CN106215802B - A kind of fluorine-containing surfactant and a kind of aqueous film-forming foam extinguishing agent - Google Patents
A kind of fluorine-containing surfactant and a kind of aqueous film-forming foam extinguishing agent Download PDFInfo
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- CN106215802B CN106215802B CN201610557793.6A CN201610557793A CN106215802B CN 106215802 B CN106215802 B CN 106215802B CN 201610557793 A CN201610557793 A CN 201610557793A CN 106215802 B CN106215802 B CN 106215802B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
- A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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Abstract
The present invention relates to fluoride-containing PMMA technical fields, in particular to common fluorine-containing surfactant in a kind of fire foam: sulfonyl fluoride chlorine, alkyl diamine, solvent, acid binding agent reaction, it is filtered to remove the hydrochloride of by-product, obtain crude product, by crude product, rectifying removes solvent under negative pressure, oxidant reaction is added, water washing filters to obtain the final product.A kind of aqueous film-forming foam extinguishing agent contains fluorine-containing surfactant, non-fluorinated surfactant and hyperbranched surfactant.The fluorine-containing surfactant being prepared using the technical solution of the application, reaction temperature low energy consumption is low, high income, can reduce production cost, improves product competitiveness；The addition of hyperbranched surfactant in aqueous film-forming foam extinguishing agent not only has the function of cosolvent, but also can reduce the use of fluorine-containing surfactant, improves extinguishing chemical performance, so that the harm to environment is reduced, more friendly, cleaning and environmental protection.
Description
Technical field
The present invention relates to fluoride-containing PMMA technical field, in particular to common fluorine-containing table in a kind of fire foam
Face activating agent further relates to the aqueous film-forming foam extinguishing agent containing this fluorine-containing surfactant.
Background technique
Fluorinated surfactant (fluorinated surfactant), abbreviation FSA.It is using fluorocarbon chain as non-polar group
Surfactant, i.e., partly or entirely replace the hydrogen atom on hydrocarbon chain with fluorine atom.Fluorocarbon surfactant has high table
Face activity, high thermodynamic and chemical stability.
Fluorinated alkyl sulfonate is using most common fluorinated surfactant in fire foam, in CN102491923A
Disclosed one kind takes water as a solvent the chemically synthesized perfluorinated surfactant of continuity method: being that starting is former with per-fluoroalkyl sulfonyl chlorine
Material, takes water as a solvent, and hydrogen halides agent for capturing is added, and with N, N- alkyl propane diamine reacts, and 40-80 DEG C of reaction temperature, the reaction time
8-16 hours, it is directly added into sodium chloroacetate reactant aqueous solution, temperature is 80-110 DEG C, reacts 10-24 hours, then directly dilutes
It is configured to solution.Hc-surfactant and foam stabiliser is added, obtains aqueous film-forming foam extinguishing agent.It is anti-in this technical solution
Answer temperature higher, energy consumption is big.
CN101293860A discloses a kind of preparation method of quaternary ammonium salt fluorine surfactant, to perfluorinated nonene oxygroup benzene
Sulfonic acid chloride and N, N- dimethylated propyl diethylenetriamine is raw material, and in the presence of base catalyst, it is anti-that amidation is carried out at subzero 20-120 DEG C
Answer, reactant through separation with iodomethane carry out quaternary ammonium reaction to get.But its yield only has 80% or so.
Summary of the invention
In order to solve, above in the prior art reaction temperature high energy consumption present in fluorinated alkyl sulfonate is high, receives preparing
The low problem of rate, common fluorine-containing table in a kind of this application discloses reaction temperature low energy consumption low, high income fire foam
Face activating agent.
Disclosed herein as well is a kind of aqueous film-forming foam extinguishing agents containing above-mentioned fluorine-containing surfactant.
The present invention is achieved by the following measures:
A kind of fluorine-containing surfactant, is obtained through the following steps:
(1) sulfonyl fluoride chlorine, alkyl diamine, solvent, acid binding agent are added in closed reactor, reacts 6 at -10~50 DEG C
~24 hour, it is filtered to remove the hydrochloride of by-product, obtains crude product,
(2) by crude product, rectifying removes solvent under negative pressure, and oxidant is added and reacts 6~24 hours at 50~80 DEG C, and adds
Enter diluent and is formulated to a certain concentration to get fluorine-containing surfactant is arrived；
Wherein sulfonyl fluoride chlorine, propane diamine, solvent, acid binding agent mass ratio are 1.0~1.5:1:20:1.0~1.5,
Oxidant additional amount is 1.1~3 times of the amount of crude material.
The fluorine-containing surfactant, the molecular formula of the sulfonyl fluoride chlorine are RfSO2Cl, wherein Rf is CxFyHz,
2x=y+z-1 and x >=4, y >=z, preferably trifluoromethanesulfonyl chloride CF3SO2Cl。
The fluorine-containing surfactant, alkyl diamine molecular formula are R1R2N(CH2) nNR3R4, one in R1, R2
Or two are H, R3, R4 are methyl or ethyl, preferably 1,2- propane diamine.
The fluorine-containing surfactant, the acid binding agent are in liquefied ammonia, trimethylamine, triethylamine, tripropyl amine (TPA) and tri-n-butylamine
More than one.
The fluorine-containing surfactant, the oxidant are one or more of sodium hypochlorite and hydrogen peroxide.
The fluorine-containing surfactant, the diluent are deionized water, ethyl alcohol, isopropanol, butanol, ethylene glycol and third
One or more of glycol.
A kind of aqueous film-forming foam extinguishing agent contains the fluorine-containing surfactant, non-fluorinated surfactant and hyperbranched
Surfactant qualities ratio is 1:0.2~8:0.1~0.2.
The aqueous film-forming foam extinguishing agent, the non-fluorinated surfactant are polysaccharide glycosides, alkyl betaine, alkyl oxidation
One or more of amine.
The aqueous film-forming foam extinguishing agent, what the hyperbranched surfactant was obtained through the following steps:
(1) equimolar diisopropanolamine (DIPA) and methyl acrylate are taken, reaction obtains AB2Monomer；
(2) by AB2Monomer, p-methyl benzenesulfonic acid and triethanolamine reaction to get,
Wherein triethanolamine and AB2The molar ratio of monomer is 1:3.
The aqueous film-forming foam extinguishing agent, fluorine-containing surfactant, non-fluorinated surfactant and hyperbranched surface-active
Agent is formed according to mass ratio 1:6~7:0.1~0.2.
Beneficial effects of the present invention:
1. using the fluorine-containing surfactant that is prepared of technical solution of the application, reaction temperature low energy consumption is low, yield
Height can reduce production cost, improve product competitiveness；
2, in aqueous film-forming foam extinguishing agent hyperbranched surfactant addition, not only have the function of cosolvent, but also
The use of fluorine-containing surfactant can be reduced, extinguishing chemical performance is improved, thus harm of the reduction to environment, more cleaning and ring
It protects.
Specific embodiment
In order to better understand the present invention, it further illustrates combined with specific embodiments below.
What hyperbranched surfactant was obtained through the following steps:
(1) lead to 10 min of nitrogen into 250 mL there-necked flasks, equimolar diisopropanolamine (DIPA) and methyl acrylate is taken to be dissolved in
It in methanol, is added in there-necked flask after mixing in small beaker, mixture leads to 10 min of nitrogen at room temperature, stirs 30 min
40 DEG C of 4 h of reaction are warming up to, vacuum distillation removes methanol, obtains colorless and transparent oily AB2Monomer；
(2) lead to 10 min of nitrogen into 250 mL four-hole bottles, the AB of synthesis is added2Monomer, p-methyl benzenesulfonic acid and three ethyl alcohol
Amine, AB2The molar ratio of monomer and triethanolamine is 3:1, is warming up to 85 DEG C, continues logical nitrogen, is stirred to react 24 h, then depressurize
Be distilled off reaction in methanol and unreacted small molecule compound to get.
Embodiment 1
(1) trifluoromethanesulfonyl chloride, 1,2- propane diamine, methanol, trimethylamine are added in closed reactor, is reacted at 50 DEG C
6 hour, it is filtered to remove the hydrochloride of by-product, obtains crude product,
(2) by crude product, rectifying removes solvent under negative pressure, and oxidants hydrogen peroxide is added and reacts 6 hours at 80 DEG C, washing
Filtering is washed to get to fluorine-containing surfactant, measures purity 99.1%, then diluent deionized water tune is added in yield 92.1%
It is fitted on a certain concentration；
Wherein trifluoromethanesulfonyl chloride, 1,2- propane diamine, methanol, trimethylamine mass ratio are 1.0:1:20:1.5,
Oxidant additional amount is 1.1 times of the amount of crude material.
Embodiment 2
(1) trifluoromethanesulfonyl chloride, 1,2- propane diamine, methanol, trimethylamine are added in closed reactor, is reacted at 40 DEG C
8 hour, it is filtered to remove the hydrochloride of by-product, obtains crude product,
(2) by crude product, rectifying removes solvent under negative pressure, and oxidants hydrogen peroxide is added and reacts 8 hours at 60 DEG C, washing
Filtering is washed to get to fluorine-containing surfactant, measures purity 99.3%, then diluent deionized water tune is added in yield 91.5%
It is fitted on a certain concentration；
Wherein trifluoromethanesulfonyl chloride, 1,2- propane diamine, methanol, trimethylamine mass ratio are 1.5:1:20:1.0,
Oxidant additional amount is 2 times of the amount of crude material.
Embodiment 3
Aqueous film-forming foam extinguishing agent, the fluorine-containing surfactant being prepared by embodiment 1, dodecyl dimethyl beet
Alkali and hyperbranched surfactant are formed according to mass ratio 1:6:0.2, also contain other necessary additives.
Embodiment 4
Aqueous film-forming foam extinguishing agent, the fluorine-containing surfactant being prepared by embodiment 2, octadecyl dihydroxy ethyl oxygen
Change amine and hyperbranched surfactant to form according to mass ratio 1:7:0.1, also contains other necessary additives.
Comparative example 1
Hyperbranched surfactant is added without compared with embodiment 3, in aqueous film-forming foam extinguishing agent, remaining is the same as embodiment 3
It is identical.
Comparative example 2
Hyperbranched surfactant is added without compared with embodiment 4, in aqueous film-forming foam extinguishing agent, remaining is the same as embodiment 4
It is identical.
Comparative example 3
Aqueous film-forming foam extinguishing agent, the fluorine-containing surfactant and octadecyl dihydroxy ethyl be prepared by embodiment 2
Amine oxide is formed according to mass ratio 1:5, also contains other necessary additives.
Performance detection
Above-described embodiment 3,4 and comparative example 1,2 obtain aqueous film-forming foam extinguishing agent and foam solution are made, according to
GB15308-2006 surveys its performance, see the table below
It can be seen that be added to the embodiment 3,4 of hyperbranched surfactant more real than the comparison that do not add from upper table data
Example 1,2 is applied with better surface-active and better extinguishing effect, and can with the comparison of comparative example 3 from embodiment 4
To find out, when reaching similar effect, the adding proportion of fluorine-containing surfactant is smaller than comparative example 3 in embodiment 4, so
The addition of hyperbranched surfactant, it is possible to reduce the additive amount of fluorine-containing surfactant, thus more environment-friendly.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the limit of embodiment
System, other any changes made without departing from the spirit and principles of the present invention, modification, combination, substitution, simplification should be
Equivalence replacement mode, is included within the scope of the present invention.
Claims (6)
1. a kind of aqueous film-forming foam extinguishing agent, which is characterized in that contain fluorine-containing surfactant, non-fluorinated surfactant and over-expense
The mass ratio for changing surfactant is 1:0.2~8:0.1~0.2；
The fluorine-containing surfactant, is obtained through the following steps:
(1) sulfonyl fluoride chlorine, propane diamine, solvent, acid binding agent are added in closed reactor, it is small in -10~50 DEG C of reactions 6~24
When, it is filtered to remove the hydrochloride of by-product, obtains crude product,
(2) by crude product, rectifying removes solvent under negative pressure, and oxidant is added and reacts 6~24 hours at 50~80 DEG C, water washing mistake
Filter to get；
Wherein sulfonyl fluoride chlorine, propane diamine, solvent, acid binding agent mass ratio are 1.0~1.5:1:20:1.0~1.5,
Oxidant additional amount is 1.1~3 times of the amount of crude material；
What the hyperbranched surfactant was obtained through the following steps:
(1) equimolar diisopropanolamine (DIPA) and methyl acrylate are taken, reaction obtains AB2Monomer；
(2) by AB2Monomer, p-methyl benzenesulfonic acid and triethanolamine reaction to get,
Wherein triethanolamine and AB2The molar ratio of monomer is 1:3.
2. aqueous film-forming foam extinguishing agent according to claim 1, it is characterised in that the molecular formula of the sulfonyl fluoride chlorine is
RfSO2Cl, wherein RfFor CxFyHz, 2x=y+z-1 and x >=4, y >=z.
3. aqueous film-forming foam extinguishing agent according to claim 1, it is characterised in that the acid binding agent be liquefied ammonia, trimethylamine,
One or more of triethylamine, tripropyl amine (TPA) and tri-n-butylamine.
4. aqueous film-forming foam extinguishing agent according to claim 1, it is characterised in that the oxidant is sodium hypochlorite and mistake
One or more of hydrogen oxide.
5. aqueous film-forming foam extinguishing agent according to claim 1, it is characterised in that the non-fluorinated surfactant is polysaccharide
One or more of glycosides, alkyl betaine, alkyl amine oxide.
6. aqueous film-forming foam extinguishing agent according to claim 1, it is characterised in that fluorine-containing surfactant, non-fluorine surface are living
Property agent and hyperbranched surfactant according to mass ratio 1:6~7:0.1~0.2 form.
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| CN201610557793.6A CN106215802B (en) | 2016-07-15 | 2016-07-15 | A kind of fluorine-containing surfactant and a kind of aqueous film-forming foam extinguishing agent |
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| CN111840878A (en) * | 2020-05-26 | 2020-10-30 | 摩力方科技(北京)有限公司 | Lithium ion battery water-based fire extinguishing agent and preparation method thereof |
| CN114874783A (en) * | 2022-06-07 | 2022-08-09 | 浙江睦田消防科技开发有限公司 | Fluorine-containing surfactant, application and preparation method thereof, and fire extinguishing agent comprising fluorine-containing surfactant |
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|---|---|---|---|---|
| US6162869A (en) * | 1999-06-22 | 2000-12-19 | Eastman Chemical Company | Waterborne acrylic polymers containing polymeric fluorescent compounds |
| CN102188781A (en) * | 2011-03-31 | 2011-09-21 | 上海大学 | High-temperature phase-transitional temperature-sensitive fire-extinguishing gel and preparation method thereof |
| CN102351755A (en) * | 2011-08-15 | 2012-02-15 | 华中师范大学 | Fluorine-containing imine cationic surfactant preparation method and application thereof |
| CN103408764A (en) * | 2013-07-15 | 2013-11-27 | 中山大学 | Photo-convertible hyperbranched polymer and preparation method thereof |
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- 2016-07-15 CN CN201610557793.6A patent/CN106215802B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6162869A (en) * | 1999-06-22 | 2000-12-19 | Eastman Chemical Company | Waterborne acrylic polymers containing polymeric fluorescent compounds |
| CN102188781A (en) * | 2011-03-31 | 2011-09-21 | 上海大学 | High-temperature phase-transitional temperature-sensitive fire-extinguishing gel and preparation method thereof |
| CN102351755A (en) * | 2011-08-15 | 2012-02-15 | 华中师范大学 | Fluorine-containing imine cationic surfactant preparation method and application thereof |
| CN103408764A (en) * | 2013-07-15 | 2013-11-27 | 中山大学 | Photo-convertible hyperbranched polymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 全氟己基磺酰类化合物的合成及表面性能;彭历等;《消防科学与技术》;20111015;第30卷(第10期);第938页左栏第1.2-1.3节、第938页右栏-第939页左栏第2.2节和第3节 |
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