CN102146038A

CN102146038A - Method for preparing ditrimethylolpropane tetraacrylate

Info

Publication number: CN102146038A
Application number: CN2010105571561A
Authority: CN
Inventors: 黄凤岐; 李健
Original assignee: TIANJIN TIANJIAO RADIATION CURABLE MATERIAL CO Ltd
Current assignee: Tianjin Tiaojiao Chemical Co., Ltd.
Priority date: 2010-11-24
Filing date: 2010-11-24
Publication date: 2011-08-10

Abstract

The invention discloses a method for preparing ditrimethylolpropane tetraacrylate. The method comprises the following steps of: (1) putting ditrimethylolpropane and acrylic acid serving as main materials into an esterification reaction container, adding a solvent, a catalyst and a polymerization inhibitor A, and performing stirring reaction to obtain a reaction material; (2) controlling the pressure in the esterification reaction container at -0.04 to -0.08MPa, raising the temperature in the esterification reaction container till reflux liquid flows out, preserving the heat, and starting cooling to normal temperature when no reflux liquid flows out or the detected acid value in a reaction solution is 30 to 50mgKOH/g; (3) transferring the reaction material into a washing container, adding alkali liquor, controlling the pH value of the reaction material at 7 to 8, standing, and discharging the wastewater of the lower layer after the reaction material is demixed; and (4) transferring the wastewater-removed reaction material to a distillation container, adding a polymerization inhibitor B, vacuumizing the distillation container, and removing methylbenzene by distillation to obtain the product. The product prepared by adopting the method disclosed by the invention has high purity, good color and high yield.

Description

The preparation method of ditrimethylolpropane tetraacrylate

Technical field

The present invention relates to a kind of synthetic technology of preparing of Chemicals, particularly a kind of preparation method of ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate are applicable to and do radiation curing reactive diluent.

Background technology

At present, the method for preparing production technology employing normal pressure esterification of ditrimethylolpropane tetraacrylate, reaction process easily causes the material polymerization, product colour is dark, and look is number usually greater than No. 70, and product yield is low, product yield generally is lower than 70%, can not satisfy the needs that high-quality product is produced in preparation.

Summary of the invention

The present invention provides a kind of preparation method of ditrimethylolpropane tetraacrylate for solving the technical problem that exists in the known technology, and this method can reduce the generation of polymkeric substance, and product colour is shallow, quality height, yield height.

The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is: a kind of preparation method of ditrimethylolpropane tetraacrylate, may further comprise the steps: (1) puts into the esterification container with major ingredient ditrimethylolpropane and vinylformic acid, add solvent, add catalyzer, add stopper A, stirring reaction obtains reaction mass; (2) the esterification container vacuumizes, pressure in the control esterification container is-0.04～-0.08Mpa, temperature in the rising esterification container is to there being phegma to flow out, insulation, flow out or acid number in detecting reaction soln when being 30～50mgKOH/g until no phegma, begin to be cooled to normal temperature; (3) reaction mass is transferred in the washing container, adds alkali lye, the pH value of control reaction mass is 7～8, leaves standstill, and after the reaction mass layering, the waste water of lower floor is discharged; (4) reaction mass that will remove waste water is transferred to distil container, adds stopper B, and distil container vacuumizes, and toluene is removed in distillation, can obtain product.

The present invention can also adopt following technical scheme:

Described solvent is toluene or dimethylbenzene.

Described catalyzer is phosphoric acid or tosic acid.

Described stopper A is a thiodiphenylamine, and described stopper B is the 2.6-di-tert-butyl-4-methy phenol.

Described stopper A is a cupric chloride, and described stopper B is 2 tertiary butyls-4-methylphenol.

The alkali lye that adds in the described step (3) is any one in sodium hydroxide, yellow soda ash and the sodium hydrogen carbonate solution.

Advantage and positively effect that the present invention has are: adopt the vacuum esterification method to produce the ditrimethylolpropane tetraacrylate, the product purity height the invention solves problems such as easy polymerization of product and product colour be dark, has improved product yield, and technology is simple, convenient control.

Embodiment

For further understanding summary of the invention of the present invention, characteristics and effect, exemplify following examples now, be described in detail as follows:

A kind of preparation method of ditrimethylolpropane tetraacrylate may further comprise the steps:

(1) method with existing normal pressure esterification is identical, major ingredient ditrimethylolpropane and vinylformic acid are put into the esterification container, add toluene according to 50～90% of ditrimethylolpropane and vinylformic acid total amount mass percent, add tosic acid according to 1.2～4.2% of ditrimethylolpropane and vinylformic acid total amount mass percent, add thiodiphenylamine according to 0.3～0.5% of ditrimethylolpropane and vinylformic acid total amount mass percent, stirred 2～9 hours, carry out esterification, obtain reaction mass;

(2) vacuum pump on the unlatching esterification container, pressure in the control esterification container is-0.04～-0.08Mpa, temperature in the rising esterification container is to there being phegma to flow out, begin insulation, toluene and water azeotropic will react the water that generates and constantly flow out by water trap, until no longer including that phegma flows out or acid number in detecting reaction mass when being 30～50mgKOH/g, looking esterification finishes, temperature in the esterification container is reduced to normal temperature, and normal temperature is often referred to 20～25 ℃; Step (2) is different with the method for existing normal pressure esterification, employing be the vacuum esterification method.

(3) reaction mass is transferred in the washing container, adds sodium hydroxide solution, the pH value of control reaction mass is 7～8, leaves standstill, and after the reaction mass layering, the waste water of lower floor is discharged; The pH value of control reaction mass is 7～8, is in one preferably in the acid base equilibrium to guarantee reaction mass.

(4) method with existing normal pressure esterification is identical, the reaction mass of removing waste water is transferred to distil container, add the 2.6-di-tert-butyl-4-methy phenol according to 0.4～0.6% of ditrimethylolpropane and vinylformic acid total amount mass percent, open the vacuum pump on the distil container, the pressure of control in the distil container is-0.06～-0.07Mpa, toluene is removed in distillation, can obtain product.The toluene of removing is recyclable to be utilized again, and the product that obtains is after cooling, filtering, and packing gets final product.

The something in common that aforesaid method and available technology adopting normal pressure esterification legal system are equipped with the method for ditrimethylolpropane tetraacrylate also has:

Above-mentioned solvent is toluene or dimethylbenzene.

Above-mentioned catalyzer is phosphoric acid or tosic acid.

When above-mentioned stopper A was thiodiphenylamine, stopper B was the 2.6-di-tert-butyl-4-methy phenol.

When above-mentioned stopper A was cupric chloride, stopper B was 2 tertiary butyls-4-methylphenol.

The alkali lye that adds in the above-mentioned steps (3) is any one in sodium hydroxide, yellow soda ash and the sodium hydrogen carbonate solution.

Table 1 prepares the process control data table of three embodiment of ditrimethylolpropane tetraacrylate for adopting above-mentioned steps:

Table 1:

Table 2 is the correlated tabulation of relevant data of above-mentioned three embodiment and normal pressure esterification method.

Table 2:

Embodiment	Product ester content %	Product look APHA	Product yield %
				1	97.82	60	87.3
2	99.21	55	85.1
				3	98.86	65	89.2
The normal pressure esterification method	92.56	100	67.1

By contrast in the table data as can be known, adopt the vacuum esterification, its degree of esterification is good, the ester content height, look is number little, the yield height.

Claims

1. the preparation method of a ditrimethylolpropane tetraacrylate is characterized in that, this method may further comprise the steps:

(1) major ingredient ditrimethylolpropane and vinylformic acid are put into the esterification container, add solvent, add catalyzer, add stopper A, stirring reaction obtains reaction mass;

(2) the esterification container vacuumizes, pressure in the control esterification container is-0.04～-0.08Mpa, temperature in the rising esterification container is to there being phegma to flow out, insulation, flow out or acid number in detecting reaction soln when being 30～50mgKOH/g until no phegma, begin to be cooled to normal temperature;

(3) reaction mass is transferred in the washing container, adds alkali lye, the pH value of control reaction mass is 7～8, leaves standstill, and after the reaction mass layering, the waste water of lower floor is discharged;

(4) reaction mass that will remove waste water is transferred to distil container, adds stopper B, and distil container vacuumizes, and toluene is removed in distillation, can obtain product.

2. the preparation method of ditrimethylolpropane tetraacrylate according to claim 1 is characterized in that, described solvent is toluene or dimethylbenzene.

3. the preparation method of ditrimethylolpropane tetraacrylate according to claim 1 is characterized in that, described catalyzer is phosphoric acid or tosic acid.

4. the preparation method of ditrimethylolpropane tetraacrylate according to claim 1 is characterized in that, described stopper A is a thiodiphenylamine, and described stopper B is the 2.6-di-tert-butyl-4-methy phenol.

5. the preparation method of ditrimethylolpropane tetraacrylate according to claim 1 is characterized in that, described stopper A is a cupric chloride, and described stopper B is 2 tertiary butyls-4-methylphenol.

6. the preparation method of ditrimethylolpropane tetraacrylate according to claim 1 is characterized in that, the alkali lye that adds in the described step (3) is any one in sodium hydroxide, yellow soda ash and the sodium hydrogen carbonate solution.