WO2013172412A1 - Procédé de production d'un composé de type sulfonylamide contenant un groupe aliphatique fluoré et procédé de production d'un tensioactif anionique contenant un groupe hydrophile - Google Patents

Procédé de production d'un composé de type sulfonylamide contenant un groupe aliphatique fluoré et procédé de production d'un tensioactif anionique contenant un groupe hydrophile Download PDF

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WO2013172412A1
WO2013172412A1 PCT/JP2013/063657 JP2013063657W WO2013172412A1 WO 2013172412 A1 WO2013172412 A1 WO 2013172412A1 JP 2013063657 W JP2013063657 W JP 2013063657W WO 2013172412 A1 WO2013172412 A1 WO 2013172412A1
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compound
group
fluorinated aliphatic
aliphatic group
diamine
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PCT/JP2013/063657
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English (en)
Japanese (ja)
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健治 正村
弘行 濱野
鈴木　秀也
洋三 山科
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Dic株式会社
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Priority to JP2014502929A priority Critical patent/JP5522501B2/ja
Publication of WO2013172412A1 publication Critical patent/WO2013172412A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof

Definitions

  • 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. .
  • the foam 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.
  • 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)
  • 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.
  • 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).
  • a diamine such as 1,3-propanediamine
  • 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.
  • 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 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.
  • the target product is obtained using one molecule of a sulfonyl chloride compound containing a fluorinated aliphatic group
  • 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.
  • 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
  • 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.
  • 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 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.
  • the reaction between the diamine compound and the ketone compound is a reversible reaction
  • 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
  • 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.
  • 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.
  • 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 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.
  • 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.
  • a method for producing a sulfonylamide compound containing a fluorinated aliphatic group with high yield can be provided.
  • 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.
  • 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)].
  • 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
  • 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.
  • 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.
  • alicyclic diamine examples include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and the like.
  • diaminoorganosiloxane examples include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane.
  • aromatic diamine examples 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 ′-
  • 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.
  • 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.
  • 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.
  • 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.
  • 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)].
  • 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.
  • 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.
  • the temperature of the reaction system during the reaction is usually 100 to 160 ° C, preferably 105 to 140 ° C.
  • 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.
  • 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
  • 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.
  • 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.
  • the compound (A) having an amino group and a ketimine group is obtained in a mixture state.
  • 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).
  • a compound in which a ketimine group is generated is included.
  • 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.
  • 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.
  • the group-containing compound (C) is obtained.
  • 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.
  • the compound (1 mol) per mole of the sulfonyl chloride group of the sulfonyl chloride compound (B) containing a fluorinated aliphatic group 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.
  • 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.
  • 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.
  • 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.
  • cationic polyamine polymer compound examples include the following.
  • 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.
  • 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.
  • 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.
  • 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.
  • additives can be further added.
  • 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.
  • 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.
  • 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
  • a fire extinguisher 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.
  • any known and commonly used radiating nozzle used for various extinguishing agent applications can be used, and desired performance can be exhibited.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

Abstract

La présente invention concerne un procédé de production, caractérisé par un rendement élevé, d'un composé de type sulfonylamide contenant un groupe aliphatique fluoré. Ledit procédé comprend les étapes consistant à ajouter un composé cétonique (a1) comportant de 5 à 10 atomes de carbone et un composé de type diamine (a2) à un solvant organique (a3), de façon à ce que le rapport entre les groupes carbonyle (a1-1) du composé cétonique (a1) et les groupes amine (a2-1) du composé de type diamine (a2) se situe dans un intervalle de 0,3 à 0,95 dans le rapport molaire [(a1-1)/(a2-2)] et à faire réagir le composé cétonique (a1) et le composé de type diamine (a2) dans le solvant organique (a3) afin d'obtenir un composé (A) contenant un groupe amine et un groupe cétimine ; à faire réagir le composé (A) avec un composé de type chlorure de sulfonyle (B) contenant un groupe aliphatique fluoré afin d'obtenir un composé (C) contenant un groupe aliphatique fluoré possédant un groupe cétimine ; et à hydrolyser le groupe cétimine du composé (C) pour générer un groupe amine dans le composé (C).
PCT/JP2013/063657 2012-05-18 2013-05-16 Procédé de production d'un composé de type sulfonylamide contenant un groupe aliphatique fluoré et procédé de production d'un tensioactif anionique contenant un groupe hydrophile WO2013172412A1 (fr)

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JP5920024B2 (ja) * 2012-05-25 2016-05-18 Dic株式会社 フッ素化脂肪族基を含むスルホニルアミド化合物の製造方法及びアニオン性親水基含有界面活性剤の製造方法

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WO2011005642A1 (fr) * 2009-07-10 2011-01-13 E. I. Du Pont De Nemours And Company Polyfluorosulfonamido amides utiles en tant qu’intermédiaires dans la synthèse de polyfluorosulfonamido amines
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JPS5826850A (ja) * 1981-08-11 1983-02-17 Dainippon Ink & Chem Inc フルオロアルキル界面活性化合物の製造法
JP2001269421A (ja) * 2000-01-17 2001-10-02 Dainippon Ink & Chem Inc 消火薬剤
WO2011005642A1 (fr) * 2009-07-10 2011-01-13 E. I. Du Pont De Nemours And Company Polyfluorosulfonamido amides utiles en tant qu’intermédiaires dans la synthèse de polyfluorosulfonamido amines
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CN115028961A (zh) * 2022-05-31 2022-09-09 台州市黄岩区武汉理工高性能复合材料技术研究院 一种快速固化环氧树脂的制备方法
CN115028961B (zh) * 2022-05-31 2024-01-12 台州市黄岩区武汉理工高性能复合材料技术研究院 一种快速固化环氧树脂的制备方法

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