CN103406062B - Gemini amine salt type fluorated surfactant and preparation method thereof - Google Patents

Abstract

The invention discloses a Gemini amine salt type fluorosurfactant and a preparation method thereof. The Gemini amine salt-type fluorosurfactant is shown in formula I. In formula I, R is a group represented by C _m H _2m+1 , wherein m is an integer between 0 and 3, and n is between 2 and 8. Integer between. The preparation method of Gemini amine salt type fluorosurfactant represented by formula I provided by the present invention comprises the following steps: (1) reacting 3-perfluorohexyl-1,2-propylene oxide with diamine represented by formula II to obtain Compound shown in formula III; wherein, n is an integer between 2 and 8; R is a group represented by C _m H _2m+1 , m is an integer between 0 and 3; (2) to the compound shown in formula III HCl gas is passed into the alcoholic solution, and the Gemini amine salt type fluorosurfactant shown in formula I is obtained through a salt-forming reaction. The Gemini amine salt type fluorosurfactant provided by the invention has excellent surface performance and good foaming performance. The preparation method of the Gemini amine salt type fluorosurfactant provided by the invention has the advantages of cheap and easy-to-obtain raw materials, simple preparation method, easy control of reaction conditions and easy purification of products.

Description

Gemini amine salt type fluorosurfactant and preparation method thereof

technical field

The invention relates to a Gemini amine salt type fluorosurfactant and a preparation method thereof.

Background technique

Ordinary surfactants only include one hydrophilic group and one lipophilic group, which are single-chain single-head groups. Gemini-type surfactants are composed of two single-chain single-head group ordinary surfactants connected by chemical bonds at the ionic head group. The presence of chemical bonds strengthens the hydrophobic binding force between the hydrocarbon chains and inhibits the surfactant Headgroup separation force during ordered aggregation and thus higher surface activity. The special molecular structure makes it have many unique advantages, such as easy adsorption on the gas-liquid surface, low surface tension, and the tendency to reduce the surface tension of aqueous solution is much greater than the tendency to aggregate to form micelles; the critical micelle concentration is higher than that of ordinary surface The active agent is 2-3 orders of magnitude lower; it has a very low Krafft point; it can produce a greater synergistic effect with common surfactants, especially non-ionic surfactants; it can be used as an excellent wetting agent and hair in many occasions foaming agent.

Contents of the invention

The object of the present invention is to provide a Gemini amine salt type fluorosurfactant and a preparation method thereof. The amine salt type fluorosurfactant provided by the present invention has excellent surface properties and good foaming performance.

The Gemini amine salt type fluorosurfactant shown in the formula I provided by the present invention,

In formula I, R is a group represented by C _m H _2m+1 , wherein m is an integer between 0 and 3, and n is an integer between 2 and 8.

In the above-mentioned Gemini amine salt type fluorosurfactant, m is preferably 0, and n is preferably 6.

The preparation method of Gemini amine salt type fluorosurfactant shown in formula I provided by the invention comprises the steps:

(1) Reacting 3-perfluorohexyl-1,2-propylene oxide with a diamine represented by formula II to obtain a compound represented by formula III;

Wherein, n is an integer between 2 and 8; R is a group represented by C _m H _2m+1 , and m is an integer between 0 and 3;

(2) HCl gas is introduced into the alcohol solution of the compound represented by formula III, and the Gemini amine salt type fluorosurfactant represented by formula I is obtained through a salt-forming reaction.

In the above preparation method, n is preferably 6, and m is preferably 0.

In the above preparation method, in step (1), the molar ratio of 3-perfluorohexyl-1,2-propylene oxide to the diamine represented by formula II may be 2:1-1.5.

In the above preparation method, in step (1), the reaction temperature may be 10-80° C., and the reaction time may be 3-12 hours, specifically 3 hours or 12 hours. After the reaction, THF may be used for recrystallization.

In the above preparation method, in step (1), the temperature of the reaction may specifically be 35-80°C, specifically 35°C or 80°C.

In the above preparation method, in step (2), the temperature of the salt-forming reaction may be 20-90° C., and the time may be 5-10 hours. After the reaction, THF may be used for recrystallization.

In the above preparation method, in step (2), the temperature of the salt-forming reaction may preferably be 60-80°C, specifically 70°C, and the time may preferably be 6-8h, specifically 6h.

In the above preparation method, in step (2), the alcohol solution may specifically be methanol or ethanol, preferably ethanol.

The Gemini amine salt type fluorosurfactant provided by the invention has excellent surface performance and good foaming performance. The preparation method of the Gemini amine salt type fluorosurfactant provided by the invention has the advantages of cheap and easy-to-obtain raw materials, simple preparation method, easy control of reaction conditions and easy purification of products.

detailed description

The experimental methods used in the following examples are conventional methods unless otherwise specified.

The materials and reagents used in the following examples can be obtained from commercial sources unless otherwise specified.

Example 1, Synthesis of N,N'-di(3-perfluorohexyl-2-hydroxypropyl)hexamethylenediamine (Formula III-1)

In a 500ml three-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, add 11.6g (0.1mol) of hexamethylenediamine and 75.2g (0.2mol) of 3-perfluorohexyl-1,2-epoxypropane. The reaction was stirred at 80°C for 3 h, followed by TLC (developer: V _{ethyl acetate} : V _methanol = 2:1). After the reaction, a yellow viscous mixture was obtained. The product was recrystallized with 200 ml THF to obtain 43.2 g of a white solid product.

Example 2, Synthesis of N,N'-di(3-perfluorohexyl-2-hydroxypropyl)hexamethylenediamine (Formula III-1)

In a 500ml four-necked bottle equipped with a mechanical stirrer, a thermometer, a reflux condenser, and a constant pressure dropping funnel, add 11.6 g (0.1 mol) of hexamethylenediamine and absolute ethanol as a solvent, and use a constant pressure dropping funnel to drop 3-perfluorohexyl-1,2-epoxypropane 75.2g (0.2mol), stirred at 35°C for 12h after the dropwise addition, followed by TLC (developing agent: V _{ethyl acetate} : V _methanol = 2:1 ), a solid-liquid mixture was obtained after the reaction was completed, ethanol was removed, and the product was recrystallized with methanol and ether to obtain 72.5 g of a white solid product.

Example 3, Synthesis of N,N'-bis(3-perfluorohexyl-2-hydroxypropyl)hexamethylenediamine hydrochloride (Formula I-1)

In a 500ml four-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer, add 58.0g (0.067mol) of the compound shown in formula III-1 and 250ml of ethanol, pass HCl (g) into the ethanol solution, and The reaction was stirred at 70° C. for 6 h to obtain a solid-liquid mixture. The ethanol was removed, and the solid was recrystallized with THF to finally obtain 58.2 g of a white solid product.

The characterization data of formula I-1 are as follows:

¹ H NMR (400MHz, CD ₃ OD, δ/ppm): δ=1.484(m,4H,N-CH ₂ -CH ₂ -(CH ₂ ) ₂ -CH ₂ -CH ₂ -N), δ=1.775( m,4H,N-CH ₂ -CH ₂ -(CH ₂ ) ₂ -CH ₂ -CH ₂ -N), δ=2.466(m,4H,2CH ₂ -C ₆ F ₁₃ ), δ=3.04-3.32( m,8H,4CH ₂ -N),δ=4.409(m,2H,CH-O).

¹⁹ F NMR (300MHz, CDCl ₃ ,δ/ppm): δ=-82.418(m,6F,CF ₃ ),δ=-113.834(m,4F,CF ₂ α),δ=-122.760(m,4F, CF ₂ β), δ=-123.858(m, 4F, CF ₂ γ), δ=-124.582(m, 4F, CF ₂ δ), δ=-127.307(m, 4F, CF ₂ ω). The structure is correct.

Example 4, Synthesis of N,N'-bis(3-perfluorohexyl-2-hydroxypropyl)hexamethylenediamine hydrochloride (Formula I-1)

In a 500ml four-neck flask equipped with a mechanical stirrer, a reflux condenser and a thermometer, add 58.0g (0.067mol) of the compound shown in formula III-1 and 350.0ml methanol, and pass the amount of HCl (g) into the methanol solution, The reaction was stirred at 60-65° C. for 6 h to obtain a solid-liquid mixture. Methanol was removed, and the solid was recrystallized with THF to finally obtain 49.6 g of a white solid product.

Example 5, Synthesis of N,N'-di(3-perfluorohexyl-2-hydroxypropyl)hexamethylenediamine hydrochloride (Formula I-1)

In a 500ml four-neck flask equipped with a mechanical stirrer, a reflux condenser and a thermometer, add 58.0g (0.067mol) of the compound shown in formula III-1 and 250.0ml of ethanol, and pass the amount of HCl (g) into the ethanol solution, Reflux at 75-78°C for 6 hours to obtain a solid-liquid mixture. After removal of ethanol, the solid was recrystallized with THF to finally obtain 56.5 g of a white solid product.

Embodiment 6, use high-purity water (ρ=18.23MΩ.cm) to prepare the pure aqueous solution of Gemini amine salt type fluorosurfactant shown in formula I-1, after equilibrating at room temperature for 48h, utilize surface tensiometer (K12, Kruss Co., Germany) used the suspension ring method to measure the surface tension of aqueous solutions with different concentrations at 25°C.

The critical micelle concentration CMC (mol/L) and the surface tension γ _cmc (mN/m) under the critical micelle concentration of the amine salt type fluorosurfactant prepared by the present invention were measured to be 0.1009mmol/L and 27.03mN/m respectively. m, it can be known that the Gemini amine salt type fluorosurfactant synthesized by the present invention has lower surface tension, and the tendency to reduce the surface tension of aqueous solution is far greater than the tendency of aggregation to generate micelles; the critical micelle concentration is higher than that of common surfactant 2 to 3 orders of magnitude lower.

Claims (6)

1. the amine salt of Gemini shown in formula I type fluorine surfactant,

In formula I, R is C _mh _2m+1shown group, wherein m is the integer between 0 ~ 3, and n is the integer between 2 ~ 8.

2. fluorine surfactant according to claim 1, is characterized in that: m is 0, n is 6.

3. the preparation method of the amine salt of Gemini shown in formula I type fluorine surfactant, comprises the steps:

(1) diamines shown in 3-perfluoro hexyl-1,2-expoxy propane and formula II carries out being obtained by reacting compound shown in formula III;

Wherein, n is the integer between 2 ~ 8; R is C _mh _2m+1shown group, m is the integer between 0 ~ 3;

(2) in the alcoholic solution of compound shown in formula III, pass into HCl gas, obtain the amine salt of Gemini shown in formula I type fluorine surfactant through salt-forming reaction;

In step (1), the temperature of described reaction is 10 ~ 80 DEG C, and the time is 3 ~ 12h;

In step (1), the mol ratio of diamines shown in 3-perfluoro hexyl-1,2-expoxy propane and formula II is 2:1 ~ 1.5;

In step (2), the temperature of described salt-forming reaction is 20 ~ 90 DEG C, and the time is 5 ~ 10h.

4. preparation method according to claim 3, is characterized in that: in step (1), and the temperature of described reaction is 35 ~ 80 DEG C.

5. preparation method according to claim 3, is characterized in that: in step (2), and the temperature of described salt-forming reaction is 60 ~ 80 DEG C, and the time is 6 ~ 8h.

6. the preparation method according to claim 3 or 5, is characterized in that: in step (2), and described alcoholic solution is methanol solution or ethanolic solution.