CN103432708B - Perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent and preparation method thereof and application - Google Patents
Perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent and preparation method thereof and application Download PDFInfo
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- CN103432708B CN103432708B CN201310429096.9A CN201310429096A CN103432708B CN 103432708 B CN103432708 B CN 103432708B CN 201310429096 A CN201310429096 A CN 201310429096A CN 103432708 B CN103432708 B CN 103432708B
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Abstract
The invention discloses class perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent and preparation method thereof and application.The general structure of this tensio-active agent is such as formula shown in I: wherein, R
1and R
2for-CH
3,-CH
2cH
3, or-CH
2cH
2oH.Be fluorine-containing precursor material with perfluoro hexyl sulfonic acid fluoride, through carrying out sulfonic acid esterification with p-Hydroxybenzylalcohol, carrying out chloro with halogenating agent, carrying out ammonification with secondary amine and be oxidized with hydrogen peroxide, obtain perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent.Amine oxide type tensio-active agent of the present invention is containing the perfluoro capryl class group of lasting organic pollutant feature, and surfactivity is high, and micelle-forming concentration is low, is carried out that the composite aqueous film-forming foam extinguishing agent water-to-film spreading rate obtained is fast, extinguishing property is excellent.
formula I.
Description
Technical field
The present invention relates to tensio-active agent, be specifically related to class perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent and preparation method thereof and application.
Background technology
Fluorochemical surfactant is compared with common tensio-active agent, outstanding performance is " three high two hate ", i.e. high surface, high heat-resistant stability and unreactiveness, i.e. hydrophobic but also hate oil, fluorochemical surfactant, due to the character of its uniqueness, has been widely used at field tools such as oil, fire-fighting, sterilization, papermaking, weaving, clean-out systems.As in oil production, fluorochemical surfactant, due to its low surface tension, can improve oil displacement efficiency; In fire-fighting, fluorochemical surfactant adds in regular foam fire-fighting medium, and blow-off velocity can mention 3-4 doubly, and has good resistance to resume combustion.
The model ylid bloom action power that fluorochemical surfactant has between solvent molecule is little, and easy strong adsorption, in solvent and Air Interface, presents high surfactivity.Because C-F bond energy is higher than c h bond, and due to the shielding effect of fluorine atom, the perfluoroalkyl chain in fluorochemical surfactant molecule has the physical and chemical stability of height.Fluorochemical surfactant particularly containing long perfluoroalkyl chain, has especially outstanding high surface and physical and chemical stability.But; fluorochemical surfactant containing long perfluoroalkyl chain also has the biological metabolism stability of height, remote migrate attribute, high bioconcentration and potential bio-toxicity (NeuroToxicology29 (2008) 160 – 169), causes and pay close attention to widely in environment and ecological protection.The international Convention of Stockholm of such as perfluoro octyl sulfonic acid (PFOS) and derivative Yi Bei thereof is classified as one of lasting organic pollutant (POPs), is restricted and prohibits the use.The Environmental and ecological problems that other the tensio-active agent containing perfluor long alkyl chain brings as the application of Perfluorocaprylic Acid (PFOA) and derivative thereof is also subject to the great attention (Chemosphere, 58 (2005) 1471 – 1496) of people.The environmentally friendly fluorochemical surfactant of Development of Novel, substitutes containing long-chain perfluoroalkyl fluorochemical surfactant, has important economy and social effect.
In recent years, the fluorochemical surfactant research both at home and abroad about substituting PFOS and PFOA has more report.The fluorochemical surfactant of these reports is broadly dassified into: 1) PFPE chain class (H.Horietal./AppliedCatalysisB:Environmental82 (2008) 58 – 66); 2) partially fluorinated long-chain class (JournalofFluorineChemistry130 (2009) 1192-1199); 3) the perfluoroolefine class of collateralization, as hexafluoropropylene trimer class (ColloidsandSurfacesA:Physicochem.Eng.Aspects384 (2011) 331-336); 4) simple perfluorobutyl potassium, perfluoro hexyl potassium sulfonate also can as tensio-active agent; 5) perfluoro butyl of short perfluoroalkyl chain or perfluoro hexyl sulfonic acid fluoride and amino alcohol or polyamines are derived, fluorochemical surfactant (the such as patent: WO2001030873 of the various perfluoro butyl obtained or perfluoro hexyl sulphonamide; US6664354; US7662896); These derivative perfluoro butyls or perfluoro hexyl sulphonamide can embed various polymer further, and preparation has the hydrophobic coated material of anti-soil (such as patent: US8030430; US20100227148).In the fluorochemical surfactant that these have been reported, PFPE surfactivity synthesis technique is complicated, severe reaction conditions; Tensio-active agent containing part alkyl oxide chain, under extreme condition, molecular structure stabilized is poor; Simple fluorochemical surfactant, its surface tension activity is not high, is difficult to meet real requirement.
Perfluoro hexyl sulfonic acid fluoride can obtain by electrofluorination method is convenient.Be fluorine-containing precursor material with perfluoro hexyl sulfonic acid fluoride, the fluorochemical surfactant that design and synthesis is novel substitutes the one effective approach of tradition containing PFOS and PFOA tensio-active agent.Such fluorine-containing surfactants due to its perfluoroalkyl chain shorter, not there is the hazard profile of the lasting organic pollutant of PFOS/PFOA, the use restriction of the international Convention of Stockholm of Bu Shou.But due to the perfluoroalkyl chain that it is shorter, surfactivity is relatively poor, need to carry out molecular designing, improve the surfactivity containing this kind of perfluoroalkyl structural unit compound.
Aqueous film-forming foam extinguishing agent is the new and effective fire foam of a class grown up the beginning of the sixties, and the main ingredient of this kind of fire foam is formulated by fluorocarbon surfactant, hc-surfactant and stablizer, solubility promoter, antifreezing agent and water.When aqueous film-forming foam extinguishing agent being ejected into the pasta of burning, its foam at pasta rapid deployment, can form water membrane, suppresses the evaporation of oil product and isolated air, thus reaches the object putting out oil product burning.The fire foam of current use is mostly containing PFOA/PFOS class fluorochemical surfactant, although effective, large to environmental hazard; Part is not containing the fire foam of this kind of fluorochemical surfactant, and such as, containing fluoridizing albumen in filling a prescription, its extinguishing effect can not reach perfect condition.The fluorine-containing aqueous film-forming foam extinguishing agent of a composite class not containing lasting organic pollutant is very necessary.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming overcoming prior art is with not enough, provides a class perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent.
Another object of the present invention is to the preparation method that above-mentioned perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent is provided.Being fluorine-containing precursor material with perfluoro hexyl sulfonic acid fluoride, through carrying out sulfonic acid esterification, halo, ammonification and oxidation with p-Hydroxybenzylalcohol, preparing perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent.
Another object of the present invention is the application providing above-mentioned perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent.
Object of the present invention is achieved through the following technical solutions:
One class perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent, its general structure is such as formula shown in I:
Wherein: R
1and R
2for-CH
3,-CH
2cH
3or-CH
2cH
2oH.
Preferably, described perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent comprises N, N-dimethyl-4-(perfluoro hexyl sulfonyloxy) benzyl amine oxide (A
1), N, N-diethyl-4-(perfluoro hexyl sulfonyloxy) benzyl amine oxide (A
2), N-methyl-N-hydroxyethyl-4-(perfluoro hexyl sulfonyloxy) benzyl amine oxide (A
3) structural formula is respectively as shown in embodiment Chinese style 1 ~ 3.
The preparation method of above-mentioned perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent, comprises the steps:
(1) p-Hydroxybenzylalcohol is under acid binding agent exists, and with perfluoro hexyl sulfonic acid fluoride generation nucleophilic substitution reaction in solvent, obtains intermediate perfluoro hexyl sulfonic acid-4-(methylol) phenylester (M
1).
(2) perfluoro hexyl sulfonic acid-4-(methylol) phenylester is obtained by reacting intermediate perfluoro hexyl sulfonic acid-4-(monochloromethyl) phenylester (M in solvent with halogenating agent
2).
(3) perfluoro hexyl sulfonic acid-4-(monochloromethyl) phenylester is under acid binding agent exists, and is obtained by reacting intermediate perfluoro hexyl sulfonic acid-4-(N, N-dialkyl amino methyl) phenylester in solvent with secondary amine.
(4) perfluoro hexyl sulfonic acid-4-(N, N-dialkyl amino methyl) phenylester is obtained by reacting perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent in solvent with hydrogen peroxide.
Step (1) and the acid binding agent described in step (3) are preferably salt of wormwood, and described solvent is preferably acetonitrile.
Solvent described in step (2) is preferably acetonitrile or Isosorbide-5-Nitrae-dioxane etc., and described halogenating agent is preferably thionyl chloride or phosphorus tribromide etc.
Secondary amine described in step (3) is preferably dimethylamine, diethylamine or N-Mono Methyl Ethanol Amine, and the intermediate that correspondence obtains is respectively perfluoro hexyl sulfonic acid-4-(N, N-dimethyl aminomethyl) phenylester (M
3), perfluoro hexyl sulfonic acid-4-(N, N-diethylamino methyl) phenylester (M
4), perfluoro hexyl sulfonic acid-4-(N-methyl-N-hydroxyethylaminomethylphosphonic) phenylester (M
5).
Solvent described in step (4) is preferably ethanol or acetonitrile etc.
The application of above-mentioned perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent in aqueous film-forming foam extinguishing agent.A kind of aqueous film-forming foam extinguishing agent, comprises above-mentioned perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent.
The present invention has the following advantages and effect relative to prior art tool:
The perfluoro capryl class group of perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent of the present invention not containing lasting organic pollutant feature, has excellent surfactivity; All amine oxide type tensio-active agent lowest surface tension all reach below 18mN/m, and micelle-forming concentration (CMC) value is 1.0 × 10
-3about mol/L.(lowest surface tension 22mN/m, CMC value is 8.5 × 10 with commercial perfluoro octyl sulfonic acid sodium
-3mol/L) (lowest surface tension 34mN/m, CMC value is 8.7 × 10 for (J.Phys.Chem.C2008,112,16850), sodium laurylsulfonate
-3mol/L) (J.ColloidInterf.Sci.2012,370,102) etc. are compared, and have significant advantage.
Perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent of the present invention is carried out composite, obtains aqueous film-forming foam extinguishing agent, there is water-to-film spreading rate fast, the feature of extinguishing property excellence.
Accompanying drawing explanation
Fig. 1 is intermediate (M
1~ M
5) synthetic route schematic diagram.
Embodiment
Below in conjunction with embodiment and accompanying drawing, further detailed description is done to the present invention, but embodiments of the present invention are not limited thereto.
Intermediate (M
1~ M
5) synthetic route as shown in Figure 1.
Embodiment 1 intermediate (M
1) preparation
12.4g (0.1mol) p-Hydroxybenzylalcohol is added in the 250mL flask of drying, 17.9g (0.13mol) salt of wormwood, 200mL acetonitrile, reflux, slow dropping 65.3g (0.13mol) perfluoro hexyl sulfonic acid fluoride, continue reaction 0.5h, TLC and monitor reaction end.In reaction solution, add 150mL ethyl acetate, wash 3 times with saturated nacl aqueous solution, organic over anhydrous dried over sodium sulfate, precipitation, obtain colourless liquid intermediate perfluoro hexyl sulfonic acid-4-(methylol) phenylester (M
1), 44.53g, yield is 84%.
1hNMR (400MHz, CDCl
3): δ 2.50 (s, 1H, OH), 4.61 (s, 2H, CH
2), 6.89 (d, 2H, J=7.8Hz, phH), 7.33 (d, 2H, J=7.8Hz, phH);
19fNMR (376MHz, CDCl
3): δ-126.494 (2F) ,-123.057 (2F) ,-122.182 (2F) ,-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); MS (EI): 506.03 (M
+) (calculated value: 505.99).
Embodiment 2 intermediate (M
2) preparation
55.6g (0.11mol) perfluoro hexyl sulfonic acid-4-(methylol) phenylester (M is added in the 1000mL flask of drying
1), 200mL1,4-dioxane, slowly drips 19.47g (0.165mol) thionyl chloride under ice bath, drip off rear reaction 30min, is warmed up to 60 DEG C and continues reaction 1.0h, TLC monitoring reaction end.Slowly pour in frozen water, add 200mL ethyl acetate, wash three times with saturated nacl aqueous solution, organic over anhydrous dried over sodium sulfate, precipitation, obtain colourless liquid intermediate perfluoro hexyl sulfonic acid-4-(chloromethyl) phenylester (M
2) 45.0g, yield is 78%.
1hNMR (400MHz, CDCl
3): δ 3.42 (s, 2H, CH
2), 7.22 (d, 2H, J=3.9Hz, phH), 7.41 (d, 2H, J=4.2Hz, phH);
19fNMR (376MHz, CDCl
3): δ-126.494 (2F) ,-123.057 (2F) ,-122.182 (2F) ,-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); MS (EI): 524.02 (M
+) (calculated value: 523.95).
Embodiment 2 intermediate (M
3 ~ 5) preparation
6.36g (0.015mol) perfluoro hexyl sulfonic acid-4-(chloromethyl) phenylester (M is added in the 250mL flask of drying
2), 8.4g (0.06mol) salt of wormwood, 1.46g (0.018mol) dimethylamine hydrochloride, 100mL acetonitrile, 70 ~ 80 DEG C of reaction 2.0h, TLC monitorings, reaction terminates.In reaction solution, add 200mL ethyl acetate, wash three times with saturated nacl aqueous solution, organic over anhydrous dried over sodium sulfate, precipitation, obtain colourless liquid intermediate perfluoro hexyl sulfonic acid-4-(N, N-dimethyl aminomethyl) phenylester (M
3) 5.85g, yield is 75%.
1hNMR (400MHz, CDCl
3): δ 3.07 (s, 6H, CH
3), 4.66 (s, 2H, CH
2), 7.69 (d, 2H, J=8.8Hz, phH), 7.79 (d, 2H, J=8.8Hz, phH);
19fNMR (376MHz, CDCl
3): δ-126.494 (2F) ,-123.057 (2F) ,-122.182 (2F) ,-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); MS (EI): 533.04 (M
+) (calculated value: 533.03).
6.36g (0.015mol) perfluoro hexyl sulfonic acid-4-(chloromethyl) phenylester (M is added in the 250mL flask of drying
2), 8.4g (0.06mol) salt of wormwood, 1.31g (0.018mol) diethylamide, 100mL acetonitrile, 70 ~ 80 DEG C of reaction 2.0h, TLC monitorings, reaction terminates.In reaction solution, add 200mL ethyl acetate, wash three times with saturated nacl aqueous solution, organic over anhydrous dried over sodium sulfate, precipitation, obtain colourless liquid intermediate perfluoro hexyl sulfonic acid-4-(N, N-diethylamino methyl) phenylester (M
4) 5.75g, yield is 75%.
1hNMR (400MHz, CDCl
3): δ 1.02 (t, 6H, J=7.2Hz, CH
3,), 2.48 (q, 4H, J=13.6Hz, CH
2), 3.53 (d, 2H, J=12HzCH
2), 7.20 (t, 2H, J=8.0Hz, phH), 7.38 (t, 2H, J=12.0Hz, phH);
19fNMR (376MHz, CDCl
3): δ-126.494 (2F) ,-123.057 (2F) ,-122.182 (2F) ,-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); MS (EI): 524.02 (M
+) (calculated value: 523.95).
6.36g (0.015mol) perfluoro hexyl sulfonic acid-4-(chloromethyl) phenylester (M is added in the 250mL flask of drying
2), 8.4g (0.06mol) salt of wormwood, 1.098g (0.018mol) N-Mono Methyl Ethanol Amine, 100mL acetonitrile, 70 ~ 80 DEG C of reaction 2.5h, TLC monitorings, reaction terminates.In reaction solution, add 200mL ethyl acetate, wash three times with saturated nacl aqueous solution, organic over anhydrous dried over sodium sulfate, precipitation, obtain colourless liquid intermediate perfluoro hexyl sulfonic acid-4-(N-methyl-N-hydroxyethylaminomethylphosphonic) phenylester (M
5) 5.59g, yield is 75%.
1hNMR (400MHz, CDCl
3): δ 2.22 (s, 3H, CH
3), 2.60 (t, 3H, J=5.6Hz, CH
3), 3.58 (q, 2H, J=8.0Hz, CH
2), 7.23 (d, 2H, J=8.4Hz, phH), 7.38 (d, 2H, J=8.4Hz, phH);
19fNMR (376MHz, CDCl
3): δ-126.494 (2F) ,-123.057 (2F) ,-122.182 (2F) ,-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); MS (EI): 564.2 (M
+) (calculated value: 563.33).
Embodiment 3N, N-dimethyl-4-(perfluoro hexyl sulfonyloxy) benzyl amine oxide (A
1) synthesis
7.9g (0.015mol) perfluoro hexyl sulfonic acid-4-(N, N-dimethyl aminomethyl) phenylester (M is added in the 250mL flask of drying
3), the hydrogen peroxide of 3.4g (0.03mol) 30% (mass concentration), 150mL dehydrated alcohol, 80 DEG C of reactions are spent the night, and steam solvent, gained solid washed with ether three times, and finally obtaining white solid is target compound (A
1), 7.82g, yield is 95%.
1hNMR (400MHz, DMSO): δ 2.96 (s, 6H, N (CH
3)
2), 4.34 (s, 2H, CH
2), 7.51 (d, 2H, J=7.2Hz, phH), 7.77 (d, 2H, J=8.4Hz, phH);
19fNMR (376MHz, DMSO): δ-126.494 (2F) ,-123.057 (2F),-122.182 (2F),-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); HPLC/MS (ESI): 550.3 (M
+) (calculated value: 550.03).
Embodiment 4N, N-diethyl-4-(perfluoro hexyl sulfonyloxy) benzyl amine oxide (A
2) synthesis
8.4g (0.015mol) perfluoro hexyl sulfonic acid-4-(N, N-diethylamino methyl) phenylester (M is added in the 250mL flask of drying
4), the hydrogen peroxide of 3.4g (0.03mol) 30%, 150mL dehydrated alcohol, 80 DEG C of reactions are spent the night, and steam solvent, gained solid washed with ether three times, and finally obtaining white solid is target compound (A
2), 7.77g, yield is 93%.
1hNMR (400MHz, DMSO): δ 3.13 (s, 6H, CH
3), 3.94 (d, 4H, J=3.6Hz, CH
2), 4.72 (s, 2H, CH
2), 7.67 (d, 2H, J=8.4Hz, phH), 7.82 (d, 2H, J=8.8Hz, phH);
19fNMR (376MHz, DMSO): δ-126.494 (2F) ,-123.057 (2F),-122.182 (2F),-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); HPLC/MS (ESI): 578.2 (M
+) (calculated value: 578.06).
Embodiment 5N-methyl-N-hydroxyethyl-4-(perfluoro hexyl sulfonyloxy) benzyl amine oxide (A
3) synthesis
8.4g (0.015mol) perfluoro hexyl sulfonic acid-4-(N-methyl-N-hydroxyethylaminomethylphosphonic) phenylester (M is added in the 250mL flask of drying
5), the hydrogen peroxide of 3.4g (0.03mol) 30%, 150mL dehydrated alcohol, 80 DEG C of reactions are spent the night, and steam solvent, gained solid washed with ether three times, and finally obtaining white solid is target compound (A
3), 7.81g, yield is 90%.
1hNMR (400MHz, DMSO): δ 2.99 (s, 3H, CH
3), 3.36 (d, 2H, J=8.4Hz, CH
2), 3.91 (d, 2H, J=7.6HzCH
2), 4.51 (s, 2H, CH
2), 5.25 (s, 1H, OH), 7.53 (d, 2H, J=6.4Hz, phH), 7.75 (d, 2H, J=6.8Hz, phH);
19fNMR (376MHz, DMSO): δ-126.494 (2F) ,-123.057 (2F),-122.182 (2F),-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); HPLC/MS (ESI): 580.2 (M
+) (calculated value: 580.4).
The test of embodiment 6 surface tension and micelle-forming concentration (CMC)
Get a certain amount of the said products (perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent), the solution that amount of substance mark is 5/1000mol/L is made into respectively with distilled water, place 5h, after solution-stabilized, it be diluted to successively concentration be 4/1000,3/1000,2/1000,1/1000,8/10000,5/10000,3/10000,1/10000,8/100000,5/100000,3/100000, the solution of 1/100000mol/L, carry out capillary mensuration (suspension ring method), to determine its surface tension.Measured by 25 DEG C, experimental data is as shown in table 1.
Table 1. perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent lowest surface tension and micelle-forming concentration
| Product designation | Lowest surface tension (mN/m) | CMC(mol/L) |
| A 1 | 16.4 | 1.09×10 -3 |
| A 2 | 17.6 | 8.68×10 -4 |
| A 3 | 16.8 | 9.92×10 -4 |
The preparation of embodiment 7 aqueous film-forming foam extinguishing agent
The typical composite parameter of table 2. aqueous film-forming foam extinguishing agent
| 3% aqueous film-forming foam extinguishing agent concentrated solution | 100g |
| Perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent | 3g |
| Amphoterics (CAB-35) | 15g |
| Sodium octyl | 2.5g |
| Xanthan gum | 1g |
| Urea | 30g |
| Frostproofer | 1.5g |
| Frothing aid | 3g |
| Anticorrosive additive | 0.1g |
| Alkyl glycoside | 1g |
| Corrosion resistant agent | 0.5g |
| Sequestrant | 0.5g |
| Water | 41.9g |
According to the typical composite parameter of table 2 aqueous film-forming foam extinguishing agent (reference literature: FireScienceandTechnology30 (2011), 825-828), with perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent (A prepared by embodiment 4 ~ 6
1~ A
3) preparation fire-fighting medium, wherein frostproofer can be: ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol or hexylene glycol; Frothing aid can be ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether or Dipropylene glycol mono-n-butyl Ether; Corrosion resistant agent can be benzotriazole; Sequestrant: EDTA, Trisodium Citrate or sodium tartrate.
Embodiment 8 aqueous film-forming foam extinguishing agent technical parameters and performance
That prepares according to table 2 contains arbitrary perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent (A
1~ A
3) fire foam, reference literature (ChemicalResearchandApplication20 (2008) 569-572) carries out extinguishing property test.Fire-extinguishing test step is: in 500mL beaker, add 100mL hexanaphthene, lights afterfire 5 minutes; The strong solution prepared by table 2, according to mass ratio 3: 100 dilute with water, is got 10mL fire foam after being blown into air foaming in 1 minute and is added just in the beaker of fire ring hexane, observe fiery extinguishing situation.The result of fire-extinguishing test shows that the fire foam obtained has excellent water-to-film spreading rate and extinguishing property.Test with reference to the technical indicator of GB15308-2006 to fire foam, result is as shown in table 3.
Table 3. aqueous film-forming foam extinguishing agent technical indicator
| Surface tension (mN/m) | 17-19 |
| Hexanaphthene interfacial tension (mN/m) | 2.3 |
| Frost resistance, melting | Without visible delamination and heterogeneous |
| PH value | 7.5-8.1 |
| Hexanaphthene is sprawled the time (S) | ＜0.5 |
| Foam expansion | 7.5-8 |
| 25% drainage time 20 DEG C (min) | 8-9 |
| Stability test | Long-term without considerable change |
| Anti-hard water test | Character is without considerable change |
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a class perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent, is characterized in that general structure is such as formula shown in I:
Wherein: R
1and R
2for-CH
3,-CH
2cH
3or-CH
2cH
2oH.
2. perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent according to claim 1, it is characterized in that: described perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent comprises N, N-dimethyl-4-(perfluoro hexyl sulfonyloxy) benzyl amine oxide, N, N-diethyl-4-(perfluoro hexyl sulphonyl oxygen) benzyl amine oxide, N-methyl-N-hydroxyethyl-4-(perfluoro hexyl sulfonyloxy) benzyl amine oxide.
3. the preparation method of the perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent described in claim 1 or 2, is characterized in that comprising the steps:
(1) p-Hydroxybenzylalcohol is under acid binding agent exists, and with perfluoro hexyl sulfonic acid fluoride generation nucleophilic substitution reaction in solvent, obtains intermediate perfluoro hexyl sulfonic acid-4-(methylol) phenylester;
(2) perfluoro hexyl sulfonic acid-4-(methylol) phenylester is obtained by reacting intermediate perfluoro hexyl sulfonic acid-4-(monochloromethyl) phenylester in solvent with halogenating agent;
(3) perfluoro hexyl sulfonic acid-4-(monochloromethyl) phenylester is under acid binding agent exists, and is obtained by reacting intermediate perfluoro hexyl sulfonic acid-4-(N, N-dialkyl amino methyl) phenylester in solvent with secondary amine;
(4) perfluoro hexyl sulfonic acid-4-(N, N-dialkyl amino methyl) phenylester is obtained by reacting perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent in solvent with hydrogen peroxide.
4. the preparation method of perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent according to claim 3, is characterized in that reaction conditions is:
Step (1) and the acid binding agent described in step (3) are salt of wormwood, and described solvent is acetonitrile;
Solvent described in step (2) is acetonitrile or Isosorbide-5-Nitrae-dioxane;
Solvent described in step (4) is ethanol or acetonitrile.
5. the preparation method of perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent according to claim 3, is characterized in that reaction raw materials is:
Halogenating agent described in step (2) is thionyl chloride or phosphorus tribromide;
Secondary amine described in step (3) is dimethylamine, diethylamine or N-Mono Methyl Ethanol Amine, the intermediate that correspondence obtains is respectively perfluoro hexyl sulfonic acid-4-(N, N-dimethyl aminomethyl) phenylester, perfluoro hexyl sulfonic acid-4-(N, N-diethylamino methyl) phenylester, perfluoro hexyl sulfonic acid-4-(N-methyl-N-hydroxyethylaminomethylphosphonic) phenylester.
6. the application of perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent in aqueous film-forming foam extinguishing agent described in claim 1 or 2.
7. an aqueous film-forming foam extinguishing agent, is characterized in that: comprise the perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent described in claim 1 or 2.
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| CN201310429096.9A CN103432708B (en) | 2013-09-18 | 2013-09-18 | Perfluoro hexyl sulfonyloxy benzyl amine oxide type tensio-active agent and preparation method thereof and application |
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| CN103432708B true CN103432708B (en) | 2016-03-30 |
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| CN102489216A (en) * | 2011-12-06 | 2012-06-13 | 华中师范大学 | Preparation method and application of amphoteric fluorinion-containing ionic surfactant |
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| JPS55157691A (en) * | 1979-05-29 | 1980-12-08 | Sanyo Chemical Ind Ltd | Fluorine surfactant |
| US6323367B1 (en) * | 2000-11-22 | 2001-11-27 | Council Of Scientific And Industrial Research | Process for the preparation of amine oxides |
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| CN102500087A (en) * | 2011-10-24 | 2012-06-20 | 徐衡 | Method for preparing perfluorohexane surfactant serving as main agent of aqueous film-forming extinguishing agent directly |
| CN102489216A (en) * | 2011-12-06 | 2012-06-13 | 华中师范大学 | Preparation method and application of amphoteric fluorinion-containing ionic surfactant |
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