CN113559783B - Fluorocarbon surfactant and preparation method and application thereof - Google Patents
Fluorocarbon surfactant and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorocarbon surfactant, a preparation method and application thereof, and belongs to the technical field of high polymer materials. The fluorocarbon surfactant is a symmetrical structure with hydrocarbon chain carboxylic acid groups at two ends and a fluorocarbon chain in the middle, and has a structural formula of R-R F -R, wherein R F Is a perfluoroalkyl chain: CF 2 ‑(CF 2 ) n ‑CF 2 N =4, 6; r is a tertiary amine end chain containing a hydroxyl structure: -CH = CH-C (CH3) (OH) -CH 2 ‑N + (CH 2 COO ‑ )～R 1 R 2 ，R 1 =～CH 3 ，R 2 =～CH 3 、～CH 2 CH 2 OH、～CH 2 COONa. The fluorocarbon surfactant has the characteristics of high surface activity, good temperature resistance, good fire extinguishing performance, mild synthesis conditions and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a fluorocarbon surfactant, and preparation and application thereof.
Background
The Fluorocarbon Surfactant (FS) is one of all the known surfactants with the highest surface activity, is used in occasions where the common surfactant is difficult to be qualified due to the special properties (three-high and two-hydrophobic) of the fluorocarbon surfactant which are different from those of the common surfactant, greatly widens the application range of the fluorocarbon surfactant, and is mostly applied to the industries of detergents, fire extinguishing materials, disinfection and sterilization, demisting, agriculture, national defense and the like at present. The characteristic can be particularly shown in the fact that the lowest surface tension (gamma cmc) of the fluorocarbon surfactant aqueous solution is far lower than that of the hydrocarbon surfactant, and in terms of the capability of reducing the surface tension of the liquid, the lowest surface tension of the fluorocarbon surfactant aqueous solution can reach below 20mN/m and even about 15mN/m, while the lowest gamma cmc of the hydrocarbon surfactant can only reach about 30-35 mN/m generally. Due to the outstanding low surface tension of fluorocarbon surfactant, water solution can form water Film on oil surface, isolate oxygen and absorb heat at lower concentration, so that an efficient fire-extinguishing Agent for extinguishing oil fire, namely water Film Forming foam fire-extinguishing Agent (AFFF) is developed. Compared with the defects of single component and small application range of the traditional fire extinguishing agent, the AFFF has various components and is a complex mixture of a solvent (such as glycol ether) and a surfactant (particularly a fluorocarbon surfactant). For B-type fire: the fire extinguishing agent is used for extinguishing fire caused by inflammable liquid or gas (such as petroleum grease, tar and solvent) at four times of the fire extinguishing speed of common fire extinguishing agents, and can effectively inhibit B-type fire.
The currently commercially preferred AFFF product is E500 developed by the national Tai corporation, and the main component of the product is betaine FS F1157N (C15H20F13N2O4S) developed by the U.S. DuPont corporation. At 0.1%, γ cmc is 15.8 mN/m; when the amount of the surfactant was 30s, the foaming number was 330 mL. F1157N main component is fluoro terminal group sulfamide alkyl betaine, the preparation method is that perfluoroalkyl iodide and thiourea are added to generate perfluoroalkyl thio, then S-H end bond is generated by alkali elimination, Cl2 is introduced to generate perfluoroalkyl sulfonic acid chlorine, and finally the perfluoroalkyl terminal group sulfamide alkyl betaine is generated by reaction with dimethylamine under alkaline condition. Although the toxicity of the product is less than that of the traditional PFOS FS, the product can be widely metabolized by the perna canaliculus and the large water chestnut which are mixed in the formula, and the light conversion product is nontoxic and harmless, the production process of the FS is complex, the byproduct Cl2 is greatly polluted, and the production cost is high, so that the breakthrough of the production process is urgently needed.
Disclosure of Invention
The invention aims to provide a fluorocarbon surfactant which has high surface activity, good fire extinguishing performance and convenient manufacture and a preparation method thereof, and can be applied to an aqueous film-forming foam extinguishing agent.
The technical solution of the invention is as follows: the fluorocarbon surfactant has a symmetrical structure with hydrocarbon chain carboxylic acid groups at two ends and perfluoroalkyl chain in the middle, and has the following structure: r to CF 2 -(CF 2 ) n -CF 2 ～R，
Wherein n is 4, 6;
r is a tertiary amine terminal chain containing a hydroxyl structure:
R 1 ＝～CH 3 ，R 2 ＝～CH 3 、～CH 2 CH 2 OH、～CH 2 COONa。
preferably, when n is 6, R 1 ＝～CH 3 ，R 2 ＝～CH 2 CH 2 OH。
The preparation method of the fluorocarbon surfactant comprises the following steps:
(1) performing an addition reaction on the tertiary amine intermediate and 1, 8-perfluoroalkyl iodide to generate a hydrophobic compound with hydrophilic middle at two ends;
(2) a step of subjecting a hydrophilic intermediate hydrophobic compound at two ends and alkali to elimination reaction to generate olefin;
(3) quaternizing olefin and sodium chloroacetate to generate a fluorocarbon surfactant;
preferably, in the step (1), the molar ratio of the 1, 8-perfluoroalkyl iodide to the tertiary amine compound is 1:1, the reaction temperature is 100-120 ℃, and the reaction time is 3-4 h.
Preferably, in the step (2), the alkali is 70% sodium hydroxide aqueous solution, the reaction temperature is 80-90 ℃, the reaction time is 5-6 hours, and the molar ratio of the hydrophilic intermediate hydrophobic compound at two ends to the alkali is 1: 1.
Preferably, in the step (3), the molar ratio of the olefin to the sodium chloroacetate is 1:1, the reaction temperature is 50-60 ℃, and the reaction time is 3-4 hours.
The invention also provides the application of the fluorocarbon surfactant in an aqueous film-forming foam extinguishing agent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the inherent hydrophilic one-end hydrophobic structure of the traditional fluorocarbon surfactant is optimized, the hydrophilic middle hydrophobic structure at two ends is used, the carbon chain is increased, and the surface activity is optimized.
(2) The preparation method is simple and easy to implement and is easy for industrial application. The fluorocarbon surfactant prepared by the method has the advantages of high surface activity, good temperature resistance, good solubility, small dosage, mild synthesis conditions and the like, and can effectively reduce the surface tension of an aqueous solution.
(3) Compared with the preparation method of the PFOA substitute developed at home and abroad at present, the preparation method has the advantages of high process production cost and great environmental pollution, mild reaction conditions and simple preparation flow, optimizes reaction steps on the basis of full feeding, and meets the requirement of green chemistry.
Drawings
FIG. 1 is an infrared plot of the tertiary amine (a) and final product (b) prepared in example 1.
Detailed Description
The solution of the present invention is described in detail below with reference to the accompanying drawings and examples.
In order to obtain the fluorocarbon surfactant which meets the PFOS limit standard and has good spreadability and burning resistance, the invention provides the perfluoro short carbon chain betaine surfactant which is different from the traditional PFOS fluorocarbon surfactant, the FS meets the international standard and has good fire extinguishing and surface activity, the reaction condition of the preparation method is mild, the preparation flow is simple, the reaction step is optimized on the basis of full feeding, and the green chemistry is met.
The innovation points of the invention are as follows: since the surfactant molecules have relatively large lipophilic (hydrophobic) groups, there is a tendency to escape from the water and thus adsorption is easily formed on the surface portion. When the adsorption reaches saturation, i.e. the surface is occupied by oriented surfactant molecules (no more molecules are held), the energy of the system will be minimized in another way, i.e. association in water to form ordered assemblies of molecules, micelles, and the lowest concentration at which surfactant molecules in solution produce micelles is called the critical micelle concentration (cmc) of the surfactant. It has been shown that as the carbon chain of the surfactant increases, its cmc decreases, i.e., increasing the carbon chain length of the surfactant decreases the concentration of surfactant required to produce surfactant activity. In contrast, the surfactant with longer carbon chain at the same concentration has higher surface activity, so that the surfactant with longer carbon chain provided by the invention has higher surface activity than the conventional surfactant.
Example 1:
fluorocarbon surfactant:
in a four-necked flask equipped with a condenser and a magnetic stirrer, N-methyl monoethanolamine was added: 15g, heating to 60 ℃ with stirring, introducing nitrogen, and dropwise adding isoprene monoxide within 0.5 h: 17g, reacting for 2 hours to generate an epoxy cured product; azobisisobutyronitrile (X-25) was added with stirring: 4.5g, sodium metabisulfite (NJ): 6.1g, hexanediol (EC): 30g, and dropwise adding 1, 8-diiodoperfluorooctane in 0.5 h: 91.5g, and reacting for 3 hours at 120 ℃ to generate an addition product; then, 70% sodium hydroxide aqueous solution was added dropwise over 0.5 h: 37.5g, and reacting for 5 hours at 90 ℃ to generate an elimination product; finally, sodium chloroacetate aqueous solution (LV) was added: 71.6g, reacting for 3h at 50 ℃ to generate the fluorocarbon surfactant.
Nuclear magnetic data are as follows 1 HNMR: theoretical δ (CDCl 3): 5.31, 5.43(1H), 6.07(2H), 4.04(3H), 3.63, 3.38(5H), 3.75(6H), 2.62, 2.37(7H), 2.26(10H), 3.47(11H),5.37 (9H); as can be seen from the actual 1HNMR, δ (CDCl 3): 5.27, 5.28(1H), 6.07(2H), 4.03(3H), 3.64, 3.39(5H), 3.75(6H), 2.62, 2.36(7H), 2.26(10H), 3.36(11H),5.3 (9H).
Its infrared spectrum is shown in figure 1, and figure 1a, 1646.88cm-1 is the absorption peak of-C ═ C-H double bond, 3421.91cm -1 An absorption peak of-OH hydroxyl group at 761.12cm -1 Absorption peak of tertiary amine, and carboxylic acid group at 1252.82cm -1 、1337cm -1 And (4) judging that a tertiary amine intermediate is successfully formed by having absorption peaks at equal positions. FIG. 1b, curve at 1580cm -1 The almost no infrared absorption is a smooth curve, which shows that the precursor has almost no carbon-carbon double bond and has been completely reacted, and the reaction is successfully carried out by combining nuclear magnetic data.
Surface activity: preparing 0.1% aqueous solution of fluorocarbon surfactant, and measuring surface tension and foaming ratio in BZY-2 full-automatic meter/interfacial tensiometer and Roche foam meter, wherein the data are shown in Table 1.
The fire extinguishing effect is as follows: according to a certain formula, the fluorocarbon surfactant is prepared into 3% AFFF (aqueous film-forming foam fire-extinguishing agent) aqueous solution, and the size of the oil pan is 0.25m 2 And the fuel is 120# solvent oil, the application mode is strong application, the application time is 1.5min, and the fire extinguishing performance parameters such as liquid separation time, fire control time, fire extinguishing time and the like are respectively measured, and the data are shown in table 2.
Example 2:
fluorocarbon surfactant:
in a four-necked flask equipped with a condenser and a magnetic stirrer, dimethylamine: 8.1g, heated to 60 ℃ with stirring, nitrogen was bubbled in, and isoprene monoxide was added dropwise over 0.5 h: 17g, reacting for 2 hours to generate an epoxy cured product; the azobisisobutyronitrile was added with stirring: 4.5g, sodium metabisulfite: 6.1g, hexanediol: 30g, and dropwise adding 1, 8-diiodoperfluorooctane in 0.5 h: 91.5g, and reacting for 3 hours at 120 ℃ to generate an addition product; then, 70% sodium hydroxide aqueous solution was added dropwise over 0.5 h: 37.5g, and reacting for 5 hours at 90 ℃ to generate an elimination product; finally adding sodium chloroacetate aqueous solution: 71.6g, reacting for 3h at 50 ℃ to generate the fluorocarbon surfactant.
Nuclear magnetic data are as follows 1 HNMR: theoretical δ (CDCl 3): 5.29, 5.25(1H), 6.15(2H), 4.26(3H), 3.35, 3.38(5H), 3.89(6H),; as can be seen from the actual 1HNMR, δ (CDCl 3): 5.27, 5.28(1H), 6.18(2H), 4.26(3H), 3.35, 3.39(5H), 3.90 (6H). The reaction was successfully performed as indicated by the infrared data.
Surface activity: preparing 0.1% aqueous solution of fluorocarbon surfactant, and measuring surface tension and foaming ratio in BZY-2 full-automatic meter/interfacial tensiometer and Roche foam meter, wherein the data are shown in Table 1.
The fire extinguishing effect is as follows: according to a certain formula, the fluorocarbon surfactant is prepared into 3% AFFF (aqueous film-forming foam fire-extinguishing agent) aqueous solution, and the size of the oil pan is 0.25m 2 And the fuel is 120# solvent oil, the application mode is strong application, the application time is 1.5min, and the fire extinguishing performance parameters such as liquid separation time, fire control time, fire extinguishing time and the like are respectively measured, and the data are shown in table 2.
Example 3:
fluorocarbon surfactant:
in a four-neck flask equipped with a condenser and a magnetic stirrer, 40% aqueous sodium sarcosinate solution: 50g, heating to 60 ℃ with stirring, introducing nitrogen, and dropwise adding isoprene monoxide within 0.5 h: 17g, reacting for 2 hours to generate an epoxy cured product; the azobisisobutyronitrile was added with stirring: 4.5g, sodium metabisulfite: 6.1g, hexanediol: 30g, and dropwise adding 1, 8-diiodoperfluorooctane in 0.5 h: 91.5g, and reacting for 3 hours at 120 ℃ to generate an addition product; then, 70% sodium hydroxide aqueous solution was added dropwise over 0.5 h: 37.5g, and reacting for 5 hours at 90 ℃ to generate an elimination product; finally adding sodium chloroacetate aqueous solution: 71.6g, and reacting for 3 hours at 50 ℃ to generate the fluorocarbon surfactant.
Nuclear magnetic data are as follows 1 HNMR: theoretical δ (CDCl 3): 5.48, 5.43(1H), 6.46(2H), 4.45(3H), 3.22, 3.11(5H), 3.90(6H), 2.26, 2.37(7H), 5.69 (9H); as known from the actual 1HNMR, δ (CDCl 3): 5.47, 5.42(1H), 6.45(2H), 4.44(3H), 3.22, 3.11(5H), 3.90(6H), 2.26, 2.36(7H), 5.68(9H), combined with infrared data, indicate that the reaction was successful.
Surface activity: preparing 0.1 percent aqueous solution of the fluorocarbon surfactant, and respectively measuring the surface tension and the foaming times in a BZY-2 full-automatic surface/interface tensiometer and a Roche foam meter, wherein the data are shown in Table 1.
The fire extinguishing effect is as follows: according to a certain formula, the fluorocarbon surfactant is prepared into 3% AFFF (aqueous film-forming foam fire-extinguishing agent) aqueous solution, and the size of the oil pan is 0.25m 2 And the fuel is 120# solvent oil, the application mode is strong application, the application time is 1.5min, and the fire extinguishing performance parameters such as liquid separation time, fire control time, fire extinguishing time and the like are respectively measured, and the data are shown in table 2.
Example 4:
fluorocarbon surfactant:
in a four-necked flask equipped with a condenser and a magnetic stirrer, N-methyl monoethanolamine was added: 15g, heating to 60 ℃ with stirring, introducing nitrogen, and dropwise adding isoprene monoxide within 0.5 h: 17g, reacting for 2 hours to generate an epoxy cured product; the azobisisobutyronitrile was added with stirring: 4.5g, sodium metabisulfite: 6.1g, hexanediol: 30g, and 1, 6-diiodoperfluorohexane was added dropwise over 0.5 h: 77.5g, and reacting for 3 hours at 120 ℃ to generate an addition product; then, 70% sodium hydroxide aqueous solution was added dropwise over 0.5 h: 37.5g, and reacting for 5 hours at 90 ℃ to generate an elimination product; finally adding sodium chloroacetate aqueous solution: 71.6g, reacting for 3h at 50 ℃ to generate the fluorocarbon surfactant.
Nuclear magnetic data are as follows 1 HNMR: theoretical δ (CDCl 3): 5.56, 5.76(1H), 6.24(2H), 4.04(3H), 3.63, 3.38(5H), 3.89(6H), 2.53, 2.40(7H), 2.25(10H), 5.45 (9H); as known from the actual 1HNMR, δ (CDCl 3): 5.57, 5.76(1H), 6.25(2H), 4.03(3H), 3.64, 3.39(5H), 3.89(6H), 2.53, 2.41(7H), 2.26(10H), 5.46(9H), and infrared data are combined to indicate that the reaction is successfully carried out.
Surface activity: preparing 0.1 percent aqueous solution of the fluorocarbon surfactant, and respectively measuring the surface tension and the foaming times in a BZY-2 full-automatic surface/interface tensiometer and a Roche foam meter, wherein the data are shown in Table 1.
The fire extinguishing effect is as follows: according to a certain formula, the fluorocarbon surfactant is prepared into 3% AFFF (aqueous film-forming foam fire-extinguishing agent) aqueous solution, and the size of the oil pan is 0.25m 2 And the fuel is 120# solvent oil, the application mode is strong application, the application time is 1.5min, and the fire extinguishing performance parameters such as liquid separation time, fire control time, fire extinguishing time and the like are respectively measured, and the data are shown in table 2.
Comparative example 1:
fluorocarbon surfactant:
adding N-methyl monoethanolamine into a four-neck flask provided with a condenser pipe and a magnetic stirrer: 15g, heating to 60 ℃ with stirring, introducing nitrogen, and dropwise adding isoprene monoxide within 0.5 h: 17g, reacting for 2 hours to generate an epoxy cured product; the azobisisobutyronitrile was added with stirring: 4.5g, sodium metabisulfite: 6.1g, hexanediol: 30g, and adding perfluorooctyl iodide dropwise in 0.5 h: 71.8g, and reacting for 3 hours at 120 ℃ to generate an addition product; then, 70% sodium hydroxide aqueous solution was added dropwise over 0.5 h: 37.5g, and reacting for 5 hours at 90 ℃ to generate an elimination product; finally adding sodium chloroacetate aqueous solution: 71.6g, reacting for 3h at 50 ℃ to generate the fluorocarbon surfactant.
Surface activity: preparing 0.1 percent aqueous solution of the fluorocarbon surfactant, and respectively measuring the surface tension and the foaming times in a BZY-2 full-automatic surface/interface tensiometer and a Roche foam meter, wherein the data are shown in Table 1.
Fire extinguishing effectAnd (4) fruit: according to a certain formula, the fluorocarbon surfactant is prepared into 3% AFFF (aqueous film-forming foam fire-extinguishing agent) aqueous solution, and the size of the oil pan is 0.25m 2 And the fuel is 120# solvent oil, the application mode is strong application, the application time is 1.5min, and the fire extinguishing performance parameters such as liquid separation time, fire control time, fire extinguishing time and the like are respectively measured, and the data are shown in table 2.
Comparative example 2:
fluorocarbon surfactant:
in a four-necked flask equipped with a condenser and a magnetic stirrer, dimethylamine: 8.1g, warm to 60 ℃ with stirring, introduce nitrogen, add dropwise isoprene monoxide over 0.5 h: 17g, reacting for 2 hours to generate an epoxy cured product; the azobisisobutyronitrile was added with stirring: 4.5g, sodium metabisulfite: 6.1g, hexanediol: 30g, and adding perfluorooctyl iodide dropwise in 0.5 h: 71.8g, and reacting for 3 hours at 120 ℃ to generate an addition product; then, 70% sodium hydroxide aqueous solution was added dropwise over 0.5 h: 37.5g, and reacting for 5 hours at 90 ℃ to generate an elimination product; finally adding sodium chloroacetate aqueous solution: 71.6g, and reacting for 3 hours at 50 ℃ to generate the fluorocarbon surfactant.
Surface activity: preparing 0.1 percent aqueous solution of the fluorocarbon surfactant, and respectively measuring the surface tension and the foaming times in a BZY-2 full-automatic surface/interface tensiometer and a Roche foam meter, wherein the data are shown in Table 1.
The fire extinguishing effect is as follows: according to a certain formula, the fluorocarbon surfactant is prepared into 3% AFFF (aqueous film-forming foam fire-extinguishing agent) aqueous solution, and the size of the oil pan is 0.25m 2 The fuel is 120# solvent oil, the application mode is strong application, the application time is 1.5min, and the fire extinguishing performance parameters such as liquid separation time, fire control time, fire extinguishing time and the like are respectively measured, and the data are shown in the table 2.
Comparative example 3:
fluorocarbon surfactant:
in a four-neck flask equipped with a condenser and a magnetic stirrer, 40% aqueous solution of sodium sarcosinate: 50g, heating to 60 ℃ with stirring, introducing nitrogen, and dropwise adding isoprene monoxide within 0.5 h: 17g, reacting for 2 hours to generate an epoxy cured product; the azobisisobutyronitrile was added with stirring: 4.5g, sodium metabisulfite: 6.1g, hexanediol: 30g, and adding perfluorooctyl iodide dropwise in 0.5 h: 71.8g, and reacting for 3 hours at 120 ℃ to generate an addition product; then, 70% sodium hydroxide aqueous solution was added dropwise over 0.5 h: 37.5g, and reacting for 5 hours at 90 ℃ to generate an elimination product; finally adding sodium chloroacetate aqueous solution: 71.6g, reacting for 3h at 50 ℃ to generate the fluorocarbon surfactant.
Surface activity: preparing 0.1 percent aqueous solution of the fluorocarbon surfactant, and respectively measuring the surface tension and the foaming times in a BZY-2 full-automatic surface/interface tensiometer and a Roche foam meter, wherein the data are shown in Table 1.
The fire extinguishing effect is as follows: according to a certain formula, the fluorocarbon surfactant is prepared into 3% AFFF (aqueous film-forming foam fire-extinguishing agent) aqueous solution, and the size of the oil pan is 0.25m 2 The fuel is 120# solvent oil, the application mode is strong application, the application time is 1.5min, and the fire extinguishing performance parameters such as liquid separation time, fire control time, fire extinguishing time and the like are respectively measured, and the data are shown in the table 2.
Comparative example 4:
fluorocarbon surfactant:
in a four-neck flask equipped with a condenser and a magnetic stirrer, 40% aqueous sodium sarcosinate solution: 50g, warm to 60 ℃ with stirring, introduce nitrogen and add dropwise the allyl glycidyl ether: 26g, reacting for 2 hours to generate an epoxy cured product; the azobisisobutyronitrile was added with stirring: 4.5g, sodium metabisulfite: 6.1g, hexanediol: 30g, and adding perfluorooctyl iodide dropwise in 0.5 h: 71.8g, and reacting for 3 hours at 120 ℃ to generate an addition product; then, 70% sodium hydroxide aqueous solution was added dropwise over 0.5 h: 37.5g, and reacting for 5 hours at 90 ℃ to generate an elimination product; finally adding sodium chloroacetate aqueous solution: 71.6g, reacting for 3h at 50 ℃ to generate the fluorocarbon surfactant.
Surface activity: preparing 0.1 percent aqueous solution of the fluorocarbon surfactant, and respectively measuring the surface tension and the foaming times in a BZY-2 full-automatic surface/interface tensiometer and a Roche foam meter, wherein the data are shown in Table 1.
The fire extinguishing effect is as follows: according to a certain formula, the fluorocarbon surfactant is prepared into 3% AFFF (aqueous film-forming foam fire-extinguishing agent) aqueous solution, and the size of the oil pan is 0.25m 2 And the fuel is 120# solvent oil, the application mode is strong application, the application time is 1.5min, and the fire extinguishing performance parameters such as liquid separation time, fire control time, fire extinguishing time and the like are respectively measured, and the data are shown in table 2.
Table 1: fluorocarbon surfactant reaction raw material and performance
Table 2: fire extinguishing performance data table for each example and comparative example
In table 1, under the same test conditions, the eight fluorocarbon surfactants have the following sequence: example 1> example 4> comparative example 1> example 3> example 2> comparative example 3, and the expansion ratio is not different, and the comparative example 4 is the leading level at home and abroad, while the surface tension of the invention example 1 is 17mN/m, which is smaller than the international leading level of 18mN/m, which shows that the surface activity of the both-end hydrophilic middle hydrophobic structure designed by the invention is better than the international patent level, and the comparative example 1 and example 4, example 2 and comparative example 2, and example 3 and comparative example 3, on the premise that the end chain structures are consistent, the comparative example shortens the carbon chain, and the surface activity is correspondingly reduced, which shows that the long carbon chain structure proposed by the invention has certain superiority in surface activity.
In table 2, eight fluorocarbon surfactants were analyzed for fire extinguishing performance under the same test conditions, and the analysis found that the fire extinguishing performance sequence of seven fluorocarbon surfactants was as follows: example 1> comparative example 4> comparative example 1> example 3> example 2 ═ comparative example 2> comparative example 3, and example 2, comparative example 2 and comparative example 3 did not meet the international fire extinguishing standard, and the order of fire extinguishing performance agreed with the order of surface activity, further proving the superiority of the long carbon chain structure.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The above-mentioned embodiments of the present invention are only for clearly illustrating the technical solutions and the technical contents of the present invention, and all modifications made according to the present invention are within the scope of the claims of the present invention as long as they do not depart from the scope of the technical solutions of the present invention.
Claims (10)
1. The fluorocarbon surfactant is characterized in that two ends of the fluorocarbon surfactant are respectively hydrocarbon chain carboxylic acid groups, the middle of the fluorocarbon surfactant is a symmetrical structure of perfluoroalkyl chains, and the structure of the fluorocarbon surfactant is as follows: r to CF 2 -(CF 2 ) n -CF 2 ～R，
Wherein n is 4, 6;
r is a tertiary amine terminal chain containing a hydroxyl structure:
R 1 ＝～CH 3 ，R 2 ＝～CH 3 、～CH 2 CH 2 OH、～CH 2 COONa。
2. fluorocarbon surfactant according to claim 1, wherein when n is 6, R is 1 ＝～CH 3 ，R 2 ＝～CH 2 CH 2 OH。
3. A method of preparing a fluorocarbon surfactant as claimed in claim 1 comprising:
(1) performing an addition reaction on the tertiary amine intermediate and 1, 8-perfluoroalkyl iodide to generate a hydrophobic compound with hydrophilic middle at two ends;
(2) a step of subjecting a hydrophilic intermediate hydrophobic compound at two ends and alkali to elimination reaction to generate olefin;
(3) quaternizing olefin and sodium chloroacetate to generate a fluorocarbon surfactant;
4. the method according to claim 3, wherein in the step (1), the molar ratio of the 1, 8-perfluoroalkyl iodide to the tertiary amine compound is 1: 1.
5. The method of claim 3, wherein in the step (1), the reaction temperature is 100 to 120 ℃ and the reaction time is 3 to 4 hours.
6. The method of claim 3, wherein in step (2), the base is a 70% aqueous solution of sodium hydroxide.
7. The method according to claim 3, wherein in the step (2), the reaction temperature is 80-90 ℃, the reaction time is 5-6 h, and the molar ratio of the hydrophilic intermediate hydrophobic compound at two ends to the base is 1: 1.
8. The process of claim 3, wherein in step (3), the molar ratio of olefin to sodium chloroacetate is 1: 1.
9. The method according to claim 3, wherein in the step (3), the reaction temperature is 50-60 ℃ and the reaction time is 3-4 h.
10. Use of a fluorocarbon surfactant as claimed in claim 1 or claim 2 in an aqueous film forming foam fire suppressant.
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