CN110354755B - Novel fluorine-containing betaine surfactant and preparation method and application thereof - Google Patents

Novel fluorine-containing betaine surfactant and preparation method and application thereof Download PDF

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CN110354755B
CN110354755B CN201910637381.7A CN201910637381A CN110354755B CN 110354755 B CN110354755 B CN 110354755B CN 201910637381 A CN201910637381 A CN 201910637381A CN 110354755 B CN110354755 B CN 110354755B
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邹伟
郑志明
张嘉玉
陈立义
颜杰
刘波
杨虎
郑汶江
李颜利
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
Sichuan University of Science and Engineering
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Sichuan University of Science and Engineering
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Abstract

The invention discloses a novel fluorine-containing betaine surfactant and a preparation method and application thereof. The surfactant is easy to degrade, free of biological accumulation, excellent in surface activity, simple in reaction mechanism, small in environmental pollution and low in cost, the economic additional value of byproducts such as octafluoropentanol, dodecafluoroheptanol or hexadecafluorononol is improved, a new raw material which is wide in source, low in price and easy to obtain is provided for preparation of the fluorine-containing surfactant, the problem that the byproducts are difficult to treat is solved, and the novel, efficient, low-price and environment-friendly fluorine-containing surfactant is provided, so that the surfactant has a good application prospect.

Description

Novel fluorine-containing betaine surfactant and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fluorine-containing surfactants, and particularly relates to a novel fluorine-containing betaine surfactant as well as a preparation method and application thereof.
Background
The traditional fluorocarbon surfactant represented by perfluorooctanoic acid has high surface activity and unique hydrophobic and oleophobic properties, and is widely applied to the fields of fluoropolymer production, electroplating, spinning and the like. However, these surfactants are typically persistent organic pollutants because they are poorly biodegradable and are prone to bioaccumulation. And the traditional fluorocarbon surfactant consumes a large amount of electric energy in the production process, so that the production cost is extremely high, and the large-scale application of the fluorocarbon surfactant is difficult.
The betaine surfactant has excellent salt resistance due to the structural characteristics of internal salts in molecules, can keep good surface activity in a wide pH range, and has excellent synergistic effect with anionic, cationic and nonionic surfactants. The bactericidal composition has the advantages of mild property, good bactericidal property, good corrosion resistance, easy biodegradation and the like, and is widely applied to the daily chemical industry. If the fluorocarbon chain is introduced into the structure of betaine, the development of a high-efficiency, green and environment-friendly fluorocarbon surfactant is of great significance. For example, patent CN201510098765.8 discloses a betaine zwitterionic surfactant containing fluorocarbon carboxylic acid, which is prepared by preparing perfluoroacyl halide and alkyl diamine to obtain perfluoroamide substituted diamine, and then reacting with chloro carboxylate. Shaoxing fur, etc. disclose the synthesis of amphoteric surfactant containing fluorosulfonyl betaine and its oil-collecting performance, and the preparation of N-perfluorooctanoyl-N, N-dimethyl-1, 3-propanediamine and 2-hydroxy-3-chloropropyl sodium sulfonate as raw materials with structural formula
Figure BDA0002130690190000011
The surfactant (Maohuanwei, Tangmeifang, organic fluorine industry of the synthesis of fluorine-containing sulfobetaine amphoteric surfactant and oil collection performance thereof, 1994(2): 1-3), but the fluorocarbon chain of the betaine surfactant is single chain, the surfactant is poor, the long fluorocarbon chain is difficult to degrade in natural environment, the betaine surfactant has the basic characteristics of persistent environmental organic pollutants, the negative effects caused by the long fluorocarbon chain are increasingly prominent, the damage to the environment, the bioaccumulation and the harm to the ecological system are not negligible, and the cost is high. Therefore, the fluorine-containing surfactant with green environmental protection and excellent application performance is researched and developedIs very gradual.
Octafluoropentanol, dodecafluoroheptanol and decahexafluorononanol are all byproducts in the production of tetrafluoropropanol, and are currently developed and utilized less and have lower additional values, thus causing a great deal of accumulation and environmental pollution. How to make good use of the by-products has become a major task in the domestic tetrafluoropropanol industry in recent years.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel fluorine-containing betaine surfactant, which utilizes a plurality of degradable short fluorine chains without biological accumulation to replace typical long fluorocarbon chains, realizes the greening of the fluorocarbon surfactant, and solves the problems of difficult degradation, environmental pollution, poor activity and high cost of the existing fluorine-containing surfactant.
The invention also provides a preparation method of the novel fluorine-containing betaine surfactant, which has the advantages of few reaction steps and simple and easily-controlled process.
In order to achieve the purpose, the invention adopts the following technical scheme: a novel fluorine-containing betaine surfactant has a chemical structural formula as follows:
Figure BDA0002130690190000021
wherein n is 4, 6 or 8; m is NH4 +Or an alkali metal cation.
Further, the alkali metal cation is Na + or K+Or Li+。
The invention also provides a preparation method of the novel fluorine-containing betaine surfactant, which comprises the following steps:
1) dissolving an alcamine compound in an organic solvent, adding a halide at-10-25 ℃, heating to 30-50 ℃, stirring for reaction for 0.5-4 h, heating to 60-80 ℃, reacting for 2-8 h, and after the reaction is finished, washing, standing and separating the product to obtain lower-layer oily liquid, namely the halogenated amine;
2) reacting fluorine-containing alcohol with strong base under anhydrous condition, slowly adding the reaction product into the halogenated amine obtained in the step 1), and carrying out etherification reaction to obtain fluorine-containing tertiary amine;
3) dissolving the fluorine-containing tertiary amine obtained in the step 2) in an organic solvent to carry out quaternization reaction with halides with different hydrophilic groups, filtering to remove solids after the reaction is finished, and evaporating the organic solvent to dryness to obtain the fluorine-containing betaine type surfactant.
Further, the alcohol amine compound is substituted amine containing a plurality of alcoholic hydroxyl groups, preferably triethanolamine, diethanolamine, tripropanolamine or dipropanolamine; the fluorine-containing alcohol is a fluorine-containing alcohol with methylene at a hydroxyl linking position, and is preferably tetrafluoropropanol, pentafluoropropanol, octafluoropentanol, dodecafluoroheptanol, hexadecafluorononol, nonafluoropentanol, tridecafluorononol or heptadecafluorononanol.
Further, the halide in the step 1) is thionyl chloride, phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus tribromide or carbon tetrabromide
Further, the strong base is sodium hydroxide or potassium hydroxide; the organic solvent is ether, amide, ketone or aromatic hydrocarbon, preferably one or a mixed solution of two of tetrahydrofuran, 1, 4-dioxane, diethyl ether, propyl ether, methyl propyl ether, ethyl propyl ether, ethylene glycol butyl ether, DMF, DMAC, DMSO, acetone, butanone, methyl ethyl ketone, cyclohexanone, ethylene glycol dimethyl ether and toluene.
Further, the etherification reaction temperature is 40-70 ℃, and the reaction time is 3-6 h;
further, the temperature of the quaternization reaction is 50-80 ℃, the reaction time is 2-8 h, and the molar ratio of the fluorine-containing tertiary amine to the halogenated matters with different hydrophilic groups is 1: 3.0 to 4.5.
Further, the hydrophilic group is a carboxyl group, a sulfonic group, a sulfate group or a phosphate group. Wherein, the raw material for introducing carboxyl can be chloroacetic acid and bromoacetic acid; the raw material for introducing sulfonic acid groups can be chloroethyl sulfonic acid; the introduced sulfuric ester and phosphoric ester can be firstly reacted with the obtained tertiary amine by using chloroethanol or bromoethanol to obtain quaternary ammonium salt, and then the quaternary ammonium salt is reacted with chlorosulfonic acid or phosphorus pentoxide to prepare the corresponding sulfuric ester and phosphoric ester.
Further, the molar ratio of the alcohol amine compound to the halide is 1: 2.5 to 4.0.
The invention also provides the application of the novel fluorine-containing betaine surfactant in the aspects of detergents, soaps, cosmetics, bacteriostats, chromium fog inhibitors or emulsifiers, and the novel fluorine-containing betaine surfactant is high in surface activity, non-toxic and capable of expanding the application range.
Compared with the prior art, the invention has the following beneficial effects:
1. the novel betaine alkaline surfactant prepared by the invention utilizes a plurality of non-bioaccumulation degradable short fluorine chains to replace typical long fluorocarbon chains, and designs the betaine row fluorocarbon surfactant with the following structure:
Figure BDA0002130690190000031
the surfactant not only has the excellent characteristics of three highs and two republics of the traditional fluorine-containing surfactant, but also is easy to degrade, non-toxic, harmless and free of biological accumulation, overcomes the problems that the typical fluorocarbon surfactant is not degradable and has high biological accumulation, and develops a new direction for the development of fluorine-containing compounds.
2. The invention takes the fluorocarbon alcohol containing methylene such as octafluoropentanol, dodecafluoroheptanol, decahexafluorononanol and the like as raw materials, sequentially carries out deprotonation, halogenation and etherification reactions to obtain the fluorine-containing tertiary amine, and carries out quaternization reaction on the fluorine-containing tertiary amine and halides with different hydrophilic groups to obtain the fluorine-containing betaine type surfactant. The preparation method has the advantages of simple reaction mechanism, easiness in operation, no toxicity, no harm, small environmental pollution, low cost and easiness in realization of large-scale industrial production, the critical micelle concentration of the obtained fluorine-containing surfactant is 0.5-2.5 g/L, the critical surface tension is 15-25 mN/m, the surface activity is high, the fluorine-containing surfactant is non-toxic, the fluorine-containing surfactant can be widely applied to multiple fields such as detergents, soaps, cosmetics, bacteriostatic agents, chromium fog inhibitors or emulsifiers, and the like, and has a good application prospect.
3. The method utilizes byproducts such as octafluoropentanol, dodecafluoroheptanol or hexadecafluorononol as raw materials, has low price per se, and changes the byproducts into a novel fluorine-containing betaine surfactant with high use value, no toxicity, no public nuisance and excellent performance, thereby not only improving the resource utilization of the octafluoropentanol and the like, but also providing a new material which has wide sources, low price and easy obtainment for the preparation of the fluorine-containing surfactant, solving the environmental pollution caused by the accumulation of a large amount of the octafluoropentanol, and having obvious social benefits, environmental benefits and economic benefits.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of tris (2-chloroethyl) amine prepared in example 1;
FIG. 2 is an IR spectrum of tris (2-octafluoropentyloxyethyl) amine prepared in example 1;
FIG. 3 is an infrared spectrum of octafluoropentanol-based fluorocarboxyl betaine surfactant prepared in example 1;
FIG. 4 is a graph of concentration versus surface tension for octafluoropentanoate fluorocarboxyl betaine surfactant prepared in example 1;
FIG. 5 is a graph showing the concentration versus surface tension of octafluoropentanol-based fluorosulfonyl betaine surfactant prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The experimental procedures are not specifically described in the following examples, and are carried out in a conventional manner using reagents which are generally commercially available.
Example 1
A preparation method of a novel octafluoropentanol-based fluorine-containing carboxyl betaine surfactant comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine. The results of the hydrogen nuclear magnetic resonance spectroscopy are shown in FIG. 1.1H NMR(600MHz,Chloroform-d)δ3.52(t,J＝7.0Hz,6H),2.98(t,J＝7.0Hz,6H).
2) Taking 56mL of octafluoropentanol and 16g of sodium hydroxide in a 250mL three-neck flask containing 100mL of tetrahydrofuran, fully stirring, slowly dropwise adding 15mL of the product obtained in the step 1) into the three-neck flask by using a constant-pressure dropping funnel, heating to 60 ℃ for reaction for 5 hours, filtering to remove solids after the reaction is finished, washing with water for several times for liquid separation, taking the lower layer liquid to evaporate excessive octafluoropentanol to obtain tris (2-octafluoropentyloxyethyl) amine, and performing infrared spectrum analysis on the tris (2-octafluoropentyloxyethyl) amine to obtain the result shown in FIG. 2, wherein the product is actually tris (2-octafluoropentyloxyethyl) amine.
3) And (2) dissolving 7.91g of the product obtained in the step 2) and 0.84g of sodium bicarbonate in 15mL of tetrahydrofuran, dissolving 1.5g of chloroacetic acid in 10mL of tetrahydrofuran in a constant-pressure dropping funnel, slowly dripping the chloroacetic acid into the reaction system, heating and refluxing for 8 hours, filtering to remove solid insoluble substances after the reaction is finished, and evaporating the tetrahydrofuran to dryness to obtain the fluorine-containing carboxyl betaine surfactant. The infrared spectrum analysis of the product showed that the product was actually fluorine-containing carboxybetaine, as shown in FIG. 3.
The fluorosurfactant obtained in this example was formulated into an aqueous solution with a certain concentration gradient, and its γ -C curve was measured at 25 ℃ by the hanging piece method of a full-automatic surface tensiometer, and the results are shown in fig. 4.
As can be seen from FIG. 4, the fluorosurfactant prepared in this example has a critical micelle concentration of 0.5g/L and a critical surface tension of 19.3 mN/m.
Example 2
A preparation method of a novel octafluoropentanol-based fluorine-containing sulfobetaine surfactant comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) Taking 56mL of octafluoropentanol and 16g of sodium hydroxide in a 250mL three-neck flask containing 100mL of toluene, fully stirring, taking 15mL of the product obtained in the step 1) by using a constant-pressure dropping funnel, slowly dropwise adding the product into the three-neck flask, heating to 60 ℃, reacting for 5 hours, filtering to remove solids after the reaction is finished, washing with water for several times for liquid separation, taking the lower layer of liquid, and evaporating the redundant octafluoropentanol to obtain the tris (2-octafluoropentoxyethyl) amine.
3) And (2) dissolving 7.91g of the product obtained in the step 2) and 0.84g of sodium bicarbonate in 15mL of tetrahydrofuran, adding 2g of 2-chloroethyl sodium sulfonate into the reaction system, heating and refluxing for 7 hours, filtering to remove solids after the reaction is finished, and evaporating the tetrahydrofuran to dryness to obtain the fluorine-containing sulfobetaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 1.2g/L and the critical surface tension is measured to be 21.12mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 3
A preparation method of a novel octafluoropentanol-based fluorosulfate betaine surfactant comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) Taking 56mL of octafluoropentanol and 16g of sodium hydroxide in a 250mL three-neck flask containing 100mL of diethyl ether, fully stirring, taking 15mL of the product obtained in the step 1) by using a constant-pressure dropping funnel, slowly dropwise adding the product into the three-neck flask, heating to 60 ℃, reacting for 5 hours, filtering to remove solids after the reaction is finished, washing with water for several times for liquid separation, taking the lower layer of liquid, and evaporating the redundant octafluoropentanol to obtain the tris (2-octafluoropentoxyethyl) amine.
3) And (2) dissolving 7.91g of the product obtained in the step 2) in 15mL of diethyl ether, adding 0.97g of 2-chloroethanol into the reaction system, heating and refluxing for reaction for 7h, adding 1.40g of chlorosulfonic acid and 0.96g of sodium hydroxide, reacting, filtering to remove solids, and evaporating the diethyl ether to obtain the fluorine-containing sulfate betaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 1.5g/L and the critical surface tension is measured to be 23.1mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 4
A preparation method of a novel octafluoropentanol-based fluorine-containing phosphate betaine surfactant comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMAC (dimethylacetamide), slowly dripping 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dripping, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) Taking 56mL of octafluoropentanol and 16g of sodium hydroxide, putting 100mL of 1, 4-dioxane 250mL of three-neck flask, fully stirring, taking 15mL of the product obtained in the step 1) by using a constant-pressure dropping funnel, slowly dropwise adding the product into the three-neck flask, heating to 60 ℃, reacting for 5 hours, filtering to remove solids after the reaction is finished, washing with water for several times for liquid separation, taking the lower layer of liquid, and evaporating the redundant octafluoropentanol to obtain the tris (2-octafluoropentoxyethyl) amine.
3) Dissolving 7.91g of the product obtained in the step 2) and 0.84g of sodium bicarbonate in 15mL of tetrahydrofuran, adding 0.97g of 2-chloroethanol into the reaction system, heating and refluxing for 7 hours, and taking 1.4g P2O5Adding into a reaction system, reacting for 3h at 40-80 ℃, filtering to remove solids after the reaction is finished, and evaporating tetrahydrofuran to dryness to obtain the fluorine-containing phosphate betaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 2.1g/L and the critical surface tension is measured to be 24.2mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 5
A preparation method of a novel fluorosulfonyl betaine surfactant based on dodecafluoroheptanol comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMSO, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) 75.48mL of dodecafluoroheptanol and 16g of sodium hydroxide are put into a 250mL three-neck flask containing 100mL of propyl ether, the mixture is fully stirred, 15mL of the product obtained in the step 1) is slowly dripped into the three-neck flask by using a constant pressure dropping funnel, the temperature is increased to 80 ℃ for reaction for 5 hours, after the reaction is finished, the solid is removed by filtration, the mixture is washed by water for several times for liquid separation, the lower layer of liquid is taken, and the excessive dodecafluoroheptanol is evaporated, so that the tris (2-dodecafluoroheptyloxyethyl) amine is obtained.
3) And (2) dissolving 10.91g of sodium product obtained in the step 2) in 15mL of tetrahydrofuran, adding 2g of 2-chloroethyl sodium sulfonate into the reaction system, heating and refluxing for 7h, filtering to remove solids after the reaction is finished, and evaporating the tetrahydrofuran to dryness to obtain the fluorine-containing sulfobetaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 0.9g/L and the critical surface tension is measured to be 18.8mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 6
A preparation method of a novel fluorosulfonyl betaine surfactant based on hexadecafluorononol comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 70 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) 172.84g of hexadecyl fluoro nonanol and 16g of sodium hydroxide are put into a 250mL three-neck flask of 100mL ethylene glycol dimethyl ether, the mixture is fully stirred, 15mL of the product obtained in the step 1) is slowly dripped into the three-neck flask by using a constant pressure dropping funnel, the temperature is raised to 60 ℃ for reaction for 5 hours, after the reaction is finished, the solid is removed by filtration, the mixture is washed by water for several times for liquid separation, the lower layer of liquid is taken, and the redundant hexadecyl fluoro nonanol is evaporated, so that the tris (2-decahexafluoro nonanoxyethyl) amine is obtained;
3) and (2) dissolving 11.91g of the product obtained in the step 2) and 0.84g of sodium bicarbonate in 15mL of tetrahydrofuran, adding 2g of 2-chloroethyl sodium sulfonate into the reaction system, heating and refluxing for 7 hours, filtering to remove solids after the reaction is finished, and evaporating the tetrahydrofuran to dryness to obtain the fluorine-containing sulfobetaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 1.5g/L and the critical surface tension is measured to be 20.7mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 7
A preparation method of a novel fluorine-containing carboxyl betaine surfactant based on dodecafluoroheptanol comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) 75.48mL of dodecafluoroheptanol and 16g of sodium hydroxide are put into a 250mL three-neck flask containing 100mL of tetrahydrofuran, the mixture is fully stirred, 15mL of the product obtained in the step 1) is slowly dripped into the three-neck flask by using a constant pressure dropping funnel, the temperature is increased to 60 ℃ for reaction for 5 hours, after the reaction is finished, the solid is removed by filtration, the mixture is washed by water for several times for liquid separation, the lower layer of liquid is taken, and the redundant dodecafluoroheptanol is evaporated, so that the tris (2-dodecafluoroheptyloxyethyl) amine is obtained.
3) And (2) dissolving 10.91g of the product obtained in the step 2) and 0.84g of sodium bicarbonate in 15mL of tetrahydrofuran, dissolving 1.5g of chloroacetic acid in 10mL of tetrahydrofuran in a constant-pressure dropping funnel, slowly dripping the chloroacetic acid into the reaction system, heating and refluxing for 8 hours, filtering to remove solid insoluble substances after the reaction is finished, and evaporating the tetrahydrofuran to dryness to obtain the fluorine-containing carboxyl betaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 2.1g/L and the critical surface tension is measured to be 21.5mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 8
A preparation method of a novel fluorine-containing carboxyl betaine surfactant based on hexadecafluorononol comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) 172.84g of hexadecylnonanol and 16g of sodium hydroxide are put into a 250mL three-neck flask containing 100mL of tetrahydrofuran, the mixture is fully stirred, 15mL of the product obtained in the step 1) is slowly dripped into the three-neck flask by using a constant pressure dropping funnel, the temperature is increased to 60 ℃, the reaction is carried out for 5 hours, after the reaction is finished, the solid is removed by filtration, the mixture is washed by water for several times for liquid separation, the lower layer of liquid is taken, and the excessive hexadecylnonanol is evaporated, so that the tris (2-decahexafluorononanoxyethyl) amine is obtained.
3) And (2) dissolving 7.91g of the product obtained in the step 2) and 0.84g of sodium bicarbonate in 15mL of tetrahydrofuran, dissolving 1.5g of chloroacetic acid in 10mL of tetrahydrofuran in a constant-pressure dropping funnel, slowly dripping the chloroacetic acid into the reaction system, heating and refluxing for 8 hours, filtering to remove solid insoluble substances after the reaction is finished, and evaporating the tetrahydrofuran to dryness to obtain the fluorine-containing carboxyl betaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 0.7g/L and the critical surface tension is measured to be 18.5mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 9
A preparation method of a novel fluorosulfate betaine surfactant based on dodecafluoroheptanes comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) 75.48mL of dodecafluoroheptanol and 16g of sodium hydroxide are put into a 250mL three-neck flask containing 100mL of ether, the mixture is fully stirred, 15mL of the product obtained in the step 1) is slowly dripped into the three-neck flask by using a constant pressure dropping funnel, the temperature is increased to 60 ℃ for reaction for 5 hours, after the reaction is finished, the solid is removed by filtration, the mixture is washed by water for several times for liquid separation, the lower layer of liquid is taken, and the excessive dodecafluoroheptanol is evaporated, so that the tris (2-dodecafluoroheptyloxyethyl) amine is obtained.
3) And (2) dissolving 7.91g of the product obtained in the step 2) in 15mL of diethyl ether, adding 0.97g of 2-chloroethanol into the reaction system, heating and refluxing for reaction for 7h, adding 1.40g of chlorosulfonic acid and 0.96g of sodium hydroxide, reacting, filtering to remove solids, and evaporating the diethyl ether to obtain the fluorine-containing sulfate betaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 1.1g/L and the critical surface tension is measured to be 19.12mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 10
A preparation method of a novel fluorine-containing phosphate betaine surfactant based on dodecafluoroheptanol comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine;
2) 75.48mL of dodecafluoroheptanol and 16g of sodium hydroxide are put into a 250mL three-neck flask containing 100mL of ethylene glycol monobutyl ether, the mixture is fully stirred, 15mL of the product obtained in the step 1) is slowly dripped into the three-neck flask by using a constant pressure dropping funnel, the temperature is increased to 60 ℃, the reaction is carried out for 5 hours, after the reaction is finished, the solid is removed by filtration, water is used for washing for several times for liquid separation, the lower layer liquid is taken, and the redundant dodecafluoroheptanol is evaporated, so that the tris (2-dodecafluoroheptyloxyethyl) amine is obtained.
3) Dissolving 7.91g of the product obtained in the step 2) and 0.84g of sodium bicarbonate in 15mL of diethyl ether, adding 0.97g of 2-chloroethanol into the reaction system, heating and refluxing for 7 hours, and taking 1.4g P2O5Adding into a reaction system, reacting for 3h at 40-80 ℃, filtering to remove solids after the reaction is finished, and evaporating diethyl ether to dryness to obtain the fluorine-containing phosphate betaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 1.3g/L and the critical surface tension is measured to be 20.9mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 11
A preparation method of a novel fluorosulfate betaine surfactant based on hexadecyl fluoro nonanol comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) 172.84g of hexadecylnonanol and 16g of sodium hydroxide are put into a 100mL 250mL three-neck flask with 1, 4-dioxane and fully stirred, 15mL of the product obtained in the step 1) is slowly dripped into the three-neck flask by using a constant pressure dropping funnel, the temperature is increased to 60 ℃ for reaction for 5 hours, after the reaction is finished, the solid is removed by filtration, the mixture is washed by water for several times for liquid separation, the lower layer of liquid is taken, and the excessive hexadecylnonanol is distilled off, so that the tris (2-decahexafluorononanoxyethyl) amine is obtained.
3) And (2) dissolving 7.91g of the product obtained in the step 2) in 15mL of 1, 4-dioxane, adding 0.97g of 2-chloroethanol into the reaction system, heating and refluxing for reaction for 7 hours, adding 1.40g of chlorosulfonic acid and 0.96g of sodium hydroxide, reacting, filtering to remove solids, and evaporating dioxane to dryness to obtain the fluorine-containing sulfate betaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 0.85g/L and the critical surface tension is measured to be 22mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Example 12
A preparation method of a novel fluoride-containing phosphate betaine surfactant based on hexadecafluorononol comprises the following steps:
1) dissolving 26.5mL of triethanolamine in 30mL of DMF, slowly dropwise adding 56.65mL of thionyl chloride by using a constant-pressure dropping funnel at a low temperature (0-15 ℃), heating to 35 ℃ after dropwise addition, stirring for about 1h, continuously heating to 60 ℃ and stirring for about 4h, stopping reaction, washing the reaction solution by using an aqueous solution of an inorganic base, adjusting the pH to about 8, standing, and separating to obtain a lower-layer oily liquid which is tris (2-chloroethyl) amine.
2) 172.84g of hexadecyl fluoro nonanol and 16g of sodium hydroxide are put into a 250mL three-neck flask containing 100mL of tetrahydrofuran and are fully stirred, 15mL of the product obtained in the step 1) is slowly dripped into the three-neck flask by using a constant pressure dropping funnel, the temperature is increased to 60 ℃ for reaction for 5 hours, after the reaction is finished, the solid is removed by filtration, water is used for washing for several times for separating liquid, the lower layer of liquid is taken, and the excessive hexadecyl fluoro nonanol is evaporated, so that the tris (2-deca-hexafluoro nonanoxyethyl) amine is obtained.
3) Dissolving 7.91g of the product obtained in the step 2) and 0.84g of sodium bicarbonate in 15mL of tetrahydrofuran, adding 0.97g of 2-chloroethanol into the reaction system, heating and refluxing for 7 hours, and taking 1.4g P2O5Adding into a reaction system, reacting for 3h at 40-80 ℃, filtering to remove solids after the reaction is finished, and evaporating tetrahydrofuran to dryness to obtain the fluorine-containing phosphate betaine surfactant.
The fluorine-containing surfactant obtained in the embodiment is prepared into an aqueous solution with a certain concentration gradient, and the critical micelle concentration is measured to be 1.56g/L and the critical surface tension is measured to be 23.47mN/m by a gamma-C curve measurement at 25 ℃ by using a hanging piece method of a full-automatic surface tension meter.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (6)

1. A novel fluorine-containing betaine surfactant is characterized in that the chemical structural formula is as follows:
Figure FDA0002956451600000011
wherein n is 4, 6 or 8; m is NH4 +Or an alkali metal cation.
2. The novel fluorobetaine surfactant according to claim 1, wherein the alkali metal cation is Na+、K+Or Li+。
3. A method for producing a novel fluorine-containing betaine type surfactant according to claim 1 or 2, comprising the steps of:
1) dissolving an alcamine compound in an organic solvent, adding a halide at-10-25 ℃, heating to 30-50 ℃, stirring for reaction for 0.5-4 h, heating to 60-80 ℃, reacting for 2-8 h, and after the reaction is finished, washing, standing and separating the product to obtain lower-layer oily liquid, namely the halogenated amine;
2) reacting fluorine-containing alcohol with strong base under anhydrous condition, slowly adding the reaction product into the halogenated amine obtained in the step 1), and carrying out etherification reaction to obtain fluorine-containing tertiary amine;
3) carrying out quaternization reaction on the fluorine-containing tertiary amine obtained in the step 2) and halides with different hydrophilic groups, filtering to remove solids after the reaction is finished, and evaporating the solvent to dryness to obtain the fluorine-containing betaine surfactant;
the alcohol amine compound is triethanolamine, diethanolamine, tripropanolamine or dipropanolamine; the fluorine-containing alcohol is tetrafluoropropanol, pentafluoropropanol, octafluoropentanol, dodecafluoroheptanol, hexadecafluorononol, nonafluoropentanol, tridecafluorononol or heptadecafluorononanol; the halide is thionyl chloride, phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus tribromide or carbon tetrabromide; the halide with different hydrophilic groups is carboxyl, sulfonic group, sulfate ester or phosphate ester.
4. The method for producing the novel fluorine-containing betaine type surfactant according to claim 3, wherein the strong base is sodium hydroxide or potassium hydroxide; the organic solvent is one or a mixed solution of two of tetrahydrofuran, 1, 4-dioxane, diethyl ether, propyl ether, methyl propyl ether, ethyl propyl ether, ethylene glycol butyl ether, DMF, DMAC, DMSO, acetone, butanone, methyl ethyl ketone, cyclohexanone, ethylene glycol dimethyl ether and toluene.
5. The method for preparing the novel fluorine-containing betaine surfactant according to claim 3, wherein the etherification reaction temperature is 40 to 70 ℃ and the reaction time is 3 to 6 hours.
6. The preparation method of the novel fluorine-containing betaine surfactant according to claim 3, wherein the quaternization reaction temperature is 50-80 ℃, the reaction time is 2-8 h, and the molar ratio of the fluorine-containing tertiary amine to the halogenated substances with different hydrophilic groups is 1: 3.0 to 4.5; the molar ratio of the alcohol amine compound to the halide is 1: 2.5 to 4.0.
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