CN105664784B

CN105664784B - fluorine-containing surfactant and preparation method thereof

Info

Publication number: CN105664784B
Application number: CN201511031114.3A
Authority: CN
Inventors: 阎育才; 史大阔; 张永明; 王汉利; 唐军柯; 刘体建; 赵栋
Original assignee: Shandong Dongyue Shenzhou New Material Co Ltd
Current assignee: Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
Priority date: 2015-12-31
Filing date: 2015-12-31
Publication date: 2018-06-01
Anticipated expiration: 2035-12-31
Also published as: CN105664784A

Abstract

The present invention relates to a kind of fluorine-containing surfactant and preparation method thereof, a kind of fluorine-containing surfactant of the present invention, the structural formula of compound is：Surface property of the present invention is excellent, the discharge without waste water and exhaust gas in preparation process, and the foam solution after compounding can be used as fire foam.It does not pollute the environment in use, it is environmentally friendly, it is widely used, can be used in the fields such as oil, chemical industry and fire-fighting foams.

Description

Fluorine-containing surfactant and preparation method thereof

Technical Field

The invention relates to a surfactant, in particular to a fluorine-containing surfactant and a preparation method thereof.

Background

The fluorine-containing surfactant has high surface activity, high thermal stability, high chemical stability, and special hydrophobic and oleophobic properties, and has some characteristics that other surfactants do not have. Surfactants such as PFOA, PFOS and derivatives thereof are used in the related industries due to their excellent properties, and are highly favored. However, because of the difficult degradability and enrichment in organisms of PFOA, PFOS and PFOS derivatives, the environment is seriously polluted, direct and indirect life threats are caused to human beings, and the period is long. In 2004, although "stockholm convention on persistent organic pollutants" was internationally effective, PFOA and PFOS and their derivatives are still in use in some fields because of their temporary irreplaceability of performance. Therefore, it is urgent to develop a safe and environmentally friendly substitute having excellent performance.

The Bola type surfactant has attracted extensive attention of researchers as a novel surfactant with special properties.

Disclosure of Invention

The invention aims to provide a fluorine-containing surfactant and a preparation method thereof, the compound has excellent surface performance, no wastewater and waste gas are discharged in the preparation process, and the compounded foam liquid can be used as a foam extinguishing agent. The environment-friendly fire-fighting foam does not pollute the environment in the using process, is environment-friendly, and can be applied to the fields of petroleum, chemical engineering, fire-fighting foam and the like.

The invention relates to a fluorine-containing surfactant, the structural formula of the compound is as follows:

wherein,

R₁、R₂、R₃、R₄all have a structure of CH₃Or straight chain CH₃(CH₂)_pP is an integer of 1 to 4;

R₅、R₆structure is H or CH₃；

m and n are integers of 1-6;

R_fis a fluorine-containing linking group having the structureWherein q is an integer of 1 to 6;

x, Y has the chemical structure (CH)₂)_sCOO^-、O^-、CH₃(CH₂)_t、(CH₂)_gSO₃ ^-Wherein s is an integer of 1 to 7, t is an integer of 0 to 7, and g is an integer of 1 to 4.

When X, Y are both (CH)₂)_sCOO^-、CH₃(CH₂)_tWhen in structure, the structure is a straight chain structure or a branched chain structure, and in the same chemical structural formula, the chemical structures of X and Y are the same or different.

An aqueous solution having a concentration of 1 wt% of the compound at 20 ℃ has a surface tension of not more than 21 mN/m; an aqueous solution having a concentration of 0.1% by weight of said compound at 20 ℃ has a surface tension of not more than 22 mN/m.

The CMC in aqueous solution is of the order of 10^-5-10^-4g/g。

The preparation method of the fluorine-containing surfactant comprises two steps of reaction, wherein the first step is amidation reaction, and the second step is quaternization reaction.

The acid-binding agent in the amidation reaction is one or more of ammonium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium carbonate, magnesium carbonate, ammonium bicarbonate or triethylamine. Sodium carbonate is preferred.

The structural general formula of diamine involved in the amidation reaction is

N, N-dimethyl-1, 3-propanediamine is preferred.

In the amidation reaction, the reaction temperature is 0-100 ℃, and the reaction time is 1-36 h; in the quaternization reaction, the reaction temperature is 50-260 ℃ and the reaction time is 4-120 h.

The molar ratio of each substance in the amidation reaction is n_{Fluorine-containing reactant}:n_Diamines:n_{Acid-binding agent}1:2.0-5.5: 2.0-10; the proportion of quaternization reactants is n_{Intermediates}:n_{Quaternary ammonium materials}＝1:2.0-5.5。

The fluorine-containing reactant has the structural formula of FSO2-R_f-COF；

The structural formula of the intermediate is

The quaternizing starting material comprises Cl (CH)₂)_hCOONa、Br(CH₂)_hCOONa、Cl(CH₂)_iSO₃Na、Br(CH₂)_iSO₃Na、H₂O₂1, 3-propane sultone, 1, 4-butane sultone; wherein h is an integer of 1-7, and i is an integer of 1-4. Quaternization reactant ratio, n when the quaternization raw material is hydrogen peroxide_{Hydrogen peroxide}:n_{Manganese dioxide}＝1:0.0001-1。

The compound of the invention is a single-chain Bola type fluorine-containing surfactant.

The Bola type surfactant is a series of fluorine-containing amphoteric surfactants which are obtained by taking perfluoroether polymers with sulfonyl fluoride and carbonyl fluoride functional groups at two molecular ends as initial raw materials and sequentially carrying out amidation reaction and quaternization reaction, and the structures and the performances of the fluorine-containing amphoteric surfactants can be well used as substitutes in the fields of PFOA, PFOS and derivatives thereof.

The compound has stable performance, no wastewater and waste gas are discharged in the preparation process, and the compounded foam liquid can be used as a foam extinguishing agent. In the using process, the actual usage amount of the fluorine-containing surfactant is very small, so that the environment is not polluted in the using process, and the method is environment-friendly. Because of the special structure of the Bola type molecule, a monomolecular film formed at the gas/liquid interface shows some unique performances, so that the polymer has wide application prospect in the synthesis of nano materials, and can be used as a foam stabilizer and a fire extinguishing agent in a high-efficiency foam extinguishing agent, as a wetting agent and a dispersing agent of hydrocarbon solid or liquid surface, as a decontamination cleaning agent of metal surface.

The compound is suitable for being used as a foam extinguishing agent additive, a metal surface treating agent and an emulsifying agent.

Compared with the prior art, the invention has the following beneficial effects:

the fluorine-containing surfactant and the preparation method thereof have excellent surface performance, no wastewater or waste gas is discharged in the preparation process, and the compounded foam liquid can be used as a foam extinguishing agent. The foam material does not pollute the environment in the using process, is environment-friendly and wide in application, and can be used in the fields of petroleum, chemical industry, fire-fighting foam and the like.

Drawings

FIG. 1 surface tension of aqueous solutions at different concentrations for example 1;

figure 2 surface tension of aqueous solutions at different concentrations in example 2.

Detailed Description

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.

Example 1

Preparation of intermediate-1 (amidation reaction): n, N-dimethyl-1, 3-propanediamine was added in sequence to a 500ml three-necked round-bottomed flask30.8g (302mmol), dichloromethane 200ml, sodium carbonate 17.2g (182mmol) were placed in an ice-water bath for 30 min. Starting the stirring, 100g (147.4mmol) of FO are introduced into a separatory constant-pressure funnel₂S-CF₂CF₂OCF(CF₃)CF₂OCF(CF₃)CF₂OCF(CF₃) COF is slowly dripped into a three-neck round-bottom flask with a temperature probe, and the reaction temperature is controlled to be less than or equal to 30 ℃. After the dropwise addition is finished, the reaction is continued for 6 hours at the temperature of less than or equal to 40 ℃, and the mixture after the reaction is filtered. The filtered white solid was dissolved in 100ml ethanol, filtered again to remove salts, the solvent was removed from the filtrate by rotary evaporation and the residue was dried under vacuum for 24h to give 118g of a yellow viscous gum in 98% yield. The structural formula of the intermediate is as follows:

quaternization reaction: 110 g (11.8mmol) of the obtained intermediate is added into a 100ml three-neck round-bottom flask, 2.8g (24.3mmol) of sodium chloroacetate, 30ml of ethanol, 0.06g of triethylamine and 0.15g of deionized water are sequentially added, and stirring and reflux reaction are carried out at 80 ℃ for 24 h. After the reaction was completed, the reaction mixture was filtered while it was hot, the solvent in the filtrate was distilled off under reduced pressure, and the yellow viscous gum was vacuum-dried at 60 ℃ for 36 hours to obtain 10.2g of a product in 85.7% yield. The product has the following structural formula:

as is clear from FIG. 1, the CMC of the aqueous solution was 4.9X 10^-5g/g，γ_CMCWas 21.5 mN/m.

Example 2

Quaternization reaction: 110 g of the intermediate from example 1, 30ml of ethanol, are taken and placed in a 100ml three-necked round-bottomed flask, and 4.3g of hydrogen peroxide (30%, wt.) are added in three portions, 1.45g being added every 8 h. Stirring at 50 ℃, and refluxing for reaction for 24 h. 0.003g of manganese dioxide was added thereto, and the reaction was continued for 3 hours. The reaction of hydrogen peroxide was verified to be completely free of residue by using starch potassium iodide paper. The hot filtrate was filtered off, the solvent was evaporated off from the filtrate and the yellow viscous gum was dried under vacuum at 60 ℃ for 48h to give 10g of product in 93.5% yield. The product has the following structural formula:

As is clear from FIG. 2, the CMC of the aqueous solution was 2.0X 10^-4g/g，γ_CMCThe concentration of the solution was 21.6 mN/m.

Example 3

Quaternization reaction: 120 g (23.7mmmol) of intermediate in example 1 and 80ml of isopropanol were taken and charged into a 250ml three-necked round-bottomed flask. The temperature is raised to 80 ℃, stirring is carried out, 6.37g (52.2mmol) of 1, 3-propane sultone is slowly dropped, and reflux reaction is carried out for 96 h. After the reaction was complete, the reaction was filtered hot, the solvent was evaporated from the filtrate and the yellow viscous gum was dried in vacuo for 48h to give 22g of product in 85% yield. The product has the following structural formula:

example 4

Quaternization reaction: 115 g (17.7mmol) of the intermediate in example 1 is taken and added into a 100ml three-neck round-bottom flask, 8.37g (42.5mmol) of bromomethyl sodium sulfonate, 50ml of isopropanol, 0.09g of triethylamine and 0.22g of deionized water are sequentially added, stirred at 80 ℃ and condensed and refluxed for reaction for 36 hours. After the reaction was completed, the mixture was filtered while hot, the solvent in the filtrate was evaporated, and the yellow viscous jelly was vacuum-dried at 60 ℃ for 56 hours to obtain 17g in 92% yield. The product has the following structural formula:

example 5

Preparation of intermediate-2 (amidation reaction): 18.2g of N, N-dimethyl-1, 3-propane diamine, 250ml of dichloromethane and 11.2g of sodium carbonate are sequentially added into a 500ml three-neck round-bottom flask, and the mixture is placed in an ice-water bath for 30 min. Starting the stirring, 100gFO₂S-CF₂(CF₂OCF(CF₃))₆COF is slowly pumped into a three-neck round-bottom flask with a temperature probe, and the reaction temperature is controlled to be less than or equal to 30 ℃. After the dropwise addition is finished, the reaction is continued for 12 hours at the temperature of less than or equal to 40 ℃, and the mixture after the reaction is filtered. The filtered white solid was dissolved in 150ml ethanol, filtered again to remove the salts, the solvent was removed from the filtrate by evaporation and the residue was dried in vacuo for 65h to give 107g of a dark yellow viscous gum in 95% yield. The structural formula of intermediate-2 is as follows:

wherein R "_fIs CF₂(CF₂OCF(CF₃))₆。

Quaternization reaction: 215 g of the intermediate obtained in example 5 was taken and put into a 100ml three-necked round-bottom flask with a temperature probe, and 3.1g of sodium chloropropionate, 35ml of ethanol, 0.67g of triethylamine and 0.16g of deionized water were added in this order, and stirred and refluxed for 45 hours at 85 ℃. After the reaction was completed, the mixture was filtered while it was hot, the solvent in the filtrate was distilled off under reduced pressure, and the dark yellow viscous jelly was vacuum-dried at 65 ℃ for 50 hours to obtain 14.6g of a product with a yield of 90.0%. The product has the following structural formula:

example 6

Preparation of intermediate-3 (amidation reaction): 51.5g of N, N-dimethyl-1, 3-propanediamine, 200ml of chloroform and 46g of sodium carbonate are sequentially added into a 250ml three-neck round-bottom flask, and the mixture is placed in an ice-water bath and kept for 25 min. Starting the stirring, 50gFO₂S-CF₂CF₂OCF(CF₃) COF is slowly dripped into a three-neck round-bottom flask with a temperature probe, and the reaction temperature is controlled to be less than or equal to 30 ℃. After the dropwise addition is finished, the reaction is continued for 9 hours at the temperature of less than or equal to 40 ℃, and the mixture after the reaction is filtered. The filtered white solid was dissolved in 60ml of propanol, filtered again to remove the salt, the solvent was removed from the filtrate by evaporation and the residue was dried in vacuo for 75h to give 72.9g of a pale yellow viscous gum in 99% yield. The structural formula of intermediate-3 is as follows:

wherein R'_fIs CF₂CF₂OCF(CF₃)。

325 g of intermediate from example 6, 45ml of propanol were taken in a 100ml three-necked round-bottom flask and 25g of hydrogen peroxide (30%, wt.) were added in three portions, 8.3g every 6 h. Stirring and refluxing the mixture for reaction for 35 hours at the temperature of 60 ℃. 0.12g of manganese dioxide was added thereto, and the reaction was continued for 7 hours. After the reaction is verified to be completely free of residual hydrogen peroxide by starch potassium iodide paper, the mixture is filtered while hot, the solvent in the filtrate is evaporated, and the yellowish yellow viscous jelly is dried in vacuum at 60 ℃ for 52 hours to obtain 24.7g of a product with the yield of 93.0%. The product has the following structural formula:

test method

The surface tension of the aqueous sample solutions at different concentrations was measured using the DuNouy sling method.

Preparing aqueous solutions of samples at a series of concentrations of 1%, 0.5%, 0.2%, 0.1%, 0.05%, 0.02%, 0.01%, 0.005%, 0.002%, 0.001% at 20 ℃, respectively, testing 10 surface tension values at each concentration of each sample, and finally taking the average value as the final surface tension value. The accuracy was. + -. 0.2 mN/m. The critical surface tension and Critical Micelle Concentration (CMC) were determined by mapping. See figures 1 and 2.

Table 1 surface tension test data for examples 1-4: (unit: mN/m, 20 ℃ C., test apparatus is KRUSS100 interfacial tension apparatus).

TABLE 1 surface tension test data for examples 1-6

Serial number	1％(wt)	0.1％(wt)	0.01％(wt)
				Example 1	21.3	21.4	22.2
Example 2	21.4	21.9	23.3
				Example 3	21.3	21.6	23.7
Example 4	21.1	22.0	23.6
				Example 5	20.5	21.1	21.9
Example 6	21.0	21.5	22.0

Claims

1. The preparation method of the fluorine-containing surfactant is characterized by comprising the following steps:

preparation of intermediate-1: adding 30.8g (302mmol) of N, N-dimethyl-1, 3-propane diamine, 200mL of dichloromethane and 17.2g (182mmol) of sodium carbonate into a 500mL three-neck round-bottom flask in sequence, and placing the flask in an ice-water bath for 30 min; starting the stirring, 100g of FO will be loaded in a separatory constant pressure funnel₂S-CF₂CF₂OCF(CF₃)CF₂OCF(CF₃)CF₂OCF(CF₃) COF was slowly added dropwise to a three-necked round-bottom flask with temperature probeControlling the reaction temperature to be less than or equal to 30 ℃; after the dropwise addition is finished, the reaction is continued for 6h at the temperature of less than or equal to 40 ℃, the reacted mixture is filtered, the filtered white solid is dissolved by 100mL of ethanol, the filtration is carried out again to remove salt, the solvent in the filtrate is removed by rotary evaporation, and the residue is dried in vacuum for 24h to obtain 118g of yellow viscous jelly with the yield of 98%; the structural formula of intermediate-1 is as follows:

quaternization reaction: adding 110 g (11.8mmol) of the obtained intermediate into a 100mL three-neck round-bottom flask, sequentially adding 2.8g (24.3mmol) of sodium chloroacetate, 30mL of ethanol, 0.06g of triethylamine and 0.15g of deionized water, stirring at 80 ℃, and carrying out reflux reaction for 24 hours; filtering the solution while the solution is hot after the reaction is finished, evaporating the solvent in the filtrate under reduced pressure, and drying the yellow viscous jelly for 36 hours in vacuum at the temperature of 60 ℃ to obtain 10.2g of a product with the yield of 85.7 percent;

the product has the following structural formula: