JP3396570B2 - Method for producing hydroxyalkanal - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a hydroxyalkanal by hydrating an unsaturated aldehyde in an aqueous solution in the presence of a catalyst.

[0002]

2. Description of the Related Art Conventionally, for example, 3-hydroxypropanal (3-hydroxypropionaldehyde), which is a kind of hydroxyalkanal, is obtained by hydrating acrolein, which is a kind of unsaturated aldehyde, in an aqueous solution in the presence of a catalyst.
Various manufacturing methods as shown below are known as methods for obtaining

That is, US Pat. No. 2,434,110 discloses a method of using a mineral acid such as sulfuric acid as an acidic homogeneous catalyst in the above reaction system. However, this method has a drawback that the selectivity of 3-hydroxypropanal is low and the 3-hydroxypropanal cannot be efficiently produced. Further, it is difficult to separate the homogeneous catalyst from 3-hydroxypropanal and to reuse the catalyst.

Therefore, as a method for solving the above drawbacks and improving the selectivity of 3-hydroxypropanal, US Pat. No. 3,536,763 discloses a method of using an acidic ion exchange resin as an acidic heterogeneous catalyst in the above reaction system. Is disclosed. JP-A-3-35932 (US Pat. No. 5,015,7
89, German Patent No. 3926136.0), Japanese Patent Laid-Open No. 4-300844 (US Pat. No. 5,171,898, German Patent No. 4038192.7), an ion exchange resin having a phosphoric acid group, an amino group or an aminophosphoric acid group is described above. A method for use as an acidic heterogeneous catalyst in a reaction system is disclosed. Japanese Unexamined Patent Publication No. 5-194291 (US Pat. No. 5,093,537) discloses a method of using an alumina-bonded zeolite as an acidic heterogeneous catalyst in the above reaction system. Japanese Unexamined Patent Publication No. 5-221912 (US Pat. No. 5,276,201, German Patent No. 4138982.4) discloses a method of using TiO ₂ carrying phosphoric acid as an acidic heterogeneous catalyst in the above reaction system. In addition, JP-A-5-279285 (US Pat. No. 5,284,979, German Patent No.
4138981.6) discloses a method of carrying out the above reaction in the presence of an acidic catalyst using a buffer solution containing a carboxylic acid and a tertiary amine.

In these methods, the concentration of the raw material acrolein in the aqueous solution is low (about 20% by weight).
Less than 3), the selectivity to 3-hydroxypropanal is good, and therefore 3-hydroxypropanal is obtained with high selectivity.

[0006]

However, according to the study by the inventors of the present invention, in the above conventional method, when the acrolein concentration is high (about 20% by weight or more), that is, it is industrially advantageous. When a high-concentration aqueous acrolein solution is reacted, 3-hydroxypropanal, which is a reaction product, has an aldehyde group, so that a sequential reaction (side reaction) of the 3-hydroxypropanal actively occurs. I understood it. That is, a decrease in selectivity from acrolein to 3-hydroxypropanal is seen, and therefore
It has a drawback that the selectivity of the 3-hydroxypropanal is lowered. Further, the acidic heterogeneous catalyst used in the above-mentioned conventional method is inferior in heat resistance, and therefore the reaction temperature is increased to increase the reaction rate of the hydration reaction (about 65%).
If it is set to be higher than 0 ° C.), the acidic heterogeneous catalyst is deactivated and the selectivity of 3-hydroxypropanal is lowered.

Therefore, in the above conventional production method, the reaction rate cannot be increased by heating, and the acrolein in the aqueous solution cannot be increased to a high concentration to improve the productivity of 3-hydroxypropanal. From an industrial point of view, it turns out that it is not a satisfactory method.

The present invention has been made in view of the above-mentioned conventional problems, and an object thereof is to increase the reaction rate by heating by using a catalyst having heat resistance, and to industrially use it. Another object of the present invention is to provide a production method capable of producing a hydroxyalkanal with a high selectivity and a high yield even when using a high-concentration unsaturated aldehyde aqueous solution which is advantageous for the above.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies as to a method for producing a hydroxyalkanal by hydrating an unsaturated aldehyde in an aqueous solution in the presence of a catalyst, and as a result, have a specific structure. Copolymerization of a carboxylic acid resin having a substituent and / or an unsaturated monomer (A) containing a carboxyl group with an unsaturated monomer (B) containing an amino group and / or an amide group It was found that the use of the carboxylic acid resin as described above as the catalyst improves the selectivity of unsaturated aldehyde to hydroxyalkanal and the yield of hydroxyalkanal. Further, it was confirmed that the carboxylic acid resin as a catalyst has excellent heat resistance, and therefore the reaction temperature can be set higher than in the conventional case and the reaction rate can be increased by heating. That is, by using a carboxylic acid resin having heat resistance, the reaction rate can be increased by heating, and a highly concentrated unsaturated aldehyde aqueous solution, which is industrially advantageous, is used to highly select hydroxyalkanal. The present invention has been completed by discovering that it can be obtained at a high rate and a high yield.

That is, in order to solve the above-mentioned problems, the method for producing hydroxyalkanal according to the first aspect of the present invention has the general formula (I)

[0011]

[Chemical 7]

(In the formula, R represents a hydrogen atom or a carbon number of 1 to
In the method for producing a hydroxyalkanal by hydrating an unsaturated aldehyde represented by a hydrocarbon group of 5) in an aqueous solution in the presence of a catalyst, the catalyst represented by the general formula (II)

[0013]

[Chemical 8]

General formula (III)

[0015]

[Chemical 9]

General formula (IV)

[0017]

[Chemical 10]

General formula (V)

[0019]

[Chemical 11]

And general formula (VI)

[0021]

[Chemical 12]

It is characterized in that a carboxylic acid resin having a substituent having at least one structure selected from the group consisting of is used.

In order to solve the above-mentioned problems, the method for producing a hydroxyalkanal according to claim 2 is the method for producing a hydroxyalkanal according to claim 1, wherein the number of nitrogen-containing groups in the carboxylic acid resin is And the number of carboxyl groups (number of nitrogen-containing groups / number of carboxyl groups) are within the range of 1/1000 to 1/1.

In order to solve the above-mentioned problems, the method for producing a hydroxyalkanal according to the third aspect of the present invention is the method for producing a hydroxyalkanal according to the first or second aspect , wherein a metal is added to the carboxylic acid resin. Is supported in the range of 0.001% by weight to 10% by weight.

In order to solve the above-mentioned problems, the method for producing hydroxyalkanal according to the invention of claim 4 is the method for producing hydroxyalkanal according to any one of claims 1 to 3 , wherein carboxylic acid is used. Resin is (meta)
It is characterized by being an acrylic acid resin.

In order to solve the above-mentioned problems, the method for producing hydroxyalkanal according to the fifth aspect of the present invention is the method for producing hydroxyalkanal according to the fourth aspect, wherein the (meth) acrylic acid resin is ( (Meth) acrylic acid- (meth) acrylamide copolymer or (meth)
It is characterized by being an acrylic acid-vinylpyrrolidone copolymer.

In order to solve the above-mentioned problems, the method for producing hydroxyalkanal according to the sixth aspect of the present invention is the method for producing hydroxyalkanal according to any one of the first to fifth aspects. The aldehyde is acrolein.

In order to solve the above-mentioned problems, the method for producing hydroxyalkanal according to claim 7 is the method for producing hydroxyalkanal according to claim 6, wherein the reaction system is 1,3-propanediol. Is added to acrolein in the range of 0.001% by weight to 10% by weight.

According to the above method, the reaction rate can be increased by heating, and the successive reaction (side reaction) of the hydroxyalkanal reaction product is suppressed, so that a highly concentrated unsaturated aldehyde aqueous solution is obtained. Even when is used, hydroxyalkanal can be produced with high selectivity and high yield. That is, by using a carboxylic acid-based resin having heat resistance, the reaction rate can be increased by heating, and an industrially advantageous high-concentration unsaturated aldehyde aqueous solution can be reacted. Canal productivity can be improved.

The present invention will be described in detail below.

The unsaturated aldehyde (2-alkenal) represented by the general formula (I) used as a raw material in the present invention is not particularly limited, but in the formula, the substituent represented by R is hydrogen. It is composed of an atom or a hydrocarbon group having 1 to 5 carbon atoms, and the hydrocarbon group is a methyl group, an ethyl group, a propyl group, a butyl group or an amyl group. Specific examples of the above-mentioned unsaturated aldehyde include acrolein, methacrolein, 2-formyl-1-
Butene, 2-formyl-1-pentene, 2-formyl-1-hexene, 2-formyl-1-heptene and the like can be mentioned. And of these unsaturated aldehydes, acrolein is preferred.

According to the method of the present invention, the corresponding 2-hydroxyalkanal or 3-hydroxyalkanal can be selectively obtained from these unsaturated aldehydes. That is, in the general formula (I), 3-hydroxypropanal (3-hydroxypropionaldehyde), which is 3-hydroxyalkanal, is selectively obtained from acrolein in which the substituent represented by R is a hydrogen atom. On the other hand, R
2-Hydroxyalkanal is selectively obtained from an unsaturated aldehyde in which the substituent represented by is a hydrocarbon group. The 3-hydroxypropanal obtained when acrolein is used as the unsaturated aldehyde is important as an industrial raw material for producing 1,3-propanediol.

The concentration of the unsaturated aldehyde in the aqueous solution (hereinafter, simply referred to as the concentration) depends on the solubility of the unsaturated aldehyde in water, the reaction temperature, etc., but is preferably in the range of 5% by weight to the saturated concentration. The range of 50 wt% to 50 wt% is more preferable, the range of 20 wt% to 50 wt% is more preferable, and the range of 25 wt% to 40 wt% is most preferable. When the concentration of unsaturated aldehyde is lower than 5% by weight, the production efficiency of hydroxyalkanal is lowered, which is not preferable. Further, if the concentration of the unsaturated aldehyde is higher than the saturated concentration, a polymerization reaction of the unsaturated aldehyde which does not dissolve occurs and the selectivity for hydroxyalkanal is lowered, which is not preferable.

The catalyst used in the present invention is selected from the group consisting of the general formula (II), the general formula (III), the general formula (IV), the general formula (V) and the general formula (VI). A carboxylic acid resin having a substituent having at least one structure, or an unsaturated monomer containing a carboxyl group (A),
If it is a carboxylic acid resin obtained by copolymerizing with an unsaturated monomer (B) containing an amino group and / or an amide group,
It is not particularly limited. That is, as the catalyst used in the present invention, a carboxylic acid-based resin having a substituent having at least one structure selected from the group consisting of general formulas (II) to (VI), and an unsaturated monomer (A),
Examples thereof include a carboxylic acid resin obtained by copolymerizing with an unsaturated monomer (B). Also, these carboxylic acid resins may be used in combination. In the formula, the portion represented by X is the carboxylic acid resin main body, and the carboxylic acid resin is a polymer containing a large number of free carboxyl groups. Further, the hydrocarbon group having 1 to 5 carbon atoms in the above general formulas (II) to (VI) is
A methyl group, an ethyl group, a propyl group, a butyl group, and an amyl group.

The carboxylic acid resin having an amide group (substituent) having the structure of the general formulas (II), (III) and (IV), and the structure of the general formulas (V) and (VI) The carboxylic acid-based resin having an amino group (substituent) provided is not particularly limited. The carboxylic acid resin main body may be a homopolymer of a monomer containing a carboxyl group, or a monomer containing a carboxyl group,
It may be copolymerized with the monomer containing the carboxyl group and another monomer copolymerizable with the monomer (hereinafter referred to as a copolymerized monomer for convenience of description).

Specific examples of the monomer containing a carboxyl group include carboxylic acids such as (meth) acrylic acid, maleic acid and fumaric acid, but are not particularly limited. Only one kind of these carboxyl group-containing monomers may be used, or two or more kinds thereof may be appropriately mixed and used.

The above-mentioned copolymerizable monomer is not particularly limited, but is a monomer having an olefin group. Specific examples of the copolymerization monomer include esters of the above carboxyl group-containing monomers, styrene, and vinylpyridine. The above-mentioned copolymerizable monomer may contain a functional group other than a carboxyl group, specifically, a functional group such as a phosphoric acid group, a sulfonic acid group, or a hydroxyl group. These copolymerizable monomers may be used alone or in combination of two or more.

Among the amide-based carboxylic acid resins having the structure of the general formula (II), the carboxylic acid-based resin in which the divalent substituent represented by Y ₁ contains a nitrogen atom or a sulfur atom is a catalyst. Is more preferable, and a carboxylic acid resin containing a sulfur atom is particularly preferable.
Further, among the carboxylic acid resins having an amide group having the structure of the general formula (III), the carboxylic acid resin having an amide group in which the repeating unit represented by q ₁ is 3 has reactivity as a catalyst. Is more preferable, so that it is more preferable.

Among the carboxylic acid resins having an amino group having the structure of the general formula (V), a carboxylic acid resin having a nitrogen atom or a sulfur atom as a divalent substituent represented by Y ₂ is a catalyst. Is more preferable, and a carboxylic acid resin containing a sulfur atom is particularly preferable.
Further, the Bronstedic acid residue in the general formula (V),
A group that releases a proton, such as a carboxyl group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, and a hydroxyl group. In the present invention, the Bronstedic acid residue also includes a hydrocarbon group having 1 to 5 carbon atoms in which at least one of hydrogen atoms is substituted with the above-mentioned proton-releasing group.

As the carboxylic acid resin (main body), a (meth) acrylic acid resin is suitable. And
When the (meth) acrylic acid-based resin has an amide group, a (meth) acrylic acid- (meth) acrylamides copolymer and a (meth) acrylic acid-vinylpyrrolidone polymers are more preferable. (Meth) acrylic acid-
Specific examples of the (meth) acrylamides copolymer include (meth) acrylic acid- (meth) acrylamide copolymer and (meth) acrylic acid-N, N-dimethyl (meth) acrylamide copolymer. , (Meth) acrylic acid-N-
Isopropyl (meth) acrylamide copolymer, (meth) acrylic acid-N, N-dimethylaminopropyl (meth)
Examples of the acrylamide copolymer include, but are not particularly limited to. Specific examples of the (meth) acrylic acid-vinylpyrrolidone polymers include acrylic acid-N-vinylpyrrolidone copolymers, but are not particularly limited.

Specific examples of the (meth) acrylic acid-based resin having an amino group include (meth) acrylic acid-2-vinylpyridine copolymers and (meth) acrylic acid-4-vinyl. Pyridine copolymer, (meth) acrylic acid-N-vinylcarbazole copolymer, (meth) acrylic acid-N-monoallylamine copolymer, (meth) acrylic acid-N, N-diallylamine copolymer Specific examples thereof include polymer, (meth) acrylic acid-N, N, N-triallylamine copolymer, and (meth) acrylic acid-4- (N, N-dialkylamino) alkylstyrene copolymer. It is not limited.

Further, the unsaturated monomer (A) and the unsaturated monomer
The carboxylic acid resin obtained by copolymerizing with (B) is not particularly limited. Examples of the unsaturated monomer (A) include, but are not particularly limited to, the above-mentioned monomer containing a carboxyl group.

Among the unsaturated monomers (B), the unsaturated monomer (B) containing an amino group is specifically, for example,
Vinylpyridines, N-vinylcarbazoles, N-monoallylamines, N, N-diallylamines, N, N, N-triallylamines, 4- (N, N-dialkylamino) alkylstyrenes, 6- ( N-propenylamino) -4-thiahexanoic acid,
And nitrogen-containing unsaturated compounds such as 6- (N, N-dipropenylamino) -4-thiahexanoic acid, but are not particularly limited. Further, in the unsaturated monomer (B), the substituent represented by the general formula (VII) may be bonded to the nitrogen atom constituting the amino group and / or the amide group.
Further, the unsaturated monomer (A), the unsaturated monomer (B) and the copolymerization monomer may be copolymerized to obtain a carboxylic acid resin. The Bronstedic acid residue in the general formula (VII) refers to a group that releases a proton, such as a carboxyl group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group and a hydroxyl group. In the present invention, the Bronstedic acid residue also includes a hydrocarbon group having 1 to 5 carbon atoms in which at least one of hydrogen atoms is substituted with the above-mentioned proton-releasing group.

Specific examples of the vinyl pyridines include, but are not limited to, 2-vinyl pyridines and 4-vinyl pyridines. Further, as the 4- (N, N-dialkylamino) alkylstyrenes, specifically, for example, general formula (VIII)

[0045]

[Chemical 13]

(In the formula, R ₁₅ and R ₁₆ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms,
j represents an integer of 1 to 5). In addition, the said C1-C5 hydrocarbon group is a methyl group, an ethyl group, a propyl group, a butyl group, and an amyl group. Among the 4- (N, N-dialkylamino) alkylstyrenes represented by the general formula (VIII), 4- (N, N-dialkylamino) alkyl in which the repeating unit represented by j is 1 to 3 Styrenes are preferable because they have good reactivity with the unsaturated monomer (A) and reactivity as a catalyst after being made into a carboxylic acid resin. The above general formula (VI
Specific examples of 4- (N, N-dialkylamino) alkylstyrenes represented by II) include 4- (N, N-dimethylamino) ethylstyrene.

These carboxylic acid resins may be used alone or in a suitable mixture of two or more kinds. The method for producing the carboxylic acid resin is not particularly limited.

The ratio of the number of nitrogen-containing groups to the number of carboxyl groups in the carboxylic acid resin (number of nitrogen-containing groups / number of carboxyl groups) depends on the type of unsaturated aldehyde and reaction conditions, but is preferable. Is in the range of 1/1000 to 1/1, more preferably in the range of 1/100 to 1 / 1.5 (that is, 2/3), and even more preferably in the range of 1/20 to 1/2. Just set it. In the present invention, the nitrogen-containing group is represented by the general formula (I
An amide group having the structure of I), (III), and (IV), the above general formula
The amino groups having the structures (V) and (VI), and the amino group residue and the amide group residue derived from the unsaturated monomer (B) are shown. When the above ratio is smaller than 1/1000 or larger than 1/1, it is not preferable because the successive reaction (side reaction) of the hydroxyalkanal reaction product cannot be suppressed. .

That is, when a (meth) acrylic acid-vinylpyridine copolymer is used as the carboxylic acid resin, the content of vinylpyridine units in the copolymer is, for example, the type of unsaturated aldehyde or It may be appropriately set within the range of 0.1 mol% to 50 mol% depending on the reaction conditions and the like. When a (meth) acrylic acid- (meth) acrylamide copolymer is used as the carboxylic acid resin, the content of the (meth) acrylamide unit in the copolymer is, for example, the type of unsaturated aldehyde. It may be appropriately set within the range of 0.1 mol% to 50 mol% depending on the reaction conditions and the like. Furthermore, when a (meth) acrylic acid-vinylpyrrolidone copolymer is used as the carboxylic acid-based resin, the content of vinylpyrrolidone units in the copolymer is, for example, the type of unsaturated aldehyde or reaction conditions. Depending on, 0.1 mol% to 50 mol%
It may be set appropriately within the range.

Further, in order to obtain hydroxyalkanal with a higher selectivity and a higher yield, it is preferable to carry a metal on the carboxylic acid resin. Specific examples of the above metal include copper, lead, nickel, zinc, iron, cobalt, bismuth, tin, antimony, and alkaline earth metals, but are not particularly limited.
Among the above-mentioned metals, copper and lead are more preferable because hydroxyalkanal can be obtained with higher selectivity and high yield, and lead is particularly preferable.

When a metal is supported on the carboxylic acid resin, the amount of the metal supported on the carboxylic acid resin is within the range of 0.001% by weight to 10% by weight, although it depends on the composition of the carboxylic acid resin. The range of 0.01 to 5% by weight is more preferable, and the range of 0.01 to 1% by weight is further preferable. If the amount of supported metal is less than 0.001% by weight, the effect of supporting the metal on the carboxylic acid resin will not be sufficiently exhibited, which is not preferable. On the other hand, if the amount of supported metal is more than 10% by weight, the yield of hydroxyalkanal is lowered, which is not preferable. The supporting as used herein may be in any form such as salt, chelate, adsorption, clathrate, and the like. The metal carried may be either an ion or a metal. The form of ions is oxide,
Examples thereof include halides and sulfides.

The method of supporting the metal on the carboxylic acid resin is not particularly limited, and a generally practiced method can be adopted. To carry a metal, for example, lead on a carboxylic acid resin, specifically, for example, by dipping the carboxylic acid resin in an aqueous solution in which a predetermined amount of a lead compound such as lead nitrate or lead acetate is dissolved, and under predetermined conditions. It is achieved by stirring the mixture at 1, to carry out cation exchange, then taking out the carboxylic acid resin by filtration and washing with water.

The form of the carboxylic acid resin thus obtained in the aqueous solution of the unsaturated aldehyde may be a uniform form by being dissolved in the above-mentioned aqueous solution. May be The form of the carboxylic acid resin in the aqueous solution of the unsaturated aldehyde is not particularly limited, but a solid form is preferable. A crosslinking agent may be used when obtaining the carboxylic acid resin. The type of the cross-linking agent and the addition amount thereof are not particularly limited.

The detailed reason why the metal-supported carboxylic acid resin in the present invention exhibits a better catalytic action in the reaction of synthesizing hydroxyalkanal from unsaturated aldehyde is not clear, but In the reaction, it is presumed that this is because the successive reaction of the reaction product hydroxyalkanal is suppressed.

When acrolein is used as the unsaturated aldehyde, in order to obtain 3-hydroxypropanal with a higher selectivity and a higher yield, 1, which is derived from the desired product, 3-hydroxypropanal 1, It is preferable to add 3-propanediol to the reaction system. The amount of 1,3-propanediol added to acrolein is 0.001% by weight
~ 10% by weight, preferably 0.01% to 5% by weight
Is more preferable, 0.1 wt% to 2 wt% is still more preferable, and about 1 wt% is the most preferable. 1,
If the amount of 3-propanediol added is less than 0.001% by weight, the effect of adding 1,3-propanediol is not sufficiently exhibited, which is not preferable. When the amount of 1,3-propanediol added is more than 10% by weight, the yield of 3-hydroxypropanal decreases,
Not preferable.

In the present invention, 1, which is added to the reaction system,
The detailed reason why 3-propanediol exhibits a superior action and effect in the reaction for synthesizing 3-hydroxypropanal from acrolein is not clear, but in the above reaction, the above reaction point in the carboxylic acid resin is used. It is speculated that 1,3-propanediol may be bound to and the reaction points may be masked to some extent to suppress the successive reaction of the reaction product 3-hydroxypropanal.

The reaction temperature is not particularly limited, but is preferably 50 ° C. to 250 ° C. For example, when acrolein is used as the unsaturated aldehyde, 50 ° C. to 140 ° C.
C is preferred. If the reaction temperature is less than 50 ° C, the reaction rate will be slow and the hydration reaction will take time, which is not economical, and if the reaction temperature exceeds 250 ° C, polymerization of unsaturated aldehyde, etc. It is not preferable because a side reaction occurs and the yield of hydroxyalkanal is lowered.

The present invention may be carried out in any of a batch system, a semi-batch system and a continuous system, but the reaction system is preferably a closed system. The reaction pressure when the reaction system is a closed system is not particularly limited,
1kg / cm ² ~20kg / cm ² is preferred. In addition, even when the reaction is carried out at a temperature lower than the boiling point of the unsaturated aldehyde, the reaction system should be set to 1 after taking the vapor pressure of the unsaturated aldehyde into consideration.
It is preferable to apply a kg / cm ² ~5kg / cm ² about the reaction pressure. The reaction pressure is, for example, a gas inert to the reaction system (eg, N ₂ gas or He gas) in the reaction vessel.
You may hang it by filling. Regarding the reaction pressure, the higher the pressure, the more the amount of unsaturated aldehyde dissolved in water increases, and the yield of hydroxyalkanal increases. On the other hand, the pressure-resistant structure of the reactor must be made stronger, There are disadvantages such as an increase in size. Therefore, the reaction pressure may be set in consideration of the balance between the two.

After completion of the reaction, the target hydroxyalkanal aqueous solution can be easily obtained by a simple separation operation such as filtration or distillation. Also, hydroxyalkanals can be easily isolated, if desired. Then, for example, taking 3-hydroxyalkanal as the hydroxyalkanal as an example, 3-hydroxyalkanal may actually exist as a hemiacetal form and an acetal form in an aqueous solution. However, they can be easily converted to 3-hydroxyalkanals. Further, hydroxyalkanal may exist as a hemiacetal form and an acetal form of the corresponding alcohol even in the presence of alcohols, but these can be easily converted into hydroxyalkanal.

The recovered water, the carboxylic acid resin as the catalyst, and the unreacted unsaturated aldehyde can be repeatedly used for the hydration reaction.

[0061]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. The conversion of unsaturated aldehyde represented by the general formula (I) and the selectivity of hydroxyalkanal are defined as follows.

Unsaturated aldehyde conversion (%) = (moles of unsaturated aldehyde consumed / moles of unsaturated aldehyde fed) x 100 hydroxyalkanal selectivity (%) = (to hydroxyalkanal Number of moles of unsaturated aldehyde converted / Number of moles of unsaturated aldehyde consumed) x 100 Selectivity of hydroxyalkanal dimer (%) = (number of moles of unsaturated aldehyde converted to hydroxyalkanal dimer) / Mol of unsaturated aldehyde consumed) × 100 The unsaturated aldehyde, hydroxyalkanal, and hydroxyalkanal dimer can be quantified by a known method such as gas chromatography (GC). In the present invention, it was measured by gas chromatography.

Example 1 A predetermined amount of water was placed in a reaction vessel equipped with a thermometer, a stirrer, etc., and a predetermined amount of acrolein as an unsaturated aldehyde was added so that the concentration in the aqueous solution would be 17% by weight. I prepared it. Next, a predetermined amount of acrylic acid-acrylamide copolymer (carboxylic acid resin) was added to the above aqueous solution as a catalyst. The content of acrylamide units in the above acrylic acid-acrylamide copolymer was 5 mol%. Acrolein was hydrated by reacting the above reaction solution at 80 ° C. for 3 hours while stirring. The above reaction conditions are summarized in Table 1.

After completion of the reaction, the reaction solution was filtered, and the filtrate was analyzed by a predetermined method. As a result, the conversion rate of acrolein was 44% and the selectivity of 3-hydroxypropanal was 57% and 3-hydroxypropanal. The selectivity of the hydroxypropanal dimer was 9%, and the selectivity as hydroxyalkanal was 66%, which is the sum of the selectivity of both. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

An aqueous solution containing 8.1% by weight of 3-hydroxypropanal obtained by the hydration reaction and 1.3% by weight of 3-hydroxypropanal dimer was prepared. And
A known Raney nickel catalyst was added to this aqueous solution to hydrogenate 3-hydroxypropanal and a 3-hydroxypropanal dimer. The reaction conditions are hydrogen pressure of 100 kg.
/ cm ² , the reaction temperature was 60 ° C, and the reaction time was 6 hours. After completion of the reaction, the aqueous solution was analyzed and as a result, production of 1,3-propanediol corresponding to the total amount of 3-hydroxypropanal and 3-hydroxypropanal dimer was confirmed. That is, 1,3-propanediol was quantitatively produced.
From this, it was found that the 3-hydroxypropanal dimer was converted to 1,3-propanediol by a conventionally known hydrogenation.

Example 2 Lead was supported on the acrylic acid-acrylamide copolymer as the catalyst in Example 1, and 2.5 wt% of 1,3-propanediol was added to the reaction system with respect to acrolein, The same reaction and analysis as in Example 1 were carried out except that the reaction temperature was 90 ° C. The amount of lead supported in the acrylic acid-acrylamide copolymer was adjusted to a predetermined value of 5% by weight or less. The above reaction conditions are summarized in Table 1.

As a result, the conversion of acrolein was 51%, and the selectivity of 3-hydroxypropanal was 77.
%, The selectivity of 3-hydroxypropanal dimer was 15%, and the total selectivity of the two was 92%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Example 3 The acrolein concentration in Example 2 was changed from 17% by weight to 28% by weight.
The same reaction and analysis as in Example 2 were carried out except that the content was changed to wt%. The above reaction conditions are summarized in Table 1.

As a result, the conversion rate of acrolein was 38% and the selectivity of 3-hydroxypropanal was 64%.
%, The selectivity of 3-hydroxypropanal dimer was 23%, and the total selectivity of the two was 87%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Example 4 The content of acrylamide unit in the acrylic acid-acrylamide copolymer as the catalyst in Example 3 was adjusted to 5
The same reaction and analysis as in Example 3 were carried out except that the mol% was changed to 20 mol%. The above reaction conditions are summarized in Table 1.

As a result, the conversion rate of acrolein was 56%, and the selectivity of 3-hydroxypropanal was 67%.
%, The selectivity of 3-hydroxypropanal dimer was 12%, and the total selectivity of the two was 79%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Example 5 The same as Example 3 except that an acrylic acid-N, N-dimethylacrylamide copolymer was used instead of the acrylic acid-acrylamide copolymer as the catalyst in Example 3. Reaction and analysis were performed. The content of N, N-dimethylacrylamide units in the acrylic acid-N, N-dimethylacrylamide copolymer was set to 5 mol%. The above reaction conditions are summarized in Table 1.

As a result, the conversion rate of acrolein was 41%, and the selectivity of 3-hydroxypropanal was 60%.
%, The selectivity of 3-hydroxypropanal dimer was 20%, and the total selectivity of the two was 80%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Example 6 A reaction similar to that in Example 3 except that an acrylic acid-N-isopropylacrylamide copolymer was used instead of the acrylic acid-acrylamide copolymer as the catalyst in Example 3. Analysis was carried out. The content of N-isopropylacrylamide unit in the above acrylic acid-N-isopropylacrylamide copolymer was 5 mol%. The above reaction conditions are summarized in Table 1.

As a result, the conversion rate of acrolein was 42%, and the selectivity of 3-hydroxypropanal was 57%.
%, The selectivity of 3-hydroxypropanal dimer was 19%, and the total selectivity of the two was 76%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Example 7 Acrylic acid-N, N-dimethylaminopropyl acrylamide copolymer was used in place of the acrylic acid-acrylamide copolymer as the catalyst in Example 3, except that
The same reaction and analysis as in Example 3 were performed. The content of N, N-dimethylaminopropylacrylamide units in the above acrylic acid-N, N-dimethylaminopropylacrylamide copolymer was 5 mol%. The above reaction conditions are summarized in Table 1.

As a result, the conversion rate of acrolein was 46%, and the selectivity of 3-hydroxypropanal was 57%.
%, The selectivity of 3-hydroxypropanal dimer was 18%, and the total selectivity of the two was 75%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Example 8 The same as Example 3 except that an acrylic acid-N, N-diethylacrylamide copolymer was used instead of the acrylic acid-acrylamide copolymer as the catalyst in Example 3. Reaction and analysis were performed. The content of N, N-diethylacrylamide unit in the acrylic acid-N, N-diethylacrylamide copolymer was set to 5 mol%. The above reaction conditions are summarized in Table 1.

As a result, the conversion of acrolein was 58% and the selectivity of 3-hydroxypropanal was 65%.
%, The selectivity of 3-hydroxypropanal dimer was 12%, and the total selectivity of the two was 77%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Example 9 Acrylic acid-N, N-dimethylaminopropyl acrylamide copolymer was used in place of the acrylic acid-acrylamide copolymer as the catalyst in Example 1, and the reaction system was used.
The same reaction and analysis as in Example 1 were carried out except that 1.3% by weight of 1,3-propanediol was added to acrolein and the reaction temperature was changed to 90 ° C. In the above acrylic acid-N, N-dimethylaminopropyl acrylamide copolymer, N,
The content of N-dimethylaminopropyl acrylamide unit was 5 mol%. The above reaction conditions are summarized in Table 1.

As a result, the conversion rate of acrolein was 30%, and the selectivity of 3-hydroxypropanal was 64%.
%, The selectivity of 3-hydroxypropanal dimer was 16%, and the total selectivity of both was 80%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Example 10 Instead of the acrylic acid-acrylamide copolymer as the catalyst in Example 1, an acrylic acid-N-vinylpyrrolidone copolymer was used, and 1,3-propanediol was acrolein-containing in the reaction system. The same reaction and analysis as in Example 1 were carried out except that 2.5% by weight was added. Acrylic acid above
The content of N-vinylpyrrolidone units in the N-vinylpyrrolidone copolymer was 5 mol%. The above reaction conditions are summarized in Table 1.

As a result, the conversion rate of acrolein was 28% and the selectivity of 3-hydroxypropanal was 71%.
%, The selectivity of 3-hydroxypropanal dimer was 8%, and the total selectivity of the two was 79%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Example 11 The concentration of acrolein in Example 10 was changed from 17% by weight.
Reaction similar to that of Example 10 except that the amount was changed to 28% by weight,
Analysis was carried out. The above reaction conditions are summarized in Table 1.

As a result, the conversion rate of acrolein was 17%, and the selectivity of 3-hydroxypropanal was 65%.
%, The selectivity of 3-hydroxypropanal dimer was 9%, and the total selectivity of the two was 74%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 2.

Comparative Example 1 Instead of the acrylic acid-acrylamide copolymer supporting lead as the catalyst in Example 2, an ion exchange resin supporting aluminum was used, the reaction temperature was 70 ° C., and the reaction was carried out. The same reaction and analysis as in Example 2 were carried out except that 1,3-propanediol was not added to the system. As the above ion exchange resin, Duolite C467 (trade name)
(Duolite), Rohm & Haas C
o.)) was used. The amount of aluminum supported on the ion exchange resin was adjusted to a predetermined value of 5% by weight or less. The above reaction conditions are summarized in Table 1.

As a result, the conversion rate of acrolein was 44%, and the selectivity of 3-hydroxypropanal was 46%.
%, The selectivity of 3-hydroxypropanal dimer was 5%, the total selectivity of the two was 51%, and a large amount of products were produced by the sequential reaction of 3-hydroxypropanal. The above results are summarized in Table 2. The catalyst was inferior in heat resistance and could not be used repeatedly in the hydration reaction.

[0088]

[Table 1]

[0089]

[Table 2]

Example 12 A predetermined amount of water was placed in a reaction vessel equipped with a thermometer, a stirrer and the like, and then a predetermined amount of acrolein was charged so that the concentration in the aqueous solution would be 17% by weight. In addition, in the aqueous solution
2.5 wt% of 1,3-propanediol was added to acrolein. Next, a predetermined amount of acrylic acid-N, N-diallylamine copolymer (carboxylic acid resin) was added to the above aqueous solution as a catalyst. The content of N, N-diallylamine units in the acrylic acid-N, N-diallylamine copolymer was 5 mol%. Acrolein was hydrated by reacting the above reaction solution at 80 ° C. for 3 hours while stirring. The above reaction conditions are summarized in Table 3.

After the reaction was completed, the reaction solution was filtered, and the filtrate was analyzed by a predetermined method. As a result, the conversion rate of acrolein was 64% and the selectivity of 3-hydroxypropanal was 91% and 3-hydroxypropanal. The selectivity of hydroxypropanal dimer was 8%, and the selectivity as hydroxyalkanal was 99%, which is the sum of the selectivity of both. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 4.

Example 13 The acrolein concentration in Example 12 was changed from 17% by weight.
Reaction similar to that in Example 12 except that the amount was changed to 28% by weight.
Analysis was carried out. The above reaction conditions are summarized in Table 3.

As a result, the conversion rate of acrolein was 56%, and the selectivity of 3-hydroxypropanal was 68%.
%, The selectivity of 3-hydroxypropanal dimer was 9%, and the total selectivity of the two was 77%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 4.

Example 14 Example 12 was repeated except that an acrylic acid-N-vinylcarbazole copolymer was used instead of the acrylic acid-N, N-diallylamine copolymer as the catalyst in Example 12. The same reaction and analysis were performed. The content of N-vinylcarbazole units in the acrylic acid-N-vinylcarbazole copolymer was set to 5 mol%. The above reaction conditions are shown in Table 3.
Summarized in.

As a result, the conversion rate of acrolein was 63%, and the selectivity of 3-hydroxypropanal was 91%.
%, The selectivity of 3-hydroxypropanal dimer was 8%, and the total selectivity of both was 99%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 4.

Example 15 Instead of acrylic acid-N, N-diallylamine copolymer as a catalyst in Example 12, acrylic acid-4- (N, N-
The same reaction and analysis as in Example 12 were carried out except that the dimethylamino) ethylstyrene copolymer was used. The content of 4- (N, N-dimethylamino) ethylstyrene units in the acrylic acid-4- (N, N-dimethylamino) ethylstyrene copolymer was set to 5 mol%. The above reaction conditions are summarized in Table 3.

As a result, the conversion rate of acrolein was 55%, and the selectivity of 3-hydroxypropanal was 69%.
%, The selectivity of 3-hydroxypropanal dimer was 10%, and the total selectivity of both was 79%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 4.

Example 16 Example 13 was repeated except that an acrylic acid-N-vinylcarbazole copolymer was used instead of the acrylic acid-N, N-diallylamine copolymer as the catalyst in Example 13. The same reaction and analysis were performed. The content of N-vinylcarbazole units in the acrylic acid-N-vinylcarbazole copolymer was set to 5 mol%. The above reaction conditions are shown in Table 3.
Summarized in.

As a result, the conversion rate of acrolein was 56%, and the selectivity of 3-hydroxypropanal was 66%.
%, The selectivity of 3-hydroxypropanal dimer was 8%, and the total selectivity of the two was 74%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 4.

Example 17 Instead of acrylic acid-N, N-diallylamine copolymer as a catalyst in Example 13, acrylic acid-4- (N, N-
The same reaction and analysis as in Example 13 were carried out except that the dimethylamino) ethylstyrene copolymer was used. The content of 4- (N, N-dimethylamino) ethylstyrene units in the acrylic acid-4- (N, N-dimethylamino) ethylstyrene copolymer was set to 5 mol%. The above reaction conditions are summarized in Table 3.

As a result, the conversion rate of acrolein was 49% and the selectivity of 3-hydroxypropanal was 51%.
%, The selectivity of 3-hydroxypropanal dimer was 10%, and the total selectivity of the two was 61%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 4.

Example 18 The same reaction and analysis as in Example 12 were carried out except that the reaction temperature in the hydration reaction of acrolein in Example 12 was changed from 80 ° C. to 90 ° C. The above reaction conditions are summarized in Table 3.

As a result, the conversion of acrolein was 72% and the selectivity of 3-hydroxypropanal was 78%.
%, The selectivity of 3-hydroxypropanal dimer was 8%, and the total selectivity of both was 86%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 4.

[0104]

[Table 3]

[0105]

[Table 4]

Example 19 A reaction container equipped with a thermometer, a stirrer and the like was charged with a predetermined amount of water, and then a predetermined amount of acrolein was charged so that the concentration in the aqueous solution was 28% by weight. In addition, in the aqueous solution
2.5 wt% of 1,3-propanediol was added to acrolein. Next, a predetermined amount of acrylic acid-N, N-diallylamine copolymer was added to the above aqueous solution as a catalyst. In the above acrylic acid-N, N-diallylamine copolymer
The content of N, N-diallylamine units was 10 mol%.
Acrolein was hydrated by reacting the above reaction solution at 80 ° C. for 3 hours while stirring. The above reaction conditions are summarized in Table 5.

After the completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by a predetermined method. As a result, the conversion of acrolein was 60% and the selectivity of 3-hydroxypropanal was 69% and 3-hydroxypropanal. The selectivity of hydroxypropanal dimer was 9%, and the selectivity as hydroxyalkanal was 78%, which is the sum of the selectivity of both. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 6.

Example 20 Instead of the acrylic acid-N, N-diallylamine copolymer as the catalyst in Example 19, acrylic acid-N, N, N-triallylamine copolymer (carboxylic acid resin) The same reaction and analysis as in Example 19 were carried out except that was used. The content of the N, N, N-triallylamine unit in the acrylic acid-N, N, N-triallylamine copolymer was 10 mol%. The above reaction conditions are summarized in Table 5.

As a result, the conversion rate of acrolein was 58%, and the selectivity of 3-hydroxypropanal was 61%.
%, The selectivity of 3-hydroxypropanal dimer was 4%, and the total selectivity of the two was 65%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 6.

[Example 21] Acrylic acid-N-monoallylamine copolymer (carboxylic acid resin) was used in place of acrylic acid-N, N-diallylamine copolymer as a catalyst in Example 19. Was subjected to the same reaction and analysis as in Example 19. The content of N-monoallylamine units in the above acrylic acid-N-monoallylamine copolymer was 5 mol%. The above reaction conditions are summarized in Table 5.

As a result, the conversion rate of acrolein was 57% and the selectivity of 3-hydroxypropanal was 62%.
%, The selectivity of 3-hydroxypropanal dimer was 12%, and the total selectivity of the two was 74%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 6.

Example 22 Instead of the acrylic acid-N, N-diallylamine copolymer as the catalyst in Example 19, an acrylic acid-N, N-diallylamineethanethiol copolymer (carboxylic acid resin) was used. The same reaction and analysis as in Example 19 were carried out except that they were used. The content of the N, N-diallylamineethanethiol unit in the acrylic acid-N, N-diallylamineethanethiol copolymer was 5 mol%. The above reaction conditions are summarized in Table 5.

As a result, the conversion rate of acrolein was 61%, and the selectivity of 3-hydroxypropanal was 74%.
%, The selectivity of 3-hydroxypropanal dimer was 11%, and the total selectivity of both was 85%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 6.

Example 23 The content of N, N-diallylamineethanethiol units in the acrylic acid-N, N-diallylamineethanethiol copolymer as a catalyst in Example 22 was changed from 5 mol% to 10%.
The same reaction and analysis as in Example 22 were carried out except that the content was changed to mol%. The above reaction conditions are summarized in Table 5.

As a result, the conversion rate of acrolein was 65%, and the selectivity of 3-hydroxypropanal was 69%.
%, The selectivity of 3-hydroxypropanal dimer was 7%, and the total selectivity of the two was 76%. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 6.

Example 24 A reaction vessel equipped with a thermometer, a stirrer and the like was charged with a predetermined amount of water, and then a predetermined amount of acrolein was charged so that the concentration in the aqueous solution was 28% by weight. In addition, in the aqueous solution
2.5 wt% of 1,3-propanediol was added to acrolein. Next, a predetermined amount of acrylic acid-6- (N, N-dipropenylamino) -4-thiahexanoic acid copolymer was added to the above aqueous solution as a catalyst. Acrylic acid-6- (N, N-
The content of 6- (N, N-dipropenylamino) -4-thiahexanoic acid unit in the dipropenylamino) -4-thiahexanoic acid copolymer was 30 mol%. Acrolein was hydrated by reacting the above reaction solution with stirring at 90 ° C. for 2.5 hours. The above reaction conditions are summarized in Table 5.

After the reaction was completed, the reaction solution was filtered, and the filtrate was analyzed by a predetermined method. As a result, the conversion rate of acrolein was 64% and the selectivity of 3-hydroxypropanal was 80% and 3-hydroxypropanal. The selectivity of hydroxypropanal dimer was 8%, and the selectivity as hydroxyalkanal was 88%, which is the sum of the two selectivities. Moreover, the catalyst was excellent in heat resistance and could be repeatedly used for the hydration reaction. The above results are summarized in Table 6.

[0118]

[Table 5]

[0119]

[Table 6]

As is clear from the results summarized in Tables 2, 4, and 6, according to the method of this example, the reaction rate is increased by heating by using the carboxylic acid resin having a nitrogen-containing group as a catalyst. In addition, since the successive reaction of the reaction product 3-hydroxypropanal is suppressed, 3-hydroxypropanal has a high selectivity and high yield even when a high-concentration aqueous acrolein solution is used. I was able to get at. It was also found that the catalyst has excellent heat resistance and can be used repeatedly.

[0121]

As described above, the method for producing a hydroxyalkanal according to claim 1 of the present invention has the general formula (I)

[0122]

[Chemical 14]

(In the formula, R represents a hydrogen atom or a carbon number of 1 to
In the method for producing a hydroxyalkanal by hydrating an unsaturated aldehyde represented by a hydrocarbon group of 5) in an aqueous solution in the presence of a catalyst, the catalyst represented by the general formula (II)

[0124]

[Chemical 15]

General formula (III)

[0126]

[Chemical 16]

General formula (IV)

[0128]

[Chemical 17]

General formula (V)

[0130]

[Chemical 18]

And general formula (VI)

[0132]

[Chemical 19]

This is a method of using a carboxylic acid resin having a substituent having at least one structure selected from the group consisting of:

In the method for producing a hydroxyalkanal according to claim 2 of the present invention, as described above, the ratio of the number of nitrogen-containing groups to the number of carboxyl groups in the carboxylic acid resin (number of nitrogen-containing groups / carboxyl group). The number of groups is within the range of 1/1000 to 1/1. As described above, the method for producing hydroxyalkanal according to claim 3 of the present invention is a method in which the metal is supported in the range of 0.001% by weight to 10% by weight with respect to the carboxylic acid resin.

The method for producing a hydroxyalkanal according to claim 4 of the present invention is a method in which the carboxylic acid resin is a (meth) acrylic acid resin as described above.
In the method for producing hydroxyalkanal according to claim 5 of the present invention, as described above, the (meth) acrylic acid-based resin is a (meth) acrylic acid- (meth) acrylamide copolymer or (meth) acrylic acid. -Vinylpyrrolidone copolymer. As described above, the method for producing hydroxyalkanal according to claim 6 of the present invention is a method in which the unsaturated aldehyde is acrolein. As described above, the method for producing hydroxyalkanal according to claim 7 of the present invention is a method of adding 1,3-propanediol to the reaction system within a range of 0.001% by weight to 10% by weight with respect to acrolein. Is.

According to the above method, the reaction rate can be increased by heating, and the successive reaction (side reaction) of the hydroxyalkanal reaction product is suppressed, so that a highly concentrated unsaturated aldehyde aqueous solution is obtained. Even when is used, hydroxyalkanal can be produced with high selectivity and high yield. That is, by using a carboxylic acid-based resin having heat resistance, the reaction rate can be increased by heating, and an industrially advantageous high-concentration unsaturated aldehyde aqueous solution can be reacted. Canal productivity can be improved. Therefore, the above method has an effect of being preferably used as a method for producing hydroxyalkanal.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadahiro Yoneda 5-8 Nishimitabicho Suita City, Osaka Prefecture Nippon Catalyst Co., Ltd. (72) Inventor Masatoshi Yoshida 5-8 Nishiomitabicho Suita City, Osaka Prefecture Incorporated by Nippon Shokubai Co., Ltd. (56) Reference JP-A-8-143502 (JP, A) JP-A-8-143501 (JP, A) JP-A-8-143500 (JP, A) JP-A-6-157378 (JP, A) JP 5-279285 (JP, A) JP 5-221912 (JP, A) JP 5-194291 (JP, A) JP 4-300844 (JP, A) Kaihei 3-135932 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 47/00 C07C 45/00

Claims (7)

(57) [Claims] 1. A compound represented by the general formula (I): In the method for producing a hydroxyalkanal, an unsaturated aldehyde represented by the formula (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms) is hydrated in an aqueous solution in the presence of a catalyst. As the above catalyst, a compound represented by the general formula (II): , The general formula (III): , The general formula (IV): , General formula (V) , And the general formula (VI): A method for producing a hydroxyalkanal, which comprises using a carboxylic acid-based resin having a substituent having at least one structure selected from the group consisting of: 2. The number of nitrogen-containing groups in a carboxylic acid resin and
Ratio with number of carboxyl groups (number of nitrogen-containing groups / carboxy
The number of radicals is within the range of 1/1000 to 1/1.
The method for producing hydroxyalkanal according to claim 1.
Law. 3. The metal is 0.001 times as heavy as the carboxylic acid resin.
Characterized in that it is supported in the range of 10% by weight to 10% by weight.
The hydroxyalkanal according to claim 1 or 2,
Manufacturing method. 4. A carboxylic acid resin is a (meth) acrylic acid resin.
4. A resin according to claim 1, wherein the resin is a resin.
The method for producing hydroxyalkanal according to Item 1. 5. The (meth) acrylic acid-based resin is (meth).
Acrylic acid- (meth) acrylamide copolymer or
(Meth) acrylic acid-vinylpyrrolidone copolymer
5. The hydroxyalkana according to claim 4, wherein
Manufacturing method. 6. The unsaturated aldehyde is acrolein.
6. The method according to any one of claims 1 to 5, characterized in that
Method for producing hydroxyalkanal. 7. Acrylic 1,3-propanediol is added to the reaction system.
Addition within the range of 0.001% to 10% by weight of rain
The hydroxyalkali according to claim 6, wherein
Method of manufacturing nar.