JPS60215650A - Preparation of glycerol acrylate for methacrylate - Google Patents

Abstract

PURPOSE:To obtain the titled compound of high quality and purity, by adding glycidyl (meth)acrylate to a mixture solution consisting of an acid catalyst, polymerization inhibitor and water, hydrolyzing epoxy groups under specific conditions, and purifying the hydrolysis product. CONSTITUTION:Glycidyl acrylate or methacrylate is added to a mixture consisting of an acid catalyst, e.g. sulfuric acid, polymerization inhibitor, e.g. hydroquinone, and water if necessary in the presence of a reaction accelerator, e.g. glycidol, and reacted preferably at 60-90 deg.C for 2-10hr. After completing the reaction, preferably an aqueous solution of an alkali in 0.1-30% concentration is added thereto at <=30 deg.C to adjust the acid value to 0.3-0.8, and dehydration is carried out at a temperature as low as 10-40 deg.C under 2-40mm.Hg reduced pressure in a thin film evaporator or vacuum dehydrator. In case salts are deposited, the salts are filtered off and removed at a temperature as low as <=30 deg.C to give the aimed compound of high quality and purity. USE:A raw material monomer for photosensitive resins, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing glycerol acrylate or methacrylate.

In general, glycerol acrylate or methacrylate is used in a wide range of fields as a raw material monomer mainly for photosensitive resins, and its production methods include (1) reaction of glycidol with acrylic acid or methacrylic acid;
2) The reaction between glycerin and acrylic acid or methacrylic acid is well known. In these conventionally known production methods, a large amount of by-products are produced during the two reactions, so the resulting glycerol acrylate or methacrylate has low purity and a poor color. There are problems such as deterioration of the hue of the product and deterioration of quality.

The present inventors aim to solve the above problems.

As a result of intensive research on the production method of glycerol acrylate or methacrylate, we found that if glycerol acrylate or methacrylate is purified by performing a hydrolysis reaction of the epoxy group under specific conditions.

The present invention was completed based on the discovery that high-quality glycerol acrylate or methacrylate can be obtained with high purity.

That is, in the present invention, glycidyl acrylate or methacrylate is added to a mixed solution consisting of an acid catalyst, a polymerization inhibitor, and water, and the acid value is adjusted to 0.3 to 0 after one reaction.
This is a method for producing glycerol rare acrylate and methacrylate, which comprises adjusting the glycerol rare acrylate to 80% and then dehydrating it under vacuum at a low temperature.

In the present invention, it is convenient to add glycidyl acrylate or methacrylate to a mixed adult cow consisting of an acid catalyst, a polymerization inhibitor, and water by a two-drop method.

, invitation The acid catalyst used in this invention is sulfuric acid.

Examples include nitric acid, paratoluenesulfonic acid, and sulfonic acid type ion exchange resins, and the amount of these catalysts used is 0 per mole of gly/dylacrylate or methacrylate.
．． 0001-005 mol, preferably 0.0005-0
02 moles. If the amount used is less than 0.0001 mol, the catalytic effect will be insufficient, and if it is more than 0.005 mol, by-products will be likely to be produced.

Polymerization inhibitors include phenothiazine, hydroquinone,
Hydroquinone monomethyl ether, t-butyl cresol, etc. are used, and the amount used is 50 to 1,000 p based on glyc/dyl acrylate or methacrylate.
pm is suitable. If the amount used is smaller than this, no polymerization inhibiting effect will be observed.

On the other hand, even if a large amount is used, no significant improvement is observed and it is economically disadvantageous.

The amount of water used in the mixed solution is not particularly limited.

Considering reaction efficiency and post-reaction purification, 8 to 3
0 mol, preferably 10 to 20 mol, and when one reaction accelerator is added, 3 to 20 mol, preferably 5 to 15
It is a mole.

In the present invention, it is preferable to add gly/dol, glycerol acrylate, glycerol methacrylate, or glycerol to the mixed solution for the purpose of promoting one reaction. The appropriate amount of these additives to be added is 0.1 to 0.5 mol per mol of glycidyl acrylate or methacrylate.

If the amount added is less than 0.1 mole, no reaction promotion effect is observed, and on the contrary, if it is more than 0.5 mole, the reaction promotion effect remains almost constant, and there is no industrial advantage even if a large amount is used.

The temperature at which glycidyl acrylate or methacrylate is added to the mixed liquid and reacted is preferably 60 to 90°C. If the reaction temperature is lower than 60"C, the reaction rate is slow, and if the temperature is higher than 90"C, by-products are likely to be produced, which is not preferable.

Further, the time required for addition is 3 to 8 hours.

When a reaction accelerator is used, the reaction time is 1.5 to 5 hours.

After the addition, an additional Ic 0.5 was added to complete the reaction.
It is preferred to continue the reaction for ~2 hours. Therefore, the reaction is usually completed in 2 to 10 hours.

In the present invention, after the reaction is completed, an alkaline aqueous solution is added to adjust the acid value of the reaction solution to 03-08.

If the acid value is lower than 03, the hue will deteriorate in subsequent steps, and if it is higher than 08, the catalyst will remain in the system, resulting in significant production of by-products.

The alkali used at this time is sodium hydroxide,
It can contain substances normally known as alkaline substances such as potassium hydroxide and sodium carbonate. As for the concentration of the alkaline aqueous solution.

Considering dehydration and generation of by-products in later steps, 01~
A concentration of 30 parts is preferred. The temperature at which the alkaline aqueous solution is added is preferably 30° C. or lower; if it is higher than this, by-products are likely to be produced, which is undesirable.

After adjusting the acid value, 10~40°C9 preferably 15~
Dehydration is carried out at a low temperature of 35°C under reduced pressure of 2 to 4.0 degrees HJ'. When the dehydration temperature is lower than 10°C, the dehydration efficiency is poor, and when it is higher than 40°C, by-products such as dimers and dimers are likely to be produced.

Dehydration can be carried out using commonly used methods, methods and equipment that meet the above conditions. For example, a thin film distiller or a vacuum dehydrator can be used.

As dehydration progresses, salts produced by neutralization may precipitate. If the salt precipitates, remove it separately at a low temperature below 1'C to obtain the glycerol acrylate or methacrylate of the present invention.

The crystallized acrylate or methacrylate obtained by the method of the present invention not only has high purity and good hue, but also has excellent storage stability, so it can be used as a raw material in a wide range of fields including photosensitive resins. Things that can be used as monomers Example 1 In a 500 ml four-lobe flask equipped with a thermometer, stirrer, reflux tube, and dropping funnel, 270 P (15 mol) of water and 0.0 ml of sulfuric acid were added. Take IJ' (0,001 mol) and 0.014 J' of hydroquinone, and add 142.2 J' (1 mol) of glycidyl methacrylate dropwise to 70-80°.
The reaction was carried out at C for 5 hours and continued for an additional hour. Next, the temperature was lowered to 30°C, and a 15% aqueous sodium hydroxide solution was added to adjust the acid value of the first reaction solution to 05. After adding 0.014 J' of hydroquinone, dehydration was carried out at a low temperature of 20 to 25°C and 23 to 40 aHJ' under reduced pressure while a small amount of air was passed through. Salt produced by neutralization precipitated and was removed by filtration at 25°C. The reaction product obtained was 15
The purity of glycerol methacrylate was 956% as measured by gas chromatography. The color of this reaction product was APHA 50.

Comparative Example 1 Glycidyl methacrylate 1 was placed in the same reaction vessel as Example 1.
42.2J' (1 mol), water 270j' (15 mol),
Sulfuric acid 0. ]J' (0,001 mol) P and 0.014 J' of hydroquinone were taken and reacted at 70-80°C for 6 hours. After the reaction was completed, the acid value was adjusted in the same manner as in Example 1, and dehydration was performed at low temperature under reduced pressure. The reaction product obtained was 154.0/
and glycerol methacrylate contains 89.5% S.
It was faded.

Comparative Example 2 A reaction was carried out in the same manner as in Example 1, and after one reaction was completed, the acid value of the reaction solution was adjusted to O, and dehydration was carried out in the same manner as in Example. The hue of the reaction product obtained was Gardner 3.

Comparative Example 3 The same procedure as in Example 1 was carried out except that the acid value of the reaction solution was adjusted to 10 after the completion of the reaction.
) A reaction product was obtained containing 82.3%.

Comparative Example 4 The reaction was carried out in the same manner as in Example 1, the acid value of the reaction solution 1 was adjusted in the same manner, and it was dehydrated at 45 to 50'C. Glycerol methacrylate I-1 in the obtained reaction product:
It was 85.5%.

Example 2 In the same reaction vessel as in Example 1, add 90P (5 moles) of water.

Glycidol 14.8 J' (0.2 mol), 61 nitric acid 0.5 J' (0,005 mol) and hydroquinone 0014! and glycidyl methacrylate 1422
The reaction was carried out at 70-80°C for 2 hours while adding P (1.0 mol) dropwise, and the reaction was continued for an additional 30 minutes.

Then, the acid value was adjusted to 04 in the same manner as in Example 1, and Example 1
Dehydration was performed under 0 conditions. A reaction product of 167.1% was obtained, which contained 94.0% of glycerol methacrylate.

Example 3 In the same manner as in Example 1, 126# (7 mol) of water was added.

Glycerol methacrylate 320j' (0.2 mol)
, sulfuric acid 0.1! (0,001 mol) and hydroquinone monomethyl ether 0.028F were taken, and glycidyl methacrylate 142.2/-(1.0 mol) f: was reacted dropwise at 70 to 80'C for 25 hours.

The reaction continued for an additional 30 minutes. The acid value was adjusted and dehydration was carried out in the same manner as in Example 1. Reaction product 186.5J'
was obtained, containing 97% glycerol methacrylate.
was included.

Example 4 90P (5 mol) of water in the same manner as in Example 1.

Glycerin 18.4 P (0.2 mol), halatoluenesulfonic acid 1.9 /' (0.01 mol) and hydroquinone 0.014. After removing P, 142.2 J' (1.0 mol) of glyc/dyl methacrylate was added dropwise to react at 70 to 80°C for 25 hours, and the reaction was continued for an additional 30 minutes. The acid value was adjusted and dehydration was performed in the same manner as in Example 1 to obtain the reaction product [69.7], P. Glycerol methacrylate was rated at 925.

Example 5 In the same manner as in Example 1, 270 tons of water (<15 moles), 0.11 tons of sulfuric acid (0,001 moles) and 70 tons of hydroxy.
014J't, glycidyl acrylate 128.2
The reaction was carried out at 70 to 8 o'C for 5 hours while adding J' (1.0 mol) dropwise, and the reaction was continued for an additional hour. Adjustment of acid value and dehydration were performed in the same manner as in Example 1 to obtain 2 reaction product 139.6F. Glycerol acrylate is 95
% was included.

Patent applicant: NOF Corporation

Claims (4)

[Claims] (1) Acid catalyst 2 Add glyzzle acrylate or methacrylate to a mixed solution consisting of a polymerization inhibitor and water and react.After 1 reaction, the acid value is adjusted to 03-08, and then at 10-40°C under reduced pressure. A method for producing glycerol acrylate or methacrylate, which comprises dehydrating the glycerol acrylate or methacrylate. (2) The manufacturing method according to claim 1, in which glycidol is present in the mixed liquid. (3) The production method according to claim 1, wherein glycerol acrylate or methacrylate is present in the mixed liquid. (4) The production method according to claim 1, wherein glycerin is present in the combined solution.