WO2013172412A1

WO2013172412A1 - Method for producing sulfonyl amide compound containing fluorinated aliphatic group and method for producing anionic hydrophilic group-containing surfactant

Info

Publication number: WO2013172412A1
Application number: PCT/JP2013/063657
Authority: WO
Inventors: 健治正村; 弘行濱野; 鈴木　秀也; 洋三山科
Original assignee: Dic株式会社
Priority date: 2012-05-18
Filing date: 2013-05-16
Publication date: 2013-11-21
Also published as: JP5522501B2; JPWO2013172412A1

Abstract

The objective of the present invention is to provide a method for producing, at a high yield, a sulfonyl amide compound containing a fluorinated aliphatic group, the method comprising: a first step of adding a ketone compound (a1) having 5 to 10 carbon atoms and a diamine compound (a2) to an organic solvent (a3) such that the ratio of carbonyl groups (a1-1) in the ketone compound (a1) and amino groups (a2-1) in the diamine compound (a2) is in a range of 0.3 to 0.95 in [(a1-1)/(a2-1)] molar ratio, and reacting the ketone compound (a1) and the diamine compound (a2) in the organic solvent (a3) to obtain a compound (A) that contains an amino group and a ketimine group; a second step of reacting the compound (A) with a sulfonyl chloride compound (B) containing a fluorinated aliphatic group to obtain a fluorinated aliphatic group-containing compound (C) that has a ketimine group; and a third step of hydrolyzing the ketimine group in the compound (C) to generate an amino group in the compound (C).

Description

Method for producing sulfonylamide compound containing fluorinated aliphatic group and method for producing anionic hydrophilic group-containing surfactant

TECHNICAL FIELD The present invention relates to a production method capable of obtaining a sulfonylamide compound containing a fluorinated aliphatic group used in the production of a fluorosurfactant contained in a fire extinguishing agent effective for a fire of a polar solvent such as alcohol in a high yield. .

In general, in the case of a fire with a polar solvent such as alcohol, ketone, ester, ether or amine, even if the fire extinguishes with a normal oil fire extinguishing agent, the foam immediately disappears when it comes into contact with the combustion liquid surface. Can not do it. As a fire extinguishing agent effective for a polar solvent fire, for example, the molecule has primary, secondary and tertiary cationic groups, and the primary cationic group is 40% by mass or less based on the total cationic groups. A fire extinguishing agent comprising a cationic polyamine polymer (A) having a secondary cationic group of 35% by weight based on the total cationic groups and an anionic hydrophilic group-containing surfactant (B) As this anionic hydrophilic group-containing surfactant (B), for example, it has a fluorinated aliphatic group having 3 to 20 carbon atoms as a hydrophobic group disclosed in paragraph 0027 and the following of Patent Document 1. In addition, a fluorine-based surfactant having a quaternary ammonium salt as an anionic group is disclosed. (For example, refer to Patent Document 1).

The fluorinated surfactant having a fluorinated aliphatic group having 3 to 20 carbon atoms and a quaternary ammonium salt as an anionic group is produced, for example, through the following steps.

Thiolation step: Compound having iodine atom and fluorinated alkyl group such as 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodooctane Is reacted with thiourea to obtain a terminal thiol compound such as 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol Process.

Sulfonyl chloride formation step: The terminal thiol compound is reacted with chlorine to produce 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1- Step of obtaining a sulfonyl chloride compound containing a fluorinated aliphatic group such as sulfonyl chloride

Sulfonyl amidation step: The sulfonyl chloride compound containing a fluorinated aliphatic group is reacted with a diamine such as 1,3-propanediamine to give 3- (3, 3, 4, 4, 5, 5, 6, 6, 7,7,8,8,8-tridecafluoro-1-octanesulfonylamino) -1-propanamine and the like compounds having a fluorinated alkyl group at one end and an amino group at one end (fluorine A sulfonylamide containing a fluorinated aliphatic group).

Quaternary amination step: A step of reacting a compound such as sodium monochloroacetate with the sulfonylamide containing the fluorinated aliphatic group to obtain a compound having a quaternary ammonium salt structure as a final product.

In the sulfonylamidation step, the target sulfonylamide containing a fluorinated aliphatic group and a sulfonyl chloride further containing a fluorinated aliphatic group on the amino group of the sulfonylamide containing the fluorinated aliphatic group as a by-product A compound to which the compound is added is also produced. This side reaction product is unnecessary for the solvent, and has a fluorinated aliphatic group at both ends and no amino group at the ends, so that a quaternary ammonium salt structure is added in the quaternary amination step. I can't. Therefore, the by-product has not been used as a raw material for the target fluorosurfactant and has been discarded.

The ratio of the desired product and by-product obtained in the sulfonylamidation step (target product: by-product) depends on the reaction conditions of the sulfonylamidation step, but is usually about 3: 1 in molar ratio. Yes, the amount of moles produced is greater for the target product. However, considering that the target product is obtained using one molecule of a sulfonyl chloride compound containing a fluorinated aliphatic group, whereas the by-product is obtained using two molecules of the compound, the fluorinated aliphatic group is Only about 60% of the sulfonyl chloride compound contained is used for the production of the target product, and the remaining 40% is used for the production of a by-product that is not a raw material for the fluorosurfactant. is there.

The sulfonyl chloride compound containing a fluorinated aliphatic group uses a compound having a very expensive fluorinated aliphatic group as a raw material. Therefore, 40% of the sulfonyl chloride compound containing a fluorinated aliphatic group in the sulfonylamidation step as described above is not used as a raw material for the fluorosurfactant. This increases the manufacturing cost of the agent. Therefore, in the sulfonylamidation process, when obtaining the sulfonylamide containing the target fluorinated aliphatic group, it is required to minimize the production of by-products.

JP 2001-269421 A

The problem to be solved by the present invention is that, in the sulfonylamidation step, an undesirable by-product containing a fluorinated aliphatic group is not generated as much as possible, and the fluorinated aliphatic group obtained in the sulfonylchloride step Production method for producing a sulfonylamide compound containing a fluorinated aliphatic group in a high yield from a sulfonyl chloride compound containing anion, and anionic hydrophilicity using the sulfonylamide compound containing a fluorinated aliphatic group obtained by the production method It is providing the manufacturing method of group-containing surfactant.

As a result of intensive studies to solve the above problems, the present inventors have found the following knowledge.
1. A compound having an amino group and a ketimine group obtained by reacting a diamine compound with a ketone compound has only one amino group. Therefore, one molecule of this compound reacts only with one molecule of a sulfonyl chloride compound containing a fluorinated aliphatic group, and a by-product in which two molecules of the sulfonyl chloride compound containing a fluorinated aliphatic group as described above are used. Do not generate.
2. By adding water to a reaction product obtained by reacting the compound having an amino group and a ketimine group with a sulfonyl chloride compound containing a fluorinated aliphatic group, the ketimine group is hydrolyzed to obtain a fluorinated aliphatic group. A sulfonylamide and a ketone containing
3. The reaction between the diamine compound and the ketone compound is a reversible reaction, and the reaction system for reacting the diamine compound with the ketone compound includes a diamine compound, a ketone compound, a reaction product of one molecule of the diamine compound and one molecule of the ketone compound (one A compound having an amino group and one ketimine group), a mixture of one molecule of a diamine compound and a reaction product (by-product) of two molecules of a ketone compound, but the mole of the amino group of the diamine compound when charged into the reaction system By controlling the amount and the molar amount of the carbonyl group of the ketone compound within a specific range, the amount of by-products can be suppressed as much as possible, and the amount of the diamine compound can be suppressed as much as possible.
4). When a diamine compound and a ketone compound are reacted, water is generated. Since this reaction is an equilibrium reaction, it is preferable to discharge this water from the reaction system in order to advance the reaction. However, if a ketone compound that is easily soluble in water is used, the ketone compound is discharged out of the system as the water is discharged. Therefore, 3. However, even if the molar amount is charged within a specific range, the ketone compound is insufficient, and it is difficult to obtain a target compound having an amine group and a ketimine group under the maximum efficiency.
5. 4. above. In order to solve the problem, it is preferable to use one having a solubility in water of a specific numerical value or less.
6). The reaction between the diamine compound and the ketone compound is carried out in an organic solvent, and the organic solvent used here is a target amine that does not react with the diamine compound and the ketone compound and is difficult to dissolve in water. A compound having a group and a ketimine group can be obtained efficiently.
The present invention has been completed based on the above findings.

That is, the present invention relates to a ketone compound (a1) having 5 to 10 carbon atoms and a diamine compound (a2), an amino acid having a carbonyl group (a1-1) in the ketone compound (a1) and a diamine compound (a2). The ketone compound is added to the organic solvent (a3) so that the ratio with the group (a2-1) is 0.3 to 0.95 in molar ratio [(a1-1) / (a2-1)] A first step of obtaining a compound (A) having an amino group and a ketimine group by reacting (a1) and the diamine compound (a2) in the organic solvent (a3);
A second step of obtaining a fluorinated aliphatic group-containing compound (C) having a ketimine group by reacting the compound (A) with a sulfonyl chloride compound (B) containing a fluorinated aliphatic group;
A method for producing a sulfonylamide compound containing a fluorinated aliphatic group, comprising a third step of generating an amino group in the compound (C) by hydrolyzing a ketimine group of the compound (C) Is to provide.

Further, the present invention is characterized in that a sulfonylamide compound containing a fluorinated aliphatic group obtained by the method for producing a sulfonylamide compound containing a fluorinated aliphatic group is reacted with a metal salt of a halogenated organic acid. A method for producing an anionic hydrophilic group-containing surfactant is provided.

According to the present invention, a method for producing a sulfonylamide compound containing a fluorinated aliphatic group with high yield can be provided. Moreover, the anionic hydrophilic group containing surfactant which is a component which comprises a fire extinguishing agent can be obtained by using this sulfonylamide compound obtained.

The method for producing a sulfonylamide compound containing a fluorinated aliphatic group of the present invention is a method comprising the following first to third steps.

First step: A ketone compound (a1) having 5 to 10 carbon atoms and a diamine compound (a2) are converted into a carbonyl group (a1-1) having a ketone compound (a1) and an amino group having a diamine compound (a2) ( The ketone compound (a1) is added to the organic solvent (a3) in such a range that the ratio with respect to a2-1) is 0.3 to 0.95 in molar ratio [(a1-1) / (a2-1)]. And the diamine compound (a2) in the organic solvent (a3) to obtain a compound (A) having an amino group and a ketimine group.

Second step: A step of reacting the compound (A) with a sulfonyl chloride compound (B) containing a fluorinated aliphatic group to obtain a fluorinated aliphatic group-containing compound (C) having a ketimine group.

3rd process: The process of producing | generating an amino group in a compound (C) by hydrolyzing the ketimine group which the compound (C) obtained at said 2nd process has.

The ketone compound (a1) used in the first step needs to have 5 to 10 carbon atoms. A ketone compound having 5 or less carbon atoms has high solubility in water. Therefore, the ketone compound having less than 5 carbon atoms can be discharged out of the reaction system as a by-product when the compound (A) having a ketimine group is produced by the reaction between the ketone compound and the diamine compound (a2). It dissolves in preferable water and is discharged out of the reaction system together with water. As a result, it is not preferable because it becomes difficult to produce a sulfonylamide compound containing a fluorinated aliphatic group in good yield. When the number of carbon atoms is larger than 10, it is not preferable because the hydrolysis reaction is difficult to proceed in the third step described later.

Examples of the ketone compound (a1) used in the present invention include diethyl ketone, methyl isobutyl ketone, and cyclohexyl ketone. Among the ketone compounds (a1), carbon is not easily discharged together with water when water is discharged from the reaction system in the first step, and is easily discharged out of the system in the third step to be described later. A ketone compound having 5 or 6 atoms is preferable, and methyl isobutyl ketone having 6 carbon atoms is more preferable.

Examples of the diamine compound (a2) used in the present invention include aliphatic diamine, alicyclic diamine, diaminoorganosiloxane, and aromatic diamine. Examples of the aliphatic diamine include ethylene diamine, propane diamine (1,3-propane diamine), tetramethylene diamine, pentamethylene diamine, and hexamethylene diamine.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and the like.

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane.

Examples of the aromatic diamine include 1,1-metaxylylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2, 2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylide ) Bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diamino Pyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diamino Carbazole, N-phenyl-3,6-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, , 4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecanoxy-2,4-diaminobenzene Zen, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2 , 5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3, 5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, 3,5- Lanostanyl diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5 -Diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, , 1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((Aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) Cyclohexane, 2,4-diamino N, N-diallyl aniline, 4-amino-benzylamine, 3-amino-benzylamine, and the like.

As the diamine compound (a2) used in the present invention, an aliphatic diamine compound is preferable because it has a high resistance to alcohols and water-soluble anionic hydrophilic group-containing surfactants, and has 2 carbon atoms. The aliphatic diamine compounds of 6 to 6 are more preferable, ethylenediamine, propanediamine, and butanediamine are more preferable, and propanediamine is particularly preferable.

As the organic solvent (a3) used in the present invention, various solvents can be used as long as they do not have a reactive group that reacts with the ketone compound (a1) and the diamine compound (a2). Is preferably less than 10% at 25 ° C. By using a compound having a solubility in water of less than 10% at 25 ° C., when the compound (A) having a ketimine group is produced by the reaction of the ketone compound and the diamine compound (a2), the reaction system is out of the reaction system. It is possible to prevent the organic solvent from being dissolved in the water discharged into the water, and it is possible to produce a sulfonylamide compound containing a fluorinated aliphatic group with good yield. Among organic solvents (a3), the solubility in water is preferably less than 5% at 25 ° C., and preferably less than 1%.

Examples of the organic solvent that does not have a reactive group that reacts with the ketone compound (a1) and the diamine compound (a2) and has a solubility in water of less than 10% at 25 ° C. include hexane, heptane, octane, Examples thereof include aliphatic solvents having 6 to 16 carbon atoms such as nonane and decane; aromatic solvents having 6 to 8 carbon atoms such as toluene and xylene. The organic solvent (a3) is preferably an aromatic solvent, and more preferably toluene or xylene.

In the first step, the ketone compound (a1) and the diamine compound (a2) are mixed with the carbonyl group (a1-1) of the ketone compound (a1) and the amino compound of the diamine compound (a2) in the organic solvent (a3). The mixture is charged so that the ratio with the group (a2-1) is 0.3 or more in terms of molar ratio [(a1-1) / (a2-1)]. When the molar ratio [(a1-1) / (a2-1)] is less than 0.3, the amount of the compound (A) having one amino group and one ketimine group obtained is This is not preferable because it is not sufficient and it becomes difficult to produce the sulfonylamide compound in a high yield. The ketone compound (a1) and the diamine compound (a2) can be charged in a molar ratio [(a1-1) / (a2-1)] in the range of 0.3 to 0.95. Since the amount of the compound (A) having a group is sufficient and the sulfonylamide compound can be produced with good yield, it is preferable to charge in the range of 0.5 to 0.95.

In the first step, the ketone compound (a1) and the diamine compound (a2) are charged as described above, and the carbonyl group (a1-1) and the diamine compound (a2) of the ketone compound (a1) in the organic solvent (a3) are charged. ) Is reacted with the amino group (a2-1) of the compound (A) to obtain a mixture containing the compound (A) having an amino group and a ketimine group. The temperature of the reaction system during the reaction is usually 100 to 160 ° C, preferably 105 to 140 ° C.

Among the compounds (A) having an amino group and a ketimine group, a compound having one amino group and one ketimine group is preferable because a sulfonylamide compound containing a fluorinated aliphatic group can be obtained in high yield.

In the first step, together with the reaction between the ketone compound (a1) and the diamine compound (a2), the water produced as a by-product in the reaction is discharged out of the reaction system, and the ketone compound (a1) and the diamine This is preferable because the compound (a2) can be efficiently reacted with the compound (A) in a high yield. The reaction between the ketone compound (a1) and the diamine compound (a2) is carried out by the amount of water produced as a by-product from the reaction between the carbonyl group (a1-1) and the amino group (a2-1). It is preferable to carry out until the amount of the compound (a2) is 0.6 to 1.95 mol per 1 mol. By reacting the ketone compound (a1) and the diamine compound (a2) until the amount of water produced is within the above range, the amount of compound (A) produced is sufficient, and the sulfonylamide compound is produced with good yield. It becomes possible. The reaction between the ketone compound (a1) and the diamine compound (a2) is carried out by the amount of water produced as a by-product from the reaction between the carbonyl group (a1-1) and the amino group (a2-1). It is preferable to carry out until the amount of the compound (a2) is 1.0 to 1.85 mol with respect to 1 mol.

The reaction time of the ketone compound (a1) and the diamine compound (a2) in the first step is usually 6 to 48 hours, and more preferably 8 to 26 hours.

In the first step, the compound (A) having an amino group and a ketimine group is obtained in a mixture state. In the mixture, a carbonyl group generally reacts with an unreacted raw material such as a compound other than the compound (A), for example, a ketone compound (a1) or a diamine compound (a2), or an amino group of the compound (A). In addition, one or more compounds such as a compound in which a ketimine group is generated (diketimine form) are included. When a large amount of the diamine compound (a2) is present in the mixture, one molecule of the diamine compound (a2) and the sulfonyl chloride compound are reacted with the sulfonyl chloride compound (B) containing a fluorinated aliphatic group in the second step described later. (B) A large amount of a compound reacted with two molecules is obtained. Since this compound is insoluble in a solvent and cannot be quaternary aminated, a fluorosurfactant cannot be obtained from this compound. Therefore, the expensive sulfonyl chloride compound (B) is wasted and the product cost is increased. In the present invention, the content of the diamine compound (a2) in the resulting mixture is about 10 parts by mass with respect to 100 parts by mass of the mixture, such as 1 molecule of the diamine compound (a2) and 2 molecules of the sulfonyl chloride compound (B). The amount of the reacted compound produced is significantly less than that of the prior art, and the expensive sulfonyl chloride compound (B) can be used without waste.

The diketimine compound does not react with the sulfonyl chloride compound (B), and may be used as a solvent for dissolving the sulfonylamide compound containing a fluorinated aliphatic group after the third step described later, or after the third step. The ketone compound (a1) and the diamine compound (a2) may be regenerated by recovery and hydrolysis, and these compounds may be reused.

In the second step of the present invention, the compound (A) in the mixture obtained in the first step is reacted with the sulfonyl chloride compound (B) containing a fluorinated aliphatic group to give a fluorinated fat having a ketimine group. In this step, the group-containing compound (C) is obtained. In this step, the amino group in compound (A) is reacted with the sulfonyl chloride group in sulfonyl chloride compound (B).

Examples of the sulfonyl chloride compound (B) include 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-sulfonyl chloride 1,1. , 2,2,3,3,4,4,5,5,6,6,6-monodecafluorohexane-1-sulfonyl chloride, 1,1,2,2,3,3,4,4,4 -Nonafluorobutane-1-sulfonyl chloride, 3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl chloride and the like.

The reaction temperature at the time of reacting the compound (A) with the sulfonyl chloride compound (B) containing a fluorinated aliphatic group is, for example, 0 to 80 ° C., preferably 5 to 50 ° C. The reaction time is, for example, 0.5 to 6 hours, preferably 1 to 4 hours.

As a reaction ratio of the compound (A) and the sulfonyl chloride compound (B) containing a fluorinated aliphatic group, the compound (1 mol) per mole of the sulfonyl chloride group of the sulfonyl chloride compound (B) containing a fluorinated aliphatic group ( The range in which the amino group of A) is 1.5 to 10 is preferable because a fluorinated aliphatic group-containing compound (C) having a ketimine group with a high yield can be obtained, and the range of 3 to 9 is more preferable. preferable.

The third step is a step of generating an amino group in the compound (C) by hydrolyzing the ketimine group of the fluorinated aliphatic group-containing compound (C) having a ketimine group obtained in the second step. The temperature of the reaction system at the time of hydrolysis is, for example, 80 to 160 ° C., preferably 100 to 140 ° C. The reaction time is, for example, 12 to 48 hours. In the third step, it is preferable to discharge the ketone compound (a1) produced by hydrolysis in order to advance hydrolysis.

A sulfonylamide compound containing a fluorinated aliphatic group can be obtained in high yield by the production method of the present invention including the first to third steps. Furthermore, by reacting a sulfonylamide compound containing a fluorinated aliphatic group and a metal salt of a halogenated organic acid, an anionic hydrophilic group suitable as a component of a fire extinguishing agent effective for a fire of a polar solvent such as alcohol. A contained surfactant can be produced.

Preferred examples of the metal salt of the halogenated organic acid include sodium chloroacetate and sodium 3-monochloro-2-hydroxypropanesulfonate. In the present invention, the combined use of sodium chloroacetate and sodium 3-monochloro-2-hydroxypropanesulfonate provides an anionic hydrophilic group-containing surfactant having high resistance to alcohol and water solubility. This is preferable.

An anionic hydrophilic group-containing surfactant having high resistance to alcohol and water-solubility as a reaction ratio when reacting a sulfonylamide compound containing a fluorinated aliphatic group and a metal salt of a halogenated organic acid Therefore, the metal salt of a halogenated organic acid is preferably 2 to 10 moles, more preferably 3 to 8 moles per mole of the sulfonylamide compound containing a fluorinated aliphatic group.

The anionic hydrophilic group-containing surfactant obtained by the production method of the present invention has, for example, primary, secondary and tertiary cationic groups in the molecule, and the primary cationic group is the entire cationic group. By mixing with 40% by weight or less of the cationic polyamine polymer compound, a fire extinguishing agent effective for a fire of a polar solvent such as alcohol can be obtained.

The cationic polyamine-based polymer compound refers to a polymer compound containing a cationic group such as an amino group, an ammonium group, a pyridinium group, or a quaternary ammonium group, and usually has a solubility in water of 0.1% by weight or more. It is a water-soluble polymer compound.

The cationic groups include primary, secondary, and tertiary types, and these cationic groups may be in the main chain or side chain of the polyamine polymer compound.

The quantitative ratio of primary, secondary, and tertiary cationic groups is not particularly limited, but the primary cationic group is preferably contained in an amount of 40% by weight or less based on the total cationic groups.

The degree of polymerization of the cationic polyamine polymer is controlled by solubility in water, but the degree of polymerization from the oligomer region is tens of thousands or more, that is, the molecular weight is 1,000 to 1,000,000 in terms of number average molecular weight. About 000, more preferably 4,000 to 300,000, and a degree of polymerization of 50,000 to 100,000 for exhibiting the most excellent fire extinguishing performance against polar solvents, weather resistance and liquid resistance Is particularly preferred.

Specific examples of the cationic polyamine polymer compound include the following.

AI Polyethyleneimine
A-II N-substituted polyethyleneimine

The N- substituted derivatives as for example _{_{-C n H 2n + 1, -CONHC}} n H 2n + 1, -COC n H 2n + 1 _{_{or, - (CH 2 CH 2 O}} ) n -H ( where, n is 1 to Represents an integer of 6.) and the like.

It is preferable to further add a polybasic acid compound to the fire extinguishing agent. The polybasic acid compound is a non-surfactant compound, for example, a dibasic acid, tribasic acid, tetrabasic acid, pentabasic acid, hexabasic acid having 3 to 24 carbon atoms having an aromatic group, an aliphatic group, a heterocyclic ring or the like. Examples include basic acids and the like, and alkali metal salts and ammonium salts thereof, and examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polybasic acid compound may be used alone or in combination of two or more. By adding a polybasic acid compound, it is possible to further improve weather resistance and liquid resistance by electrostatic interaction with the water-soluble cationic polymer compound. As long as the polybasic acid compound is a compound having an acid group in the molecule, there is no limitation on the type and number of acid groups, the length of the carbon chain, the molecular weight, and the like. Among these, as the polybasic acid compound, it is desirable to use a dibasic acid compound having 4 to 18 carbon atoms in terms of compatibility. Specific examples of the polybasic acid compound according to the present invention include the following.

In the fire extinguishing agent, various additives can be further added. Examples of the additive include an additional foam stabilizer, a freezing point depressant, a rust inhibitor, and a pH adjuster.

Additional foam stabilizers are added mainly to adjust the expansion ratio or drainage, and examples include glycerin aliphatic ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene alkyl ether, Nonionic surfactants such as polyoxyethylene polyoxypropylene ether, polyethylene glycol fatty acid ester, alkyl alkanolamide, alkyl polyglucoside, alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolium betaine, alkylamide Amphoteric surfactants such as propylbetaine and alkylhydroxysulfobetaine, polyethylene glycol, polyvinyl Alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, gum arabic, sodium alginate, polypropylene glycol, polyvinyl resins.

Freezing point depressants include ethylene glycol, propylene glycol, cellosolves (ethyl cellosolve, butyl cellosolve), carbitols (ethyl carbitol, butyl carbitol, hexyl carbitol, octyl carbitol), lower alcohols (isopropyl alcohol, butanol, octanol) ) Or urea.

As the rust preventive agent and pH adjuster, various types known in the industry can be used and are not particularly limited.

The fire extinguishing agent can be applied in various ways, i.e. by blowing or mixing low boiling fluorocarbons such as air, carbon dioxide, nitrogen, difluorodichloromethane or other suitable non-flammable gases. That is, since the viscosity of the above-mentioned extinguishing agent stock solution is relatively low, the concentrated stock solution is stored in a storage tank, and the degree of dilution is adjusted by using a normal method, for example, the way to a fire extinguisher or a foam nozzle during use. However, it can also be used by blowing or mixing incombustible gas such as air, and radiating or sending bubbles from above or below the flame. Alternatively, it may be diluted with water in advance to use concentration and filled in a fire extinguisher, a parking lot fire extinguishing facility, a hazardous material fixing fire extinguishing facility, a package type fire extinguishing facility, or the like.

As for the method of radiating the fire extinguishing agent, any known and commonly used radiating nozzle used for various extinguishing agent applications can be used, and desired performance can be exhibited.

As the nozzle, for example, a foam chamber most commonly used for oil tanks, a nozzle conforming to the ISO standard, a nozzle conforming to the UL standard, a nozzle conforming to the MIL standard, a hand nozzle attached to a chemical fire engine, etc. Examples include air foam hand nozzles, SSI nozzles, HK nozzles stipulated by the Japan Marine Equipment Association, foam heads used in parking lot fire extinguishing equipment, and spray heads.

The fire extinguishing agent can be used by various radiation methods as described above. Until now, it can be used in a wide range of applications compared to conventional fire extinguishing agents. Specifically, it can be deployed in chemical fire engines and stock transport trucks owned by public fire engines, as well as oil bases and factories that own crude oil tanks and hazardous materials facilities, airports, etc. Facilities, harbor facilities and ships loaded with dangerous goods, gas stations, underground parking lots, buildings, tunnels, bridges, etc. Moreover, it can be used suitably also for general fires other than liquid dangerous goods fires, for example, wood fires such as houses, rubber such as tires, and plastic fires. Furthermore, since the fire extinguishing agent of the present invention is excellent in liquid resistance, weather resistance, heat resistance and foaming ability, a concentrated stock solution or a low dilution aqueous solution is directly injected into the combustion oil surface. Suitable for fire suffocation or cooling fire extinguishing such as tempura oil or salad oil. In addition, since the fire extinguishing agent of the present invention is also excellent in dilution and dissolution stability, it can be used as a simple household initial fire extinguisher by filling a dilute solution in a spray can. In addition, since the foam composed of the fire extinguishing agent of the present invention can be stably present on water-based aqueous solutions, sol-gel substances, sludges, filths, various organic solvents, and organic compounds, they are volatilized from these substances. It can be used to prevent evaporation of flammables and odors.

Further, the fire extinguishing agent of the present invention is used in combination with powder fire extinguishing agent, protein foam extinguishing agent, synthetic interfacial foam extinguishing agent and the like containing sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, ammonium sulfate, ammonium phosphate, calcium carbonate and the like as components. can do.

The present invention will be described in more detail with reference to examples and comparative examples.

Example 1
A clean 3 L separable flask equipped with a reflux circulation device was charged with 216.7 g of 1,3-propanediamine, 526.1 g of methyl isobutyl ketone, and 216.7 g of toluene. The temperature in the reaction system in the flask was raised to 120 ° C., and reflux dehydration reaction was performed over 6 hours to obtain a mixture containing a compound having one amino group and one ketimine group. After dehydration was stopped, the temperature in the reaction system was lowered to 30 ° C. The amount of water produced by this reaction was 1.2 mol.

In a separate container, 78.4 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-sulfonyl chloride was dissolved in 313.2 g of toluene. A solution was prepared. This solution was put into a separable flask containing the above mixture, and after the exotherm had subsided, it was stirred at 45 ° C. for 2 hours to obtain a fluorinated aliphatic group-containing compound having a ketimine group.

Next, removal of compounds other than fluorinated aliphatic group-containing compounds having ketimine groups (1,3-propanediamine, compounds having one amino group and one ketimine group, etc.) by adding water to a 3 L separable flask Went. Specifically, 300.6 g of ion-exchanged water is put into a separable flask containing a fluorinated aliphatic group-containing compound having a ketimine group, the temperature is lowered to 30 ° C., stirred for 1 hour, and allowed to stand for 1 hour. The ketimine group of was hydrolyzed. Thereafter, the aqueous layer was separated from the separable flask. The separated aqueous layer was 406.3 parts by weight. Furthermore, 250.5 g of ion-exchanged water was put into a separable flask, stirred at 45 ° C. for 1 hour, and then allowed to stand for 1 hour to hydrolyze the ketimine group of the compound. Thereafter, the aqueous layer was separated from the separable flask. The separated aqueous layer was 294.8 g. The same water washing operation was performed again to obtain 1088.8 g of an oil layer.

To this oil layer, 76.6 g of ion-exchanged water was added and the inside of the system was kept at 88 ° C. to conduct a hydrolysis reaction over 1 hour, and the generated methyl isobutyl ketone was discharged out of the system. This operation was repeated four more times, and the product remaining in the system was dried to obtain 76.6 g of a solid content. When this solid content was analyzed by GC-MS, it was confirmed that it was a sulfonylamide compound having a molecular weight of 484 and containing a fluorinated aliphatic group having a single-terminal amino group as the target product. Fluorinated aliphatic group having one terminal amino group for 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-sulfonyl chloride used in the reaction The yield (mol conversion) of the sulfonylamide compound containing a group was 90.1% by mass.

Comparative Example 1
A clean 3 L separable flask was charged with 148.2 g of 1,3-propanediamine and 134 g of toluene. A solution was prepared by dissolving 89.3 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-sulfonyl chloride in 356.9 g of toluene. . The solution was charged into a stirring 3 L separable flask. After the exotherm subsided, the mixture was stirred at 45 ° C. for 2 hours. 400 g of 1-butanol and 342 g of ion-exchanged water were added and the temperature was raised to 80 ° C. After reaching 80 ° C, stirring was stopped and the temperature was lowered to 45 ° C. After reaching 45 ° C., the mixture was allowed to stand for 1 hour to separate the aqueous layer. The separated aqueous layer was 390 g.

286 g of ion-exchanged water was put into the separable flask, stirred at 45 ° C. for 1 hour, and allowed to stand for 1 hour to separate the aqueous layer. The separated aqueous layer was 413 g. The same water washing operation was performed again to obtain 840 g of an oil layer. The solvent portion was removed from the oil layer under reduced pressure to obtain a solid content of 60.0 g. When this solid content was analyzed by GC-MS, it was confirmed that it was a sulfonylamide compound having a molecular weight of 484 and containing a fluorinated aliphatic group having a single-terminal amino group as the target product. Fluorinated aliphatic group having one terminal amino group for 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-sulfonyl chloride used in the reaction The yield (mol conversion) of the sulfonylamide compound containing a group was 61.9% by mass.

Claims

A ketone compound (a1) having 5 to 10 carbon atoms and a diamine compound (a2) are converted into a carbonyl group (a1-1) of the ketone compound (a1) and an amino group (a2-1) of the diamine compound (a2). Is added to the organic solvent (a3) so that the molar ratio [(a1-1) / (a2-1)] is 0.3 to 0.95, and the ketone compound (a1) and the diamine are added. A first step of reacting the compound (a2) in the organic solvent (a3) to obtain a compound (A) having an amino group and a ketimine group;
A second step of obtaining a fluorinated aliphatic group-containing compound (C) having a ketimine group by reacting the compound (A) with a sulfonyl chloride compound (B) containing a fluorinated aliphatic group;
A method for producing a sulfonylamide compound containing a fluorinated aliphatic group, comprising a third step of generating an amino group in the compound (C) by hydrolyzing a ketimine group of the compound (C) .
The organic solvent (a3) does not have a reactive group that reacts with the ketone compound (a1) and the diamine compound (a2) and has a solubility in water of less than 10% at 25 ° C. A process for producing a sulfonylamide compound comprising a fluorinated aliphatic group according to 1.
2. The fluorinated aliphatic group according to claim 1, wherein in the first step, the reaction between the ketone compound (a1) and the diamine compound (a2) is performed and the water produced by the reaction is discharged from the reaction system. A method for producing a sulfonylamide compound.
The method for producing a sulfonylamide compound containing a fluorinated aliphatic group according to claim 3, wherein the water is discharged until 0.6 to 1.95 mol per 1 mol of the charged diamine compound (a2).
The method for producing a sulfonylamide compound containing a fluorinated aliphatic group according to claim 1, wherein the ketone compound (a1) is methyl isobutyl ketone and the diamine compound (a2) is propanediamine.
The method for producing a sulfonylamide compound containing a fluorinated aliphatic group according to claim 1, wherein the organic solvent (a3) is toluene or xylene.
In the second step, the compound (A) and the compound (B) are mixed in an amount of 1.5 to 10 amino groups of the compound (A) with respect to 1 mol of the sulfonyl chloride group of the compound (B). The manufacturing method of the sulfonyl amide compound containing the fluorinated aliphatic group of Claim 1 made to react in the range which becomes.
The method for producing a sulfonylamide compound containing a fluorinated aliphatic group according to claim 1, wherein the ketone compound (a1) and the diamine compound (a2) are reacted in an environment of 100 to 160 ° C.
An anionic hydrophilic group-containing interface characterized by reacting a sulfonylamide compound containing a fluorinated aliphatic group obtained by the production method according to any one of claims 1 to 8 and a metal salt of a halogenated organic acid. A method for producing an activator.