylic acid was charged instead of methacrylic acid, to obtain 70 g of 3-hydroxy-1-adamantyl monoacrylate. Three
Metal impurities in -hydroxy-1-adamantyl monomethacrylate are as follows: Na: 65 ppb, Ca: 28 ppb,
Mg: 9 ppb, Fe: 97 ppb, Zn: 11 ppb
K, Al, Cr, Cu, Ni, and Pb were 20 ppb or less and free chlorine was 118 ppb.

Comparative Example 1 A sodium hydroxide aqueous solution 8
After washing once with 40 g, the same operation as in Example 1 was performed, except that washing was performed five times with 375 g of ion-exchanged water. The metal impurity in the obtained 3-hydroxy-1-adamantyl monomethacrylate was Na: 150 ppb.

[0027]

According to the present invention, adamantyl (meth) acrylates containing almost no metal impurities can be obtained.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kikuo Furukawa 22nd Wadai, Tsukuba-shi, Ibaraki F-term (reference) in Mitsubishi Gas Chemical Company, Ltd. 4H006 AA02 AC48 AD16 BA08 BA10 BA12 BA14 BA66 BA67 BC50 KA03 KA06 KD10 KE20 4H039 CA66 CD10 CD30

Claims (6)

[Claims] An adamantyl (meth) acrylate comprising reacting an adamantanol with a (meth) acrylic acid (ester) in the presence of an esterification catalyst, and then washing the reaction solution with an alkali and an acid. Manufacturing method. 2. The esterification catalyst is a mineral acid such as sulfuric acid or hydrochloric acid,
The production method according to claim 1, wherein the production method is a compound selected from the group consisting of organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and compounds of Group 3 to 8 metal elements. 3. The method according to claim 1, wherein the alkali washing is carried out with an aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonium hydroxide. 4. The method according to claim 1, wherein the acid washing is carried out with an aqueous solution selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, oxalic acid and methanesulfonic acid. 5. The production method according to claim 1, wherein water washing is performed after the acid washing, and the water washing is repeated until the electric conductivity of the washing wastewater becomes 10 mS / m or less. 6. The method according to claim 1, wherein a reactor washed until the electric conductivity of the washing wastewater becomes 5 mS / m or less is used for the reaction.