JP3305066B2 - Process for producing bis (isopropenylphenoxycarbonyloxyethyl) ether - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for controlling polymerization,
The present invention relates to a method for producing bis (isopropenylphenoxycarbonyloxyethyl) ether, which is useful as a raw material for a transparent resin having a high surface hardness and excellent heat resistance.

[0002]

2. Description of the Related Art Methacrylic resin, polycarbonate resin, polystyrene resin, etc. have transparency, heat resistance, workability,
It is used in glazing materials and optical lenses for vehicles and balconies because of its excellent mass productivity. However, the above-mentioned general-purpose transparent resins have insufficient surface hardness, heat resistance, and the like, and have been proposed to solve these problems, such as diethylene glycol diallyl carbonate resin and urethane polyacrylic ester resin (Japanese Patent Laid-Open No.
JP-75022-A) has a problem that it is difficult to control the polymerization, and it takes a long time to obtain a resin having a good surface condition and a small polymerization distortion.

In order to solve these problems, the present inventors have proposed a high-hardness transparent resin (JP-A-3-47817).
In which bis (isopropenylphenoxycarbonyloxyethyl) is used as one of the monomer components.
The use of ether was proposed. Conventionally, as a method for producing bis (isopropenylphenoxycarbonyloxyethyl) ether, a general method for synthesizing a dicarbonate compound,
Chi, an alkali metal salt of isopropenylphenol and diethylene dichloro formate, dichloromethane - be synthesized by a method of reacting with water mixed solvent system
I can . However, in this method, since dichloromethane has a low boiling point, it is difficult to handle it,
It was needed a long time for separation purification very poor dichloromethane and aqueous layers, and there are problems such as the industrial yield and purity is low.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems and to provide a method for obtaining bis (isopropenylphenoxycarbonyloxyethyl) ether of high purity in high yield. is there.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted a reaction in a mixed solvent system of water, a polar solvent and a non-polar solvent to produce bis (isopropenylphenoxycarbonyloxyethyl) ether. We studied the law diligently. As a result, by using a polar solvent such as acetone or ethyl methyl ketone in combination with a non-polar solvent such as benzene, toluene or xylene, and performing a reaction in a mixed solvent system of water, a polar solvent and a non-polar solvent, In yield
It has been found that bis (isopropenylphenoxycarbonyloxyethyl) ether of high purity can be obtained, and the present invention has been completed. That is, the present invention relates to a general formula (I) in which an alkali metal salt of isopropenylphenol and diethylene glycol dichloroformate are reacted in a mixed solvent system of water, a polar solvent and a nonpolar solvent.
And a process for producing bis (isopropenylphenoxycarbonyloxyethyl) ether represented by the formula:

[0006]

Embedded image

In the above method, 2.0 mol to 3.0 mol of an alkali metal salt of isopropenylphenol is reacted with 1 mol of diethylene glycol dichloroformate, wherein the polar solvent is acetone or ethyl methyl ketone. The method, wherein the non-polar solvent is benzene, toluene or xylene, the reaction temperature is 0 to 45 ° C
Is a method. The method of the present invention solves the problem that the purification step requires a long time without using a low-boiling-point solvent that is not easy to handle, and provides a high-yield, high-purity bis (isopropenylphenoxy). This is a method for obtaining carbonyloxyethyl) ether.

[0008] The isopropenylphenol used in the method of the present invention is commercially available, and diethylene glycol dichloroformate can be easily obtained by reacting diethylene glycol with phosgene. In the method of the present invention, the amount of isopropenylphenol used is 2.0 to 3.0 moles, preferably 2.0 to 3.0 moles per mole of diethylene glycol dichloroformate.
2.2 moles. The amount of sodium hydroxide or potassium hydroxide used is 2.0 to 3.0 moles, and preferably 2.0 to 2.2 moles, per mole of diethylene glycol dichloroformate. The amount of water used is 400 to 2000 ml, preferably 800 to 2000 mol, per mol of diethylene glycol dichloroformate, in order to dissolve the sodium or potassium salt of isopropenylphenol and the reaction product salt during the reaction.
1000 ml is required. If the amounts of isopropenylphenol and sodium hydroxide or potassium hydroxide exceed 3.0 moles per mole of diethylene glycol dichloroformate, excess sodium or potassium salt of isopropenylphenol is removed. Therefore, it is necessary to increase the number of washings, and the purification step tends to be complicated.

The polar solvent may be any organic solvent which has no reactivity with the raw materials, dissolves diethylene glycol dichloroformate and bis (isopropenylphenoxycarbonyloxyethyl) ether, and has compatibility with water. , Preferably acetone or ethyl methyl ketone. The amount of these polar solvents to be used is 5 to 400 ml, preferably 120 to 18 mol per mol of diethylene glycol dichloroformate.
0 ml. When the amount of the polar solvent used is less than 5 ml, the reaction between the sodium or potassium salt of isopropenylphenol and diethylene glycol dichloroformate does not easily proceed, and the amount of the polar solvent used is 400 ml.
When it exceeds, the contact between diethylene glycol dichloroformate and water becomes severe, and the hydrolysis of diethylene glycol dichloroformate tends to proceed.

As the non-polar solvent, an organic solvent which has no reactivity with the raw materials, dissolves diethylene glycol dichloroformate and bis (isopropenylphenoxycarbonyloxyethyl) ether, and has compatibility with the polar solvent And benzene, toluene or xylene is preferably used. The amount of the nonpolar solvent used is 300 to 3000 m per 1 mol of diethylene glycol dichloroformate.
1, preferably 800 to 1500 ml. If the amount of the nonpolar solvent used is less than 300 ml, the contact between diethylene glycol dichloroformate and water becomes intense, and the hydrolysis of diethylene glycol dichloroformate proceeds. The reaction between the sodium salt or potassium salt and diethylene glycol dichloroformate does not easily proceed, and the yield tends to decrease.

The reaction temperature of the alkali metal salt of isopropenylphenol and diethylene glycol dichloroformate in the mixed solvent system of water, a polar solvent and a non-polar solvent of the present invention is from 0 to 45 ° C, preferably from 2 to 45 ° C.
0 ° C, particularly preferably 3 to 10 ° C. Reaction temperature is 0
If the temperature is lower than 0 ° C, the sodium or potassium salt of isopropenylphenol and the reaction product salt precipitate, and the reaction hardly proceeds due to solidification of water and a solvent, and the yield tends to decrease. When the reaction temperature exceeds 45 ° C., dimerization of isopropenylphenol, coloring by oxidation of isopropenylphenol, and hydrolysis of diethylene glycol dichloroformate tend to proceed. The drop time of 1 mol of diethylene glycol dichloroformate is 0.5 to 10
Hours, preferably 3 to 4 hours. Good results can be obtained by stirring at 0 to 45 ° C for 1 to 5 hours, preferably 2 to 3 hours, in order to complete the reaction after completion of the dropwise addition. If the dropping time is less than 0.5 hour, hydrolysis of the diethylene glycol dichloroformate staying in the reaction system occurs, and if the dropping time exceeds 10 hours, coloring due to oxidation of isopropenylphenol tends to occur. In addition, a good result can be obtained by adding a small amount of sodium hydrosulfite during the reaction to prevent dimerization and oxidation of isopropenylphenol.

A general embodiment of the method of the invention is as follows. First, 400 to 2000 ml of 2.0 to 3.0 moles of sodium hydroxide or potassium hydroxide is added to 1 mole of diethylene glycol dichloroformate.
And add a small amount of sodium hydrosulfite. Next, 2.0 to 3.0 moles of isopropenylphenol are added to 1 mole of diethylene glycol dichloroformate and dissolved. At this time, the internal temperature is maintained at 0 to 45 ° C. while flowing nitrogen into the reaction system to prevent oxidation of isopropenylphenol. Then 300 to 30
A non-polar solvent such as 00 ml of benzene, toluene or xylene and a polar solvent such as 5-400 ml of acetone or ethyl methyl ketone are added and mixed.
Keep at 45 ° C. Next, 1 mol of diethylene glycol dichloroformate is added dropwise over 0.5 to 10 hours. After completion of the dropwise addition, the mixture is stirred at an internal temperature of 0 to 45 ° C for 1 to 5 hours to complete the reaction.

After completion of the reaction, bis (isopropenylphenoxycarbonyloxyethyl) ether is removed, if necessary, by adding a solvent such as benzene, toluene or xylene. Next, the solution of bis (isopropenylphenoxycarbonyloxyethyl) ether is washed with an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, washed with water, and further concentrated to obtain high-purity bis (isopropenylphenoxycarbonyloxyethyl).
Ethers can be obtained in high yields. The purification process during this period can be completed in a short time.

[0014]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In addition,
All parts shown in the examples are parts by weight. Example 1 29.5 parts of sodium hydroxide (0.70 parts) was added to 300 parts of water.
Mol) and 0.5 parts of sodium hydrosulfite were dissolved and cooled to keep the internal temperature at 5 ° C. 90.8 parts (0.64 mol) of p-isopropenylphenol were added to the reaction system while flowing nitrogen slowly while maintaining the internal temperature at 3 to 10 ° C, and the mixture was stirred for 30 minutes in this state. Next, 260 parts of toluene and 40 parts of acetone were added, and the internal temperature was 3 to 5 ° C.
Kept. Next, 73.3 parts (0.32 mol) of diethylene glycol dichloroformate was added dropwise over 3.5 hours while maintaining the internal temperature at 3 to 5 ° C. After completion of the dropwise addition, the mixture was stirred at an internal temperature of 3 to 5 ° C. for 1 hour and at room temperature for 1.5 hours. After the completion of the reaction, the reaction solution began to separate into a toluene layer and an aqueous layer. Next, the toluene layer was
Washed with 300 parts by weight aqueous sodium hydroxide solution,
The mixture was allowed to stand for minutes and separated. This washing operation was repeated twice. Further, the toluene layer was washed with 300 parts of water, allowed to stand still for 30 minutes, and separated. This washing operation was repeated twice. Next, 15 parts of calcium chloride was added to the toluene layer to add 3 parts.
Stir for 0 minutes and dry. After the drying was completed, the calcium chloride was filtered off, and the toluene layer was concentrated to obtain 129.6 parts of a colorless syrup-like bis (p-isopropenylphenoxycarbonyloxyethyl) ether. As a result of analysis by liquid chromatography, the purity was 98 wt%.
The yield was 93 mol%. The elemental analysis values were as follows.

Example 2 46.2 parts (0.70 mol) of potassium hydroxide and 0.5 part of sodium hydrosulfite were dissolved in 300 parts of water, and cooled to keep the internal temperature at 7 ° C. 90.8 parts (0.64 mol) of m-isopropenylphenol was added to the reaction system while gently flowing nitrogen while maintaining the internal temperature at 7 to 10 ° C, and the mixture was stirred for 30 minutes in this state. Then
Add 350 parts of benzene and 32 parts of acetone, and adjust the internal temperature to 7 ~
It was kept at 10 ° C. Next, 73.3 parts (0.32 mol) of diethylene glycol dichloroformate was added at an internal temperature of 7%.
The solution was added dropwise over 3 hours while maintaining the temperature at 10 ° C. After completion of the dropwise addition, the mixture was stirred at an internal temperature of 7 to 10 ° C for 1 hour and at room temperature for 1 hour. After completion of the reaction, the reaction solution began to separate into a benzene layer and an aqueous layer. Next, the benzene layer was washed with 300 parts of a 5 wt% aqueous solution of potassium hydroxide, and allowed to stand for 30 minutes to be separated. This washing operation was repeated twice. Further, the benzene layer was washed with 300 parts of water, allowed to stand for 30 minutes, and separated. This washing operation was repeated twice. Next, calcium chloride 15 was added to the benzene layer.
Then, the mixture was stirred for 30 minutes and dried. After the drying was completed, the calcium chloride was filtered off, and the benzene layer was concentrated to obtain 126.6 parts of a colorless syrup-like bis (m-isopropenylphenoxycarbonyloxyethyl) ether. As a result of analysis by liquid chromatography, the purity was 97 w
t%, and the yield was 90 mol%. The elemental analysis values were as follows.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that 260 parts of toluene and 40 parts of acetone were replaced with 320 parts of dichloromethane. After completion of the reaction, the reaction solution began to separate into a dichloromethane layer and an aqueous layer. Next, the dichloromethane layer was washed with 300 parts of a 5 wt% aqueous sodium hydroxide solution. At this time, the separation was so bad that it had to be left overnight. Further, the dichloromethane layer was immersed in a 5 wt% aqueous sodium hydroxide solution 30.
Washed with 0 parts. This washing operation was repeated twice. The time required for liquid separation at this time was 1 hour in each case. Next, the dichloromethane layer was washed with 300 parts of water. This washing operation was repeated three times. The time required for liquid separation at this time was 2 hours in each case. After washing, the dichloromethane layer was dried over 15 parts of calcium chloride, filtered and concentrated to obtain 118.5 parts of bis (p-isopropenylphenoxycarbonyloxyethyl) ether as a pale yellow syrup.
As a result of analysis by liquid chromatography, purity 80 w
t% (yield 69 mol%)
Purified by luffy. Purity is 97wt%, yield is
85 parts .

[0017]

According to the method of the present invention, the polymerization can be easily controlled,
Bis (isopropenylphenoxycarbonyloxyethyl) ether, which is useful as a raw material for transparent resins with high surface hardness and excellent heat resistance, can be produced without using a low boiling point solvent, and is easy to purify. It is a way. According to the present invention, bis (isopropenylphenoxycarbonyloxyethyl) ether of high purity can be obtained in high yield.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C07C 68/02 C07C 69/96

Claims (5)

(57) [Claims] 1. A compound of the general formula (I), wherein an alkali metal salt of isopropenylphenol and diethylene glycol dichloroformate are reacted in a mixed solvent system of water, a polar solvent and a non-polar solvent. A process for producing the represented bis (isopropenylphenoxycarbonyloxyethyl) ether. Embedded image 2. The process for producing bis (isopropenylphenoxycarbonyloxyethyl) ether according to claim 1, wherein 2.0 to 3.0 moles of an alkali metal salt of isopropenylphenol are reacted with 1 mole of diethylene glycol dichloroformate. . 3. The process for producing bis (isopropenylphenoxycarbonyloxyethyl) ether according to claim 1, wherein the polar solvent is acetone or ethyl methyl ketone. 4. The bis (isopropenylphenoxycarbonyloxyethyl) according to claim 1, wherein the non-polar solvent is benzene, toluene or xylene.
Method for producing ether. 5. The method according to claim 1, wherein the reaction temperature is 0 to 45 ° C.
5. The method for producing bis (isopropenylphenoxycarbonyloxyethyl) ether according to any one of claims 1 to 4.