CN103446943A - Gemini perfluoroalkylsulfonyloxybenzyl cationic surfactant as well as preparation and application thereof - Google Patents
Gemini perfluoroalkylsulfonyloxybenzyl cationic surfactant as well as preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a gemini perfluoroalkylsulfonyloxybenzyl cationic surfactant as well as preparation and application thereof. The structural general formula of the surfactant is as shown in a formula I, wherein Rf is perfluorobutylsulfonyl or perfluorohexylsulfonyl; n is 2, 3, 4 or 6; X is a counter anion. The perfluorobutylsulfonyl or the perfluorohexylsulfonyl is a fluorine-containing precursor material; the gemini perfluoroalkylsulfonyloxybenzyl cationic surfactant is obtained through the sulfonation of the fluorine-containing precursor material with p-hydroxybenzylalcohol, chlorination with a halogenating reagent and quaternization with tetramethyl alkyl diamine. The gemini cationic surfactant provided by the invention is free of a perfluorooctyl group with a lasting organic pollutant characteristic, high in surface activity and low in critical micelle concentration; an aqueous film-forming foam fire extinguishing agent obtained by compounding the gemini cationic surfactant with additives is quick in aqueous film-forming spreading speed and excellent in fire extinguishing performance.
Description
Technical field
The present invention relates to surfactant, be specifically related to class double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant and preparation and application thereof.
Background technology
Fluorine-containing surfactant is compared with common surfactant, outstanding performance is " three high two hate ", it is high surface, high heat-resistant stability and chemical inertness, be that hydrophobic is hated again oil, fluorine-containing surfactant, due to its unique character, has purposes widely in fields such as oil, fire-fighting, sterilization, papermaking, weaving, cleaning agents.As in oil exploitation, fluorine-containing surfactant, due to its low surface tension, can improve oil displacement efficiency; In fire-fighting, fluorine-containing surfactant adds in the regular-type foam extinguishing chemical, and blow-off velocity can be mentioned 3-4 doubly, and has good anti-resume combustion.
Fluorine-containing surfactant have and solvent molecule between model ylid bloom action power little, easily strong adsorption, in solvent and Air Interface, presents high surface-active.Due to the C-F bond energy, higher than c h bond, and, due to the shielding action of fluorine atom, the perfluoroalkyl chain in the fluorine-containing surfactant molecule has the physical and chemical stability of height.The fluorine-containing surfactant that particularly contains long perfluoroalkyl chain, have especially outstanding high surface and physical and chemical stability.Yet; the fluorine-containing surfactant that contains long perfluoroalkyl chain also has the biological metabolism stability of height, remote migrate attribute, high bioconcentration and potential bio-toxicity (NeuroToxicology 29 (2008) 160 – 169), pays close attention to causing aspect environment and ecological protection widely.For example the international Convention of Stockholm of perfluoro octyl sulfonic acid (PFOS) and derivative Yi Bei thereof is classified one of lasting organic pollution (POPs) as, is restricted and bans use of.Other the surfactant that contains the perfluor long alkyl chain is as the application of perfluoro caprylic acid (PFOA) and derivative thereof and the Environmental and ecological problems brought also is subject to people's great attention (Chemosphere, 58 (2005) 1471 – 1496).The environmentally friendly fluorine-containing surfactant of Development of Novel, substitute and contain long-chain perfluoroalkyl fluorine-containing surfactant, has important economy and social effect.
In recent years, about the fluorine-containing surfactant research that substitutes PFOS and PFOA, more report is arranged both at home and abroad.The fluorine-containing surfactant rough classification of these reports is: 1) PFPE chain class (H.Hori et al./Applied Catalysis B:Environmental82 (2008) 58 – 66); 2) partially fluorinated long-chain class (Journal of Fluorine Chemistry130 (2009) 1192-1199); 3) the perfluoroolefine class of collateralization, as hexafluoropropylene trimer class (Colloids and Surfaces A:Physicochem.Eng.Aspects384 (2011) 331-336); 4) simple perfluoro butyl potassium sulfonate, perfluoro hexyl potassium sulfonate also can be used as surfactant; 5) perfluoro butyl of short perfluoroalkyl chain or perfluoro hexyl sulfuryl fluoride and amino alcohol or polyamines is derivative, the various perfluoro butyls that obtain or the fluorine-containing surfactant of perfluoro hexyl sulfonamide (patent: WO2001030873 for example; US6664354; US7662896); The perfluoro butyl that these are derivative or perfluoro hexyl sulfonamide can further embed various macromolecules, and preparation has the hydrophobic coating material of anti-soil (patent: US8030430 for example; US20100227148).In the fluorine-containing surfactant of having reported at these, PFPE surface-active synthesis technique complexity, severe reaction conditions; The surfactant that contains part alkyl ether chain, under extreme condition, molecular structure stabilized is poor; Simple fluorine-containing surfactant, its surface tension activity is not high, is difficult to meet real requirement.
The double type surfactant is connected two surfactant monomers, the surfactant of formation.The double type surfactant often more easily adsorbs on gas-liquid interface, show better surface-active (patent is as US7164014B1, US6706923B2, paper is as Journal of Colloid and Interface Science, 379 (2012), 72).
Perfluoro butyl sulfonic acid fluoride and perfluoro hexyl sulfuryl fluoride can obtain by the electrofluorination method is convenient.Take perfluoro butyl sulfonic acid fluoride or perfluoro hexyl sulfuryl fluoride as fluorine-containing precursor material, and the fluorine-containing surfactant of design synthesizing new, be to substitute a kind of effective approach that tradition contains PFOS and PFOA surfactant.Such fluorine-containing surfactants is because its perfluoroalkyl chain is shorter, do not have the use restriction of the international Convention of Stockholm of hazard profile ，Bu Shou of the lasting organic pollution of PFOS/PFOA.Yet, due to its shorter perfluoroalkyl chain, surface-active is relatively poor, need to carry out MOLECULE DESIGN, improve the surface-active containing this class perfluoroalkyl construction 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 key component of this class A foam A extinguishing chemical is formulated by fluorocarbon surfactant, hc-surfactant and stabilizing agent, cosolvent, antifreeze and water.When aqueous film-forming foam extinguishing agent is ejected into to the pasta of burning, its foam can form water membrane at the pasta rapid deployment, suppresses evaporation the isolated air of oil product, thereby reaches the purpose of putting out the oil product burning.The fire foam used at present contains PFOA/PFOS class fluorine-containing surfactant mostly, although effective, large to environmental hazard; Part, containing the fire foam of this class fluorine-containing surfactant, does not for example contain in the formula and fluoridizes albumen, and its fire extinguishing effect can not reach perfect condition.The fluorine-containing aqueous film-forming foam extinguishing agent that a composite class does not contain lasting organic pollution is very necessary.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming that overcomes prior art, with not enough, provides a class double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant.
Another object of the present invention is to provide the preparation method of above-mentioned double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant.Take perfluoro butyl sulfonic acid fluoride, perfluoro hexyl sulfuryl fluoride is fluorine-containing precursor material, through with p-Hydroxybenzylalcohol, carrying out sulfonic acid esterification, halo and quaternized, prepares double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant.
A further object of the present invention is to provide the application of above-mentioned double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant.
Purpose of the present invention is achieved through the following technical solutions:
One class double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant, its general structure is suc as formula shown in I:
Wherein: R
ffor perfluoro butyl sulfonyl, perfluoro hexyl sulfonyl; N is 2,3,4,6; X is to anion, comprises Cl
-, Br
-or I
-deng, can by anion exchange, be also other anion easily.
Preferably, described double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant comprises N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) second-1,2-di-ammonium salts (A
1), N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) second-1,2-di-ammonium salts (A
2), N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) the third-1,3-di-ammonium salts (A
3), N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) the third-1,3-di-ammonium salts (A
4), N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) fourth-Isosorbide-5-Nitrae-di-ammonium salts (A
5), N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) fourth-Isosorbide-5-Nitrae-di-ammonium salts (A
6), N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) oneself-1,6-di-ammonium salts (A
7), N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) oneself-1,6-di-ammonium salts (A
8), structural formula is respectively as shown in specific embodiment Chinese style 1～8.
The preparation method of above-mentioned double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant, comprise the steps:
(1) p-Hydroxybenzylalcohol, under acid binding agent exists, with perfluoroalkyl sulfonyl fluoride generation nucleophilic substitution, obtains intermediate perfluoro alkyl sulfonic acid-4-(methylol) phenylester in solvent;
(2) perfluoro alkyl sulfonic acid-4-(methylol) phenylester reacts with halogenating agent and obtains intermediate perfluoro alkyl sulfonic acid 4-(halomethyl) phenylester in solvent.
(3) perfluoro alkyl sulfonic acid-4-(halomethyl) phenylester reacts with the tetramethyl alkyl diamine and obtains double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant in solvent.
The described acid binding agent of step (1) is preferably potash, and described solvent is preferably acetonitrile.
Solvent described in step (2) is preferably acetonitrile or Isosorbide-5-Nitrae-dioxane, and described halogenating agent is preferably thionyl chloride or phosphorus tribromide etc.
Solvent described in step (3) is preferably acetonitrile, and described tetramethyl alkyl diamine is preferably tetramethylethylenediamine, 4-methyl-diaminopropane, tetramethyl butane diamine or 4-methyl hexamethylene diamine etc.
Preferably, the perfluoroalkyl sulfonyl fluoride described in step (1) is perfluoro butyl sulfonic acid fluoride or perfluoro hexyl sulfuryl fluoride, and the halogenating agent described in step (2) is thionyl chloride; Accordingly, the intermediate that step (1) obtains is perfluoro butyl sulfonic acid-4-(methylol) phenylester (M
1) or perfluoro hexyl sulfonic acid-4-(methylol) phenylester (M
2); The intermediate that step (2) obtains is perfluoro butyl sulfonic acid-4-(chloromethyl) phenylester (M
3) and perfluoro hexyl sulfonic acid 4-(chloromethyl) phenylester (M
4).
The application of above-mentioned double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant in aqueous film-forming foam extinguishing agent.A kind of aqueous film-forming foam extinguishing agent, comprise above-mentioned double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant.
The present invention has following advantage and effect with respect to prior art:
It is fluorine-containing precursor material that perfluoro butyl sulfonic acid fluoride and perfluoro hexyl sulfuryl fluoride are take in the present invention, prepare double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant, it does not contain the perfluoro capryl class group of lasting organic pollution feature, surface-active excellence; Part surface activating agent lowest surface tension reaches below 18mN/m, and critical micelle concentration (CMC) is worth 1.0 * 10
-the 3mol/L left and right.With commercial perfluoro octyl sulfonic acid sodium, (lowest surface tension 22mN/m, the CMC value is 8.5 * 10
-3mol/L) (Journal of Physical Chemisty C, 112 (2008), 16850), (lowest surface tension 34mN/m, the CMC value is 8.7 * 10 to dodecyl sodium sulfate
-3mol/L) (Journal of Colloid and Interface Science, 370 (2012), 102) etc. are compared, and have significant advantage.
Double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant of the present invention is carried out composite, obtain aqueous film-forming foam extinguishing agent, there is the MJPZ spreading rate fast, the characteristics of extinguishing property excellence.
The accompanying drawing explanation
Fig. 1 is double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant A
1～A
8synthetic route chart, wherein: R
ffor perfluoro butyl sulfonyl, perfluoro hexyl sulfonyl, n=2,3,4,6.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is done to further detailed description, but embodiments of the present invention are not limited to this.
Double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant A
1～A
8synthetic route chart as shown in Figure 1.
Embodiment 1 intermediate (M
1, M
2) preparation
Add 12.4g(0.1mol in dry 1000mL flask) p-Hydroxybenzylalcohol, 17.9g(0.13mol) potash, 200mL acetonitrile, add hot reflux, slowly drip 52.26g(0.13mol) perfluoro butyl sulfonic acid fluoride, continue reaction 2.5h, TCL monitoring reaction terminal.Add 150mL ethyl acetate in reactant liquor, wash 3 times with saturated nacl aqueous solution, organic layer is through anhydrous sodium sulfate drying, and precipitation, obtain colourless transparent liquid intermediate perfluoro butyl sulfonic acid-4-(methylol) phenylester (M
1), 35.7g, yield is 88%.
1h NMR (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);
19f NMR (376MHz, CDCl
3): δ-128.827 (2F) ,-123.802 (2F) ,-111.125 (2F) ,-84.248 (3F); MS (EI): 406 (M
+) (calculated value: 405.99).
Add 12.4g(0.1mol in the 1000mL there-necked flask) p-Hydroxybenzylalcohol, 17.9g(0.13mol) potash, 200mL acetonitrile, add hot reflux, slowly drip 65.3g(0.13mol) the perfluoro hexyl sulfuryl fluoride, continue reaction 2.5h, TCL monitoring reaction terminal.Add 150mL ethyl acetate in reactant liquor, wash 3 times with saturated nacl aqueous solution, organic layer is through anhydrous sodium sulfate drying, and precipitation, obtain colourless liquid intermediate perfluoro hexyl sulfonic acid-4-(methylol) phenylester (M
2), 44.53g, yield is 84%.
1h NMR (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);
19f NMR (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).
Add 44.66g(0.11mol in dry 1000mL flask) perfluoro butyl sulfonic acid-4-(methylol) phenylester (M
1), 200mL1, the 4-dioxane, slowly drip 38.6g(0.22mol under ice bath) thionyl chloride, drip off rear reaction 30min, be warmed up to 60 ℃ and continue reaction 1h, TLC monitoring reaction terminal.Slowly pour in frozen water, add 200mL ethyl acetate, wash three times with saturated nacl aqueous solution, organic layer is through anhydrous sodium sulfate drying, and precipitation, obtain colourless liquid intermediate perfluoro butyl sulfonic acid-4-(chloromethyl) phenylester (M
3), 37.7g, yield is 81%.
1h NMR (400MHz, CDCl
3): δ 4.56 (s, 2H, CH
2), 6.90 (d, 2H, J=3.9Hz, phH), 7.40 (d, 2H, J=4.2Hz, phH);
19f NMR (376MHz, CDCl
3): δ-128.827 (2F) ,-123.802 (2F) ,-111.125 (2F) ,-84.248 (3F); MS (EI): 424 (M
+) (calculated value: 423.95).
Add 55.6g(0.11mol in dry 1000mL flask) perfluoro hexyl sulfonic acid-4-(methylol) phenylester (M
2), 200mL1, the 4-dioxane, slowly drip 38.6g(0.22mol under ice bath) thionyl chloride, drip off rear reaction 30min, be warmed up to 60 ℃ and continue reaction 1h, TLC monitoring reaction terminal.Slowly pour in frozen water, add 200mL ethyl acetate, wash three times with saturated nacl aqueous solution, organic layer is through anhydrous sodium sulfate drying, and precipitation, obtain colourless liquid intermediate perfluoro hexyl sulfonic acid-4-(chloromethyl) phenylester (M
4) 45.0g, yield is 78%.
1h NMR (400MHz, CDCl
3): δ 4.56 (s, 2H ,-CH
2-), 6.90 (d, 2H, J=3.9Hz, phH), 7.40 (d, 2H, J=4.2Hz, phH);
19f NMR (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 3N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) second-1,2-di-ammonium salts (A
1) synthetic
Add 6.36g(0.015mol in dry 250mL flask) perfluoro butyl sulfonic acid-4-(chloromethyl) phenylester (M
3), 0.8g(7mmol) tetramethylethylenediamine, the 150mL anhydrous acetonitrile, back flow reaction is spent the night, suction filtration, ether washing three times for the gained solid, finally obtaining white solid is target compound (A
1), 6.41g, yield is 95%.
1h NMR (600MHz, DMSO): δ 3.18 (s, 12H, N (CH
3)
2), 4.096 (s, 4H, CH
2), 4.762 (s, 4H, CH
2), 7.71 (d, 4H, J=7.8Hz, phH), 7.85 (d, 4H, J=12.0Hz, phH);
19f NMR (376MHz, DMSO): δ-128.827 (2F) ,-123.802 (2F) ,-111.125 (2F) ,-84.248 (3F); HPLC/MS (ESI): 931.1 (M
+) (calculated value: 930.09).
Embodiment 4N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) second-1,2-di-ammonium salts (A
2) synthetic
Add 7.86g(0.015mol in dry 250mL flask) perfluoro hexyl sulfonic acid-4-(chloromethyl) phenylester (M
4), 0.8g(7mmol) tetramethylethylenediamine, the 150mL anhydrous acetonitrile, back flow reaction is spent the night, suction filtration, ether washing three times for the gained solid, finally obtaining white solid is target compound (A
2), 7.33g, yield is 90%.
1h NMR (400MHz, CD
3oD): δ 3.24 (s, 12H, N (CH
3)
2), 4.27 (s, 4H, CH
2), 4.85 (s, 4H, CH
2), 7.59 (d, 4H, J=8.4Hz, phH), 7.89 (d, 4H, J=8.4, phH);
19f NMR (376MHz, CD
3oD): δ-126.494 (2F) ,-123.057 (2F) ,-122.182 (2F) ,-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); HPLC/MS (ESI): 1129.5 (M
+) (calculated value: 1128.54).
Embodiment 5N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) the third-1,3-di-ammonium salts (A
3) synthetic
Add 6.36g(0.015mol in dry 250mL flask) perfluoro butyl sulfonic acid-4-(chloromethyl) phenylester (M
3), 0.91g(7mmol) 4-methyl-diaminopropane, the 150mL anhydrous acetonitrile, back flow reaction is spent the night, suction filtration, ether washing three times for the gained solid, finally obtaining white solid is target compound (A
3), 6.4g, yield is 93%.
1h NMR (400MHz, CD
3oD): δ 2.52 (s, 2H, CH
2), 3.16 (s, 12H, N (CH
3)
2), 3.47 (s, 4H, CH
2), 4.72 (s, 2H, CH
2), 7.57 (d, 4H, J=8.4Hz, phH), 7.82 (d, 4H, J=8.4Hz, phH);
19f NMR (376MHz, CD
3oD): δ-128.827 (2F) ,-123.802 (2F) ,-111.125 (2F) ,-84.248 (3F); HPLC/MS (ESI): 943.4 (M
+) (calculated value: 942.05).
Embodiment 6N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) the third-1,3-di-ammonium salts (A
4) synthetic
Add 7.86g(0.015mol in dry 250mL flask) perfluoro hexyl sulfonic acid-4-(chloromethyl) phenylester (M
4), 0.91g(7mmol) 4-methyl-diaminopropane, the 150mL anhydrous acetonitrile, back flow reaction is spent the night, suction filtration, ether washing three times for the gained solid, finally obtaining white solid is target compound (A
4), 7.87g, yield is 90%.
1h NMR (400MHz, CD
3oD): δ 2.52 (s, 2H, CH
2), 3.16 (s, 12H, N (CH
3)
2), 3.47 (s, 4H, CH
2), 4.72 (s, 2H, CH
2), 7.57 (d, 4H, J=8.4Hz, phH), 7.82 (d, 4H, J=8.4Hz, phH);
19f NMR (376MHz, CD
3oD): δ-126.494 (2F) ,-123.057 (2F) ,-122.182 (2F) ,-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); HPLC/MS (ESI): 1143.2 (M
+) (calculated value: 1142.54).
Embodiment 7N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) fourth-Isosorbide-5-Nitrae-di-ammonium salts (A
5) synthetic
Add 6.36g(0.015mol in dry 250mL flask) perfluoro butyl sulfonic acid-4-(chloromethyl) phenylester (M
3), 1g(7mmol) tetramethyl butane diamine, the 150mL anhydrous acetonitrile, back flow reaction is spent the night, suction filtration, ether washing three times for the gained solid, finally obtaining white solid is target compound (A5), 6.3g, yield is 91%.
1h NMR (400MHz, CD
3oD): δ 1.97 (s, 4H, CH
2), 3.10 (s, 12H, N (CH
3)
2), 3.48 (s, 4H, CH
2), 4.65 (s, 4H, CH
2), 7.59 (d, 4H, J=7.2Hz, phH), 7.80 (d, 2H, J=7.2Hz, phH);
19f NMR (376MHz, CD
3oD): δ-128.827 (2F) ,-123.802 (2F) ,-111.125 (2F) ,-84.248 (3F); HPLC/MS (ESI): 957.4 (M
+) (calculated value: 956.5).
Embodiment 8N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) the third-1,3-di-ammonium salts (A
6) synthetic
Add 7.86g(0.015mol in dry 250mL flask) perfluoro hexyl sulfonic acid-4-(chloromethyl) phenylester (M
4), 1g(7mmol) tetramethyl butane diamine, the 150mL anhydrous acetonitrile, back flow reaction is spent the night, suction filtration, ether washing three times for the gained solid, finally obtaining white solid is target compound (A
6), 7.42g, yield is 89%.
1h NMR (400MHz, CD
3oD): δ 1.97 (s, 4H, CH
2), 3.10 (s, 12H, N (CH
3)
2), 3.48 (s, 4H, CH
2), 4.65 (s, 4H, CH
2), 7.59 (d, 4H, J=7.2Hz, phH), 7.80 (d, 2H, J=7.2Hz, phH);
19f NMR (376MHz, CD
3oD): δ-126.494 (2F) ,-123.057 (2F) ,-122.182 (2F) ,-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); HPLC/MS (ESI): 1157.3 (M
+) (calculated value: 1156.54).
Embodiment 9N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) oneself-1,6-di-ammonium salts (A
7) synthetic
Add 6.36g(0.015mol in dry 250mL flask) perfluoro butyl sulfonic acid-4-(chloromethyl) phenylester (M
3), 1.2g(7mmol) 4-methyl hexamethylene diamine, the 150mL anhydrous acetonitrile, back flow reaction is spent the night, suction filtration, ether washing three times for the gained solid, finally obtaining white solid is target compound (A
7), 6.7g, yield is 94%.
1h NMR (400MHz, CD
3oD): δ 1.51 (s, 4H, CH
2), 1.97 (s, 4H, CH
2), 3.08 (s, 12H, N (CH
3)
2), 3.40 (s, 4H, CH
2), 4.65 (s, 4H, CH
2), 7.56 (d, 4H, J=6.8Hz, phH), 7.79 (d, 4H, J=7.6Hz, phH);
19f NMR (376MHz, CD
3oD): δ-128.827 (2F) ,-123.802 (2F) ,-111.125 (2F) ,-84.248 (3F); HPLC/MS (ESI): 985.6 (M
+) (calculated value: 984.61).
Embodiment 10N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) oneself-1,6-di-ammonium salts (A
8) synthetic
Add 7.86g(0.015mol in dry 250mL flask) perfluoro hexyl sulfonic acid-4-(chloromethyl) phenylester (M
4), 1.2g(7mmol) 4-methyl hexamethylene diamine, the 150mL anhydrous acetonitrile, back flow reaction is spent the night, suction filtration, ether washing three times for the gained solid, finally obtaining white solid is target compound (A
8), 7.86g, yield is 92%.
1h NMR (400MHz, CD
3oD): δ 1.51 (s, 4H, CH
2), 1.97 (s, 4H, CH
2), 3.08 (s, 12H, N (CH
3)
2), 3.40 (s, 4H, CH
2), 4.65 (s, 4H, CH
2), 7.56 (d, 4H, J=6.8Hz, phH), 7.79 (d, 4H, J=7.6Hz, phH);
19f NMR (376MHz, CD
3oD): δ-126.494 (2F) ,-123.057 (2F) ,-122.182 (2F) ,-120.690 (2F) ,-112.682 (2F) ,-81.136 (3F); HPLC/MS (ESI): 1185.6 (M
+) (calculated value: 1184.6).
The test of embodiment 11 surface tension and critical micelle concentration (CMC)
Get a certain amount of the said goods (double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant), be made into respectively with distilled water the solution that the amount of substance mark is 5/1000mol/L, place 5h, after solution-stabilized, it is diluted to successively to concentration is 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.As shown in table 1 25 ℃ of measured experimental datas of experiment.
Table 1. double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant lowest surface tension and critical micelle concentration
| Product designation | Lowest surface tension (mN/m) | CMC（mol/L） |
| A 1 | 16.8 | 8.05×10 -4 |
| A 2 | 24.9 | 9.43×10 -4 |
| A 3 | 24.2 | 7.26×10 -4 |
| A 4 | 29.2 | 9.15×10 -4 |
| A 5 | 25.1 | 6.86×10 -4 |
| A 6 | 29.3 | 8.78×10 -4 |
| A 7 | 25.5 | 3.49×10 -4 |
| A 8 | 30.0 | 1.12×10 -4 |
The preparation of embodiment 12 aqueous film-forming foam extinguishing agents
The typical composite parameter of table 2. aqueous film-forming foam extinguishing agent
| 3% aqueous film-forming foam extinguishing agent concentrate | 100g |
| Double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant | 2g |
| Amphoteric surfactant (CAB-35) | 15g |
| Sodium octyl | 2.5g |
| Xanthans | 1g |
| Urea | 30g |
| Antifreezing agent | 1.5g |
| Blowing promotor | 3g |
| Anticorrosive additive | 0.1g |
| APG | 1g |
| The corrosion resistant agent | 0.5g |
| Chelating agent | 0.5g |
| Water | 42.9g |
According to the typical composite parameter of table 2 aqueous film-forming foam extinguishing agent (reference literature: Fire Science and Technology 30 (2011), 825-828), the double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant (A prepared with embodiment 3～10
1～A
8) the preparation extinguishing chemical, wherein antifreezing agent can be: ethylene glycol, diethylene glycol, propane diols, DPG or hexylene glycol; Blowing promotor can be ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether or Dipropylene glycol mono-n-butyl Ether; The corrosion resistant agent can be BTA; Chelating agent: EDTA, natrium citricum or sodium tartrate.
Embodiment 13 aqueous film-forming foam extinguishing agent technical indicator and performances
Arbitrary double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant (A that contains according to table 2 preparation
1～A
8) fire foam, reference literature (Chemical Research and Application20 (2008) 569-572) carries out performance test.The fire-extinguishing test step is: add the 100mL cyclohexane in the 500mL beaker, light after-combustion 5 minutes; The concentrated solution of table 2 preparation, according to mass ratio 3:100 dilute with water, is blown into after air foaming in 1 minute and gets the 10mL fire foam and just join in the beaker of fire ring hexane, observe fire and extinguish situation.The result of fire-extinguishing test shows that the fire foam obtained has excellent MJPZ spreading rate and extinguishing property.With reference to GB15308-2006, the technical indicator of fire foam is tested, result is as shown in table 3.
Table 3. aqueous film-forming foam extinguishing agent technical indicator
| Surface tension (mN/m) | 17～19 |
| Cyclohexane interfacial tension (mN/m) | 2.3 |
| Frost resistance, melting | Without visible delamination and heterogeneous |
| The pH value | 7.5 |
| Sprawl the time (S) on cyclohexane | ＜0.5 |
| Coefficient of foaming | 7.7 |
| 25% 20 ℃ of drainage times (min) | 8 |
| Stability test | For a long time without significant change |
| Anti-hard water test | Character is without significant change |
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. a class double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant is characterized in that general structure is suc as formula shown in I:
Wherein: R
ffor perfluoro butyl sulfonyl, perfluoro hexyl sulfonyl; N is 2,3,4,6; X is to anion.
2. double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant according to claim 1 is characterized in that: described anion is comprised to Cl
-, Br
-, I
-or be other anion by anion exchange.
3. double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant according to claim 1, it is characterized in that: described double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant comprises N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) second-1, the 2-di-ammonium salts, N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) second-1, the 2-di-ammonium salts, N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) the third-1, the 3-di-ammonium salts, N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) the third-1, the 3-di-ammonium salts, N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) fourth-1, the 4-di-ammonium salts, N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) fourth-1, the 4-di-ammonium salts, N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro butyl sulfonyloxy) benzyl) own-1, the 6-di-ammonium salts, N, N, N ' N '-tetramethyl-N, N '-bis-((4-perfluoro hexyl sulfonyloxy) benzyl) own-1, the 6-di-ammonium salts.
4. the preparation method of the described double type perfluoroalkyl of claim 1-3 any one sulfonyloxy benzyl cationic surfactant, is characterized in that comprising the steps:
(1) p-Hydroxybenzylalcohol, under acid binding agent exists, with perfluoroalkyl sulfonyl fluoride generation nucleophilic substitution, obtains intermediate perfluoro alkyl sulfonic acid-4-(methylol) phenylester in solvent;
(2) perfluoro alkyl sulfonic acid-4-(methylol) phenylester reacts with halogenating agent and obtains intermediate perfluoro alkyl sulfonic acid-4-(halomethyl) phenylester in solvent;
(3) perfluoro alkyl sulfonic acid-4-(halomethyl) phenylester reacts with the tetramethyl alkyl diamine and obtains double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant in solvent.
5. the preparation method of double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant according to claim 4 is characterized in that reaction condition is:
The described acid binding agent of step (1) is potash, and described solvent is acetonitrile;
Solvent described in step (2) is acetonitrile or Isosorbide-5-Nitrae-dioxane;
Solvent described in step (3) is acetonitrile.
6. the preparation method of double type perfluoroalkyl sulfonyloxy benzyl cationic surfactant according to claim 4 is characterized in that reaction raw materials is:
Perfluoroalkyl sulfonyl fluoride described in step (1) is perfluoro butyl sulfonic acid fluoride or perfluoro hexyl sulfuryl fluoride, and the intermediate obtained is perfluoro butyl sulfonic acid-4-(methylol) phenylester or perfluoro hexyl sulfonic acid-4-(methylol) phenylester;
Halogenating agent described in step (2) is thionyl chloride, and the intermediate obtained is perfluoro butyl sulfonic acid-4-(chloromethyl) phenylester and perfluoro hexyl sulfonic acid 4-(chloromethyl) phenylester;
Tetramethyl alkyl diamine described in step (3) is tetramethylethylenediamine, 4-methyl-diaminopropane, tetramethyl butane diamine or 4-methyl hexamethylene diamine.
7. the application of the described double type perfluoroalkyl of claim 1-3 any one sulfonyloxy benzyl cationic surfactant in aqueous film-forming foam extinguishing agent.
8. an aqueous film-forming foam extinguishing agent, is characterized in that: comprise the described double type perfluoroalkyl of claim 1-3 any one sulfonyloxy benzyl cationic surfactant.
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