KR100748437B1 - Reaction process for 4-hydroxybutyl acrylate production using cation exchange resin - Google Patents

Abstract

Provided is a method for preparing 4-hydroxybutyl acrylate used as a material for preparing a paint for the top coating of automobiles, with high yield and high selectivity. A method comprises the step of reacting acrylic acid and 1,4-butanediol with a cation exchange resin catalyst as a solid acid catalyst to prepare 4-hydroxybutyl acrylate, wherein the amount of acrylic acid, 1,4-butanediol and the cation exchange resin catalyst are 55-65 wt%, 34-45 wt% and 0.4-1.7 wt%, respectively. The cation exchange resin catalyst is any one selected from Amberlyst 15 (wt) catalyst or Amberlyst 15 (dry) (Rohm and Hass). Preferably the reaction is carried out at a temperature of 100-110 deg.C.

Description

Reaction process for 4-hydroxybutyl acrylate production using cation exchange resin}

1 is a cation exchange resin catalyst of the present invention for the catalyst DOWEX HCR-S (E) and heteropolyacid-type cesium partial substitution salts compared to Amberlyst 15 (wet), Amberlyst 15 (dry) This is a graph comparing the production performance of 4-hydroxybutyl acrylate (4-HBA) obtained for 6 hours after the reaction,

2 is a 4-hydroxybutyl acrylate obtained by changing the amount to 50, 100, 200 mg of the cation exchange resin catalyst Amberlyst 15 (dry) of the present invention for 6 hours after the reaction (4- HBA) is a graph comparing the production yield,

3 is a table showing examples of physicochemical properties and preferred conditions of use of the catalyst Amberlyst 15 (dry) used in the present invention.

The present invention relates to a method for producing 4-hydroxybutyl acrylate (4-HBA) using a cation exchange resin catalyst, specifically 4-hydroxybutyl acrylate (4-HBA) which is a raw material of high-grade paint for automotive tower coating The present invention relates to the development of environmentally friendly high yield and high selectivity manufacturing process technology using a cation exchange resin catalyst.

The technical field of the present invention relates to an esterification technique using an acid catalyst, and this esterification reaction is conventionally using a homogeneous reaction technique using a liquid acid catalyst such as sulfuric acid, hydrochloric acid, hydrofluoric acid, and the like.

As a prior art using a liquid acid catalyst, European Patent No. 0465853B1 discloses preparation of 4-hydroxybutyl (meth) acrylate using a liquid acid catalyst, and US Patent No. 6078528 discloses a hydroxyalkyl monoacryl using a Stannoxane catalyst. Rate production is disclosed.

U. S. Patent No. 6552218 also describes the preparation of hydroxyalkyl (meth) acrylates by reaction of acrylic acid with alkylene oxide.

However, the use of the conventional liquid acid catalyst including the prior art as described above has problems such as post-reaction treatment, reactor corrosion problems, discharge of environmental pollutants, etc., which requires the development of a solid acid catalyst that can replace the liquid acid catalyst. (Mark A. Harmer, Qun Sun, Applied Catalysis A, Vol. 221, 45-62, 2001).

An object of the present invention for solving the above problems is to use 4-hydroxybutyl acrylate (4-HBA), which is a raw material of high-grade paint for automobile tower coating, using a cation exchange resin catalyst which is a solid acid catalyst. It is to provide a process for producing in high yield and high selectivity.

The present invention, which achieves the object as described above and removes the drawbacks of the prior art, is more resistant to light, chemical and abrasion than 2-hydroxyethyl acrylate (2-HEA), which is conventionally used as a paint and an adhesive. In the synthesis of 4-hydroxybutyl acrylate (4-HBA), which is a raw material of this strong and high-grade paint for automobile tower coating, high yield and high selectivity using an environmentally friendly cation exchange resin Amberlyst 15 as a solid acid catalyst. Was developed for the production of 4-hydroxybutyl acrylate (4-HBA).

In addition, the optimum concentration of the cation exchange resin catalyst for producing high yield and high selectivity of 4-hydroxybutyl acrylate (4-HBA) was determined.

As the solid acid catalyst used in the present invention, a cation exchange resin catalyst is used, which reacts with the reaction product in the esterification reaction of acrylic acid and 1,4-butanediol to produce 4-hydroxybutyl acrylate (4-HBA). It is an environmentally friendly catalyst that can be separated and the catalyst can be reused.

The cation exchange resin catalysts are Amberlyst 15 (wet) and Amberlyst 15 (dry), which are cation exchange resin catalysts of ROHM AND HAAS.

Amberlyst 15 catalyst, a cation exchange resin, is very active and selectable for 4-hydroxybutyl acrylate (4-HBA) production.

Amberlyst 15 is a solid acid catalyst that is insoluble in organic solvents, is easy to separate from reaction products after reaction, and can be reused as a catalyst to reduce environmental pollution by discarding acid catalyst generated after acrylate production. It is an excellent environmentally friendly catalyst.

The solid acid catalyst has the advantage of being very easy to separate from the liquid product, and can be reused after separation. The separation between the catalyst and the reaction product is carried out when the reactor is stored for a certain time after the reaction due to the difference in density between the solid catalyst and the liquid product. At the bottom, the solid catalyst settles and the liquid product is easily separated. The catalyst thus recovered can be used again.

The use concentration of Amberlyst 15 as catalyst is 0.4 to 1.7 weight percent based on the weight of the reactants, which is most suitable for the production of high yield and high selectivity of 4-hydroxybutyl acrylate (4-HBA).

Looking at the composition ratio that is added to the reaction between the reactant and the catalyst of the present invention including the above catalyst is as follows.

In the present invention, 55 to 65% by weight acrylic acid (AA), 35 to 45% by weight 1,4-butanediol (BD) and 0.4 to 1.7% by weight cation exchange resin as a catalyst are mixed as reactants .

In addition, the reaction temperature in the reaction is in the range of 100 ~ 110 ℃ is very preferred for high yield and high selectivity 4-hydroxybutyl acrylate, and also most preferable in terms of production reaction rate.

In the reactant composition, the molar ratio of acrylic acid (AA) and 1,4-butanediol (BD) is most preferably 60:40 at AA: BD = 70: 30.

In addition, the reaction time when the reactant and the catalyst is added is most preferably 5 hours to 8 hours.

When the reactant acrylic acid is larger than the upper limit in the numerical range, the yield of 1,4-butanediol diacrylate, which is the second product, is high, resulting in a lower yield of 4-hydroxybutyl acrylate. If less, there is a problem in that an unreacted amount of reactant 1,4-butanediol is present, which makes it very difficult to separate the product later.

In addition, the upper limit and the lower limit of the reactant 1,4-butanediol concentration are the same as the lower limit and the upper limit of the reactant acrylic acid concentration.

The upper limit and the lower limit of the reaction temperature are high when the reaction temperature is 110 ℃ or higher, the yield of 1,4-butanediol diacrylate as the second product is very high, and the loss of the reactant is caused by the evaporation of the reactant acrylic acid. In addition, when the temperature is 100 ° C. or less, the reaction rate is very slow, and thus, it takes a long time to obtain the product 4-hydroxybutyl acrylate in high yield.

In addition, when the value of the catalyst is lower than the above limit, the production rate of 4-hydroxybutyl acrylate is too low, and the operation cost of the reaction process is required a lot. -Manufacturing reaction with butanediol diacrylate is advanced.

If the reaction time of the reactant and the catalyst is less than 5 hours, the reaction does not occur smoothly, if the reaction time is greater than 8 hours because there is an economic problem.

Also, as cation exchange resins, Amberlyst 15 (wet) and Amberlyst 15 (dry) are the two catalysts described by Rohm & Haas, which are based on catalyst performance, operating temperature, average pore size, surface area and porosity. And the same, but only the percentage of moisture content contained in the two catalysts is different.

Amberlyst 15 (dry); Moisture content percentage is 1.5% or less

Amberlyst 15 (wet); 52% moisture content

Hereinafter, the configuration and the operation of the embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1 is a cation exchange resin catalyst of the present invention for the catalyst DOWEX HCR-S (E) and heteropolyacid-type cesium partial substitution salts compared to Amberlyst 15 (wet), Amberlyst 15 (dry) As a graph comparing the production performance of 4-hydroxybutyl acrylate (4-HBA) obtained for 6 hours after the reaction, the amount of added acrylic acid and 1,4-butanediol and each catalyst is shown in Examples 1,2 and Comparative Examples described below. Same as 1,2

As shown, it can be seen that the yield by using the catalyst of the present invention is significantly higher than the yield of the catalyst to be compared.

The reason for this is that the high yield activity of the Amberlyst 15 catalyst is higher in catalytic acid amount than other solid acid catalysts, and moreover, the pore structure of the catalyst is very suitable for preparing 4-hydroxybutyl acrylate.

Figure 2 is a 4-hydroxybutyl acrylate (4-HBA obtained for 6 hours after the reaction while changing the amount to 50, 100, 200 mg in the cation exchange resin catalyst Amberlyst 15 (dry) of the present invention ) As a graph comparing the production yield, the amounts of the added acrylic acid, 1,4-butanediol and the catalyst are the same as in Example 3 described below.

As shown, the yield according to the amount of the catalyst used in the present invention can be seen that the highest dose of 0.83wt% of 100mg including 7g acrylic acid and 5g 1,4-butanediol reference catalyst.

As mentioned previously in the catalyst concentration effect, when the concentration is high, the reaction rate is very high, so that the yield of the second product, 1,4-butanediol diacrylate is obtained, and the yield of 4-hydroxybutyl acrylate is relatively low. . On the contrary, when the concentration is low, the reaction rate is lowered, and the yield of 4-hydroxybutyl acrylate obtained in a certain time is lowered.

3 is a table illustrating the physicochemical properties and preferred conditions of use of the catalyst Amberlyst 15 (dry) used in the present invention.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, these examples do not limit the scope of the present invention.

Example 1

As a reaction product, 7 g (6.7 ml) of acrylic acid and 5 g (4.9 ml) of 1,4-butanediol were added to 200 mg of a cation exchange resin Amberlyst 15 (wet) catalyst under a reaction temperature of 100 ° C. The 4-hydroxybutyl acrylate (4-HBA) yield obtained for the reaction 6 hours was 45% by weight.

At this time, just to determine the effect of the catalyst, all the conditions were kept the same and the experiment was performed by changing the type of catalyst.

Example 2

Under the same experimental conditions as in Example 1, 200 mg of a cation exchange resin Amberlyst 15 (dry) catalyst was added thereto, and as a result of reaction, 54 weight percent of 4-hydroxybutyl acrylate (4-HBA) was added for 6 hours. Prepared.

Example 3

In the preparation of 4-hydroxybutyl acrylate using acrylic acid and 1,4-butanediol, an appropriate use concentration of cation exchange resin Amberlyst 15 (dry) as a catalyst was investigated.

Using reactant 7g (6.7 ml) and 5g (4.9 ml) of 1,4-butanediol, 50, 100 and 200 mg of cation exchange resin Amberlyst 15 (dry) catalyst were added at a reaction temperature of 120 ° C., respectively. As a result of the experiment, the yield of 4-hydroxybutyl acrylate obtained during 6 hours of reaction using the 100 mg catalyst was the highest at 60 weight percent.

 [Comparative Example 1]

Reaction experiment under the same experimental conditions as in Example 1 using 200 mg of the cation exchange resin DOWEX HCR-S (E) catalyst for comparison with the activity of the cation exchange resin Amberlyst 15 (wet) catalyst of Example 1 As a result, 17 weight percent of 4-hydroxybutyl acrylate (4-HBA) was prepared during the reaction for 7 hours.

[Comparative Example 2]

In order to compare the activity of the cation exchange resin Amberlyst 15 (wet) catalyst of Example 1, the reaction was carried out under the same experimental conditions as in Example 1 using 200 mg of an acidic cesium partial substitution salt catalyst of heteropolyacid. 18 weight percent of 4-hydroxybutyl acrylate was prepared for 6 hours of reaction.

The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.

As shown in the above and Examples and Comparative Examples, the present invention shows high yield, high selectivity, and environmentally friendly cation exchange resin amber in the production of 4-hydroxybutyl acrylate, which is used as a raw material for high-end paint for automobile top coating. The advantage is the development of a reaction process using Amberlyst 15.

Specifically, the production of 4-hydroxybutyl acrylate using a cation exchange resin as a solid acid catalyst significantly improves problems such as device corrosion and environmental pollutant emissions generated by using a uniform catalyst such as sulfuric acid, hydrofluoric acid, and hydrochloric acid. It is very environmentally friendly.

In addition, this invention is a useful invention with the advantage of developing a process that can determine the amount of catalyst added in the production of high yield and high selectivity of 4-hydroxybutyl acrylate based on the amount of reactants to be treated. will be.

Claims (5)

delete In the manufacturing method of 4-hydroxybutyl acrylate which is a raw material of high-grade paint for automotive top coating, 4-hydroxybutyl acrylate was prepared by adding a cation exchange resin catalyst, which is a solid acid catalyst, to acrylic acid and 1,4-butanediol. The input ratio of the acrylic acid, 1,4-butanediol and cation exchange resin catalyst is 55 ~ 65wt% acrylic acid, 34 ~ 45wt% 1,4-butanediol and 0.4 ~ 1.7wt% cation exchange resin, The cation exchange resin catalyst is any one selected from Rohm & Haas Co., Ltd. brand name Amberlyst 15 (wet) catalyst or Amberlyst 15 (dry) catalyst using a cation exchange resin catalyst Method for preparing 4-hydroxybutyl acrylate (4-HBA). delete The method of claim 2, Preparation of 4-hydroxybutyl acrylate (4-HBA) using a cation exchange resin catalyst, characterized in that the temperature of the reaction by adding the acrylic acid, 1,4-butanediol and cation exchange resin catalyst is 100 ~ 110 ℃ Way. The method of claim 2, 4-hydroxybutyl acrylate (4-HBA) using a cation exchange resin catalyst, characterized in that the reaction time by adding the acrylic acid, 1,4-butanediol and cation exchange resin catalyst is 5 hours to 8 hours Manufacturing method.

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