JP2002060358A - Method for producing propargyl alcohol its intermediate, and use of the intermediate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for industrially and advantageously producing propargyl alcohol. SOLUTION: This method for production comprises (1) a step of reacting 2,3-dichloro-1-propanol with an amine and thereby efficiently producing chloroallyl alcohol and (2) a step of reacting the chloroallyl alcohol obtained in the step (1) with an alkaline compound and producing the propargyl alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing propargyl alcohol and intermediates thereof, which are useful raw materials for organic products, and uses thereof.

[0002]

2. Description of the Related Art As one of methods for producing propargyl alcohol, a method of reacting acetylene with formaldehyde is known, and is described in, for example, Japanese Patent Application Laid-Open No. 64-90145. However, this method has a problem of handling highly explosive acetylene.

A method for producing propargyl alcohol by dehydrochlorination of chloroallyl alcohol is also known. For example, US Pat. No. 3,383,427, Khi
m. Prom-st. , 4 , 251 (1987);
Org. Chem. , 15 , 654 (1950). As a method for producing chloroallyl alcohol used as a raw material, a method of reacting 1,2,3-trichloropropane with an alkali is known.
It is described in U.S. Pat. No. 2,285,329.

However, in order to produce propargyl alcohol, it is necessary to add a sufficient amount of an amine compound or ammonia in addition to the alkali metal hydroxide. In the case of ammonia, it is necessary to add one mole of 2-chloroallyl alcohol. On the other hand, there is a problem that 5 to 20 mol of ammonia is used. In addition, the produced chloroallyl alcohol and propargyl alcohol are liable to be polymerized, resulting in a problem that the productivity is reduced, and the separated and purified propargyl alcohol is also poor in thermal stability, and is liable to be decomposed or polymerized. .

[0005]

SUMMARY OF THE INVENTION The present invention has been made under such a background, and the present invention provides a method for industrially and advantageously producing propargyl alcohol and chloroallyl alcohol as an intermediate thereof. The task is to provide.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that 2,3-dichloro-
The present inventors have found that a method for producing propargyl alcohol including a step of producing chloroallyl alcohol by reacting 1-propanol with an amine is suitable for the purpose, and have completed the present invention. The present invention provides the following (1) to (2)
8) A method for producing propargyl alcohol and an intermediate thereof, and the use thereof as described in 8).

[1] A method for producing propargyl alcohol, comprising the following two steps: (1) Step of producing chloroallyl alcohol by reacting 2,3-dichloro-1-propanol with an amine (2) Reaction of chloroallyl alcohol obtained in the above step (1) with an alkali compound to produce propargyl Step of Producing Alcohol [2] The method of producing propargyl alcohol according to the above [1], wherein the steps (1) and (2) are performed in one step. [3] The propargyl alcohol according to [1] or [2], wherein the step (1) is performed at a temperature in the range of 20 ° C to 300 ° C, and the step (2) is performed at a temperature in the range of 20 ° C to 200 ° C. Manufacturing method. [4] The method for producing propargyl alcohol according to any one of [1] to [3], wherein the step (1) and / or (2) is performed under pressure. [5] The alkali compound in the step (2) is a hydroxide or oxide of an alkali metal and an alkaline earth metal;
The method for producing propargyl alcohol according to any one of the above [1] to [4], which is at least one compound selected from the group consisting of carbonate, hydrogen carbonate, phosphate and hydrogen phosphate.

[6] The above (1) to (5), wherein the steps (1) and / or (2) are carried out in the presence of a polymerization inhibitor.
The method for producing propargyl alcohol according to any one of the above. [7] The method for producing propargyl alcohol according to any one of the above [1] to [6], wherein the method for producing propargyl alcohol includes a step of purifying in the presence of a polymerization inhibitor. [8] The propargyl alcohol according to the above [6] or [7], wherein the polymerization inhibitor is at least one compound selected from the group consisting of a phenol derivative, a vinyl compound, a sulfur-containing compound, a nitrogen-containing compound, and a metal compound. Manufacturing method.

[9] A method for producing chloroallyl alcohol, comprising reacting 2,3-dichloro-1-propanol with an amine. [10] The above wherein the reaction is carried out at a temperature selected from the range of 20 ° C to 300 ° C.

The method for producing chloroallyl alcohol according to [9].

[11] The above wherein the reaction is carried out under pressure.

The method for producing chloroallyl alcohol according to [9] or [10]. [12] The above wherein the reaction is carried out in the presence of a polymerization inhibitor.

The method for producing chloroallyl alcohol according to any one of [9] to [11]. [13] The method for producing chloroallyl alcohol according to [12], wherein the polymerization inhibitor is at least one compound selected from the group consisting of a phenol derivative, a vinyl compound, a sulfur-containing compound, a nitrogen-containing compound, and a metal compound. . [14] Propargyl alcohol comprising a polymerization inhibitor. [15] The propargyl alcohol according to [14], wherein the polymerization inhibitor is at least one compound selected from the group consisting of a phenol derivative, a vinyl compound, a sulfur-containing compound, a nitrogen-containing compound, and a metal compound.

[16] A formaldehyde content of 10
A propargyl alcohol having a reduced formaldehyde content of not more than 00 ppm. [17] A propargyl alcohol having reduced formaldehyde, wherein the content of formaldehyde is 100 ppm or less. [18] A propargyl alcohol having reduced formaldehyde, wherein the content of formaldehyde is 5 ppm or less. [19] A resin composition comprising a resin obtained using the propargyl alcohol having reduced formaldehyde according to any one of [16] to [18]. [20] A resin composition containing a resin obtained by using propargyl alcohol obtained by the production method according to any one of [1] to [8].

[21] Formaldehyde content of 10
The resin composition according to the above [19] or [20], which has a content of 00 ppm or less. [22] The resin composition according to the above [19] or [20], wherein the content of formaldehyde is 100 ppm or less. [23] The resin composition according to [19] or [20], wherein the content of formaldehyde is 5 ppm or less. [24] A resin composition for a cationic electrodeposition coating, comprising a resin obtained by using the propargyl alcohol having reduced formaldehyde according to [16] to [18]. [25] A resin composition for a cationic electrodeposition coating, comprising a resin obtained using propargyl alcohol obtained by the production method according to any one of [1] to [8].

[26] A formaldehyde content of 10
The resin composition for a cationic electrodeposition coating composition according to the above [24] or [25], which has a content of 00 ppm or less. [27] The resin composition for a cationic electrodeposition coating composition according to [24] or [25], wherein the content of formaldehyde is 100 ppm or less. [28] The resin composition for a cationic electrodeposition coating composition according to the above [24] or [25], wherein the content of formaldehyde is 5 ppm or less.

That is, the present invention relates to 2,3-dichloro-
It has been achieved based on a novel finding that 1-propanol and an amine are reacted to produce chloroallyl alcohol, and "the reaction of 2,3-dichloro-1-propanol with an amine to produce chloroallyl alcohol. A method for producing propargyl alcohol, comprising: a step of producing, and a step of producing propargyl alcohol by reacting the chloroallyl alcohol obtained in this step with an alkali compound "," 2,3-dichloro-1 −
A method for producing chloroallyl alcohol, which comprises reacting propanol and an amine, a propargyl alcohol containing a polymerization inhibitor, and a formaldehyde content of 1000 ppm or less. `` Propargyl alcohol '', `` a resin composition characterized by containing a resin obtained by using the propargyl alcohol obtained by the method '', and `` containing a resin obtained by using the propargyl alcohol obtained by the method '' Characteristic resin composition for cationic electrodeposition paint ".

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the method for producing propargyl alcohol of the present invention will be described. The method for producing propargyl alcohol of the present invention comprises the following two steps,
Step (1) is a novel reaction. (1) Step of producing chloroallyl alcohol by reacting 2,3-dichloro-1-propanol with an amine (2) Production of propargyl alcohol by reacting the chloroallyl alcohol obtained in the above step with an alkali compound Here, the chloroallyl alcohol obtained in the step (1) of the present invention is 2-chloroallyl alcohol, cis-3
-Chloroallyl alcohol, trans-3-chloroallyl alcohol or a mixture of two or more of the three.

In the step (1) of the present invention, 2,3-
Dichloro-1-propanol is not particularly limited as long as it is commercially available or industrially available. In this case, for example, in the epichlorohydrin production process,
2,3-dichloro- obtained by reacting allyl alcohol and chlorine, or allyl chloride and hypochlorous acid
It is also possible to use 1-propanol. As for purity, purified high-purity 2,3-dichloropropanol is preferable, but impurities may be contained as long as they have no effect on the reaction and can be removed in the purification step.

The amine used in the step (1) of the present invention is not particularly limited as long as it is commercially available or industrially available. Examples of the amine include ammonia and the general formula NR ¹ R ² R ^A primary amine represented by ³ ,
Secondary amines and tertiary amines can be used. The amine may contain an imino group, and a polyamine such as a diamine or a triamine having two or more amino groups in a molecule can be used, and a cyclic amine can also be used.

Specific examples of the monoamine include, for example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, i-propyl Amine, di-i
-Propylamine, tri-i-propylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, i-butylamine, di-i-butylamine, tri-i-butylamine, sec-butylamine, di-s
ec-butylamine, tri-sec-butylamine, t
tert-butylamine, di-tert-butylamine,
Tri-tert-butylamine, allylamine, diallylamine, triallylamine, cyclohexylamine,
Dicyclohexylamine, tricyclohexylamine,
n-octylamine, di-n-octylamine, tri-
n-octylamine, benzylamine, dibenzylamine, tribenzylamine, diaminopropylamine, 2
-Ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, 3-methoxypropylamine,
3-ethoxypropylamine, 3- (diethylamino)
Propylamine, bis (2-ethylhexyl) amine,
3- (dibutylamino) propylamine, α-phenylethylamine, β-phenylethylamine, aniline,
N-methylaniline, N, N-dimethylaniline, diphenylamine, triphenylamine, o-toluidine,
m-toluidine, p-toluidine, o-anisidine, m
-Anisidine, p-anisidine, o-chloroaniline,
m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline,
o-nitroaniline, m-nitroaniline, p-nitroaniline, 2,4-dinitroaniline, 2,4,6-trinitroaniline, p-aminobenzoic acid, sulfanilic acid, sulfanilamide, monoethanolamine, diethanolamine, Triethanolamine and the like.

Examples of the diamine include 1,2-diaminoethane, N, N, N ', N'-tetramethyl-1,
2-diaminoethane, N, N, N ', N'-tetraethyl-1,2-diaminoethane, 1,3-diaminopropane, N, N, N', N'-tetramethyl-1,2-diaminopropane , N, N, N ', N'-tetraethyl-
1,2-diaminopropane, 1,4-diaminobutane,
N-methyl-1,4-diaminobutane, 1,2-diaminobutane, N, N, N ', N'-tetramethyl-1,2
-Diaminobutane, 3-aminopropyldimethylamine, 1,6-diaminohexane, 3,3-diamino-N
-Methyldipropylamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, benzidine and the like. As triamine, for example, 2,4,6-triaminophenol,
1,2,3-triaminopropane, 1,2,3-triaminobenzene, 1,2,4-triaminobenzene, 1,
Examples of 3,5-triaminobenzene and the like, and examples of tetraamine include β, β ′, β ″ -triaminotriethylamine.

As the cyclic amine, specifically,
For example, pyrrole, pyridine, pyrimidine, pyrrolidine, piperidine, purine, imidazole, oxazole, thiazole, pyrazole, 3-pyrroline, quinoline, isoquinoline, carbazole, piperazine, pyridazine, 1,2,3-triazine, 1,2,4- Triazine, 1,3,5-triazine, 1,2,3-triazole, 1,2,5-triazole, 1,2,4-triazole, 1,3,4-triazole, morpholine and the like can be mentioned. The amine used in the present invention is not limited to the above compounds, and may be an asymmetric compound having different types of substituents, for example, ethyl methylamine. Moreover, only one amine can be used alone, or two or more amines can be used in combination at an arbitrary ratio.

Preferably, ammonia, methylamine,
Dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, i-propylamine, di-i-propylamine, tri-i-propylamine, n -Butylamine, di-n-
Butylamine, tri-n-butylamine, i-butylamine, di-i-butylamine, tri-i-butylamine, sec-butylamine, di-sec-butylamine, tri-sec-butylamine, tert-butylamine, di-tert-butylamine, Tri-tert-
Butylamine, cyclohexylamine, dicyclohexylamine, tricyclohexylamine, benzylamine, dibenzylamine, tribenzylamine, diaminopropylamine, aniline, N-methylaniline, N,
N-dimethylaniline, diphenylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, p-
Aminobenzoic acid, sulfanilic acid, ethylmethylamine, monoethanolamine, diethanolamine, triethanolamine, 1,2-diaminoethane, N, N,
N ′, N′-tetramethyl-1,2-diaminoethane,
N, N, N ′, N′-tetraethyl-1,2-diaminoethane, 1,3-diaminopropane, N, N, N ′,
N′-tetramethyl-1,2-diaminopropane, N,
N, N ', N'-tetraethyl-1,2-diaminopropane, 1,4-diaminobutane, N-methyl-1,4-
Diaminobutane, 1,2-diaminobutane, N, N,
N ′, N′-tetramethyl-1,2-diaminobutane,
3-aminopropyldimethylamine, 1,6-diaminohexane, 3,3-diamino-N-methyldipropylamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, benzidine, 2,4,6-triaminophenol, 1,2,3
-Triaminopropane, 1,2,3-triaminobenzene, 1,2,4-triaminobenzene, 1,3,5-triaminobenzene, β, β ′, β ″ -triaminotriethylamine, pyrrole, pyridine , Pyrimidine, pyrrolidine, piperidine, purine, imidazole, oxazole, thiazole, pyrazole, 3-pyrroline, quinoline, isoquinoline, carbazole, piperazine, pyridazine, 1,3,5-triazine, 1,2,3-triazole, 1,2 , 5-triazole and morpholine.

In the method of the present invention, the reaction temperature in the step (1) for producing chloroallyl alcohol is 20 ° C. to 3 ° C.
00 ° C, preferably 50 ° C to 250 ° C, is suitable. When the reaction temperature is higher than 300 ° C., problems such as decomposition and polymerization of chloroallyl alcohol occur. On the other hand, when the reaction temperature is 20
If the temperature is lower than ℃, the reaction rate is slow, and problems such as a decrease in productivity occur. The reaction pressure in the step (1) of the present invention is 1
0 kPa to 10000 kPa, preferably 50 kPa
~ 5000 kPa is suitable. Reaction pressure is 10 kPa
Even if the pressure is lower or higher than 10,000 kPa, it is difficult to carry out the method industrially, which is not preferable.

In the step (1) of the present invention, the molar ratio of 2,3-dichloro-1-propanol to amine is as follows: amine / 2,3-dichloro-1-propanol = 0.001
１０００1000, preferably 0.01-100. If the molar ratio of amine / 2,3-dichloro-1-propanol is more than 1000, problems such as the necessity of recovering excess unreacted organic base are caused. In addition, amine /
The molar ratio of 2,3-dichloro-1-propanol is 0.0
If it is smaller than 01, problems such as the need to recover excess 2,3-dichloro-1-propanol occur. Furthermore, the use amount of the amine of the present invention is preferably not less than the stoichiometric amount, but is not limited thereto.

The step (1) of the present invention can be carried out in the presence of a solvent. Solvents include water, hydrocarbons, ethers, ketones, amides, nitriles, esters,
Examples include alcohols, but are not limited thereto, and the above amines can be used as solvents. In addition, a solvent and 2,3-dichloro-1-
The mass ratio with propanol is solvent / 2,3-dichloro-1
-Propanol = 0 to 10000, preferably 0 to 10
00 is suitable, but not limited to this.

The heat generated by the reaction between 2,3-dichloro-1-propanol and the amine can be kept outside the system by water, hot water or a heating medium to keep the reaction temperature within a certain range. is there. In addition, heat extracted by water, hot water, or a heat medium can be used as a heat source of another facility, which is advantageous.

As a reaction method for carrying out the step (1) of the present invention, any known method can be used, and a batch system, a semi-batch system, a continuous system, etc. can be used. It is not limited. The method of introducing the raw material of the present invention into the reactor can be performed by any known method, and is not particularly limited. For example, in advance,
It is also possible to introduce 3-dichloro-1-propanol and amine into the reactor to initiate the reaction. Also,
It is also possible to carry out the reaction while introducing 2,3-dichloro-1-propanol and amine.

Further, the amine is 2,3-dichloro-1
It is also possible to introduce it after premixing with propanol. For example, a static mixer (chemical equipment, 5
Monthly, 74-78 (1994)).
A method in which 3-dichloro-1-propanol is mixed and then introduced into the reactor may be mentioned, but the method is not limited thereto. Alternatively, a method of separately introducing 2,3-dichloro-1-propanol and an amine is also possible. Then, 2,3-dichloro-1-propanol may be introduced by diluting with a solvent, but the method is not limited thereto.

The chloroallyl alcohol obtained by the present invention is 2-chloroallyl alcohol, cis-3-
Chloroallyl alcohol and trans-3-chloroallyl alcohol. These three isomers can be separated and purified by a known method, for example, can be separated and purified by distillation, rectification and the like. However, when used for the production of propargyl alcohol in step (2) of the present invention, a mixture of chloroallyl alcohol obtained in step (1) is used as a raw material without separating the three isomers. Can be.

Next, the step (2) in the method for producing propargyl alcohol of the present invention will be described.
The step (2) is a step of producing propargyl alcohol by reacting the chloroallyl alcohol obtained in the step (1) with an alkali compound. This step (2) can be performed by any known method. For example, US Pat. No. 3,383,427, Kh
im. Prom-st. , 4 , 251 (1987),
J. Org. Chem. , 15 , 654 (1950) and the like, chloroallyl alcohol can be reacted with an alkali compound to produce propargyl alcohol.

The alkali compound used in step (2) of the present invention is not particularly limited as long as it is commercially available or industrially available. As the alkali compound used in the present invention, a compound containing at least one element selected from alkali metals and alkaline earth metals is suitable. That is, the alkali metals are Li, Na, K,
Rb, Cs, the alkaline earth metal is Be,
It is selected from Mg, Ca, Sr, and Ba. Compounds containing these elements include hydroxides, oxides, carbonates, bicarbonates, phosphates, hydrogen phosphates, oxyhalides, basic carbonates, carboxylate salts, organometallic complexes and the like. Preferably, the alkali metal is Na or K, and the alkaline earth metal is Mg or Ca, and their hydroxides, oxides, carbonates, bicarbonates,
Phosphates, hydrogen phosphates or carboxylates are preferred. One of these alkali compounds can be used alone, or two or more of them can be used in combination at an arbitrary ratio.

Further, as the alkali compound used in the step (2) of the present invention, ammonia, amine and the like can also be used. It is also possible to use a mixture of a compound containing at least one element selected from an alkali metal or an alkaline earth metal with ammonia, amine or the like.

In the step (2) of the present invention, the reaction temperature for producing propargyl alcohol is from 20 ° C. to 20 ° C.
0 ° C., preferably 50 ° C. to 170 ° C., is suitable. If the reaction temperature is higher than 200 ° C., problems such as decomposition and polymerization of propargyl alcohol occur. On the other hand, if the reaction temperature is lower than 20 ° C., the reaction rate is low, and problems such as a decrease in productivity occur. Further, the step (2) of the present invention can be carried out in the presence of a solvent. Solvents include water, hydrocarbons, ethers, ketones, amides, nitriles, esters,
Examples include, but are not limited to, alcohols. When the steps (1) and (2) are performed in the presence of a solvent, there is no effect in either step,
If possible, it is preferable to select the same solvent. Also,
The mass ratio of the solvent to chloroallyl alcohol is chloroallyl alcohol / solvent = 0 to 10,000, preferably 0 to 10,000.
１０００1000 is suitable, but not limited to these.

The reaction pressure in the step (2) of the present invention is 10 kPa to 10000 kPa, preferably
50 kPa to 5000 kPa is suitable. Even if the reaction pressure is lower than 10 kPa or higher than 10,000 kPa, it is industrially difficult to carry out the reaction, which is not preferable.

The molar ratio of chloroallyl alcohol and alkali compound is such that alkali compound / chloroallyl alcohol = 0.001 to 1000, preferably 0.01 to 1
00 is suitable. When the molar ratio of the alkali compound / chloroallyl alcohol is larger than 1000, problems such as the necessity of collecting excess unreacted alkali compound are caused. On the other hand, if the molar ratio of the alkali compound / chloroallyl alcohol is smaller than 0.001, problems such as the necessity of recovering excess chloroallyl alcohol will arise. Furthermore, the use amount of the alkali compound is preferably a stoichiometric amount or more, but is not limited thereto.

The heat generated by the reaction between the chloroallyl alcohol and the alkali compound can be kept in a certain range by discharging the heat out of the system with water, hot water or a heating medium. In addition, heat extracted by water, hot water, or a heat medium can be used as a heat source of another facility, which is advantageous.

As a reaction method for carrying out the step (2) of the present invention, any known method can be used, and a batch system, a semi-batch system, a continuous system, and the like can be used. Also,
The method for introducing the raw materials into the reactor may be any known method, and is not particularly limited. For example, the reaction can be started by introducing chloroallyl alcohol and an alkali compound into the reactor in advance. Also,
It is also possible to carry out the reaction by continuously introducing chloroallyl alcohol and an alkali compound.

Further, the alkali compound can be introduced after being previously mixed with chloroallyl alcohol. For example, a method in which an alkali compound and chloroallyl alcohol are preliminarily mixed with a static mixer (chemical apparatus, May issue, 74 to 78 (1994)) and then introduced into the reactor may be used, but the method is not limited thereto. Not something.

It is also possible to introduce chloroallyl alcohol and an alkali compound separately. Then, a method of introducing chloroallyl alcohol by diluting it with a solvent may be mentioned, but the method is not limited thereto. Similarly,
A method in which an alkali compound is diluted with a solvent and introduced is also included, but the method is not limited thereto.

Although the method for producing propargyl alcohol of the present invention has been described above by dividing it into the steps (1) and (2), the present invention provides a method of reacting 2,3-dichloro-1-propanol with an amine. (1) step of producing chloroallyl alcohol by reacting chloroallyl alcohol obtained in step (1) with an alkali compound to produce propargyl alcohol (2) continuously, that is, one step It can also be performed step by step under different conditions.

The production method of the present invention can be carried out in the presence of a polymerization inhibitor in both of the above two steps. Examples of the polymerization inhibitor used in the present invention include, but are not limited to, phenol derivatives, vinyl compounds, sulfur-containing compounds, nitrogen-containing compounds, and metal compounds. Phenol derivatives include phenol, 4-t-butylphenol, 4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2-t-butyl-4-methylphenol, 2,6-
Examples thereof include, but are not limited to, di-t-butylphenol, 2,4,6-trimethylphenol, and 2-i-propyl-5-methylphenol. As the vinyl compound, styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-nitrostyrene, m-nitrostyrene, p-nitro Styrene, o-cyanostyrene, m-cyanostyrene, p-cyanostyrene, divinylbenzene, p-styrenesulfonic acid, p-styrenesulfonic acid sodium salt, 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-5 Ethyl pyridine, 2-methyl-5-vinyl pyridine, acrylamide, methyl acrylate, methyl methacrylate and the like can be exemplified, but not limited thereto.

As the sulfur-containing compound, phenothiazine,
Examples thereof include 2,2′-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole sodium salt, and thiouric acid, but are not limited thereto. Examples of the nitrogen-containing compound include N-nitroso-diphenylamine, 4-nitrosodiphenylamine, 2-methyl-2-nitrosopropane, α-phenyl (t-butyl) nitrone, N-phenyl-N′-i-propylphenylenediamine, , 5-Dimethyl-N-phenyl-
Examples include, but are not limited to, N'-i-propylphenylenediamine, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, nitrosobenzene and the like.

Examples of the metal of the metal compound include, but are not limited to, manganese, zinc, lithium, iron, copper and the like. Further, as the metal compound, halide, oxyhalide, phosphate, hydrogen phosphate, oxide, hydroxide, carbonate, hydrogen carbonate, basic carbonate,
Examples thereof include carboxylate and organometallic complex, but are not limited thereto. By adding a polymerization inhibitor, it is possible to suppress side reactions such as decomposition and polymerization of chloroallyl alcohol and propargyl alcohol, thereby improving productivity. Further, there is a possibility that formaldehyde and the like generated by decomposition, polymerization and the like of propargyl alcohol can be reduced. The amount of the polymerization inhibitor used in the reaction of the 2,3-dichloro-1-propanol and the amine of the present invention is, based on the molar ratio of 2,3-dichloro-1-propanol to the polymerization inhibitor / 2,3- Dichloro-1-propanol = 1.0 × 10 ^{−8 to} 10.0, preferably 1.0 × 1
0 ^-7 preferably employed in the range of 1.0. Further, only one polymerization inhibitor can be used alone, and two or more polymerization inhibitors can be used in combination at an arbitrary ratio.

In the step (2), the step (2) can be carried out as it is in the presence of the polymerization inhibitor used in the step (1). Good. The type of polymerization inhibitor to be added may be the same as that used in the reaction between 2,3-dichloro-1-propanol and the amine, or may be different depending on the situation. It is possible. The amount of the polymerization inhibitor was the polymerization inhibitor / chloroallyl alcohol = 1.0 × in molar ratio with respect to chloroallyl alcohol.
10 ^{-8 to} 10.0, preferably 1.0 × 10 ^{-7 to} 1.0
It is preferable to use in the range of.

The propargyl alcohol obtained by using the present invention can be separated and purified by a known method, for example, a method such as distillation and rectification can be used. It may include a step of purifying in the presence of the agent. The amount of the polymerization inhibitor used in the purification step, with respect to propargyl alcohol, a polymerization inhibitor in a molar ratio / propargyl alcohol = 1.0 × 10 ^-8 ~10.0, preferably 1.0 × 10 ^{- 7} ~1 It is preferably used in the range of 0.0.

Further, in the presence of the polymerization inhibitor used in the reaction of the chloroallyl alcohol with the alkali compound,
Propargyl alcohol can be separated and purified, or a new polymerization inhibitor may be added. The type of polymerization inhibitor to be added may be the same type as that used in the reaction between the chloroallyl alcohol and the alkali compound and that used in the purification step, or may be a different type depending on the situation, application, etc. It is possible to choose. By adding a polymerization inhibitor, side reactions such as decomposition and polymerization of propargyl alcohol can be suppressed, and productivity is improved. Further, there is a possibility that formaldehyde and the like generated by decomposition, polymerization and the like of propargyl alcohol can be reduced.

A polymerization inhibitor can be added to propargyl alcohol obtained through the production method or the purification step of the present invention. The amount of the polymerization inhibitor is, based on the molar ratio of propargyl alcohol, the polymerization inhibitor / propargyl alcohol = 1.0 × 10 ^{−8 to} 10.0, preferably 1.
It is preferably used in the range of 0 × 10 ^{−7 to} 1.0. In addition, if the propargyl alcohol obtained through the purification step contains the polymerization inhibitor added during the purification step, it may be used as it is or may be newly added. The type of the polymerization inhibitor to be added may be the same type as that used in the above-mentioned production step or purification step, or may be a different type depending on the situation, application, and the like.

Next, the propargyl alcohol of the present invention will be described. The propargyl alcohol of the present invention has a formaldehyde content of 1000 ppm or less, preferably has a formaldehyde content of 500 ppm or less, and more preferably 100 pp or less.
m, particularly preferably 5 ppm or less. Formaldehyde has a strong chemical affinity, coagulates or denatures cytoplasmic proteins, inhibits and kills all cell functions, and has an adverse effect on the human body.In terms of environmental problems, formaldehyde is contained. However, propargyl alcohol having a low formaldehyde content is desired. Since the propargyl alcohol according to the present invention does not use formaldehyde as a starting material, the content of formaldehyde can be 1000 ppm or less.

Next, the use of the propargyl alcohol of the present invention will be described. Examples of the use of the propargyl alcohol of the present invention include the use described in JP-A-5-239365. For example, a resin composition for coatings, can be used for a curable resin composition that can also be used as a molding resin, moisture resistance, water resistance,
It is excellent in salt water resistance, solvent resistance, alkali resistance, acid resistance, and recoatability, and is preferably used because it cures at a low temperature and does not decrease in volume after curing. Further, regarding the use of the propargyl alcohol of the present invention, for example, WO 98/0
No. 3701, which can be used for a resin containing a triple bond such as an ethynyl group or a nitrile group in a molecule, and the present invention relates to a propargyl alcohol, particularly a formaldehyde content obtained by the above-mentioned method of the present invention. The present invention relates to a cationic electrodeposition coating composition containing, for example, a resin obtained by using propargyl alcohol of 1000 ppm or less, in which the content of the resin is reduced. Cationic electrodeposition coating can be applied to the details even to the object to be coated having a complicated shape, and has a large and complicated shape such as an automobile body,
It is widely used as an undercoating method for substrates requiring high rust resistance. Further, the use efficiency of the paint is extremely high as compared with other coating methods, so that it is economical and widely used as an industrial coating method.

The propargyl alcohol of the present invention has a formaldehyde content of 1000 ppm as described above.
Since it is characterized by the following, it can be preferably used from the viewpoint of effects on the human body and environmental problems. The resin and the resin composition obtained by using the propargyl alcohol of the present invention, and the resin composition for a cationic electrodeposition coating containing the resin have a formaldehyde content of 100 as described above.
Since it is 0 ppm or less, it can be preferably used from the viewpoint of effects on the human body and environmental problems.

[0049]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. (Example 1) 2,3-dichloro-1-propanol 1
2.90 g (0.10 mol), triethylamine 1
0.12 g (0.10 mol), diethylene glycol
20.0 g of di-n-butyl ether was added to 100 ml of S
The mixture was charged in a US-made autoclave and reacted at a reaction temperature of 150 ° C. for 2 hours while sufficiently stirring in a closed system. The reaction solution after the reaction was quantified by gas chromatography,
Table 1 shows the yield of chloroallyl alcohol based on 3-dichloropropanol and its composition ratio (mol%).

Example 2 A reaction was carried out in the same manner as in Example 1 except that 18.54 g (0.10 mol) of tri-n-butylamine was used instead of triethylamine. The results are shown in Table 1.

Example 3 A reaction was carried out in the same manner as in Example 1 except that 26.95 g (0.10 mol) of tri-n-hexylamine was used instead of triethylamine. The results are shown in Table 1.

Example 4 A reaction was carried out in the same manner as in Example 1 except that 28.74 g (0.10 mol) of tribenzylamine was used instead of triethylamine. The results are shown in Table 1.

Example 5 A reaction was carried out in the same manner as in Example 1 except that 7.31 g (0.10 mol) of diethylamine was used instead of triethylamine. Table 1 shows the results
It was shown to.

Example 6 12.93 g (0.10 mol) of di-n-butylamine instead of triethylamine
The reaction was carried out in the same manner as in Example 1 except that was used. The results are shown in Table 1.

Example 7 A reaction was carried out in the same manner as in Example 1 except that 7.31 g (0.10 mol) of n-butylamine was used instead of triethylamine. The results are shown in Table 1.

Example 8 A reaction was carried out in the same manner as in Example 1 except that 7.31 g (0.10 mol) of i-butylamine was used instead of triethylamine. The results are shown in Table 1.

Example 9 A reaction was carried out in the same manner as in Example 1 except that 10.72 g (0.10 mol) of benzylamine was used instead of triethylamine. The results are shown in Table 1.

Example 10 A reaction was carried out in the same manner as in Example 1 except that 7.91 g (0.10 mol) of pyridine was used instead of triethylamine. The results are shown in Table 1.

Example 11 A reaction was carried out in the same manner as in Example 1 except that 6.01 g (0.10 mol) of 1,2-diaminoethane was used instead of triethylamine. The results are shown in Table 1.

Example 12 A reaction was carried out in the same manner as in Example 1 except that 8.82 g (0.10 mol) of 1,4-diaminobutane was used instead of triethylamine. The results are shown in Table 1.

Example 13 Instead of triethylamine, 11.62 g (0.10 g) of 1,6-diaminohexane was used.
The reaction was carried out in the same manner as in Example 1 except that (mol) was used. The results are shown in Table 1.

Example 14 Instead of triethylamine, 10.81 g of 1,2-phenylenediamine (0.1
Reaction was carried out in the same manner as in Example 1 except that 0 mol) was used. The results are shown in Table 1.

Example 15 The procedure of Example 1 was repeated except that 11.62 g (0.10 mol) of N, N, N ', N'-tetramethyl-1,2-diaminoethane was used instead of triethylamine. The reaction was performed similarly. The results are shown in Table 1.

Example 16 A reaction was carried out in the same manner as in Example 1 except that 8.61 g (0.10 mol) of piperazine was used instead of triethylamine. The results are shown in Table 2.

Example 17 Instead of triethylamine, 12.12 g of N, N-dimethylaniline (0.10 g) was used.
The reaction was carried out in the same manner as in Example 1 except that (mol) was used. The results are shown in Table 2.

Example 18 A reaction was carried out in the same manner as in Example 1 except that 8.01 g (0.10 mol) of pyridazine was used instead of triethylamine. The results are shown in Table 2.

Example 19 A reaction was carried out in the same manner as in Example 1 except that 6.91 g (0.10 mol) of 1,2,4-triazole was used instead of triethylamine. The results are shown in Table 2.

Example 20 Acetonitrile was used instead of diethylene glycol di-n-butyl ether.
The reaction was carried out in the same manner as in Example 1 except that 0 g was used. The results are shown in Table 2.

Example 21 Instead of diethylene glycol di-n-butyl ether, benzonitrile
The reaction was carried out in the same manner as in Example 1 except that 0 g was used. The results are shown in Table 2.

Example 22 A reaction was carried out in the same manner as in Example 1 except that 20.0 g of N, N-dimethylformamide was used instead of diethylene glycol di-n-butyl ether. The results are shown in Table 2.

Example 23 A reaction was carried out in the same manner as in Example 1 except that 20.0 g of 1,2-ethanediol was used instead of diethylene glycol di-n-butyl ether. The results are shown in Table 2.

Example 24 A reaction was conducted in the same manner as in Example 1 except that 20.0 g of 1,2-propanediol was used instead of diethylene glycol di-n-butyl ether. The results are shown in Table 2.

Example 25 A reaction was conducted in the same manner as in Example 1 except that 20.0 g of 1,4-butanediol was used instead of diethylene glycol di-n-butyl ether. The results are shown in Table 2.

Example 26 A reaction was carried out in the same manner as in Example 1 except that 20.0 g of dimethyl sulfoxide was used instead of diethylene glycol di-n-butyl ether. The results are shown in Table 2.

Example 27 A reaction was carried out in the same manner as in Example 1 except that 20.0 g of 1,2-dicyanoethane was used instead of diethylene glycol di-n-butyl ether. The results are shown in Table 2.

Example 28 A reaction was carried out in the same manner as in Example 1 except that 20.0 g of 1,4-dicyanobutane was used instead of diethylene glycol di-n-butyl ether. The results are shown in Table 2.

Example 29 A reaction was carried out in the same manner as in Example 1 except that 20.0 g of H ₂ O was used instead of diethylene glycol di-n-butyl ether. The results are shown in Table 2.

Example 30 Triethylamine was added to 40.
The reaction was carried out in the same manner as in Example 1 except that the amount was changed to 48 g (0.40 mol). The results are shown in Table 2.

Example 31 Triethylamine was converted to 5.0
The reaction was carried out in the same manner as in Example 1 except that the amount was changed to 6 g (0.05 mol). The results are shown in Table 3.

(Example 32)
48 g (0.40 mol), diethylene glycol
The reaction was carried out in the same manner as in Example 1 except that di-n-butyl ether was not used. The results are shown in Table 3.

Example 33 A reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at a reaction temperature of 100 ° C. for 2 hours. The results are shown in Table 3.

(Example 34) A reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at a reaction temperature of 200 ° C for 2 hours. The results are shown in Table 3.

(Example 35) A reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at a reaction temperature of 150 ° C for 6 hours. The results are shown in Table 3.

Example 36 12.90 g (0.10 mol) of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine, styrene
0.104 g (0.0010 mol), acetonitrile
20.0 g was charged into a 100 ml SUS-made autoclave, and the reaction temperature was set to 15 while stirring sufficiently in a closed system.
The reaction was performed at 0 ° C. for 2 hours. The results are shown in Table 3.

Example 37 12.90 g (0.10 mol) of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine, 0.116 g (0.0010 mol) of lithium phosphate And 20.0 g of acetonitrile were charged into a 100 ml SUS-made autoclave, and reacted at a reaction temperature of 150 ° C. for 2 hours while sufficiently stirring in a closed system. The results are shown in Table 3.

Example 38 12.90 g (0.10 mol) of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine, 0.198 g (0.0010 mol) of N-nitrosodiphenylamine ), 20.0 g of acetonitrile in 100 ml of SU
It was charged into an S-manufactured autoclave and reacted at a reaction temperature of 150 ° C. for 2 hours while sufficiently stirring in a closed system. The results are shown in Table 3.

(Example 39) The reaction solution obtained by scaling up Example 20 to 10 times was distilled under normal pressure, and acetonitrile was added first from the top of the distillation column, and then
A small amount of triethylamine was obtained. When the distillation was further continued, the desired product, chloroallyl alcohol, was obtained. The yield of chloroallyl alcohol was 74.2 g (0.80 mol), and the yield of chloroallyl alcohol based on 2,3-dichloro-1-propanol was 80%. 74.2 g (0.80 mol) of this chloroallyl alcohol and 640.0 g (1.
60 mol) was charged into a reactor and reacted at a reaction temperature of 100 ° C. for 4 hours while sufficiently stirring under normal pressure. When the reaction solution was quantified by gas chromatography (FID),
The conversion of chloroallyl alcohol was 100%, and the yield of propargyl alcohol based on chloroallyl alcohol was 71%.

Further, the above reaction solution was neutralized with 35% by mass of hydrochloric acid. After adding 100 g of diethyl ether and stirring vigorously, an oil phase was collected by liquid-liquid separation. The same extraction operation was repeated twice, and the obtained oil phase components were combined and distilled under normal pressure. From the top of the distillation column, first, diethyl ether as a fraction having a boiling point of 34 to 35 ° C. was distilled. Obtained.
Next, an azeotropic component consisting of water and propargyl alcohol, which is a fraction having a boiling point of 97 to 98 ° C., was obtained. When the distillation was further continued, propargyl alcohol which was a fraction having a boiling point of 114 to 115 ° C. was obtained. The yield of propargyl alcohol was 28.6 g (0.51 mol), and the yield of propargyl alcohol based on 2,3-dichloro-1-propanol was 51%. When the propargyl alcohol was analyzed by high performance liquid chromatography (HPLC), the formaldehyde content was 5 ppm or less, which is the lower limit of detection.

Example 40 0.520 g of styrene (0.020 g) was added to the oil phase obtained by the extraction operation.
050 mol), and distillation was carried out under normal pressure, in the same manner as in Example 39, to obtain propargyl alcohol as a fraction having a boiling point of 114 to 115 ° C. The yield of propargyl alcohol was 32.2 g (0.57 mol), and the yield of propargyl alcohol based on 2,3-dichloro-1-propanol was 57%. When the propargyl alcohol was analyzed by high performance liquid chromatography (HPLC), the formaldehyde content was 5 ppm or less, which is the lower limit of detection.

Example 41 Combination of oil phase components obtained by extraction operation 0.579 g of lithium phosphate
(0.0050 mol) and the distillation was carried out under normal pressure, and the same operation as in Example 39 was carried out, and the boiling point was 114 to 11
Propargyl alcohol, a fraction at 5 ° C., was obtained. The yield of propargyl alcohol was 30.8 g (0.55 mol), and the yield of propargyl alcohol based on 2,3-dichloro-1-propanol was 55%. When the propargyl alcohol was analyzed by high performance liquid chromatography (HPLC), the formaldehyde content was 5 ppm or less, which is the lower limit of detection.

Example 42 N-Nitrosodiphenylamine was combined with the oil phase obtained by the extraction operation.
The same operation as in Example 39 was carried out except that 0.991 g (0.0050 mol) was added and distillation was performed under normal pressure, to obtain propargyl alcohol which was a fraction having a boiling point of 114 to 115 ° C. The yield of propargyl alcohol is 31.3 g
(0.56 mol), and the yield of propargyl alcohol based on 2,3-dichloro-1-propanol was 56%.
Met. When this propargyl alcohol was analyzed by high performance liquid chromatography (HPLC),
The formaldehyde content is 5 ppm, which is the lower limit of detection
It was below.

Example 43 9.25 g (0.10 mol) of chloroallyl alcohol obtained by distillation in the same manner as in Example 39, 0.104 g (0.0010 mol) of styrene,
80.0 g (0.20 mol) of a 10% by mass aqueous NaOH solution was charged into the reactor and, under normal pressure, with sufficient stirring,
The reaction was performed at a reaction temperature of 100 ° C. for 4 hours. When the reaction solution was quantified by gas chromatography (FID), the yield of propargyl alcohol based on chloroallyl alcohol was 83%.

(Example 44) 9.25 g (0.10 mol) of chloroallyl alcohol obtained by distillation in the same manner as in Example 39, 0.116 g (0.0010 mol) of lithium phosphate, and a 10% by mass aqueous solution of NaOH 80 0.0 g (0.2
(0 mol) was charged into a reactor and reacted at a reaction temperature of 100 ° C. for 4 hours while sufficiently stirring under normal pressure. When the reaction liquid was quantified by gas chromatography (FID), the yield of propargyl alcohol based on chloroallyl alcohol was 82%.

(Example 45) 9.25 g (0.10 mol) of chloroallyl alcohol obtained by distillation in the same manner as in Example 39, and 0.198 g of N-nitrosodiphenylamine
(0.0010 mol) 10 mass% NaOH aqueous solution 8
0.0 g (0.20 mol) was charged into a reactor, and under normal pressure,
The reaction was performed at a reaction temperature of 100 ° C. for 4 hours while sufficiently stirring. When the reaction liquid was quantified by gas chromatography (FID), the yield of propargyl alcohol based on chloroallyl alcohol was 81%.

(Example 46) 9.25 g (0.10 mol) of chloroallyl alcohol obtained by distillation in the same manner as in Example 39 and 112.2 g (0.2%) of a 10% by mass aqueous KOH solution
(0 mol) was charged into a reactor and allowed to react for 4 hours at a reaction temperature of 100 ° C. while sufficiently stirring under normal pressure. When the reaction liquid was quantified by gas chromatography (FID), the yield of propargyl alcohol based on chloroallyl alcohol was 80%.

(Example 47) The reaction solution obtained by scaling up Example 35 to 10 times was distilled under normal pressure, and triethylamine was first obtained from the top of the distillation column.
When the distillation was further continued, chloroallyl alcohol was obtained. The yield of chloroallyl alcohol is 73.1 g.
(0.79 mol), and the yield of chloroallyl alcohol based on 2,3-dichloro-1-propanol was 79%.
Met. 73.1 g of this chloroallyl alcohol
(0.79 mol) and a 10% by mass aqueous NaOH solution 632
g (1.58 mol) was charged into a reactor and allowed to react at a reaction temperature of 100 ° C. for 4 hours while sufficiently stirring under normal pressure.
When the reaction liquid was quantified by gas chromatography (FID), the yield of propargyl alcohol based on chloroallyl alcohol was 72%.

Further, the above reaction solution was neutralized with 35% by mass of hydrochloric acid. After adding 100 g of diethyl ether and stirring vigorously, an oil phase was collected by liquid-liquid separation. The same extraction operation was repeated twice, and the obtained oil phase components were combined and distilled under normal pressure. From the top of the distillation column, first, diethyl ether as a fraction having a boiling point of 34 to 35 ° C. was distilled. Obtained.
Next, an azeotropic component consisting of water and propargyl alcohol, which is a fraction having a boiling point of 97 to 98 ° C., was obtained. When the distillation was further continued, propargyl alcohol which was a fraction having a boiling point of 114 to 115 ° C. was obtained. The yield of propargyl alcohol was 29.6 g (0.53 mol), and the yield of propargyl alcohol based on 2,3-dichloro-1-propanol was 53%. When the propargyl alcohol was analyzed by high performance liquid chromatography (HPLC), the formaldehyde content was 5 ppm or less, which is the lower limit of detection.

Example 48 12.90 g (0.10 mol) of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine and 20.0 g of diethylene glycol di-n-butyl ether were added to S
The mixture was charged in a US-made autoclave and reacted at a reaction temperature of 150 ° C. for 6 hours while sufficiently stirring in a closed system. After cooling, the pressure was adjusted to normal pressure, and a 10% by mass aqueous NaOH solution 80.0%
g (0.20 mol) were added and the reaction temperature was increased to 100
The reaction was performed at 4 ° C. for 4 hours. When the reaction solution was quantified by gas chromatography (FID), 2,3-dichloro-1 was obtained.
The conversion of -propanol was 100%, and the yield of propargyl alcohol based on 2,3-dichloro-1-propanol was 74.8%.

Example 49 12.90 g (0.10 mol) of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine, styrene
0.104 g (0.0010 mol), diethylene glycol di-n-butyl ether 20.0 g
The mixture was charged in an autoclave made from the above and reacted at a reaction temperature of 150 ° C. for 6 hours while sufficiently stirring in a closed system. After cooling, the pressure was adjusted to normal pressure, and 80.0 g of a 10% by mass aqueous NaOH solution (0.
20 mol), and the mixture was further reacted at a reaction temperature of 100 ° C. for 4 hours. The reaction solution was subjected to gas chromatography (FI
As determined by D), the yield of propargyl alcohol based on 2,3-dichloro-1-propanol was 83%.

Example 50 12.90 g (0.10 mol) of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine, 0.116 g (0.0010 mol) of lithium phosphate , 20.0 g of diethylene glycol di-n-butyl ether as S
The mixture was charged in a US-made autoclave and reacted at a reaction temperature of 150 ° C. for 6 hours while sufficiently stirring in a closed system. After cooling, the pressure was adjusted to normal pressure, and a 10% by mass aqueous NaOH solution 80.0%
g (0.20 mol) were added and the reaction temperature was increased to 100
The reaction was performed at 4 ° C. for 4 hours. When the reaction solution was quantified by gas chromatography (FID), 2,3-dichloro-1 was obtained.
-The yield of propargyl alcohol based on propanol was 81%.

Example 51 12.90 g (0.10 mol) of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine, 0.198 g (0.0010 mol) of N-nitrosodiphenylamine ) And 20.0 g of diethylene glycol di-n-butyl ether were charged into an autoclave made of SUS and reacted at a reaction temperature of 150 ° C for 6 hours while sufficiently stirring in a closed system. After cooling to normal pressure, 10% by mass NaOH
80.0 g (0.20 mol) of an aqueous solution was added, and the mixture was further reacted at a reaction temperature of 100 ° C. for 4 hours. When the reaction solution was quantified by gas chromatography (FID),
The yield of propargyl alcohol based on 2,3-dichloro-1-propanol was 82%.

(Example 52) (Stability test 1) Propargyl alcohol 5.6 obtained in the same manner as in Example 39
1 g (0.10 mol) and 0.0010 g of styrene (1.
0 × 10 ⁻⁵ mol) and heated at 60 ° C. for 100 days. When this was analyzed by high performance liquid chromatography (HPLC), the content of formaldehyde was 5 ppm or less, which is the lower limit of detection.

(Example 53) (Stability test 2) Propargyl alcohol 5.6 obtained in the same manner as in Example 39
1 g (0.10 mol) of lithium phosphate 0.0012
g (1.0 × 10 ⁻⁵ mol) was added and heated at 60 ° C. for 100 days. This was subjected to high performance liquid chromatography (HP
As a result of analysis by LC), the content of formaldehyde was 5 ppm or less, which is the lower limit of detection.

(Example 54) (Stability test 3) Propargyl alcohol 5.6 obtained in the same manner as in Example 39
0.001 g (1.0 × 10 ⁻⁵ mol) of N-nitrosodiphenylamine was added to 1 g (0.10 mol), and
Heat at 0 ° C. for 100 days. When this was analyzed by high performance liquid chromatography (HPLC), the content of formaldehyde was 5 ppm or less, which is the lower limit of detection.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

As described above, according to the method of the present invention, propargyl alcohol can be efficiently produced from chloroallyl alcohol obtained by reacting 2,3-dichloro-1-propanol with an amine. it can.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Haruki Ishigami 5-1 Ogimachi, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Showa Denko K.K. -1 Within Showa Denko Corporation Kawasaki Production & Technology Division (72) Inventor Toshitaka Hiro 5-1 Ogimachi, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Showa Denko Corporation Kawasaki Production & Technology Division F-term (reference) 4H006 AA02 AC13 BA94 BC10 BC11 BD70 BE10 BE11 BE12 BE13 EA03 4J038 CN001 PA04

Claims (28)

[Claims] 1. A method for producing propargyl alcohol, comprising the following two steps. (1) Step of producing chloroallyl alcohol by reacting 2,3-dichloro-1-propanol with an amine (2) Reaction of chloroallyl alcohol obtained in the above step (1) with an alkali compound to produce propargyl Process for producing alcohol 2. The method for producing propargyl alcohol according to claim 1, wherein the steps (1) and (2) are performed in one step. 3. The propargyl alcohol according to claim 1, wherein the step (1) is carried out at a temperature in the range of 20 ° C. to 300 ° C., and the step (2) is carried out at a temperature in the range of 20 ° C. to 200 ° C. Production method. 4. The method for producing propargyl alcohol according to claim 1, wherein the steps (1) and / or (2) are performed under pressure. 5. The method according to claim 2, wherein the alkali compound in the step (2) is a hydroxide of an alkali metal and an alkaline earth metal,
The method for producing propargyl alcohol according to any one of claims 1 to 4, wherein the method is at least one compound selected from the group consisting of oxides, carbonates, bicarbonates, phosphates, and hydrogen phosphates. 6. The method for producing propargyl alcohol according to claim 1, wherein the steps (1) and / or (2) are performed in the presence of a polymerization inhibitor. 7. The method for producing propargyl alcohol according to claim 1, wherein the method for producing propargyl alcohol includes a step of purifying in the presence of a polymerization inhibitor. 8. The propargyl alcohol according to claim 6, wherein the polymerization inhibitor is at least one compound selected from the group consisting of phenol derivatives, vinyl compounds, sulfur-containing compounds, nitrogen-containing compounds and metal compounds. Production method. 9. A process for producing chloroallyl alcohol, comprising reacting 2,3-dichloro-1-propanol with an amine. 10. The method for producing chloroallyl alcohol according to claim 9, wherein the reaction is performed at a temperature selected from the range of 20 ° C. to 300 ° C. 11. The method according to claim 9, wherein the reaction is performed under pressure.
Or the method for producing chloroallyl alcohol according to item 10. 12. The method for producing chloroallyl alcohol according to claim 9, wherein the reaction is carried out in the presence of a polymerization inhibitor. 13. The production of chloroallyl alcohol according to claim 12, wherein the polymerization inhibitor is at least one compound selected from the group consisting of phenol derivatives, vinyl compounds, sulfur-containing compounds, nitrogen-containing compounds and metal compounds. Method. 14. A propargyl alcohol containing a polymerization inhibitor. 15. The propargyl alcohol according to claim 14, wherein the polymerization inhibitor is at least one compound selected from the group consisting of a phenol derivative, a vinyl compound, a sulfur-containing compound, a nitrogen-containing compound, and a metal compound. 16. The content of formaldehyde is 1000.
A propargyl alcohol having reduced formaldehyde, which is not more than ppm. 17. A formaldehyde content of 100 p
pm or less, the formaldehyde reduced propargyl alcohol. 18. The content of formaldehyde is 5 ppm
A propargyl alcohol having reduced formaldehyde, characterized in that: 19. A resin composition comprising a resin obtained by using the propargyl alcohol having reduced formaldehyde according to any one of claims 16 to 18. 20. A resin composition comprising a resin obtained by using propargyl alcohol obtained by the production method according to claim 1. 21. A formaldehyde content of 1000
The resin composition according to claim 19, wherein the content is at most ppm. 22. A formaldehyde content of 100 p
The resin composition according to claim 19 or 20, which is not more than pm. 23. A formaldehyde content of 5 ppm
The resin composition according to claim 19, wherein: 24. A resin composition for a cationic electrodeposition coating composition, comprising a resin obtained by using the propargyl alcohol having reduced formaldehyde according to claim 16 to 18. 25. A resin composition for a cationic electrodeposition paint, comprising a resin obtained by using propargyl alcohol obtained by the production method according to claim 1. Description: 26. A formaldehyde content of 1000
The resin composition for a cationic electrodeposition coating composition according to claim 24 or 25, which is at most ppm. 27. A formaldehyde content of 100 p
The resin composition for a cationic electrodeposition paint according to claim 24 or 25, which is not more than pm. 28. A formaldehyde content of 5 ppm
The resin composition for a cationic electrodeposition paint according to claim 24 or 25, which is: