KR20160020901A - Method for the production process of butyl methacrylate - Google Patents

Abstract

The present invention relates to a preparation method of butyl methacrylate, which comprises the steps of: a) preparing butyl methacrylate through ester exchange reaction of n-butanol and methyl methacrylate in the presence of titanium tetrabutoxide catalyst; and b) removing the catalyst by adding glycerol to butyl methacrylate after the ester exchange reaction. The preparation method of butyl methacrylate in the present invention improves removal rate of residual solvents remaining after recovering the products after the ester exchange reaction, and has the catalyst removal process at low costs.

Description

METHOD FOR THE PRODUCTION PROCESS OF BUTYL METHACRYLATE [0002]

The present invention relates to a process for producing butyl methacrylate, and more particularly, to a process for producing butyl methacrylate which can effectively remove a catalyst using an inexpensive glycerol.

After the ester exchange reaction, the residues that are left after recovering the product are generally subjected to an incineration treatment. In this case, since the catalyst contains the catalyst, the catalyst must be removed before incineration to prevent environmental pollution. However, the titanium tetrabutoxide used as a catalyst in the transesterification reaction is not easily removed by the distillation owing to the boiling point of 203 ° C, and can be a polymer which is difficult to remove due to the condensation reaction when the temperature is increased. Therefore, a method for removing the catalyst after the transesterification reaction is a method of removing the catalyst by hydrolyzing the catalyst by adding water or removing the catalyst by using the coagulant / water, and the method of removing the catalyst by using alcohol such as ethylene glycol, pentaerythritol, And the like. Specifically, Japanese Patent Publication No. 5093103 discloses a method in which water is added to a reaction mixture after an ester exchange reaction to hydrolyze the catalyst to insolubilize it, followed by filtration to remove the catalyst. Japanese Patent Application Laid-Open No. 2011-37313 And JP-A-2007-37762 disclose a method of removing a catalyst by introducing a coagulant and water into a reaction mixture after an ester exchange reaction, and in Japanese Patent Publication No. 4591733, pentaerythritol is added to a reaction mixture after transesterification reaction To remove the catalyst.

However, in the case of the catalyst removal method using the hydrolysis, the insolubilized catalyst particles are fine and difficult to be filtered, and when the coagulant is used, the coagulant used in the reaction mixture may remain. Further, in the case of a catalyst removal method using an alcohol such as ethylene glycol or pentaerythritol, there is a problem of increase in cost due to toxicity to the environment and expensive price.

Therefore, a new catalyst removal method for solving the above problems is desperately required.

Japanese Patent Registration No. 5093103 Japanese Laid-Open Publication No. 2011-37313 Japanese Laid-Open Publication No. 2011-37762 Japanese Patent Registration No. 4591733

In order to solve the above problems of the prior art,

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a method for producing a novel butyl methacrylate which is low in the cost of the catalyst removal process, while improving the removal rate of the catalyst contained in residues remaining after transesterification.

In order to achieve the above object,

The present invention relates to a process for the production of butyl methacrylate by a) transesterifying n-butanol with methyl methacrylate under titanium tetrabutoxide catalyst; And b) removing the catalyst by adding glycerol after the transesterification reaction. The present invention also provides a process for producing butyl methacrylate.

According to the process for producing butyl methacrylate of the present invention,

The addition of glycerol after the production of butyl methacrylate has the advantage of being able to effectively remove the catalyst without the use of hydrolysis, flocculants and harmful and expensive alcohols.

Hereinafter, the method for producing butyl methacrylate of the present invention will be described in detail.

The present invention relates to a process for removing catalyst residues produced after an ester exchange reaction, which is not a conventional catalyst removal method using a hydrolysis, a coagulant, or an alcohol, To a process for producing butyl methacrylate.

To this end, the process for producing butyl methacrylate of the present invention comprises a) transesterification of n-butanol with methyl methacrylate under a titanium tetrabutoxide catalyst, Butyl methacrylate; And b) removing the catalyst by adding glycerol after the transesterification reaction.

The process for producing butyl methacrylate of the present invention comprises the steps of a) transesterifying n-butanol with methyl methacrylate under titanium tetrabutoxide catalyst to obtain butyl methacrylate Lt; / RTI > rate.

In the process for producing butyl methacrylate of the present invention, the titanium tetrabutoxide is used as a catalyst in the transesterification reaction between n-butanol and methyl methacrylate . When the titanium tetrabutoxide is added to the transesterification reaction, it is preferably added in an amount of 0.15 to 0.21% by weight based on the total weight of the reactants.

In the process for producing butyl methacrylate of the present invention, n-butanol and methyl methacrylate can be used without any particular limitation, To 99.8% can be used.

In the method for producing butyl methacrylate of the present invention, the reaction molar ratio of n-butanol to methyl methacrylate is preferably 1: 1.5 to 1: 2.45.

In the method for producing butyl methacrylate of the present invention, the transesterification reaction temperature of n-butanol and methyl methacrylate is preferably 105 to 125 ° C.

The method for producing butyl methacrylate of the present invention may further include the step b) after the step (a), adding glycerol after the transesterification to remove the catalyst.

In the method for producing butyl methacrylate of the present invention, the glycerol is preferably added in a proportion of 1 to 4 moles based on the molar amount of the titanium tetrabutoxide. If the addition ratio of glycerol is less than 1 mol, the insolubilization of the catalyst is insufficient. If the molar ratio exceeds 4 mol, the amount of the residue to be treated is increased.

In the process for producing butyl methacrylate of the present invention, it is preferable to carry out the reaction in the temperature range of 25 to 100 ° C in the case of removing the catalyst by adding the glycerol. When the temperature is lower than 25 ° C, there is a problem that the reaction rate of the catalyst and glycerol is slowed, and when it exceeds 100 ° C, unnecessary energy cost is increased.

In the method for producing butyl methacrylate of the present invention, the treatment time for removing the catalyst by adding the glycerol is preferably 1 minute to 5 hours, more preferably 1 to 2 hours. When the treatment time is less than 1 minute, there is a problem that the reaction time is short and the catalyst is not sufficiently insolubilized. When the treatment time is more than 5 hours, the process time is unnecessarily increased.

More specifically, after removal of the catalyst by the addition of glycerol, glycerol is added to insolubilize the catalyst after the transesterification reaction is completed, and the precipitated catalyst insolubles are filtered to remove the catalyst. The catalyst insolubles may be in the form of a white powder. The filtration method is not particularly limited, but preferably filter paper can be used. The pore size of the filter paper is preferably 5 to 15 μm Can be used.

The removal of the catalyst in the step b) may be performed by removing the catalyst by adding glycerol after recovering the raw material and the butyl methacrylate after the completion of the reaction.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

Example

Butyl Methacrylate  Produce

[Production Example 1]

496.4 g of methyl methacrylate and 150.0 g of n-butanol were added to a 1 L glass reactor equipped with a distillation apparatus. Then, 0.076 g of 4-hydroxy TEMPO and 0.94 g of titanium tetrabutoxide were added. Thereafter, the mixture was heated for a total of 2 hours until the internal temperature reached 111 DEG C, and methylmethacrylate as a reactant and methanol as a reaction by-product were distilled. Thereafter, the reaction mixture was cooled to room temperature. The reaction mixture was analyzed by GC and it was confirmed that the conversion rate was 94.5%. The resultant reaction mixture was distilled under reduced pressure to recover the raw material and butyl methacrylate. In this reaction, 229.4 g of butyl methacrylate was obtained and 37.9 g of a residue containing Ti was obtained as the remainder.

Removal of Catalyst

[Example 1]

25.0 g of the residue (Ti content: 3,500 ppm) obtained through the process of Preparation Example 1 was introduced into a 100 ml 1-necked flask, and 0.35 g of glycerol was added thereto. The mixture was stirred at 25 ° C for 2 hours, After cooling to room temperature, the reaction mixture containing the formed catalyst insolubles was filtered through a filter paper having a pore size of 8 μm and a diameter of 55 mm, which had a Celite 545 having a thickness of 5 mm, to obtain a filtrate of 10.3 g

[Example 2]

After the addition of glycerol, the catalyst was removed in the same manner as in Example 1 except that stirring was carried out at 100 ° C to obtain 9.7 g of filtrate.

[Comparative Example 1]

Except that 4.0 g of the residue (Ti content: 3,500 ppm) obtained through the process of Preparation Example 1 was added to a 100 ml 1-necked flask, 20.0 g of methanol was added thereto, and then the mixture was stirred. , The catalyst was removed to obtain 21.0 g of filtrate.

Experimental Example

The amounts of Ti contained in the filtrates obtained in Examples 1 and 2 and Comparative Example 1 were analyzed using ICP spectrometry (inductively coupled plasma spectrometry), and the results are shown in Table 1 below.

Ti content Ti removal rate (%) Example 1 <1 ppm 100 Example 2 <1 ppm 100 Comparative Example 1 580ppm 13

As shown in Table 1, in the case of Examples 1 and 2 prepared by the production method of butyl methacrylate of the present invention, the removal rate was almost 100% even though cheap glycerol was used. On the contrary, in Comparative Example 1, the removal rate was lower than that in Examples 1 and 2. Accordingly, it was confirmed that the production method of butyl methacrylate of Examples 1 and 2 can reduce the cost and the removal rate as compared with the case of using the conventional alcohol to remove the catalyst.

Claims (8)

a) preparing butyl methacrylate by transesterifying n-butanol with methyl methacrylate under titanium tetrabutoxide catalyst; And
b) removing the catalyst by adding glycerol after the transesterification reaction. The method according to claim 1,
Wherein the glycerol is added in an amount of 1 to 4 moles based on the molar amount of the titanium tetrabutoxide. The method of claim 2,
Wherein the step b) is carried out by adding glycerol, and then removing the catalyst insolubles precipitated by filtration. The method according to claim 1,
Wherein the reaction molar ratio of n-butanol to methyl methacrylate is from 1: 1.5 to 1: 2.45. The method according to claim 1,
Wherein the temperature of the ester exchange reaction between the n-butanol and methyl methacrylate is 105 to 125 ° C. The method according to claim 1,
Wherein the step b) is carried out at a treatment temperature of from 25 캜 to 100 캜. The method according to claim 1,
Wherein the step b) is carried out at a treatment time of 1 minute to 5 hours. The method according to claim 1,
Wherein the step b) is a step of recovering n-butanol, methyl methacrylate and butyl methacrylate after the transesterification reaction and then adding glycerol. &Lt; / RTI &gt;