JPH08141402A - Catalyst for production of tertiary n-alkenylcarboxylic acid amide and production of tertiary n-alkenylcarboxylic acid amide - Google Patents

Abstract

PURPOSE: To continuously and efficiently produce tert. N-alkenylcarboxylic acid amide from tert. N-(2-hydroxyalkyl)carboxylic acid amide without using any subsidiary starting material. CONSTITUTION: When tert. N-(2-hydroxyalkyl)carboxylic acid amide is brought into a vapor phase intramolecular dehydration reaction to produce the objective tert. N-alkenylcarboxylic acid amide, a catalyst made of an oxide contg. an alkali metal and/or an alkaline earth metal and silicon is used.

Description

Detailed Description of the Invention

The present invention relates to a catalyst for producing tertiary N-alkenylcarboxylic amides and a method for producing tertiary N-alkenylcarboxylic amides.

[0002] N-alkenyl-N'-alkyl-amide compounds and N-alkenyl-2-pyrrolidone are widely used as raw materials for flocculants, reagents, petroleum mining agents, fiber treating agents, resin additives and the like. It is a compound useful as a raw material monomer for N-vinyl-amines.

The following method is disclosed as a method for producing tertiary N-alkenyl carboxylic acid amides.

A) Method for producing N-vinyl-N'-alkyl-amide compound N-vinyl-N-alkyl-amide compound is reacted with acetylene at a high temperature and a high pressure in the presence of a basic catalyst to obtain an N-vinyl-N-alkyl-amide compound. A method for producing an N'-alkyl-amide compound is well known (Reppe method). However, this method generally produces low yields of bisethylidene type by-products from the reaction of 2 moles of N, N'-dialkylamide compound with 1 mole of acetylene, and also has the danger of acetylene decomposition explosion. Accompanied by

[0005] Alternatively, N-ethylhalide-
A method based on a dehydrohalogenation reaction of an N'-alkylamide compound and a method based on a deacetic acid reaction of an N-acetoxylated ethyl compound are known. However, in these methods, the raw materials are not easily available, and in some cases, a large cost is required for synthesizing the raw materials. In addition, a large amount of elimination by-products is generated during the N-vinylation reaction, Since a great deal of labor and cost are required for their recovery and treatment, they are not industrially excellent production methods.

Accordingly, an industrially available organic carboxylic acid or its ester compound and 2-alkylamino-1
N- (2) which can be easily produced by a reaction with an ethanol compound or a reaction between an NN'-dialkylamide compound and an oxirane or ethylene carbonate.
-Hydroxyethyl) -N'-alkyl-amide compound as a raw material and high yield of N
If a vinyl-N'-alkyl-amide compound could be prepared, it would be a low cost, labor-saving and industrially superior N
-A method for producing a vinyl-N'-alkyl-amide compound.

B) Method for producing N-vinyl-2-pyrrolidone At present, N-vinyl-2-pyrrolidone is prepared by reacting 2-pyrrolidone and acetylene shown in the following reaction formula (7) in the presence of a catalyst. It is manufactured industrially by the Reppe method.

[0008]

[Chemical 9]

This method is carried out in a liquid phase reaction using an alkali catalyst under pressure. However, disadvantages are that acetylene may decompose and explode under high pressure, and that the reaction yield may be reduced. And the control of the reaction such as the catalyst preparation step and the control of the conversion of 2-pyrrolidone are complicated.

On the other hand, N-
As a method for producing vinyl-2-pyrrolidone, various methods using N- (2-hydroxyethyl) -2-pyrrolidone obtained as a raw material by a reaction between γ-butyrolactone and monoethanolamine in a high yield have been attempted.

The method shown in the following reaction formula (8), that is, N- (2) obtained by reacting N- (2-hydroxyethyl) -2-pyrrolidone with thionyl chloride.
-Chloroethyl) -2-pyrrolidone is dehydrochlorinated (USP 2,775,599) or the method shown in the following reaction formula (9), that is, N- (2-hydroxyethyl) -2-pyrrolidone and anhydrous A method of deaceticating the acetic acid ester intermediate obtained by the reaction with acetic acid has been proposed. However, the method via these intermediates requires an auxiliary material equivalent to N- (2-hydroxyethyl) -2-pyrrolidone, requires a large production cost of the intermediate, and furthermore, originates from the auxiliary material. Since there is a problem that a large amount of by-products are generated, these are, from an industrial viewpoint,
Not a good manufacturing method.

[0012]

[Chemical 10]

As a method for solving such a problem, a method represented by the following reaction formula (10), that is, N- (2
A method for producing N-vinyl-2-pyrrolidone by performing an intramolecular dehydration reaction of (-hydroxyethyl) -2-pyrrolidone in the gas phase in the presence of a catalyst has been proposed.

[0014]

[Chemical 11]

In this method, it is important that the catalyst used exhibits high activity and high selectivity, as well as maintaining stable catalytic activity over time. As a catalyst for this reaction, activated alumina is disclosed in U.S. Pat. No. 2,669,570, cerium oxide, zinc oxide, chromium oxide and the like are disclosed in JP-A-47-18882 and JP-B-47-40792. Zirconium, thorium oxide, JP-A-48-
No. 44251 discloses lanthanum oxide, neodymium oxide and the like, and JP-A-6-256306 discloses IIb group (zinc,
Disclosed are acidic heterogeneous catalysts other than oxides of metals of cadmium, mercury), group IIIb (scandium, yttrium), group IVb (titanium, zirconium, hafnium), and group VIb (chromium, molybdenum, tungsten). .

However, the method using activated alumina disclosed in US Pat. No. 2,669,570 is disclosed in JP-B-47-40.
According to the reference example of Japanese Patent No. 792, the reaction rate (conversion rate) of N- (2-hydroxyethyl) -2-pyrrolidone is 31.
The value is as low as 7 mol%, and N-vinyl-based on N- (2-hydroxyethyl) -2-pyrrolidone reacted.
Since the yield (selectivity) of 2-pyrrolidone is as low as 62.8 mol% and the by-product ratio of the polymer is as high as 22.8 mol%, economic efficiency and separation / purification of products, etc. It is not an excellent method from the industrial point of view. Among the other catalysts, zirconium oxide has the highest performance, and in Example 6 of JP-B-47-40792, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone is 88.6 mol%. N-vinyl-2-pyrrolidone has a selectivity of 9
At 2.6 mol%, 2-pyrrolidone has a selectivity of 5.6 mol%.
It is disclosed that the above can be obtained. Although this catalytic performance is at a relatively high level, the development of a catalyst that exhibits stable activity over time with a higher selectivity is desired as an industrially efficient production method. In addition, in an experiment conducted by the present inventors using zirconium oxide as a catalyst under the reaction conditions of the above invention, as shown in Comparative Example 2 described later, the conversion rate of N- (2-hydroxyethyl) -2-pyrrolidone Was as high as 84.7 mol%, but the selectivity of N-vinyl-2-pyrrolidone was 71.0 mol%, which was not always satisfactory.

As described above, Japanese Patent Application Laid-Open No. 6-256306
In the publication, group IIb (zinc, cadmium, mercury), I
Disclosed are methods using an acidic heterogeneous catalyst other than an oxide of a Group IIb (scandium, yttrium), Group IVb (titanium, zirconium, hafnium) or Group VIb (chromium, molybdenum, tungsten) metal. However, this disclosure merely affirmatively excludes from the claim some of the catalytic elements described in other prior art, with the speculation that all elements not excluded are valid. Since it is based, it is unreasonably wide and unclear. As is well known, even though the catalyst contains the same element, the reaction results vary greatly depending on the composition, the calcination temperature, and the like. Not at all. In the examples of the publication, only two examples of the catalyst, H ₃ PO ₄ and La (H ₂ PO ₄ ) ₃ , are specifically shown. N
The selectivity of N-vinyl-2-pyrrolidone in the dehydration reaction of-(2-hydroxyethyl) -2-pyrrolidone is 80.
Although it is relatively good at about 90%, it is not industrially satisfactory at this level. Also, this catalyst is not sufficient with respect to the stability of the activity over time.

As described above, N- (2-hydroxyethyl) -2-pyrrolidone is subjected to an intramolecular dehydration reaction in the gas phase using a catalyst to produce N-vinyl-2-pyrrolidone. For this purpose, a catalyst that produces N-vinyl-2-pyrrolidone with high performance, particularly high selectivity, is desired, but a catalyst showing satisfactory performance has not yet been developed.

It is an object of the present invention to use no auxiliary material at all.
When used in a process for producing tertiary N-alkenylcarboxylic amides from tertiary N- (2-hydroxyalkyl) carboxylic amides by a gas phase intramolecular dehydration reaction, extremely high selectivity and high yield are obtained. It is to provide a catalyst which can be used.

Another object of the present invention is to provide a method for producing a tertiary N- (2-hydroxyalkyl) carboxylic acid amide from a tertiary N- (2-hydroxyalkyl) carboxylic amide by using a gas phase intramolecular dehydration reaction without using any auxiliary material.
Alkenyl carboxylic amides can be obtained in very high selectivity and high yield, and do not generate waste derived from auxiliary materials at the same time, and are simple and reasonable tertiary N-alkenyl carboxylic amides. It is to provide a manufacturing method.

The present inventors have solved the above-mentioned various problems in the prior art, and in order to find a method for easily and efficiently producing tertiary N-alkenylcarboxylic amides, tertiary N- ( The present inventors have conducted intensive studies on catalysts for dehydrating 2-hydroxyalkyl) carboxylic acid amides in the gas phase, and found that an oxide containing an alkali metal element and / or an alkaline earth metal element and silicon is tertiary N-type.
They have been found to be effective catalysts for obtaining tertiary N-alkenylcarboxylic amides from (2-hydroxyalkyl) carboxylic amides with high selectivity and high yield in a long period of time and stably.

Thus, according to the present invention, a tertiary N-alkenyl carboxylic acid amide is produced which is an oxide containing an alkali metal element and / or an alkaline earth metal element and silicon. A catalyst is provided. According to the present invention, when obtaining a tertiary N-alkenylcarboxylic acid amide from a tertiary N- (2-hydroxyalkyl) carboxylic acid amide by a gas phase intramolecular dehydration reaction,
There is provided a method for producing a tertiary N-alkenylcarboxylic acid amide, which comprises using the catalyst.

Hereinafter, the present invention will be described in detail.

The catalyst of the present invention comprises N- (2-hydroxyethyl) -2-pyrrolidone and tertiary N- (2-hydroxyalkyl) carboxylic acid represented by the following general formulas (2) and (4): It acts very effectively in the reaction for producing the corresponding tertiary N-alkenylcarboxylic acid amides from the amides by a gas phase intramolecular dehydration reaction.

[0025]

[Chemical 12]

Wherein R ₁ and R ₂ are independent groups and R ₁
And R ₂ is any one selected from the group consisting of hydrocarbon groups having 1 to 6 carbon atoms. )

[0027]

[Chemical 13]

(Wherein R ₁ , R ₂ and R ₃ are independent groups, and R ₁ and R ₂ are any one selected from the group consisting of hydrocarbon groups having 1 to 6 carbon atoms, R ₃ is any one selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 6 carbon atoms.) As the reaction raw material in the present invention, any of the above-mentioned tertiary N- (2-hydroxyalkyl) s Carboxamides are used. Specifically, N-methyl-acetamide, N-ethyl-acetamide, N-propyl-acetamide, N-butyl-acetamide N-2-hydroxyethyl compound and N-2-hydroxypropyl compound; N-methyl-propyl N-2-hydroxyethyl and N-2-hydroxypropyl compounds of amide, N-ethyl-propylamide, N-propyl-propylamide, N-butyl-propylamide; N- (2-
Hydroxyethyl) -2-pyrrolidone and the like are preferable, but not limited thereto. From these N-2-hydroxyethyl compounds, corresponding tertiary N-vinylcarboxylic acid amide compounds are obtained, and from N-2-hydroxypropyl compounds, corresponding tertiary N- (1-propenyl) carboxylic acid amides and 3 A class N- (2-propenyl) carboxylic acid amide is obtained.

The catalyst of the present invention has very little carbon (coke) deposition on the catalyst which is a problem in this type of reaction, so-called coking, and its activity hardly decreases even if the reaction is continued for a long period of time. . Also, if coking progresses,
After stopping the reaction and burning and removing coke through a gas containing oxygen molecules as a catalyst, the reaction can be continued again.

The greatest feature of the catalyst of the present invention in terms of the reaction performance is the extremely high tertiary N-alkenylcarboxylic acid amide selectivity not found in the prior art catalysts. This is mainly
The catalyst is provided by suppressing the decomposition and decarbonylation of tertiary N- (2-hydroxyalkyl) carboxylic acid amides as raw materials. Taking the production of N-vinyl-2-pyrrolidone as an example, the so-called decomposition reaction of N- (2-hydroxyethyl) -2-pyrrolidone to 2-pyrrolidone and acetaldehyde is significantly suppressed as compared with the conventional catalyst.

[0031] The catalyst of the present invention is an oxide comprising an alkali metal element and / or alkaline earth metal element and silicon, preferably general formula _{(1) M a Si b X} c O d (1 Wherein M is at least one element selected from the group consisting of an alkali metal element and an alkaline earth metal element;
Represents silicon, X represents at least one element selected from the group consisting of boron, aluminum and phosphorus, and O represents oxygen.
The subscripts a, b, c and d represent the number of atoms of each element, and when a = 1, the range is b = 1 to 500, c = 0 to 1, and d is the value of a, b and c and It is a numerical value determined by the bonding state of various constituent elements. ) Is an oxide represented by. The ratio of the alkali metal element and / or the alkaline earth metal element to silicon is 1: 1 to 500, preferably 1: 1.
5 to 200. The ratio of the alkali metal element and / or the alkaline earth metal element and one or more element X components selected from the group consisting of boron, aluminum and phosphorus to be added as needed is preferably 1: 0 to 1. It is.

The method for preparing the catalyst is not particularly limited.
It can be prepared by any conventionally known method. Raw materials for the alkali metal element and / or alkaline earth metal element which are essential elements of the catalyst include oxides, hydroxides,
Halides, salts (carbonates, nitrates, carboxylates,
Phosphates, sulfates, etc.) and metals. As another raw material of silicon which is an essential component, silicon oxide, silicic acid, silicates (alkali metal silicate, alkaline earth metal silicate, etc.), silicon-containing molecular sieves (aluminosilicate, silicoaluminophosphate, etc.), And organic silicate ester etc. can be used. Further, as a raw material of the component X added as needed, oxides, hydroxides, halides, salts (carbonates,
(Nitrate, carboxylate, phosphate, sulfate, etc.) and metal can be used.

The following is a specific example of a preferred method for preparing the catalyst of the present invention.

(1) A method for obtaining a catalyst by dissolving or suspending a raw material of an alkali metal element and / or an alkaline earth metal element and a raw material of silicon in water, heating and concentrating with stirring, drying and calcining. .

(2) A method of obtaining a catalyst by immersing previously molded silicon oxide in an aqueous solution of a raw material of an alkali metal element and / or an alkaline earth metal element, heating to dryness, drying and calcining.

(3) An aqueous solution of a raw material of an alkali metal element and / or an alkaline earth metal element is added to various silicates or organic silicates, mixed, and dried.
A method of obtaining a catalyst by calcining.

(4) A method of obtaining a catalyst by supporting an alkali metal element and / or an alkaline earth metal element on silicon-containing molecular sieves by an ion exchange method, followed by drying and calcination.

The X component may be added at any point during the preparation of the catalyst or before the drying. For example, a method using a raw material containing an X component as a raw material of an alkali metal element and / or an alkaline earth metal element and / or a raw material of silicon, a method of individually adding a raw material of the X component at the time of preparing a catalyst, Can be adopted.

The catalyst of the present invention can be supported on a known carrier such as alumina, silicon carbide or the like, or can be used as a mixture with such a carrier.

The calcination temperature of the catalyst can be in a wide range of 300 to 1000 ° C., preferably 400 to 800 ° C., depending on the composition of the catalyst and the type of the catalyst raw material used.

The process for producing tertiary N-alkenylcarboxylic amides according to the present invention comprises the steps of producing a tertiary N-alkenylcarboxylic amide from a tertiary N- (2-hydroxyalkyl) carboxylic amide by a gas phase intramolecular dehydration reaction. In the production of a product, a catalyst having the above composition is used.

The process of the present invention can be carried out in any of fixed bed flow type, fluidized bed type and moving bed type reactors. The reaction is a tertiary N- (2-hydroxyalkyl) which is a raw material.
Carboxylic amides are carried out at a reaction pressure and a reaction temperature capable of maintaining a gas phase state. The reaction temperature is 300 to 500
C., preferably in the range of 350 to 450.degree.
When the reaction temperature is lower than 300 ° C., the tertiary N-
Since the conversion rate of (2-hydroxyalkyl) carboxylic acid amides is significantly reduced, the productivity is reduced. If the reaction temperature is higher than 500 ° C., the ratio of side reactions increases, the selectivity of the target tertiary N-alkenylcarboxylic acid amides decreases remarkably, and the activity decrease due to an increase in the coking rate becomes remarkable. Cause inconvenience.

The reaction pressure is such that the partial pressure of the tertiary N- (2-hydroxyalkyl) carboxylic amide as the raw material is 5-6.
There is no particular limitation as long as it can be controlled within the range of 00 mmHg, preferably 10 to 300 mmHg. Material partial pressure is 5
When it is less than mmHg, the reaction itself can be carried out without any trouble, but the production efficiency is lowered due to the difficulty of collecting the product, the size of the repair device, and the like. 600m partial pressure of raw material
If it is higher than mHg, the rate of side reactions increases, and the selectivity of the target tertiary N-alkenylcarboxylic amides decreases. Specifically, (1) a method in which a gas whose raw material is controlled in partial pressure by dilution with a substance inert to the reaction such as nitrogen, helium, argon, or a hydrocarbon is passed through a catalyst (reaction pressure is Any).

(2) A method in which only the reaction raw materials are passed through a catalyst and the reaction system is depressurized to control the partial pressure of the raw materials to carry out the reaction.

Etc. are preferred.

The space velocity (GHSV), which represents the supply amount of the tertiary N- (2-hydroxyalkyl) carboxylic acid amides as a raw material per unit catalyst volume, is the kind of the raw material, the reaction conditions, the reaction method, etc. Depending on the standard state (volume at 25 ° C., gas at 1 atm) of the supplied tertiary N- (2-hydroxyalkyl) carboxylic acid amides, it is ¹ to 1000 h ⁻¹ , preferably 10 to 500, though it is slightly different depending on
It is in the range of h ⁻¹ . When the space velocity is smaller than 1 h ^-1 , the selectivity of the target substance is lowered because the reaction proceeds successively due to the long contact time, while the space velocity is 1000 h ^-1.
If it is larger, the contact time will be insufficient, resulting in a disadvantage such as a decrease in the conversion rate.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

The conversion, selectivity and single-stream yield in the examples follow the following definitions.

Conversion (mol%) = 100 × (3 consumed)
Number of moles of primary N- (2-hydroxyalkyl) carboxylic amide) / (number of moles of tertiary N- (2-hydroxyalkyl) carboxylic acid supplied) Selectivity (mol%) = 100 × (3 Number of moles of tertiary N-alkenylcarboxylic acid amide) / (consumed tertiary N-
(Mole number of (2-hydroxyalkyl) carboxylic acid amide) Single stream yield (mol%) = 100 × (mol number of tertiary N-alkenylcarboxylic acid amide generated) / (tertiary N supplied)
-Number of moles of-(2-hydroxyalkyl) carboxylic acid amide) Examples 1 to 35 shown below show tertiary N-vinyl carboxylic acids by intramolecular dehydration of tertiary N- (2-hydroxyethyl) carboxylic acid amides It is an example about production of acid amides.

[0050]

Example 1 (Catalyst preparation) 0.7 g of lithium hydroxide monohydrate was added to 10 parts of water.
30 g of spherical silica gel (5 to 10 mesh) was immersed in a solution of 0 g for 2 hours. Thereafter, the mixture was heated to dryness on a hot water bath, dried in air at 120 ° C. for 20 hours, and then calcined in air at 600 ° C. for 2 hours to obtain a catalyst having a composition of Li ₁ Si _{30 in} atomic ratio excluding oxygen. .

(Reaction) 5 ml of this catalyst was charged into a stainless steel reaction tube having an inner diameter of 10 mm, and the reaction tube was immersed in a molten salt bath at 380 ° C. When the partial pressure of N- (2-hydroxyethyl) -N'-methyl-acetamide is 76
The raw material gas diluted with nitrogen to a pressure of
(2-Hydroxyethyl) -N'-methyl-acetamide was supplied at a space velocity of 200 h ^-1 and reacted at normal pressure. As a result of analyzing the gas at the outlet of the reactor one hour after the start of the reaction by gas chromatography, the conversion of N- (2-hydroxyethyl) -N'-methyl-acetamide, N-
The vinyl-N'-methyl-acetamide selectivities and single stream yields were 73.6 mol%, 89.2 mol% and 65.7 mol%, respectively.

Example 2 (Preparation of catalyst) 30 g of spherical silica gel (5 to 10 mesh) was immersed in a solution of 0.43 g of sodium nitrate in 100 g of water for 2 hours. Then, it is dried by heating in a hot water bath and dried in air at 120 ° C. for 20 hours.
By calcining at 0 ° C. for 2 hours, a catalyst having a composition of Na ₁ Si _{100 in an} atomic ratio excluding oxygen was obtained.

(Reaction) Using this catalyst, a reaction temperature of 4
The reaction was conducted and analyzed in the same manner as in Example 1 except that the temperature was changed to 00 ° C. N- (2-hydroxyethyl) 1 hour after the start of the reaction
-N'-methyl-acetamide conversion, N-vinyl-
The N'-methyl-acetamide selectivity and single flow yield are
75.2 mol%, 87.1 mol% and 65.5 mol% respectively
It was mol%.

Example 3 (Preparation of catalyst) 5.06 g of potassium nitrate was dissolved in 250 g of water, and while heating and stirring at 90 ° C., 30 g of silicon oxide was added. The mixture was heated and concentrated, and then dried in air at 120 ° C. for 20 hours. did. The obtained solid was crushed to 9 to 16 mesh and calcined in air at 500 ° C. for 2 hours to obtain a catalyst having a composition of K ₁ Si ₁₀ in terms of atomic ratio excluding oxygen.

(Reaction) Using this catalyst, a reaction temperature of 3
The reaction and analysis were performed in the same manner as in Example 1 except that the temperature was 90 ° C. N- (2-hydroxyethyl) 1 hour after the start of the reaction
-N'-methyl-acetamide conversion, N-vinyl-
The N'-methyl-acetamide selectivity and single flow yield are
77.3 mol%, 85.6 mol% and 66.1 respectively
It was mol%.

Example 4 (Catalyst preparation) 7.38 g of rubidium nitrate was dissolved in 250 g of water, and 30 g of silicon oxide was added while heating and stirring at 90 ° C., and the mixture was heated and concentrated, and then heated in air at 120 ° C. for 20 hours. Dried. Crush the resulting solid into 9-16 mesh,
By firing in air at 500 ° C. for 2 hours, a catalyst having a composition of Rb ₁ Si ₁₀ in terms of atomic ratio excluding oxygen was obtained.

(Reaction) Using this catalyst, the reaction was carried out in the same manner as in Example 1, and the reaction was analyzed. N- (2
-Hydroxyethyl) -N'-methyl-acetamide conversion, N-vinyl-N'-methyl-acetamide selectivity and single-stream yield were 74.9 mol% and 88.8 mol, respectively.
% And 66.5 mol%.

Example 5 (Preparation of catalyst) 7.76 g of cesium carbonate was dissolved in 250 g of water, 30 g of silicon oxide was added to the mixture while heating and stirring at 90 ° C., and the mixture was concentrated by heating and then in air at 120 ° C. for 20 hours. Dried. The obtained solid was crushed to 9 to 16 mesh and calcined in air at 500 ° C. for 2 hours to obtain a catalyst having a composition of Cs ₁ Si _{10 in an} atomic ratio excluding oxygen.

(Reaction) Using this catalyst, the reaction was carried out in the same manner as in Example 1, and the reaction was analyzed. N- (2
-Hydroxyethyl) -N'-methyl-acetamide conversion, N-vinyl-N'-methyl-acetamide selectivity and single stream yield were 76.2 mol% and 89.1, respectively.
Mol% and 67.9 mol%.

Example 6 (Catalyst preparation) 8.15 g of cesium carbonate, 0.66 g of diammonium phosphate and 30 g of silicon oxide and 150 g of water.
Was added, and the mixture was concentrated to dryness with heating and mixing on a hot water bath. Then dried 20 hours at 120 ° C. in air, crushed into 9-16 mesh, by calcining 2 hours at 450 ° C. in air, the Cs ₁ Si ₁₀ P _{0. 1} catalyst having a composition of atomic ratio excluding oxygen Obtained.

(Reaction) As Example 1 except that the partial pressure of N- (2-hydroxyethyl) -N'-methyl-acetamide was changed to 38 mmHg and the space velocity was 100 h ^-1 using this catalyst. It reacted similarly and analyzed. N- (2-hydroxyethyl) 1 hour after the start of the reaction
-N'-methyl-acetamide conversion, N-vinyl-
The N'-methyl-acetamide selectivity and single flow yield are
73.9 mol%, 92.6 mol% and 68.4 respectively
It was mol%.

Example 7 Using the catalyst of Example 1, the reaction was carried out and analyzed in the same manner as in Example 1, except that N- (2-hydroxyethyl) -N'-methyl-propylamide was used as a reaction raw material. . The conversion rate of N- (2-hydroxyethyl) -N′-methyl-propylamide, the N-vinyl-N′-methyl-propylamide selectivity and the single-flow yield one hour after the start of the reaction were 87.1, respectively. Mol%, 91.3 mol% and 79.5 mol%
Met.

Example 8 (Catalyst preparation) 0.29 g of magnesium hydroxide, 6.64 g of rubidium nitrate and 30 g of silicon oxide were added to 150 g of water.
Was added, and the mixture was concentrated to dryness with heating and mixing on a hot water bath. Then dried 20 hours at 120 ° C. in air, crushed into 9-16 mesh, by calcining 2 hours at 500 ° C. in air, in the atomic ratio excluding oxygen _{Rb 0. 9 Mg 0. 1} Si 10 comprising composition A catalyst was obtained.

(Reaction) Using this catalyst, a reaction was conducted in the same manner as in Example 6 and an analysis was conducted. N- (2-
The conversion of (hydroxyethyl) -N'-methyl-propylamide, the N-vinyl-N'-methyl-propylamide selectivity and the single stream yield are 85.4 mol% and 93.
1 mol% and 79.1 mol%.

Example 9 (Catalyst preparation) 3.16 g of barium hydroxide octahydrate, 7.80 g of cesium nitrate and 30 g of silicon oxide and 150 g of water.
Was added and the mixture was concentrated to dryness while heating and mixing on a hot water bath. Then dried 20 hours at 120 ° C. in air, crushed into 9-16 mesh, Cs ₀ in terms of atomic ratio when oxygen was excluded by calcining 2 hours at 500 ° C. in air. ₈ Ba _{0. 2} Si ₁₀ catalyst having a composition of Got

(Reaction) Using this catalyst, a reaction was conducted in the same manner as in Example 6 and an analysis was conducted. N- (2-
The conversion of (hydroxyethyl) -N'-methyl-propylamide, the N-vinyl-N'-methyl-propylamide selectivity and the single stream yield are 87.1 mol% and 92.
4 mol% and 80.5 mol%.

Example 10 (Catalyst preparation) 1.40 g of potassium hydroxide and 0,0 boric acid.
30 g of spherical silica gel (5 to 10 mesh) was immersed in a solution of 15 g dissolved in 100 g of water for 3 hours, and then concentrated and dried on a hot water bath. Then 2 at 120 ℃ in air
It dried 0 hours, by further calcined for 2 hours at 600 ° C. in air to obtain a K ₁ Si ₂₀ B _{0. 1} catalyst having a composition of atomic ratio excluding oxygen.

(Reaction) Using this catalyst, a reaction was conducted in the same manner as in Example 6 and an analysis was conducted. N- (2-
The conversion of (hydroxyethyl) -N'-methyl-propylamide, the N-vinyl-N'-methyl-propylamide selectivity and the single-flow yield are 88.8 mol% and 91.
4 mol% and 81.2 mol%.

Example 11 (Reaction) After 5 ml of the catalyst of Example 1 was filled in a stainless reaction tube having an inner diameter of 10 mm, the reaction tube was immersed in a molten salt bath at 370 ° C. Then, the pressure at the outlet of the reactor was reduced to 3 by depressurizing the reaction tube from the rear with a vacuum pump.
It was adjusted to 8 mmHg. N- (2-hydroxyethyl) -N'-methylpropylamide was supplied to the reaction tube at a space velocity of 100 h ^-1 to cause a reaction. After the reaction is continued for 50 hours, the supply of the raw material is stopped, the pressure in the reactor is returned to normal pressure with nitrogen, and then air is passed at 100 cc / min for 24 hours to burn the carbonaceous material deposited on the catalyst. The catalyst was regenerated by removing it. Thereafter, the reaction was performed again for another 50 hours under the above-described reaction conditions. The reactor outlet gas was analyzed by gas chromatography at 1 and 50 hours from the start of the raw material supply and at 1 and 50 hours after regeneration. N- (2-hydroxyethyl)-
Conversion of N'-methyl-propylamide, N-vinyl-
Table 1 shows N'-methyl-propylamide selectivity and single-stream yield.

Table 1 -------------------------------------------- ---- Elapsed time Conversion rate Selectivity Single stream yield (hour) (mol%) (mol%) (mol%) --------------------- --------------------------- 1 86.4 94.2 81.4 50 80.0 95.6 76.5 After playback 1 86.6 94.3 81.7 50 80.1 95.8 76.7 ----- ------------------------------------------- Example 12 (Preparation of catalyst) 3.45 g of lithium nitrate was dissolved in 50 g of water, 30 g of silicon oxide was added while heating and stirring at 90 ° C., and the mixture was concentrated by heating, and then dried in air at 120 ° C. for 20 hours.
The solid obtained is crushed to 9-16 mesh and 50 in air.
By calcining at 0 ° C. for 2 hours, a catalyst having a composition of Li ₁ Si _{10 in an} atomic ratio excluding oxygen was obtained.

(Reaction) 5 ml of this catalyst was filled in a stainless steel reaction tube having an inner diameter of 10 mm, and the reaction tube was immersed in a molten salt bath at 400 ° C. A raw material gas diluted with nitrogen so that the partial pressure of N- (2-hydroxyethyl) -2-pyrrolidone was 76 mmHg was fed to the reaction tube, and the space velocity of N- (2-hydroxyethyl) -2-pyrrolidone was 200 h ^{−. It} was fed at ¹ and reacted at atmospheric pressure. As a result of analyzing the gas at the outlet of the reactor one hour after the start of the reaction by gas chromatography, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone and the single-stream yield were as follows: 59.2 mol%, 99.2 mol% and 58.7 mol%, respectively.

Examples 13 to 16 (Catalyst preparation) In Example 12, 3.4 parts of lithium nitrate were used.
5 g of sodium nitrate 4.25 g (Example 13), potassium nitrate 5.06 g (Example 14), rubidium nitrate 7.38 g (Example 15) and cesium nitrate 9.75 g
Except having changed into (Example 16), it carried out similarly to Example 12, and obtained the catalyst (expressed by atomic ratio except oxygen) shown in Table-2.

(Reaction) A reaction was carried out in the same manner as in Example 12 except that the reaction temperature was changed using these catalysts, and the reaction was analyzed.
N- (2-hydroxyethyl) -2 one hour after the start of the reaction
Table 2 shows the conversion of -pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone, and the single-stream yield.

Table-2 -------------------------------------------- -------------------------- Example Catalyst Reaction temperature Conversion rate Selectivity Single flow yield number (℃) (mol%) (mol% ) (Mol%) --------------------------------------------- ------------------------- 13 Na ₁ Si ₁₀ 370 57.0 98.7 56.3 14 K ₁ Si ₁₀ 370 85.9 95.1 81.7 15 Rb ₁ Si ₁₀ 370 89.8 94.2 84.6 16 Cs ₁ Si ₁₀ 350 80.9 96.2 77.8 --------------------------------------- ------------------------------- Comparative Example 1 In Example 12, the catalyst was activated alumina (500 ° C.,
2 hours fired product)
analyzed. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone and the single-stream yield were 93.8 mol% and 33.6 mol%, respectively. And 31.5 mol%.

Comparative Example 2 In Example 12, the catalyst was changed to zirconium oxide (900
C. for 2 hours) and the reaction temperature was changed to 370.degree. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone and the single-stream yield were 84.7 mol% and 71.0 mol%, respectively.
And 60.3 mol%.

Comparative Example 3 In Example 12, the reaction was carried out in the same manner as in Example 12, except that the catalyst was reacted with silicon oxide (500 ° C., fired for 2 hours), and the reaction temperature was changed to 370 ° C., respectively. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone, and the single-stream yield were 16.3 mol% and 94.2 mol%, respectively. And 1
It was 5.4 mol%.

Example 17 (Preparation of catalyst) Spherical silica gel (5 to 10 mesh) was placed in a solution obtained by dissolving 0.81 g of cesium carbonate in 40 g of water.
30 g was soaked for 2 hours. Thereafter, the mixture is heated to dryness in a hot water bath, dried in air at 120 ° C. for 20 hours, and then dried in air at 800 ° C.
By firing for 2 hours, the atomic ratio excluding oxygen is C
A catalyst having a composition of s ₁ Si ₁₀₀ was obtained.

(Reaction) Using this catalyst, a reaction temperature of 3
The reaction was carried out in the same manner as in Example 12, except that the temperature was changed to 60 ° C.
analyzed. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone, and the single-stream yield were 93.8, respectively.
%, 93.1 mol% and 87.3 mol%.

Example 18 (Preparation of catalyst) The procedure of Example 17 was repeated, except that the amount of cesium carbonate was changed from 0.81 g to 0.41 g.
A catalyst having an atomic ratio of Cs ₁ Si ₂₀₀ excluding oxygen was prepared.

(Reaction) Using this catalyst, a reaction temperature of 3
The reaction was carried out in the same manner as in Example 12, except that the temperature was changed to 70 ° C.
analyzed. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone and the single-stream yield were 90.7 mol% and 91.1 mol%, respectively. And 82.6 mol%.

Example 19 (Catalyst preparation) Cesium carbonate 0.81 in Example 17
g was changed to 0.88 g of sodium carbonate and the baking temperature was changed to 7
A catalyst having a composition of Na ₁ Si _{30 in} atomic ratio excluding oxygen was obtained in the same manner except that the temperature was changed to 00 ° C.

(Reaction) Using this catalyst, a reaction temperature of 3
The reaction was carried out in the same manner as in Example 12, except that the temperature was changed to 70 ° C.
analyzed. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone and the single-stream yield were 92.7 mol% and 92.1 mol%, respectively. And 85.4 mol%.

Example 20 (Preparation of catalyst) In Example 17, cesium carbonate 0.8 was used.
1 g was changed to 1.15 g of potassium carbonate and the firing temperature was 7
A catalyst having a composition of K ₁ Si _{30 in} atomic ratio excluding oxygen was obtained in the same manner except that the temperature was changed to 00 ° C.

(Reaction) Using this catalyst, the reaction temperature was set to 3
The reaction was carried out in the same manner as in Example 12, except that the temperature was changed to 70 ° C.
analyzed. The conversion rate of N- (2-hydroxyethyl) -2-pyrrolidone, the N-vinyl-2-pyrrolidone selectivity and the single-flow yield one hour after the start of the reaction were 91.1 mol% and 91.8 mol%, respectively. And 83.6 mol%.

Example 21 (Preparation of catalyst) In Example 17, cesium carbonate 0.8 was used.
A catalyst having a composition of Rb ₁ Si _{30 in} atomic ratio excluding oxygen was obtained in the same manner except that 1 g was changed to 1.71 g of rudium hydroxide and the calcination temperature was changed to 700 ° C.

(Reaction) Using this catalyst, the reaction temperature was adjusted to 3
The reaction was carried out in the same manner as in Example 12, except that the temperature was changed to 60 ° C.
analyzed. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone and the single-stream yield were 93.5 mol% and 91.0 mol%, respectively. And 85.1 mol%.

Example 22 (Catalyst preparation) In Example 12, 3.4 parts of lithium nitrate were used.
A catalyst having a composition of Cs ₁ Si ₁₀ in terms of atomic ratio excluding oxygen was obtained in the same manner except that 5 g was changed to 7.5 g of cesium hydroxide.

(Reaction) Using this catalyst, the reaction temperature was adjusted to 3
The reaction was carried out in the same manner as in Example 12, except that the temperature was changed to 60 ° C.
analyzed. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone and the single-stream yield were 94.6 mol% and 94.6 mol%, respectively. And 89.5 mol%.

Example 23 (Preparation of catalyst) 150 g of water was added to 2.9 g of magnesium hydroxide and 30 g of silicon oxide, and the mixture was concentrated to dryness while heating and mixing on a hot water bath. Next, after drying in air at 120 ° C. for 20 hours, the obtained solid was crushed to 9 to 16 mesh, and then calcined in air at 500 ° C. for 2 hours to obtain a composition having a composition of Mg ₁ Si _{10 in an} atomic ratio excluding oxygen. A catalyst was obtained.

(Reaction) Using this catalyst, the reaction was carried out in the same manner as in Example 12, and the reaction was analyzed. N- 1 hour after the start of the reaction
(2-hydroxyethyl) -2-pyrrolidone conversion,
N-vinyl-2-pyrrolidone selectivity and single flow yield are
54.6 mol%, 88.6 mol% and 48.4 mol% respectively
It was mol%.

Examples 24 to 26 (Preparation of catalyst) In Example 23, 2.9 g of magnesium hydroxide was replaced by 3.7 g of calcium hydroxide (Example 24).
13.3 g of strontium hydroxide octahydrate (Example 2)
5) and 15.8 g of barium hydroxide octahydrate (Example 26), respectively, in the same manner as in Example 23 except that the catalysts shown in Table 3 (expressed in atomic ratio excluding oxygen) were used.
I got

(Reaction) Using these catalysts, Example 1
Reaction and analysis were carried out in the same manner as in 2. N hour after the start of the reaction
Table 3 shows the conversion rate of-(2-hydroxyethyl) -2-pyrrolidone, the N-vinyl-2-pyrrolidone selectivity and the single-stream yield.

Table-3 -------------------------------------------- -------------------------- Example Catalyst Reaction temperature Conversion rate Selectivity Single flow yield number (℃) (mol%) (mol% ) (Mol%) --------------------------------------------- ------------------------- 24 Ca ₁ Si ₁₀ 400 51.1 85.2 43.5 25 Sr ₁ Si ₁₀ 400 58.9 89.2 52.4 26 Ba ₁ Si ₁₀ 400 50.8 99.8 50.7 ---------------------------------------------------------------- ---------------------- Example 27 (Catalyst preparation) 3.9 g of cesium nitrate and 0.34 g of lithium nitrate were dissolved in 100 g of water, 30 g of silicon oxide was added, and the mixture was concentrated to dryness while heating and mixing on a hot water bath. Then dried at 120 ° C. in air, crushed into 9-16 mesh, by calcining 2 hours at 500 ° C. in air, Cs ₀ at the atomic ratio excluding oxygen. ₈ Li _{0. 2} Si ₂₀ catalyst having a composition of Got

(Reaction) Using this catalyst, the reaction temperature was adjusted to 3
Reaction was carried out in the same manner as in Example 12 except that the temperature was changed to 50 ° C.
analyzed. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone, and the single-stream yield were 82.8 mol% and 94.3 mol%, respectively. And 78.1 mol%.

Example 28 (Catalyst preparation) 30 g of silicon oxide was added to a solution of 5.9 g of rubidium nitrate and 3.2 g of barium hydroxide octahydrate dissolved in 100 g of water, and the mixture was heated and concentrated on a hot water bath. It was concentrated to dryness. Then dried 20 hours at 120 ° C. in air, crushed into 9-16 mesh, by calcining 2 hours at 500 ° C. in air, Rb ₀ in atomic ratio excluding oxygen. ₈
Ba _0. To give a ₂ Si ₁₀ catalyst having a composition of.

(Reaction) Using this catalyst, a reaction temperature of 3
The reaction was carried out in the same manner as in Example 12, except that the temperature was changed to 60 ° C.
analyzed. One hour after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone and the single-stream yield were 80.8 mol% and 97.8 mol%, respectively. And 79.0 mol%.

Example 29 (Catalyst preparation) 15.8 g of barium hydroxide octahydrate, 0.66 g of diammonium phosphate and 30 g of silicon oxide were combined with 150 g of water, and concentrated to dryness while heating and concentrating on a water bath. did. Then, dry in air at 120 ° C. for 20 hours, and
After crushing to 6 mesh by baking for 2 hours at 450 ° C. in air to obtain a catalyst of the Ba ₁ Si ₁₀ P _{0. 1} having a composition in terms of atomic ratio excluding oxygen.

(Reaction) Using this catalyst, the reaction was carried out in the same manner as in Example 12, and the reaction was analyzed. N- 1 hour after the start of the reaction
(2-hydroxyethyl) -2-pyrrolidone conversion,
N-vinyl-2-pyrrolidone selectivity and single flow yield are
67.2 mol%, 96.1 mol% and 64.6 mol%, respectively.
It was mol%.

Example 30 (Catalyst preparation) 19.5 g of cesium nitrate and 4.9 boric acid
30 g of silicon oxide was added to a solution of g in 100 g of water, and the mixture was concentrated to dryness while being heated and concentrated on a water bath. Then dried 20 hours at 120 ° C. in air, crushed into 9-16 mesh, by calcining 2 hours at 500 ° C. in air, Cs ₁ Si ₅ B ₀ in atomic ratio excluding oxygen. ₅ catalyst having a composition of the Obtained.

(Reaction) Using this catalyst, the reaction was continued for 100 hours in the same manner as in Example 12. Reaction start 1 hour, 2
Conversion of N- (2-hydroxyethyl) -2-pyrrolidone at 0 and 100 hours, N-vinyl-2
-Pyrrolidone selectivity and single flow yield are shown in Table-4.

Table-4 -------------------------------------------- ---- Elapsed time Conversion rate Selectivity Single-flow yield (time) (mol%) (mol%) (mol%) --------------------- --------------------------- 1 84.5 96.0 81.1 20 83.8 96.6 81.0 100 82.0 98.0 80.4 ----------- ------------------------------------- Example 31 (Catalyst preparation) 19.5 g of cesium nitrate and Phosphoric acid second
1.2 g of aluminum phosphate and 30 g of silicon oxide in a solution prepared by dissolving 9.2 g of ammonium in 100 g of water.
Was added, and the mixture was concentrated to dryness while heating and concentrating on a hot water bath. Then dried 20 hours at 120 ° C. in air, crushed into 9-16 mesh, by calcining 2 hours at 600 ° C. in air, Cs ₁ Si ₅ Al ₀ in atomic ratio excluding oxygen. Becomes ₁ P _{0. 8} A catalyst having a composition was obtained.

(Reaction) Using this catalyst, a reaction and an analysis were carried out in the same manner as in Example 12. N- 1 hour after the start of the reaction
(2-hydroxyethyl) -2-pyrrolidone conversion,
N-vinyl-2-pyrrolidone selectivity and single flow yield are
53.6 mol%, 97.8 mol% and 52.4 mol% respectively
It was mol%.

Examples 32-34 (Catalyst Preparation) 9.8 g of cesium nitrate and 5.3 g of diammonium phosphate were dissolved in 100 g of water,
30 g of silicon oxide was added, and the mixture was concentrated to dryness while being heated and concentrated on a hot water bath. Then, dry in air at 120 ° C. for 20 hours, and
After crushing to ~ 16 mesh, it is fired in air at 500 ° C for 2 hours to obtain Cs ₁ Si at an atomic ratio excluding oxygen.
To obtain a ₁₀ P _{0. 8} having a composition of the catalyst.

(Reaction) Using this catalyst, the reaction conditions are shown in Table 1.
The reaction and analysis were performed in the same manner as in Example 12 except that the value was changed to the value shown in FIG. Conversion rate of N- (2-hydroxyethyl) -2-pyrrolidone 1 hour after the start of the reaction, N-vinyl-2
Table 5 shows the pyrrolidone selectivity and the single-stream yield.

Table 5 -------------------------------------------- -------------------------- eXAMPLE feedstock partial pressure space velocity reaction temperature conversion selectivity pass yield number (mmHg) (hr ^{- 1} ) (℃) (mol%) (mol%) (mol%) --------------------------------- ------------------------------------- 32 76 200 400 78.9 96.8 76.4 33 76 100 400 89.9 93.3 83.9 34 38 200 390 92.1 98.4 90.6 ------------------------------------------ ---------------------------- Example 35 (Preparation of catalyst) In a solution prepared by dissolving 8.15 g of cesium carbonate in 100 g of water. And 30 g of silicon oxide, and concentrated to dryness while heating and mixing on a hot water bath. Then, it is dried in air at 120 ° C. for 20 hours, crushed to 9 to 16 mesh, and then dried in air.
By calcining at 00 ° C. for 2 hours, a catalyst having a composition of Cs ₁ Si _{10 in an} atomic ratio excluding oxygen was obtained.

(Reaction) After filling 5 ml of this catalyst into a stainless steel reaction tube having an inner diameter of 10 mm, the reaction tube was filled with 360
C. in a molten salt bath. Then, the outlet pressure of the reactor was adjusted to 76 mmHg by depressurizing the reaction tube from the rear part with a vacuum pump. N-
(2-Hydroxyethyl) -2-pyrrolidone was supplied and reacted at a space velocity of 200 h ^-1 . After the reaction is continued for 100 hours, the supply of raw materials is stopped, the pressure in the reactor is returned to normal pressure with nitrogen, and then air is passed at 100 cc / min for 24 hours to burn carbonaceous substances deposited on the catalyst. The catalyst was regenerated by removing it. Thereafter, the reaction was performed again for another 100 hours under the above-described reaction conditions. The gas at the outlet of the reactor was analyzed by gas chromatography at 1 hour, 20 hours and 100 hours after the start of the raw material supply and at 1 hour, 20 hours and 100 hours after the regeneration. N
The conversion of-(2-hydroxyethyl) -2-pyrrolidone, the selectivity for N-vinyl-2-pyrrolidone and the single-stream yield are shown in Table-6.

Table-6 -------------------------------------------- ---- Elapsed time Conversion rate Selectivity Single-flow yield (time) (mol%) (mol%) (mol%) --------------------- --------------------------- 1 94.3 94.9 89.5 20 93.5 95.6 89.4 100 93.0 96.4 89.7 After playback 1 94.0 95.3 89.6 20 93.8 95.7 89.8 100 93.5 96.9 90.6 ---------------------------------------------------- -Examples 36 to 39 shown below are examples of producing tertiary N-propenylcarboxylic acid amides by intramolecular dehydration reaction of tertiary N- (2-hydroxypropyl) carboxylic acid amides.

Example 36 (Reaction) Using the catalyst of Example 1, the reaction raw material was N- (2-
The reaction was carried out and analyzed in the same manner as in Example 1 except that (hydroxypropyl) -N'-methyl-acetamide was used.
N- (2-hydroxypropyl)-1 hour after the start of the reaction
Conversion of N'-methyl-acetamide, N- (1-propenyl) -N'-methyl-acetamide and N- (2-propenyl) -N'-methyl-acetamide combined N
The selectivity and single-stream yield of -propenyl-N'-methyl-acetamide were 67.9 mol%, 92.2 mol% and 62.6 mol%, respectively.

Example 37 (Reaction) Example 36 except that the catalyst of Example 10 was used.
The reaction was performed in the same manner as described above and analyzed. N- 1 hour after the start of the reaction
Conversion of (2-hydroxypropyl) -N'-methyl-acetamide, combining N- (1-propenyl) -N'-methyl-acetamide and N- (2-propenyl) -N'-methyl-acetamide The selectivity and single-stream yield of N-propenyl-N'-methyl-acetamide were 84.2 mol%, 94.5 mol% and 79.6 mol%, respectively.
Met.

Example 38 (Reaction) Using the catalyst of Example 17, the reaction raw material was N--
Reaction was carried out in the same manner as in Example 36 except that (2-hydroxypropyl) -N'-methyl-propylamide was changed.
analyzed. Conversion of N- (2-hydroxypropyl) -N'-methyl-propylamide 1 hour after the start of the reaction, N
Selectivity and unity of N-propenyl-N'-methyl-propylamide combining-(1-propenyl) -N'-methyl-propylamide and N- (2-propenyl) -N'-methyl-propylamide The stream yields were 93.1 mol%, 91.6 mol% and 85.3 mol%, respectively.

Example 39 (Reaction) Using the catalyst of Example 31, the reaction was carried out in the same manner as in Example 38, and the reaction was analyzed. N- (2-
Hydroxypropyl) -N'-methyl-propylamide conversion, combining N- (1-propenyl) -N'-methyl-propylamide and N- (2-propenyl) -N'-methyl-propylamide The selectivity and single-stream yield of N-propenyl-N'-methyl-propylamide were 60.4 mol%, 95.6 mol% and 57.7 mol%, respectively.

As illustrated by the above examples,
According to the present invention, tertiary N
A tertiary N-alkenylcarboxylic acid amide can be continuously and efficiently produced from-(2-hydroxyalkyl) carboxylic acid amides. The method for producing a tertiary N-alkenylcarboxylic acid amide according to the present invention is simple because no auxiliary material is used, and is safe because no waste is generated from the auxiliary material.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 23, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

However, the method using activated alumina disclosed in US Pat. No. 2,669,570 is disclosed in Japanese Patent Publication No. 47-4 / 1976.
According to the reference example of Japanese Patent No. 0792, the reaction rate (conversion rate) of N- (2-hydroxyethyl) -2-pyrrolidone is 3
The value was as low as 1.7 mol%, and the reacted N- (2-
The yield (selectivity) of N-vinyl-2-pyrrolidone with respect to (hydroxyethyl) -2-pyrrolidone is 62.8 mol%.
And the by-product rate of the polymer is 22.8 mol%.
This is not an excellent method from an industrial viewpoint such as economy and separation and purification of a product. Among the other catalysts, zirconium oxide has the highest performance, and Example 6 of JP-B-47-40792 discloses that N- (2
-Hydroxyethyl) -2-pyrrolidone conversion 88.
It is disclosed that at 6 mol%, N-vinyl-2-pyrrolidone is obtained with a selectivity of 92.6 mol% and 2-pyrrolidone is obtained with a selectivity of 5.6 mol%. Although this catalytic performance is at a relatively high level, the development of a catalyst that exhibits stable activity over time with a higher selectivity is desired as an industrially efficient production method. The above invention (Japanese Patent Publication No. 47
In the experiment conducted by the inventors of the present invention using zirconium oxide as a catalyst under the reaction conditions of JP-A-40792) , N- (2-hydroxyethyl) was used as shown in Comparative Example 2 below.
Although the conversion of 2-pyrrolidone was as high as 84.7 mol%, the selectivity for N-vinyl-2-pyrrolidone was 71.
0 mol% was not always satisfactory.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

(Wherein R ₁ , R ₂ and R ₃ are independent groups, and R ₁ and R ₂ are any one selected from the group consisting of hydrocarbon groups having 1 to 6 carbon atoms, R ₃ is any one selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 6 carbon atoms.) As the reaction raw material in the present invention, any of the above-mentioned tertiary N- (2-hydroxyalkyl) s Carboxamides are used. Specifically, N- ( 2-hydroxyethyl ) compounds and N- ( 2-hydroxypropyl ) compounds of N-methyl-acetamide, N-ethyl-acetamide, N-propyl-acetamide, N-butyl-acetamide; N- -Methyl-propylamide, N-ethyl-propylamide, N-propyl-propylamide,
N- ( 2-hydroxyethyl ) compound and N- ( 2-hydroxypropyl ) compound of N-butyl-propylamide; N- (2-hydroxyethyl) -2-pyrrolidone and the like are preferable, but not limited thereto. is not. From these N- ( 2-hydroxyethyl ) compounds, the corresponding tertiary N-vinylcarboxylic acid amide compounds can be obtained.
From ( 2-hydroxypropyl ) compounds, the corresponding tertiary N- (1-propenyl) carboxylic acid amides and tertiary N
-(2-Propenyl) carboxylic acid amide is obtained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

The reaction pressure is such that the partial pressure of the tertiary N- (2-hydroxyalkyl) carboxylic amide as the raw material is 5-6.
There is no particular limitation as long as it can be controlled within the range of 00 mmHg, preferably 10 to 300 mmHg. Material partial pressure is 5
When it is smaller than mmHg, the reaction itself can be carried out without hindrance, but the production efficiency is lowered, for example, the collection of the product becomes difficult or the collection device becomes large. 600m partial pressure of raw material
If it is higher than mHg, the rate of side reactions increases, and the selectivity of the target tertiary N-alkenylcarboxylic amides decreases. Specifically, (1) a method in which a gas whose raw material is controlled in partial pressure by dilution with a substance inert to the reaction such as nitrogen, helium, argon, or a hydrocarbon is passed through a catalyst (reaction pressure is Any).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

Example 6 (Catalyst preparation) 8.15 g of cesium carbonate, 0.66 g of diammonium phosphate, 30 g of silicon oxide and 150 g of water
Was added, and the mixture was concentrated to dryness with heating and mixing on a hot water bath. Then, it is dried in air at 120 ° C. for 20 hours, crushed to 9 to 16 mesh, and then fired in air at 450 ° C. for 2 hours to obtain an atomic ratio of Cs ₁ Si ₁₀ P _{0 .} A catalyst having a composition of ₁ was obtained.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

Example 8 (Catalyst preparation) 0.29 g of magnesium hydroxide, 6.64 g of rubidium nitrate and 30 g of silicon oxide were added to 150 g of water.
Was added, and the mixture was concentrated to dryness with heating and mixing on a hot water bath. Next, it is dried in air at 120 ° C. for 20 hours, crushed to 9 to 16 mesh, and calcined in air at 500 ° C. for 2 hours to obtain an Rb _{0 . 9} Mg _{0 . 1} Si
A catalyst having a composition of ₁₀ was obtained.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

(Reaction) Using this catalyst, a reaction was conducted in the same manner as in Example 7 and an analysis was conducted. N- (2-
The conversion of (hydroxyethyl) -N'-methyl-propylamide, the N-vinyl-N'-methyl-propylamide selectivity and the single-flow yield are 85.4 mol% and 9%, respectively.
It was 3.1 mol% and 79.1 mol%.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction content]

Example 9 (Catalyst preparation) 3.16 g of barium hydroxide octahydrate, 7.80 g of cesium nitrate and 30 g of silicon oxide and 150 g of water.
Was added and the mixture was concentrated to dryness while heating and mixing on a hot water bath. Then, it is dried in air at 120 ° C. for 20 hours, crushed to 9 to 16 mesh, and then calcined in air at 500 ° C. for 2 hours to obtain Cs _{0 . 8} Ba _{0 .} A catalyst having a composition of ₂ Si ₁₀ was obtained.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction content]

(Reaction) Using this catalyst, a reaction was conducted in the same manner as in Example 7 and an analysis was conducted. N- (2-
The conversion of (hydroxyethyl) -N'-methyl-propylamide, the N-vinyl-N'-methyl-propylamide selectivity and the single stream yield were 87.1 mol% and 9%, respectively.
It was 2.4 mol% and 80.5 mol%.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

Example 10 (Catalyst preparation) 30 g of spherical silica gel (5 to 10 mesh) was immersed in a solution prepared by dissolving 1.40 g of potassium hydroxide and 0.15 g of boric acid in 100 g of water for 3 hours, and then bathed in a water bath. Concentrated to dryness above. Then, it is dried in air at 120 ° C. for 20 hours, and further calcined in air at 600 ° C. for 2 hours to obtain an atomic ratio of K ₁ Si ₂₀ B excluding oxygen.
_{0 .} A catalyst having a composition of ₁ was obtained.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0068

[Correction method] Change

[Correction content]

(Reaction) Using this catalyst, a reaction was conducted in the same manner as in Example 7 and an analysis was conducted. N- (2-
The conversion of (hydroxyethyl) -N′-methyl-propylamide, the N-vinyl-N′-methyl-propylamide selectivity and the single-flow yield were 88.8 mol% and 9%, respectively.
It was 1.4 mol% and 81.2 mol%.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0093

[Correction method] Change

[Correction content]

[0093] Example 27 (Catalyst preparation) 30 g of silicon oxide was added to a solution of 3.9 g of cesium nitrate and 0.34 g of lithium nitrate in 100 g of water, and the mixture was concentrated to dryness while heating and mixing on a hot water bath. Then, it is dried in air at 120 ° C., crushed to 9 to 16 mesh, and then fired in air at 500 ° C. for 2 hours to obtain Cs _{0 . 8} Li _{0 . 2} Si
A catalyst of composition ₂₀ was obtained.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction content]

Example 28 (Catalyst preparation) 30 g of silicon oxide was added to a solution of 5.9 g of rubidium nitrate and 3,2 g of barium hydroxide octahydrate dissolved in 100 g of water, and the mixture was heated and concentrated on a hot water bath. It was concentrated to dryness. Then, it is dried in air at 120 ° C. for 20 hours, crushed to 9 to 16 mesh, and then fired in air at 500 ° C. for 2 hours to obtain Rb at an atomic ratio excluding oxygen.
_{0 . 8} Ba _{0 .} A catalyst having a composition of ₂ Si ₁₀ was obtained.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0097

[Correction method] Change

[Correction content]

Example 29 (Catalyst preparation) 150 g of water was added to 15.8 g of barium hydroxide octahydrate, 0.66 g of diammonium phosphate and 30 g of silicon oxide, and concentrated to dryness while heating and concentrating in a water bath. did. Then, dry in air at 120 ° C. for 20 hours, and
After crushing into 6 mesh, it was baked in air at 450 ° C. for 2 hours to obtain an atomic ratio of Ba ₁ Si ₁₀ P excluding oxygen.
_{0 .} A catalyst having a composition of ₁ was obtained.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0099

[Correction method] Change

[Correction content]

Example 30 (Catalyst preparation) 19.5 g of cesium nitrate and 4.
30 g of silicon oxide in a solution of 9 g in 100 g of water
Was added, and the mixture was concentrated to dryness while heating and concentrating on a hot water bath. Next, it is dried in air at 120 ° C. for 20 hours, crushed to 9 to 16 mesh, and then fired in air at 500 ° C. for 2 hours to obtain an atomic ratio of Cs ₁ Si ₅ B _{0 .} A catalyst having a composition of ₅ was obtained.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0101

[Correction method] Change

[Correction content]

[0101] Example 31 (Catalyst preparation) 19.5 g of cesium nitrate and phosphoric acid second
1.2 g of aluminum phosphate and 30 g of silicon oxide in a solution prepared by dissolving 9.2 g of ammonium in 100 g of water.
Was added, and the mixture was concentrated to dryness while heating and concentrating on a hot water bath. Then, it is dried in air at 120 ° C. for 20 hours, crushed to 9 to 16 mesh, and then fired in air at 600 ° C. for 2 hours to obtain an atomic ratio of Cs ₁ Si ₅ Al _{0 . 1} P
_{0 .} A catalyst having a composition of ₈ was obtained.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0103

[Correction method] Change

[Correction content]

Examples 32 to 34 (Catalyst preparation) In a solution prepared by dissolving 9.8 g of cesium nitrate and 5.3 g of diammonium phosphate in 100 g of water,
30 g of silicon oxide was added, and the mixture was concentrated to dryness while being heated and concentrated on a hot water bath. Then, dry in air at 120 ° C. for 20 hours, and
After crushing to ~ 16 mesh, the mixture is fired in air at 500 ° C for 2 hours to obtain an atomic ratio of Cs ₁ Si ₁₀ excluding oxygen.
P _{0 .} A catalyst having a composition of ₈ was obtained.

Claims (9)

[Claims] 1. A catalyst for use in the synthesis of tertiary N-alkenylcarboxylic amides by subjecting tertiary N- (2-hydroxyalkyl) carboxylic amides to a gas phase intramolecular dehydration reaction, comprising an alkali metal A catalyst characterized by being an oxide containing an element and / or an alkaline earth metal element and silicon. Wherein said catalyst has the general formula _{(I) M a Si b X} c O d (1) ( at least one element in the formula, M is selected from the group consisting of alkali metal elements and alkaline earth metal elements , Si
Represents silicon, X represents at least one element selected from the group consisting of boron, aluminum and phosphorus, and O represents oxygen.
The subscripts a, b, c and d represent the number of atoms of each element, and when a = 1, the range is b = 1 to 500, c = 0 to 1, and d is the value of a, b and c and It is a numerical value determined by the bonding state of various constituent elements. The catalyst according to claim 1, which is an oxide represented by the formula (1). 3. A tertiary N- (2-hydroxyalkyl) carboxylic acid amide is represented by the following general formula (2): (Wherein R ₁ and R ₂ are independent groups and are any one selected from the group consisting of hydrocarbon groups having 1 to 6 carbon atoms). ) -N '
An alkyl-amide compound, which is subjected to a gas phase intramolecular dehydration reaction to obtain tertiary N-alkenylcarboxylic acid amides represented by the following general formula (3): (Wherein, R ₁ and R ₂ are the same as defined above, and general formula (2).) Represented by N- vinyl -N'- alkyl - according to claim 1 or 2 used in the synthesis of the amide compound Catalyst. 4. The method according to claim 1, wherein the tertiary N- (2-hydroxyalkyl) carboxylic acid amide is N- (2-hydroxyethyl)-
2-pyrrolidone, which is subjected to a gas phase intramolecular dehydration reaction to form tertiary N-alkenylcarboxylic amides,
The catalyst according to claim 1 or 2, which is used when synthesizing vinyl-2-pyrrolidone. 5. A tertiary N- (2-hydroxyalkyl) carboxylic acid amide is represented by the following general formula (4): (Wherein R ₁ , R ₂ and R ₃ are independent groups and R ₁ and R ₂
Is any one selected from the group consisting of hydrocarbon groups having 1 to 6 carbon atoms, and R ₃ is any one kind selected from the group consisting of hydrogen and hydrocarbon groups having 1 to 6 carbon atoms. )
Which is an N- (2-hydroxyalkyl) -N'-alkyl-amide compound represented by the formula: (5) and (6) (In the formula, R ₁ , R ₂ and R ₃ are the same as those in the general formula (4).)
The catalyst according to claim 1, which is used when synthesizing an amide compound. 6. The method according to claim 1, wherein the tertiary N- (2-hydroxyalkyl) carboxylic amide is subjected to a gas phase intramolecular dehydration reaction to obtain a tertiary N-alkenylcarboxylic amide. A method for producing tertiary N-alkenylcarboxylic amides, comprising using a catalyst. 7. A tertiary N- (2-hydroxyalkyl) carboxylic acid amide is represented by the following general formula: (Wherein R ₁ and R ₂ are independent groups and are any one selected from the group consisting of hydrocarbon groups having 1 to 6 carbon atoms). ) -N '
-Alkyl-amide compound, which is a tertiary N-alkenylcarboxylic acid amide represented by the following general formula (3): (Wherein, R ₁ and R ₂ are the same as defined above, and general formula (2).) Represented by N- vinyl -N'- alkyl - amide compound, The method according to claim 6. 8. The method of claim 1, wherein the tertiary N- (2-hydroxyalkyl) carboxylic acid amide is N- (2-hydroxyethyl)-
The production method according to claim 6, wherein the tertiary N-alkenylcarboxylic acid amide is 2-pyrrolidone, and the tertiary N-alkenylcarboxylic acid amide is N-vinyl-2-pyrrolidone. 9. A tertiary N- (2-hydroxyalkyl) carboxylic acid amide is represented by the following general formula (4): (Wherein R ₁ , R ₂ and R ₃ are independent groups and R ₁ and R ₂
Is any one selected from the group consisting of hydrocarbon groups having 1 to 6 carbon atoms, and R ₃ is any one kind selected from the group consisting of hydrogen and hydrocarbon groups having 1 to 6 carbon atoms. )
A tertiary N-alkenyl carboxylic acid amide represented by the following general formulas (5) and (6): (In the formula, R ₁ , R ₂ and R ₃ are the same as those in the general formula (4).)
The production method according to claim 6, which is an amide compound.