JPS61246157A - Production of n-substituted acrylamide or methacrylamide - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a functional high polymer material readily in high yield at a low cost without using water in the reaction, by reacting a specific amine compound with acrylic acid, etc., in the presence of an alkali metal carbonate in an organic solvnet. CONSTITUTION:An amine compound expressed by formula I (R<1> and R<2> are H or methyl; m and n are 0-20) is reacted with an acryloylor methacryloyl halide expressed by formula II (R<3> is H or methyl; X is Cl or Br) in the presence of an alkali metal carbonate, e.g. Na2CO3 or K2CO3, in an organic solvent, e.g. methanol, ethanol,2-methoxyethanol or acetone, to afford the aimed N- substituted acrylamide or methacrylamide.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to N-substituted acrylamides or methacrylamides [hereinafter referred to as N-substituted (meth)acrylamides]. ] related to the manufacturing method.

The N-substituted (meth)acrylamide provided by the present invention can be polymerized by itself or copolymerized with other polymerizable vinyl monomers to form photosensitive resins.
It is expected to be applied in various fields as a functional polymer material such as ultraviolet curable resin.

<Prior art> Conventionally known methods for synthesizing N-substituted (meth)acrylamides include, for example, producing N,-(2-hydroxyethyl)methacrylamide by reacting ethanolamine with methyl methacrylate. Method of synthesis (USSR Patent No. 173753, T. G. Kulagina et al., Sin, Modif, Sin.

Po11m, 20 (1971)), a method for synthesizing N-(2-hydroxyethyl) methacrylamide by using an aqueous sodium hydroxide solution as a reaction aid in the reaction of ethanolamine and methacrylic acid chloride (Japanese Unexamined Patent Publication No. 1973 -102089) etc.

However, the method described in the above-mentioned literature, which involves the reaction of ethanolamine and methyl methacrylate, has the disadvantage that a reduction in yield due to by-products of Michael adducts and polymerization is unavoidable.

In the method described in the above literature using an aqueous solution of ethanolamine and sodium methacrylic acid chloride, the reaction product N-(2-hydroxyethyl)methacrylamide is water-soluble, so water can be easily removed from the reaction product. rather, they usually have to be removed by distillation, during which polymerization of the product is particularly likely.
The disadvantage is that the yield is significantly reduced.

Problems to be Solved by the Present Invention The present invention aims to produce N-substituted (meth)acrylamides in high yield while avoiding the above-mentioned by-product of Michael adducts and reduction in yield due to polymerization during reaction and purification. The object of the present invention is to provide an industrially advantageous manufacturing method.

<Means and effects for solving the problems> The present inventors have conducted extensive studies on methods for producing N-substituted (meth)acrylamides to solve the above problems. N-substituted acrylamide or methacrylic acid can be easily produced in high yield by reacting the amine compound represented by formula (II) with acrylic acid or methacrylic acid oride represented by general formula (II) in the presence of an alkali metal carbonate in an organic solvent. They discovered that amides can be produced and completed the present invention.

(In the formula, Bj represents a hydrogen atom or (II)cH,=c-cox represents a methyl group, and X represents a chlorine atom or a bromine atom.) Compounds in which the terminal of polyethylene glycol is aminated, such as acylicolamine, tetraethylene glycolamine, etc., monopropanolamine, dipropylene glycolamine,
Compounds with aminated terminals of polypropylene/glycol such as tripropylene glycolamine, and general formula (I) such as jetanolamine and dibrobanolamine
Examples include compounds in which both m and n have values of 1 or more. The amine compounds represented by the above general formula (I) used in the present invention can be used alone or in a mixture of two or more.

(Meta) represented by general formula (II) used in the present invention
Examples of the acrylic halide include acrylic chloride, acrylic bromide, methacrylic chloride, and methacrylic bromide. Regarding the amount of (meth)acrylic acid halide used above, for amine compounds,
The molar ratio is in the range of 0.5 to 4.0, preferably 0.9 to 2.0. If the molar ratio is less than 0.5, the conversion rate will decrease and a large amount of unreacted amine compound will remain in the reaction system. If the molar ratio is more than 4.0, it will not only be economically disadvantageous but also make the treatment after the reaction complicated.

Examples of the alkali metal carbonate used in the present invention include sodium carbonate and potassium carbonate. The amount of the alkali metal carbonate used for the amine compound is as follows:
The molar ratio can be selected from the range of 0.3 to 3.0, preferably 0.45 to 1.5. If the molar ratio is less than 0.3, the yield of the product coating will be reduced, and if the molar ratio is greater than 3.0, it will only be economically disadvantageous.

Alkali metal carbonates such as those exemplified above have extremely low solubility in the reaction products and solvents compared to, for example, alkali metal hydroxides, and therefore, even if the alkali metal carbonates are used in excess of the amine compound, It has the advantage that it can be easily removed by filtration after the reaction. This is particularly advantageous if the reaction product is not or cannot be purified by distillation.

The organic solvent used in the present invention is preferably one that can substantially dissolve the amine compound and the N-substituted (meth)acrylamide product. Specifically, for example, methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 1-propanol, 2
-propertool, 2-methyl-1-propertool, 1-
Alcohols such as butanol and 2-butanol, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, ethers such as diethyl ether and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, N, N Examples include amides such as dimethylformamide and N,N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide, and halogen compounds such as dichloromethane and chloroform. The above organic solvents may be used alone or in a mixture of two or more.

The present invention is characterized in that the reaction is carried out substantially in the presence of water in the reaction system, but the amount of water that inevitably mixes in the raw materials is about 5% by weight in the reaction system. It is acceptable if it is within this range.

The reaction temperature is -10 to 60°C, preferably 0 to 40°C. The reaction is slow at temperatures lower than -10℃, and 60℃
At very high temperatures, side reactions such as hydrolysis and polymerization tend to occur, which is undesirable.

(9) Although it is not necessarily essential to have a polymerization inhibitor present in the reaction system, it is possible to use methoquinone, hydroquinone, phenothiazine, cupric chloride, etc., which are generally known as polymerization inhibitors, by adding them to the reaction system. good.

Embodiments of the separation and purification of the N-substituted (meth)acrylamides obtained in the present invention are described below, but these embodiments are not intended to limit the present invention. That is, after the reaction, the inorganic salts are removed by filtering the reaction mixture, the organic solvent is further removed by distillation, and if necessary, the N-substitution (meth) ) Acrylamides can be separated and purified.

<Effects of the Invention> According to the method of the present invention, by using an inexpensive alkali metal carbonate in an organic solvent without using water during the reaction, the reaction proceeds and is completed quickly, and the desired product is not produced after the reaction. There is substantially no need for a step of separating water and water, and therefore, a decrease in yield can be avoided, and N-substituted (meth)acrylamides can be obtained in high yield.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Treatment Example 1 Capacity 5 with stirrer, addition funnel, reflux condenser, thermometer
008 Ethanolamine (H, NCH, CH,
OH) 40. ON (0,655 mol) was charged anhydrous, and the internal temperature was cooled to 10° C. without stirring.

While stirring, add methacrylic acid chloride 68,5 to this.
N (0,655% #) was added dropwise over 170 minutes.

After the dropwise addition was completed, stirring was continued for an additional 120 minutes.

The internal temperature was kept below 15°C during the reaction. After the reaction was completed, the solid in the reaction mixture was filtered and washed with dichloromethane 100117. Most of the dichloromethane in the solution was distilled off by mixing the F solution and the washing solution to obtain a concentrated solution. The moisture content of this concentrate was 2.1 h. The solid produced at this time was filtered and washed again in the same manner, and then dichloromethane was distilled off to obtain 83.99 g of N-(2-hydroxyethyl)methacrylamide (yield: 99.2%). This material was further purified by distillation. boiling point 130-134
°C/2 mHg 0 Example 2 In a 300 d flask equipped with the same equipment as in Example 1, 27.0 g (0,442 mol) of ethanolamine was added.
Anhydrous sodium carbonate ao, sg (0,288 mol), 481 n9 of methoquinone, and 200 g of methanol were charged, and the internal temperature was cooled to 10° C. while stirring. While stirring, add methacrylic acid chloride 46.39 (0
, 443 mol) was added dropwise over 120 minutes. After the dripping is finished,
Stirring was continued for an additional 120 minutes. The internal temperature was kept below 15°C during the reaction. After the reaction was completed, the solid in the reaction mixture was filtered and washed with 100 WLt of methanol. Most of the methanol in the combined tear fluid and washing fluid was distilled off to obtain a concentrated solution. The moisture content of this concentrate was 1.8 h. The solid produced at this time was filtered and washed again in the same manner, and methanol was distilled off.1. , N-(2-hydroxyethyl)methacrylamide 56.9 g (yield 99.
7%).

Example 3 Ethanolamine 27.0 was added to the same reactor as in Example 2.
g (0,442 mol), anhydrous potassium carbonate 33,6
．． 9 (0,243%), Metokino 751m9. 200 d of methanol was charged, and the internal temperature was cooled to 10° C. without stirring. While stirring, 48.59 (0,464 mol) of methacrylic acid chloride was added dropwise over 75 minutes. After the dropwise addition was completed, stirring was continued for an additional 120 minutes. During the reaction, the internal temperature was kept below 15°C. After the reaction was completed, the reaction mixture was treated in the same manner as in Example 2 to obtain 56.79% of N-(2-hydroxyethyl)methacrylamide (yield: 99.3%).
I got it.

Example 4 Ethanolamine 27.0 was added to the same reactor as Example 2.
1i (0,442 mol), anhydrous potassium carbonate 33.6
11 (0,243 g mol), methokino 749, and methanol 200 mj, and while stirring, keep the internal temperature at 10°C.
It was cooled to While stirring, 42.0.9 (0,464 mol) of acrylic acid chloride was added dropwise to the mixture over 80 minutes. After the dropwise addition was completed, stirring was continued for an additional 120 minutes. The internal temperature was kept below 15°C during the reaction. After the reaction was completed, the reaction mixture was treated in the same manner as in Example 2 to obtain N-(2-hydroxyethyl)acrylamide s 0.41 (yield 99.0)
I got it.

Example 5), anhydrous potassium carbonate 33.61Co, z43 mol)
, 50 μl of methoquinone, and 200 μl of methanol were charged, and the internal temperature was cooled to 10° C. while stirring. While stirring, methacrylic acid chloride 48.5Ii (0,464
mol) was added dropwise over 80 minutes.

After the dropwise addition was completed, stirring was continued for an additional 120 minutes.

The internal temperature was kept below 15°C during the reaction. After the reaction was completed, the reaction mixture was treated in the same manner as in Example 2 to obtain 46.21 N-(2-(2-hydroxyethoxy)ethyl)methacrylamide.
(yield 99.4%).

Example 6 In a reactor similar to Example 2, jetanolamine (H
N(CH,CH,OH), )46.51 (0,442
mol), anhydrous potassium carbonate 33.6 & (0,243
mol), methokino 750m9, methanol 2ooTIL
1 was added, and the internal temperature was cooled to 10° C. without stirring. While stirring, add 48.5 g of methacrylic acid chloride to this.
(0,464 mol) was added dropwise over 80 minutes. After the dropwise addition was completed, stirring was continued for an additional 120 minutes. Internal temperature during reaction was 15℃
I kept it below. After the reaction was completed, the reaction mixture was treated in the same manner as in Example 2 to obtain N,N-bis(2-hydroxyethyl)methacrylamide 4s,si (yield 97.9%).
I got it.

Example 7 50 m9 of 1-amino-2methoquinone and 200 d of methanol were charged into the same reaction apparatus as in Example 2, and the internal temperature was cooled to 10° C. while stirring. While stirring, methacrylic acid chloride 48.5 # (0,464 mol) was added dropwise over 80 minutes.

After the dropwise addition was completed, stirring was continued for an additional 120 minutes.

The internal temperature was kept below 15°C during the reaction. The reaction mixture after the reaction process was treated in the same manner as in Example 2 to obtain N-(2-hydroxypropyl) methacrylamide 6λ0fI (yield 98.0%).
) was obtained.

Example 8 In a reactor similar to Example 1, a mixture H represented by the following formula,
N(CH,CH,0)-H (composition ratio: n=6 is 6ch, n
=7 is 11ch, n=8 is 72ch, n-9 is 8ch, n=1
0 is 3%) 153.9, anhydrous potassium carbonate 30.4 I
1 (0,230 mol), 50 μm of methoquinone, and 300 μm of methanol were charged, and the internal temperature was cooled to 10° C. while stirring. Add 45. methacrylic acid chloride to this while stirring.
9.9 (0,439 mol) was added dropwise over 80 minutes. After the dropwise addition was completed, stirring was continued for an additional 120 minutes. The internal temperature was kept below 15°C during the reaction. After the reaction is complete, the reaction mixture is 6%
, n=7 is 11%, fl=8 is 72ch, n=9 is 8
h, n = 10 was 3%) 173.1.9 was obtained.

Claims (1)

[Claims] (1) N-N-- characterized by reacting an amine compound represented by general formula (I) with an acrylic acid or methacrylic acid halide represented by general formula (II) in an organic solvent in the presence of an alkali metal carbonate. A method for producing substituted acrylamide or methacrylamide. (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R
^1, R^2 represent a hydrogen atom or a methyl group, m,
n takes a value from 0 to 20. However, m+n is 1-20. ) (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^
3 represents a hydrogen atom or a methyl group, and X represents a chlorine atom or a bromine atom. )