JP3866430B2 - Production method of (meth) acrylic acid ester - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a (meth) acrylic acid ester from a (meth) acrylic acid ammonium salt and an alcohol.
[0002]
[Prior art]
As a method for producing (meth) acrylic acid ester, a method of reacting (meth) acrylic acid and alcohol using an acid catalyst such as sulfuric acid (direct esterification reaction), a tin or titanium-based catalyst, etc. ) A method of reacting an ester such as methyl acrylate with an alcohol (transesterification reaction) is known. About these methods, in order to improve the yield of (meth) acrylic acid ester, examination, such as improving a catalyst from old times, is made | formed.
[0003]
The ammonium methacrylate salt can be obtained by, for example, a side reaction of the so-called ACH method in which a methacrylic acid ester is produced from acetone cyanohydrin (ACH). Similarly, ammonium acrylate has a low utility value.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a useful (meth) acrylic acid ester in a high yield from a (meth) acrylic acid ammonium salt having little utility value.
[0005]
[Means for Solving the Problems]
That is, the present invention is the presence of an acidic ion exchange resin, a liquid phase, in the absence of a solvent (meth) reacting an ammonium salt of acrylic acid and an alcohol (meth) acrylic acid esters, in particular porous as acidic ion-exchange resin (Meth) acrylic acid ester production method using a strong acidic ion exchange resin.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the acid catalyst is not particularly limited as long as it has acidity, and examples thereof include inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as paratoluenesulfonic acid and methanesulfonic acid, and acidic ion exchange resins. The acid catalyst is preferably an acidic ion exchange resin that allows easy separation of the reaction solution after completion of the reaction and the catalyst. Particularly, a porous strong acidic ion exchange resin has a reaction rate higher than that of a gel type or weakly acidic ion exchange resin. There is an advantage that the deterioration with time is small and the deterioration of the catalyst is small.
[0007]
In the present invention, the method for producing the (meth) acrylic acid ammonium salt, which is a raw material for the esterification reaction, is not particularly limited. For example, α-obtained by hydration reaction of acetone cyanohydrin using manganese dioxide or the like as a catalyst. Examples thereof include a method of producing hydroxyisobutyric acid amide in a gas phase contact with a phosphoric acid catalyst and the like, a method of producing by neutralization reaction of (meth) acrylic acid and ammonia, and the like. Moreover, you may utilize the ammonium methacrylate salt byproduced by the ACH method as a raw material. (Meth) acrylic acid ammonium salt can be used as a raw material in a solution state such as an aqueous solution or in a solid salt state.
[0008]
In the present invention, the type of alcohol as the other raw material is not particularly limited. For example, alkanols, alkoxyalkanols, alkenoxyalkanols, alkenols, phenoxyalkanols, cycloalkanols, alkylcycloalkanols, cyclo Alkyl alkanols, phenyl alkanols, alkylphenyl alkanols, haloalkanols, cyanoalkanols and aminoalkanols can be used, preferably alkanols, alkenols and aminoalkenols, particularly preferably Alkanols.
[0009]
Examples of such alcohol include methanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, and lauryl. Alcohol, stearyl alcohol, tridecanol, dimethylaminoethanol, diethylaminoethanol, cyclohexanol, 3,3,5-trimethylcyclohexanol, 4-tertiarybutylcyclohexanol, phenol, benzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl Alcohol, phenoxyethanol, methoxyethanol, ethoxyethanol, butoxyethanol, allyl alcohol, methallyl alcohol, etc. And the like.
[0010]
In this invention, the quantity of the alcohol used for reaction is 0.8-10000 mol normally with respect to 1 mol of (meth) acrylic acid ammonium salt, Preferably it is 1-500 mol.
[0011]
In the present invention, the reaction between the (meth) acrylic acid ammonium salt and the alcohol needs to be carried out in a liquid phase, but the reaction may be carried out either batchwise or continuously. In this case, the reaction can be carried out without a solvent, but a solvent may be used if necessary. Examples of the solvent that can be used include polar solvents such as acetone, methyl ethyl ketone, and ethyl acetate, and nonpolar solvents such as hexane, toluene, and chloroform. This reaction is preferably performed in the presence of a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether and oxygen.
[0012]
In the present invention, when water generated by the reaction is removed from the reaction system using an apparatus such as a Dean stack and a distillation column, the reaction proceeds advantageously on equilibrium. The reaction temperature varies depending on the starting alcohol. For example, in the case of an alcohol having a property of azeotropically with water such as isopropanol and 1-butanol, the azeotropic temperature is preferably set to the reaction temperature. The reaction pressure is from reduced pressure to several atmospheres.
[0013]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. The product was analyzed by gas chromatography with a flame type detector. Moreover, the reaction rate of (meth) acrylic acid ammonium salt in an Example, the selectivity of (meth) acrylic acid ester, and the yield of (meth) acrylic acid ester were computed by following Formula.
Reaction rate of ammonium (meth) acrylate (%) = (B / A) × 100
Selectivity of (meth) acrylic acid ester (%) = (C / B) × 100
Yield of (meth) acrylic acid ester (%) = (C / A) × 100
Here, A represents the number of moles of the supplied (meth) acrylic acid ammonium salt, B represents the number of moles of the reacted (meth) acrylic acid ammonium salt, and C represents the number of moles of the (meth) acrylic acid ester produced.
[0014]
[Example 1]
Using a reflux apparatus equipped with a 20-stage Oldershaw distillation column, in a 2 L four-necked flask with side tubes, 17.3 g (0.17 mol) of ammonium methacrylate, 1253 g (16.9 mol) of 1-butanol and 105 g of Amberlyst 15E (manufactured by Rohm and Haas), which is a porous strongly acidic ion exchange resin, was placed in a flask and stirred under an air stream to conduct an esterification reaction for 7 hours. During this time, water produced by the reaction was removed out of the system by azeotropy with 1-butanol. The reaction temperature at this time was 108 ° C. Next, this reaction solution was filtered at normal pressure to separate the catalyst, and then the filtrate was analyzed by gas chromatography. The reaction rate of ammonium methacrylate was 95.5% and the selectivity of butyl methacrylate was The yield of 99.9% and butyl methacrylate was 95.4%.
[0015]
[Example 2]
The reaction was conducted in the same manner as in Example 1 except that 882 g (27.3 mol) of methanol was used in place of 1-butanol and the reaction temperature was 64 ° C. The reaction rate of ammonium methacrylate was 89.5. %, Methyl methacrylate selectivity 99.9%, and methyl methacrylate yield 89.4%.
[0016]
[Example 3]
When 950 g (15.3 mol) of 2-propanol was used instead of 1-butanol and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 82 ° C., the reaction rate of ammonium methacrylate was 93. 0.5%, 2-propyl methacrylate selectivity was 99.9%, and 2-propyl methacrylate yield was 93.4%.
[0017]
[Example 4]
The reaction was conducted in the same manner as in Example 1 except that 983 g (21.4 mol) of ethanol was used instead of 1-butanol and the reaction temperature was 79 ° C. The reaction rate of ammonium methacrylate was 97.0. %, The selectivity of ethyl methacrylate was 99.9%, and the yield of ethyl methacrylate was 96.9%.
[0018]
[Example 5]
The reaction was conducted in the same manner as in Example 1 except that 1095 g (14.8 mol) of tertiary butanol was used instead of 1-butanol and the reaction temperature was 79.3 ° C. Reaction of ammonium methacrylate salt The rate was 95.0%, the selectivity for tertiary butyl methacrylate was 96.5%, and the yield of tertiary butyl methacrylate was 91.7%.
[0019]
[Example 6]
The reaction was conducted in the same manner as in Example 1 except that 18.5 g (0.21 mol) of ammonium acrylate was used instead of ammonium methacrylate, and the reaction rate of ammonium acrylate was 97.0%. The selectivity of butyl acrylate was 99.5%, and the yield of butyl acrylate was 96.5%.
[0020]
[Example 7]
The reaction was conducted in the same manner as in Example 1 except that 10.7 g of DIAION PK216 (manufactured by Mitsubishi Chemical Corporation), which is a porous strongly acidic ion exchange resin, was used instead of Amberlyst 15E. The rate was 94.0%, the selectivity for butyl methacrylate was 99.3%, and the yield of butyl methacrylate was 93.3%.
[0021]
【The invention's effect】
According to the present invention, a useful (meth) acrylic acid ester can be produced with good yield from an ammonium salt of (meth) acrylic acid having little utility value.

Claims (2)

A method for producing a (meth) acrylic acid ester, in which ammonium (meth) acrylate is reacted with an alcohol in a liquid phase and without a solvent in the presence of an acidic ion exchange resin . The method for producing a (meth) acrylic acid ester according to claim 1, wherein the acidic ion exchange resin is a porous strong acidic ion exchange resin.