TW201708185A - Method of manufacturing N-vinyl carboxylic amide - Google Patents

Abstract

The present invention provides a method of manufacturing N-vinyl carboxylic amide including a thermal decomposition step in which N-(2-oxyethyl) carboxylic amide is thermally decomposed in the presence of a solid catalyst. It is preferable that the N-(2-oxyethyl) carboxylic amide be synthesized by reacting 2-oxyethylamine with an acyl compound.

Description

Method for producing N-vinyl carboxylic acid decylamine

The present invention relates to a process for producing a N-vinylcarboxylic acid guanamine which is used in a coagulant, a tackifier, an adhesive, and the like.

The present application claims priority based on Japanese Patent Application No. 2015-133471, filed on Jan.

Conventionally, N-vinylcarboxylic acid decylamine has been used in a coagulant, a tackifier, an adhesive, and the like. As a method of producing N-vinylcarboxylic acid decylamine, the following method is known.

For example, Patent Document 1 describes a method for producing N-vinyl caprolactam which reacts caprolactam with acetylene using an alkali metal as a catalyst.

Patent Document 2 proposes the following method. N-(α-alkoxyethyl)-carboxylic acid decylamine was synthesized using carboxylic acid decylamine, acetaldehyde and alcohol as raw materials. N-(α-Alkoxyethyl)-carboxylic acid amide is used to produce an intermediate product of N-vinyl carboxylic acid decylamine. It is converted to N-vinylcarboxylic acid guanamine by thermal decomposition.

Patent Document 3 carries out a gas phase intramolecular dehydration reaction of N-(2-hydroxyethyl)-N-alkylcarboxylic acid decylamine in the presence of an oxide catalyst. Thus, a method for producing an N-vinyl-N-alkylcarboxylic acid decylamine is described.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-60558

[Patent Document 2] Japanese Patent Publication No. 6-173351

[Patent Document 3] Japanese Patent No. 2660169

However, the conventional method for producing N-vinylcarboxylic acid decylamine still has a problem to be solved.

Specifically, in the production method described in Patent Document 1, it is necessary to use acetylene which is one of the raw materials. Acetylene is a igniting gas with a wide combustion range (explosion range). Acetylene is a gas that is highly dangerous to explode when exposed to high pressure or when in contact with a specific metal. Therefore, the storage and processing methods of acetylene are severely restricted.

Further, in the method described in Patent Document 2, when an N-vinylcarboxylic acid decylamine is obtained, an intermediate N-(α-alkoxyethyl)-carboxylic acid decylamine is synthesized. Regarding the acetamide, acetaldehyde, and alcohol which are the raw materials, it is necessary to strictly manage and it is difficult to obtain.

The production method described in Patent Document 3 does not use acetylene. And / or acetaldehyde. However, the production method described in Patent Document 3 is a method of synthesizing N-vinyl-N-alkylcarboxylic acid decylamine. Patent Document 3 does not describe a method of synthesizing N-vinylcarboxylic acid decylamine.

Generally, the reactivity of N-vinyl-N-alkylcarboxylic acid decylamine is different from that of N-vinylcarboxylic acid decylamine. Therefore, the method for producing N-vinyl-N-alkylcarboxylic acid decylamine is not necessarily used for the production method of N-vinylcarboxylic acid decylamine.

The present invention has been made in view of the above, and it is an object of the invention to provide a method for producing N-vinylcarboxylic acid decylamine by providing a material having high safety and easy handling.

The inventors of the present invention actively reviewed the above problems.

As a result, it was found that N-vinylcarboxylic acid decylamine can be produced by thermally decomposing N-(2-oxyethyl)carboxylic acid decylamine in the presence of a solid catalyst. The aforementioned N-(2-oxoethyl)carboxylic acid decylamine can be synthesized from an inexpensive and readily available 2-oxoethylamine and a mercapto compound.

Further, in the present invention, the N-(2-oxoethyl)carboxylic acid amide is a 2-oxoethyl group bonded to the guanamine compound of a guanamine nitrogen atom. The 2-ethoxyoxy oxygen atom is bonded to a carbon atom at the 2-position of the ethyl group by a single bond, and a substituent of a monovalent organic group (R-) or a hydrogen atom is further bonded to the oxygen atom. The 2-oxoethyl group is represented by RO-CH ₂ CH ₂ - or HO-CH ₂ CH ₂ -.

The present invention has been completed based on the above findings, and the gist thereof is as follows.

[1] A process for producing N-vinylcarboxylic acid decylamine characterized by carrying out a N-(2-oxoethyl)carboxylic acid decylamine represented by the general formula (1) in the presence of a solid catalyst The thermal decomposition step of thermal decomposition produces the N-vinylcarboxylic acid guanamine represented by the general formula (2):

(In the formula (1), R ¹ is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms; and R ² is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, and a carbon number of 1 to 6; Any one selected by the group of 7);

(In the formula (2), R ¹ is the same as the above formula (1)).

[2] The method for producing N-vinylcarboxylic acid decylamine according to [1], wherein the solid catalyst is an oxide represented by the formula (3): A _x B _y O _z (3)

(In the general formula (3), A is derived from Al, Si, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti Any one selected from Zr, Hf, V, Nb and Ta, B is an alkali metal element, O is oxygen, x, y, z are the number of atoms of each element, x>0, y≧0, z={(A The price of the price × x) + (the price of B × y)} / 2).

[3] The method for producing N-vinylcarboxylic acid decylamine according to [2], wherein the A in the above formula (3) is selected from Y, Ce, Zr and Hf.

[4] The method for producing N-vinylcarboxylic acid decylamine according to [2] or [3], wherein y = 0 in the above formula (3).

[5] The method for producing N-vinylcarboxylic acid decylamine according to [2], wherein A in the above formula (3) is any one selected from the group consisting of Al and Si.

[6] The method for producing N-vinylcarboxylic acid decylamine according to any one of [1] to [5] wherein, prior to the thermal decomposition step, the synthesis of the aforementioned N-(2-oxyethyl)carboxylic acid a synthesis step of decylamine, wherein the aforementioned synthesis step synthesizes the aforementioned N-(2-oxyethyl group) by reacting 2-oxoethylamine represented by the formula (4) with a mercapto compound represented by the formula (5) The steps of carboxylic acid guanamine:

(in the general formula (4), R ³ is selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, and a fluorenyl group having 1 to 7 carbon atoms;

(In the formula (5), R ^{1 is the} same as the above formula (1), and X is derived from a chlorine atom, a bromine atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and a decyloxy group having 2 to 7 carbon atoms. Any one selected by Cheng Zhi).

[7] The method for producing N-vinylcarboxylic acid decylamine according to [6], wherein the 2-oxyethylamine is 2-aminoethanol.

[8] The method for producing N-vinylcarboxylic acid decylamine according to [6], wherein X in the above formula (5) is an alkoxy group having 1 to 6 carbon atoms.

[9] The method for producing N-vinylcarboxylic acid decylamine according to [1], wherein R ² in the above formula (1) is a hydrogen atom.

[10] The method for producing N-vinylcarboxylic acid decylamine according to any one of [1] to [9] wherein the reaction temperature in the thermal decomposition step is from 200 ° C to 400 ° C.

The manufacturing method of the present invention is represented by the above formula (1) N-(2-oxoethyl)carboxylic acid decylamine is thermally decomposed in the presence of a solid catalyst. Thereby, the N-vinylcarboxylic acid decylamine represented by the above formula (2) is obtained. The N-(2-oxoethyl)carboxylic acid decylamine represented by the formula (1) has high safety and easy handling compared with acetylene. Further, the N-(2-oxoethyl)carboxylic acid decylamine represented by the formula (1) can be easily synthesized by a method of reacting a 2-oxyethylamine which is a readily available raw material with a mercapto compound, and Easy to get.

Therefore, according to the production method of the present invention, N-vinylcarboxylic acid guanamine can be produced safely and easily with a low environmental load.

Hereinafter, the production method of the N-vinylcarboxylic acid guanamine of the present invention will be described in detail.

(thermal decomposition step)

The method for producing N-vinylcarboxylic acid decylamine according to the present embodiment has a thermal decomposition step of thermally decomposing N-(2-oxyethyl)carboxylic acid decylamine in the presence of a solid catalyst.

"N-(2-oxoethyl)carboxylic acid decylamine"

In the production method of the present embodiment, N-(2-oxyethyl)carboxylic acid decylamine represented by the following general formula (1) is used as a thermally decomposable raw material for thermal decomposition. The N-(2-oxoethyl)carboxylic acid decylamine represented by the formula (1) has high safety and easy handling, for example, compared with acetylene. And expressed by the general formula (1) The N-(2-oxoethyl)carboxylic acid decylamine can be easily synthesized by the method described later.

(In the formula (1), R ¹ is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms; and R ² is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, and a carbon number of 1 to 6; Any one of the groups selected by the foundation of 7).

R ¹ in the above formula (1) is preferably any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group, and is preferably a methyl group.

R ² in the formula (1) is preferably a group of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group or a benzamidine group. Any one selected, more preferably a hydrogen atom or an ethylene group.

As the N-(2-oxoethyl)carboxylic acid decylamine represented by the formula (1), N-(2-oxyethyl)formamide and N-(2-oxoethyl)acetamidine are preferred. Amine, N-(2-oxoethyl)propanamide, N-(2-oxoethyl)benzamide.

Since these compounds can be easily synthesized, they can be easily obtained and are more preferable.

Examples of such compounds are, for example, N-(2-hydroxyethyl)formamide, N-(2-methoxyethyl)formamide, N-(2-ethoxyethyl)formamide, N-(2-propoxyethyl)formamide, N-(2-isopropyl Oxyethyl)carmine, N-(2-butoxyethyl)formamide, N-(2-isobutoxyethyl)formamide, N-(2-second butoxy Ethyl)formamide, N-(2-tert-butoxyethyl)formamide, N-(2-phenoxyethyl)formamide, N-(2-methyloxyethyl) Carbenamide, N-(2-acetoxyethyl) formamide, N-(2-propoxyethyl) formamide, N-(2-benzylideneoxyethyl) Formamide, N-(2-hydroxyethyl)acetamide, N-(2-methoxyethyl)acetamide, N-(2-ethoxyethyl)acetamide, N-( 2-propoxyethyl)acetamide, N-(2-isopropoxyethyl)acetamide, N-(2-butoxyethyl)acetamide, N-(2-isobutyl) Oxyethyl)acetamide, N-(2-secondoxyethyl)acetamide, N-(2-tert-butoxyethyl)acetamide, N-(2-phenoxy Ethyl ethyl acetamide, N-(2-methyloxyethyl) acetamidine, N-(2-acetoxyethyl) acetamidine, N-(2-propoxy ethoxylate Ethylamine, N-(2-benzylideneoxyethyl)acetamide, N-(2-hydroxyethyl)propanamide, N-(2-methoxyethyl)propanamide , N-(2-ethoxyethyl)propanamide, N-(2-propoxyethyl)propanamide, N-(2-isopropoxyethyl)propyl Indoleamine, N-(2-butoxyethyl)propanamide, N-(2-isobutoxyethyl)propanamine, N-(2-secondbutoxyethyl)propanamide , N-(2-Tertiyloxyethyl)propanamide, N-(2-phenoxyethyl)propanamide, N-(2-methyloxyethyl)propanamine, N -(2-Ethyloxyethyl)propanamide, N-(2-propoxyethoxyethyl)propanamine, N-(2-benzylideneoxyethyl)propanamine, N- (2-hydroxyethyl)benzamide, N-(2-methoxyethyl)benzamide, N-(2-ethoxyethyl)benzamide, N-(2-propane Oxyethyl)benzamide, N-(2-isopropoxyethyl)benzamide, N-(2-butoxyethyl)benzamide, N-(2-isobutyl) Oxyethyl)benzamide, N-(2-secondoxyethyl)benzamide, N-(2-tert-butoxyethyl)benzamide, N-(2 -phenoxyethyl)benzamide, N-(2-methyloxyethyl)benzamide, N-(2-acetoxyethyl)benzamide, N-(2 -propenyloxyethyl)benzamide, N-(2-benzylideneoxyethyl)benzamide, and the like.

Among the N-(2-oxoethyl)carboxylic acid decylamines represented by the general formula (1), N-(2-hydroxyethyl)formamide and N-(2-methyloxoxime are particularly preferred. Base ethyl) formamide, N-(2-hydroxyethyl)acetamide, N-(2-acetoxyethyl)acetamide, N-(2-hydroxyethyl)propanamide, N-(2-propoxyethoxyethyl)propanamide, N-(2-hydroxyethyl)benzamide, N-(2-benzylideneoxyethyl)benzamide.

Since these compounds can be synthesized by reacting 2-aminoethanol which is easy and inexpensive to obtain and handle with only one sulfhydryl compound, it can be more easily obtained and preferably.

Further, the N-(2-oxoethyl)carboxylic acid decylamine represented by the formula (1) is preferably N-(2-hydroxyethyl)carboxylate wherein R ² in the formula (1) is a hydrogen atom. Acid amide.

Specific examples of N-(2-hydroxyethyl)carboxylic acid decylamine are N-(2-hydroxyethyl)formamide, N-(2-hydroxyethyl)acetamide, N-(2-hydroxyethyl) Base) acrylamide, N-(2-hydroxyethyl)benzamide, and the like.

The N-(2-hydroxyethyl)carboxylic acid decylamine is a third substance which does not use a solvent and a catalyst due to the reaction of 2-aminoethanol with a carboxylic acid ester. It is preferable to synthesize it easily and in high yield. Further, 2-aminoethanol and a carboxylic acid ester which are used as a raw material of N-(2-hydroxyethyl)carboxylic acid decylamine are easily obtained and handled, and are inexpensive, which is preferable.

"Solid Catalyst"

The method for producing N-vinylcarboxylic acid decylamine of the present invention uses a solid catalyst in a thermal decomposition step. The solid catalyst is preferably, for example, based on the following aspects, and is easily industrially utilized. The solid catalyst is packed in a tubular reactor, and the thermal decomposition step can be continuously carried out by passing the thermally decomposed raw material through the reactor. Since the solid catalyst does not dissolve in the reaction liquid containing the object formed by the thermal decomposition step, it is easy to separate the object from the reaction liquid. Solid catalysts are an easy exchange aspect.

An oxide is preferably used as the solid catalyst. Oxide is less likely to cause melting or decomposition even if it is subjected to a thermal decomposition step at a high temperature, and has excellent stability and is suitable as a solid catalyst.

The oxide used as the solid catalyst is preferably used as a separate oxide from an element selected from Group 3, Group 4 or Group 5 of the lanthanoid element of aluminum, lanthanum, or the like. A composite oxide of an oxide of an alkali metal is supported on the oxide.

The solid catalyst is more preferably an oxide represented by the formula (3).

A _x B _y O _z ...(3)

(In the general formula (3), A is derived from Al, Si, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti , Zr, Hf, V, Nb, and Ta are selected, B is Alkali metal element, O is oxygen, x, y, z are the number of atoms of each element, x>0, y≧0, z={(price of A×x)+(valence of B×y)}/ 2).

As the individual oxide used as the solid catalyst (when y = 0 in the general formula (3)), specific examples are activated alumina (Al ₂ O ₃ ), tantalum (SiO ₂ ), cerium (III) oxide, and cerium oxide ( III), cerium (III) oxide, cerium (IV) oxide, titanium oxide (IV), zirconium oxide (IV), cerium (IV) oxide, vanadium oxide (V), cerium oxide (V), cerium oxide (V) Wait.

In the above, in order to obtain N-vinylcarboxylic acid decylamine in a high yield, as the individual oxide, it is preferred that A of the above formula (3) is Group 3 or 4 containing a lanthanoid element of the periodic table. Among the group elements, the preferred system A is one selected from Y, Ce, Zr or Hf. Further, as the individual oxide, cerium (III) oxide, cerium (IV) oxide, zirconia (IV) or cerium (IV) oxide is preferably used, and zirconia is particularly preferably used.

The composite oxide used in the case of the solid catalyst (in the case of y ≠ 0 in the general formula (3)) is exemplified by a composite oxide of an oxide of an alkali metal shown below, which is supported on the above-mentioned individual oxide. Specific examples of the oxide of the alkali metal include lithium oxide, sodium oxide, potassium oxide, cerium oxide, cerium oxide, and the like. Among them, sodium oxide is preferred. The oxide of the alkali metal element contained in the composite oxide may be one type or two or more types.

When the oxide represented by the formula (3) is a composite oxide (y≠0), the atomic ratio of x to y in the formula (3) is preferably 1 ≦ x / y ≦ 1000, more preferably It is 5≦x/y≦100.

Examples of such composite oxides are, for example, sodium oxide-supported silicone (Si ₂₀ Na ₂ O ₄₁ (x = 20 in the general formula (3), y = 2)), and sodium oxide-supported zirconia (Zr ₂₀ Na) ₂ O ₄₁ (x=20 in the general formula (3), y=2)), activated alumina supported by sodium oxide (Al ₂₀ Na ₂ O ₃₁ (x=20 in the general formula (3), y=2) )Wait. Among these, in order to obtain N-vinylcarboxylic acid decylamine in a high yield, it is preferred to use sodium silicate (Si ₂₀ Na ₂ O ₄₁ ) supported by sodium oxide.

The preparation method of the composite oxide used as the solid catalyst is not particularly limited, and for example, the following preparation method can be exemplified.

The solid of the above individual oxide is impregnated with an aqueous solution of an alkali metal hydroxide and heated on a hot water bath. The method of evaporating water by this, drying in air, baking, etc.

The drying temperature is preferably in the range of 80 to 160 ° C, more preferably in the range of 100 to 140 ° C. The firing temperature is preferably in the range of 500 to 700 ° C, more preferably in the range of 550 to 650 ° C. Drying and baking can be carried out at normal pressure or under pressure or reduced pressure.

It is preferably fired while passing through the gas. The gas to be introduced at the time of firing is not particularly limited as long as it does not react with the prepared composite oxide and its raw material. The gas to be introduced during the firing is preferably air or nitrogen, more preferably nitrogen.

"thermal decomposition conditions"

In the present embodiment, as a reactor for performing a thermal decomposition step of thermally decomposing N-(2-oxyethyl)carboxylic acid decylamine represented by the general formula (1) in the presence of a solid catalyst, for example, a fixed one can be used. Bed type or fluid bed type reactor. The thermal decomposition step is preferably carried out continuously using a tubular reactor of a tubular type or the like.

The reaction temperature and the reaction pressure (temperature and pressure in the reactor) in the thermal decomposition step are preferably set to be N-(2-oxyethyl)carboxylic acid decylamine represented by the general formula (1) which can be used as a thermal decomposition raw material. Maintain the temperature and pressure in the gas phase.

Specifically, the reaction temperature in the thermal decomposition step is preferably in the range of 200 to 400 ° C, more preferably in the range of 250 to 350 ° C, and can be appropriately adjusted by other reaction conditions. When the reaction temperature in the thermal decomposition step is 200 ° C or more, the thermal decomposition reaction can be promoted, productivity can be improved, and high conversion rate can be obtained. In the present embodiment, since a material having high safety is used as the material for thermal decomposition, the reaction at a high temperature of 200 ° C or higher can be promoted. Further, when the reaction temperature is 400 ° C or lower, side reactions in the thermal decomposition reaction are less likely to occur, and a high selectivity is easily obtained.

The reaction pressure in the thermal decomposition step may be normal pressure or reduced pressure, or may be pressurized as needed. The partial pressure of N-(2-oxyethyl)carboxylic acid guanamine in the reactor is preferably from 0.01 to 20 kPa, more preferably from 0.1 to 5 kPa. The partial pressure of N-(2-oxoethyl)carboxylic acid guanamine in the reactor can be supplied to the reactor by N-(2-oxyethyl)carboxylic acid by decompression in a reactor or dilution with a diluent gas. Controlled by guanamine. When the partial pressure is 0.01 kPa or more, the thermal decomposition reaction is promoted, productivity is improved, and high conversion is obtained. Further, when the partial pressure is preferably 20 kPa or less, more preferably 5 kPa or less, since a side reaction in the thermal decomposition reaction is less likely to occur, it is easy to obtain a high selectivity.

The diluent gas used for controlling the partial pressure of N-(2-oxyethyl)carboxylic acid decylamine is in a gaseous state in the range of the reaction conditions (temperature and pressure in the reactor) in the thermal decomposition step, and is not With N-(2-oxygen B The substance which reacts with the carboxylic acid decylamine and the N-vinyl carboxylic acid decylamine is not particularly limited. Specifically, the diluent gas used for the dilution is exemplified by nitrogen gas, helium gas, hydrocarbon vapor, etc., and particularly preferably nitrogen gas.

The space velocity of N-(2-oxoethyl)carboxylic acid decylamine (the flow rate of N-(2-oxyethyl)carboxylic acid guanamine in the reactor / the catalyst volume in the reactor) is preferably 100~ The range of 30000 h ^-1 , more preferably in the range of 2000 to 15000 h ^-1 , can be appropriately adjusted by other reaction conditions and the kind of N-(2-oxyethyl)carboxylic acid decylamine. When the above space velocity is 100 h ^-1 or more, preferably more than 1000 h ^-1 , generation of a side reaction due to excessive contact time of N-(2-oxyethyl)carboxylic acid decylamine with a catalyst is suppressed. Therefore, it is easy to obtain a high selection rate. Further, when the space velocity is 30,000 h ^-1 or less, the contact time of the N-(2-oxyethyl)carboxylic acid decylamine with the catalyst is sufficiently ensured. Therefore, the thermal decomposition reaction due to the catalyst is sufficiently obtained, productivity is improved, and high conversion rate is obtained.

The reaction liquid containing the object formed by the thermal decomposition step is preferably trapped in a cooled vessel.

In the reaction liquid to be collected, the N-vinylcarboxylic acid guanamine which is formed by thermal decomposition and the N-(2-oxyethyl)carboxylic acid decylamine remaining in the reaction liquid contain a thermal decomposition-generated subsidiary. product.

The N-vinylcarboxylic acid decylamine and N-(2-oxyethyl)carboxylic acid decylamine contained in the reaction liquid can be quantified by performing composition analysis of the reaction liquid using, for example, gas chromatography.

(synthesis step)

In the production method of the present embodiment, it is preferred to have a synthesis step before the thermal decomposition step. The synthesis step is a N-(2-oxoethyl)carboxylic acid decylamine represented by the general formula (1) which is used as a thermal decomposition raw material in the synthesis thermal decomposition step.

The synthesis step is preferably a step of producing N-(2-oxoethyl)carboxylic acid decylamine by reacting 2-oxoethylamine with a mercapto compound. The 2-oxoethylamine is a primary amine compound bonded to a nitrogen atom from one 2-oxyethyl group and two hydrogen atoms.

The 2-oxoethylamine used as a raw material of the N-(2-oxoethyl)carboxylic acid decylamine represented by the formula (1) is preferably a 2-oxyethylamine represented by the formula (4). Further, the mercapto compound used as a raw material of N-(2-oxoethyl)carboxylic acid decylamine represented by the formula (1) is preferably a mercapto compound represented by the formula (5). By reacting 2-oxyethylamine represented by the general formula (4) with a mercapto compound represented by the general formula (5), N-(2-oxygen B) represented by the general formula (1) can be synthesized in a high yield. Base carboxylic acid guanamine.

(In the formula (4), R ³ is selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, and a fluorenyl group having 1 to 7 carbon atoms).

Preferred R ³ in the formula (4) is the same as the preferred R ² in the above formula (1).

(In the formula (5), R ^{1 is the} same as the above formula (1), and X is derived from a chlorine atom, a bromine atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and a decyloxy group having 2 to 7 carbon atoms. Any one selected by Cheng Zhi).

Specific examples of the 2-oxyethylamine represented by the formula (4) are 2-aminoethanol, 2-methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2- Isopropoxyethylamine, 2-butoxyethylamine, 2-isobutoxyethylamine, 2-second butoxyethylamine, 2-tert-butoxyethylamine, 2-phenoxyethyl Amine, 2-methylmethoxyethylamine, 2-ethoxymethoxyethylamine, 2-propoxyethoxyethylamine, 2-benzylideneoxyethylamine, and the like.

Among these 2-oxyethylamines, 2-aminoethanol is more preferable because it is inexpensive and easy to obtain.

Specific examples of the mercapto compound represented by the formula (5) are formic acid, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, dibutyl formate, formic acid. Third butyl ester, ethyl hydrazine chloride, acetamidine bromine, acetic acid, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, second butyl acetate, acetic acid third Butyl ester, acetic anhydride, propional chloride, propidium bromide, propionic acid, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, C Second butyl acid ester, third butyl propionate, propionic anhydride, benzene Formamidine, benzamidine bromide, benzoic acid, methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, isobutyl benzoate, second butyl benzoate , butyl benzoate, benzoic anhydride, and the like.

The mercapto compound represented by the formula (5) is preferably a carboxylic acid ester in which the X in the formula (5) is an alkoxy group having 1 to 6 carbon atoms. Specific examples of such carboxylic acid esters are methyl formate, ethyl formate, methyl acetate, ethyl acetate, acetic anhydride, methyl propionate, ethyl propionate, propionic anhydride, methyl benzoate, and ethyl benzoate. Ester, benzoic anhydride, and the like.

These carboxylic acid esters are preferred because they are easy to obtain. Further, as the mercapto compound, the N-(2-oxyethyl)carboxylic acid decylamine represented by the general formula (1) can be synthesized in a higher yield by using the above carboxylic acid ester.

Among these carboxylic acid esters, especially methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl benzoate and ethyl benzoate are more preferable because they are easy to obtain. .

"Synthesis method of N-(2-oxoethyl)carboxylic acid decylamine"

In the synthesis step, a method of reacting 2-oxyethylamine with a mercapto compound is not particularly limited. For example, a mixture obtained by mixing 2-oxyethylamine with a mercapto compound is heated to reflux. By this reaction, a method of producing N-(2-oxoethyl)carboxylic acid decylamine represented by the general formula (1) is produced. The resulting N-(2-oxoethyl)carboxylic acid decylamine can also be purified by distillation as needed.

In the production method of the present embodiment, N-(2-oxyethyl)carboxylic acid decylamine represented by the formula (1) is used as a thermal decomposition raw material. The N-(2-oxoethyl)carboxylic acid decylamine represented by the general formula (1) has high safety and is treated. Easy and easy to synthesize. By thermally decomposing the N-(2-oxoethyl)carboxylic acid decylamine represented by the general formula (1) in the presence of a solid catalyst, the N-vinyl group represented by the general formula (2) can be produced. Ammonium carboxylate.

(In the formula (2), R ¹ is the same as the above formula (1)).

As the N-vinylcarboxylic acid guanamine represented by the general formula (2), specific examples are N-vinylformamide, N-vinylacetamide, N-vinylpropanamine, N-vinyl Benzoylamine.

The N-vinylcarboxylic acid decylamine can be obtained by using N-(2-oxoethyl)formamide, N-(2-oxyethyl)acetamide, N-(2-oxyethyl)propyl Any one of decylamine and N-(2-oxoethyl)benzamide is produced as N-(2-oxoethyl)carboxylic acid decylamine represented by the formula (1). Since these N-(2-oxoethyl)carboxylic acid decylamines can be easily synthesized, they can be easily obtained, and are thermally decomposed in the presence of a solid catalyst to form N-ethylene represented by the general formula (2). Amine carboxylic acid. Therefore, N-vinylformamide, N-vinylacetamide, N-vinylpropionamine, and N-vinylbenzamide can be easily produced by the production method of the present embodiment.

The production method of the present invention is not limited to the production method of the above embodiment.

For example, in the above embodiment, the synthesis of the N-(2-oxoethyl)carboxylic acid decylamine represented by the general formula (1) by reacting 2-oxoethylamine with a mercapto compound will be described as an example. However, the raw material and synthesis method of the N-(2-oxoethyl)carboxylic acid decylamine represented by the general formula (1) are not particularly limited.

[Examples]

The invention is more specifically illustrated by the following examples, but the invention is not limited thereto.

[Example 1] (synthesis step)

A mixture of 2-aminoethanol (25 g) and ethyl acetate (27 g) was reacted by heating under reflux at a temperature of 82 to 85 ° C for 4 hours. The obtained colorless liquid was distilled under reduced pressure to give N-(2-hydroxyethyl)acetamide of N-(2- oxyethyl)carboxylic acid decylamine. The yield of the obtained N-(2-hydroxyethyl)acetamide was 98% or more.

(thermal decomposition step)

The zirconia (Zr ₂ O) particles (2 g) as a solid catalyst were packed in a stainless steel tubular reactor having an inner diameter of 9 mm and a length of 200 mm. The temperature in the reactor was maintained at 300 ° C to depressurize the pressure in the reactor so that the partial pressure of N-(2-hydroxyethyl)acetamide of the thermally decomposed raw material became 1.5 kPa. Next, N-(2-hydroxyethyl)acetamide was supplied at a space velocity of 17,000 h ^-1 to carry out a thermal decomposition reaction.

A vessel cooled with ice water was placed at the outlet of the reactor, and the reaction liquid generated by the thermal decomposition step was collected therein and recovered. The recovered reaction solution was quantified by composition analysis using a gas chromatograph, and the conversion ratio of the thermal decomposition raw material and the selectivity of N-vinylacetamide of the N-vinylcarboxylic acid guanamine produced by the thermal decomposition step were calculated. .

The results are shown in Table 1.

[Example 2]

A thermal decomposition step was carried out in the same manner as in Example 1 except that cerium oxide (HfO ₂ ) was used as a solid catalyst instead of zirconia, and the reaction liquid was recovered. The recovered reaction liquid was quantified in the same manner as in Example 1, and the conversion ratio of the thermally decomposed raw material and the selectivity of N-vinylacetamide were calculated.

The results are shown in Table 1.

[Example 3]

A thermal decomposition step was carried out in the same manner as in Example 1 except that yttria (Y ₂ O ₃ ) was used instead of zirconia as a solid catalyst, and the reaction liquid was recovered. The recovered reaction liquid was quantified in the same manner as in Example 1, and the conversion ratio of the thermally decomposed raw material and the selectivity of N-vinylacetamide were calculated.

The results are shown in Table 1.

[Example 4]

A thermal decomposition step was carried out in the same manner as in Example 1 except that cerium oxide (CeO ₂ ) was used as a solid catalyst instead of zirconia, and the reaction liquid was recovered. The recovered reaction liquid was quantified in the same manner as in Example 1, and the conversion ratio of the thermally decomposed raw material and the selectivity of N-vinylacetamide were calculated.

The results are shown in Table 1.

[Example 5]

A thermal decomposition step was carried out in the same manner as in Example 1 except that a cerium oxide supporting sodium oxide produced by the method described below was used as a solid catalyst instead of zirconia, and the reaction liquid was recovered. The recovered reaction liquid was quantified in the same manner as in Example 1, and the conversion ratio of the thermally decomposed raw material and the selectivity of N-vinylacetamide were calculated.

The results are shown in Table 1.

(Manufacturing method of silicone containing sodium oxide)

The bead-like silicone (30 g) was immersed in an aqueous solution of sodium hydroxide (2 g) dissolved in water (60 g) for 2 hours. After soaking the aqueous solution of sodium hydroxide in the silicone, the mixture was heated on a hot water bath at 100 ° C to evaporate the water and dried in air at 120 ° C. Further, the mixture was fired at 600 ° C for 2 hours while passing nitrogen gas to obtain a catalyst made of sodium silicate (Si ₂₀ Na ₂ O ₄₁ ) supporting sodium oxide.

[Example 6]

A thermal decomposition step was carried out in the same manner as in Example 1 except that sodium oxide-supporting zirconia produced by the method described below was used as a solid catalyst instead of zirconia, and the reaction liquid was recovered. The recovered reaction solution was quantified in the same manner as in Example 1 to calculate the conversion ratio of the thermally decomposed raw material and the selection of N-vinylacetamide. Choice rate.

The results are shown in Table 1.

(Manufacturing method of zirconia supporting sodium oxide)

The zirconia particles (13 g) were immersed in an aqueous solution of sodium hydroxide (0.4 g) dissolved in water (10 g) for 2 hours. After soaking the aqueous solution of sodium hydroxide in zirconia, the mixture was heated on a hot water bath at 80 ° C to evaporate the water and dried in air at 150 ° C. Further, the mixture was fired at 600 ° C for 2 hours while passing nitrogen gas to obtain a catalyst made of zirconia (Zr ₂₀ Na ₂ O ₄₁ ) supporting sodium oxide.

[Example 7] (synthesis step)

The mixture obtained by dropwise addition of acetic anhydride (184 g) to 2-aminoethanol (50 g) over 20 minutes was heated under reflux at a temperature of 100 ° C for 3 hours to carry out a reaction. The obtained colorless liquid was distilled under reduced pressure, whereby N-(2-ethyloxyethyl)acetamide of N-(2-oxoethyl)carboxylic acid decylamine was obtained. The yield of the obtained N-(2-acetoxyethyl)acetamide was 78%.

(thermal decomposition step)

A thermal decomposition step was carried out in the same manner as in Example 1 except that N-(2-acetoxyethyl)acetamide was used instead of N-(2-hydroxyethyl)acetamide as a thermal decomposition raw material, and the reaction liquid was collected. The recovered reaction liquid was quantified in the same manner as in Example 1, and the conversion ratio of the thermally decomposed raw material was calculated and the thermal decomposition step was carried out. The selectivity of the N-vinylacetamide of the N-vinylcarboxylic acid decylamine formed.

The results are shown in Table 1.

[Example 8]

A thermal decomposition step was carried out in the same manner as in Example 7 except that the cerium oxide supporting sodium oxide was used as the solid catalyst in place of zirconia in the same manner as in Example 5, and the reaction liquid was recovered. The recovered reaction liquid was quantified in the same manner as in Example 1, and the conversion ratio of the thermally decomposed raw material and the selectivity of N-vinylacetamide were calculated.

The results are shown in Table 1.

[Comparative Example 1]

A thermal decomposition step was carried out in the same manner as in Example 1 except that the solid catalyst was not used and the temperature in the reactor was maintained at 400 ° C, and the reaction liquid was recovered. The recovered reaction liquid was quantified in the same manner as in Example 1, and the conversion ratio of the thermally decomposed raw material and the selectivity of N-vinylacetamide were calculated.

The results are shown in Table 1.

[Comparative Example 2]

A thermal decomposition step was carried out in the same manner as in Example 7 except that zirconia which did not use a solid catalyst was used, and the reaction liquid was recovered. The recovered reaction liquid was quantified in the same manner as in Example 1, and the conversion ratio of the thermally decomposed raw material and the selectivity of N-vinylacetamide were calculated.

The results are shown in Table 1.

As shown in Examples 1 to 8 of Table 1, N-(2-hydroxyethyl)acetamide or N-(N-(2-oxyethyl)carboxyguanamine represented by the formula (1) 2-Ethyloxyethyl)acetamide was thermally decomposed in the presence of a solid catalyst, and it was confirmed that N-vinylacetamide represented by the formula (2) was obtained.

On the other hand, as shown in Comparative Examples 1 and 2 of Table 1, N-(2-hydroxyethyl)acetamide or N-(2-acetoxyethyl)acetamide did not use a solid catalyst even if N-vinylacetamide was also not obtained by thermal decomposition.

Claims (10)

A process for producing N-vinylcarboxylic acid decylamine characterized by thermally decomposing N-(2-oxoethyl)carboxylic acid decylamine represented by the general formula (1) in the presence of a solid catalyst a thermal decomposition step to produce an N-vinylcarboxylic acid guanamine represented by the general formula (2): (In the formula (1), R ¹ is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms; and R ² is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, and a carbon number of 1 to 6; Any one selected by the group of 7); (In the formula (2), R ¹ is the same as the above formula (1)). The method for producing N-vinylcarboxylic acid decylamine according to claim 1, wherein the solid catalyst is an oxide represented by the general formula (3): A _x B _y O _z (3) (general formula (3) Medium, A is from Al, Si, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V Any one selected from Nb and Ta, B is an alkali metal element, O is oxygen, x, y, z are the number of atoms of each element, x>0, y≧0, z={(price of A×x) + (B price y) /2). The method for producing N-vinylcarboxylic acid decylamine according to claim 2, wherein the A in the above formula (3) is selected from Y, Ce, Zr and Hf. A process for producing an N-vinylcarboxylic acid decylamine according to claim 2 or 3, wherein y = 0 in the above formula (3). The method for producing N-vinylcarboxylic acid decylamine according to claim 2, wherein A in the above formula (3) is any one selected from the group consisting of Al and Si. The method for producing N-vinylcarboxylic acid decylamine according to any one of claims 1 to 5, which has a synthetic step of synthesizing the aforementioned N-(2-oxoethyl)carboxylic acid decylamine before the thermal decomposition step The above synthesis step is carried out by reacting 2-oxoethylamine represented by the formula (4) with a mercapto compound represented by the formula (5) to synthesize the aforementioned N-(2-oxoethyl)carboxylic acid decylamine. Steps: (in the general formula (4), R ³ is selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, and a fluorenyl group having 1 to 7 carbon atoms; (In the formula (5), R ^{1 is the} same as the above formula (1), and X is derived from a chlorine atom, a bromine atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and a decyloxy group having 2 to 7 carbon atoms. Any one selected by Cheng Zhi). The method for producing N-vinylcarboxylic acid decylamine according to claim 6, wherein the 2-oxyethylamine is 2-aminoethanol. The method for producing N-vinylcarboxylic acid decylamine according to claim 6, wherein X in the above formula (5) is an alkoxy group having 1 to 6 carbon atoms. The method for producing N-vinylcarboxylic acid decylamine according to claim 1, wherein R ² in the above formula (1) is a hydrogen atom. The method for producing N-vinylcarboxylic acid decylamine according to any one of claims 1 to 9, wherein the thermal decomposition step has a reaction temperature of from 200 ° C to 400 ° C.