CN101073757A - Asymmetric Gemini surfactant and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the field of Gemini surfactants, in particular to a kind of asymmetric Gemini surfactant with chemical structural formula (I), m=6～30 in the formula (I); n=0～30; X is selected from One or a mixture of H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ ; Y is selected from Li ⁺ , Na ⁺ , K ⁺ , One or more mixtures of NH ₄ ⁺ , wherein preferably m=10-15; n=0-15. The invention also relates to the preparation method and application of the surfactant. The surfactant has two different hydrophilic groups, one is sulfonate, the other is carboxylate or carboxylate; the linking group is phenoxy. In addition to the properties of Gemini surfactants, this surfactant also has excellent water solubility, hard water resistance, alkali resistance and foaming due to its two hydrophilic groups being sulfonic acid head and carboxylic acid head respectively. It can be well used in industries such as washing, textile and tertiary oil recovery.

Description

A kind of asymmetric Gemini surfactant and its preparation method and application

technical field

The invention belongs to the field of Gemini surfactants, in particular to an asymmetric Gemini surfactant.

Background technique

Gemini surfactant is two traditional surfactant molecules, which are chemically bonded into a new type of surfactant through a special linking group, that is, a molecular structure contains two hydrophilic groups and two lipophilic chains . From the molecular structure of the Gemini surfactant, it can be known that the surfactant not only enhances the hydrophobic effect of the hydrocarbon chain, but also adjusts the distance of the hydrophilic group through the linking group, changing the geometry of the unit molecule, making the surface of the micelle Changes in charge density, degree of hydration, and micelle shape give it certain properties. Compared with traditional surfactants, Gemini surfactants have the following characteristics:

(1) The two ionic head groups of the Gemini surfactant are connected by a linking group through a chemical bond, resulting in a fairly tight connection between the two surfactant monomer molecules, resulting in a strong bond between the hydrophobic hydrocarbon chains. The interaction inhibits the separation effect caused by the electrostatic repulsion between the hydrophilic ion head groups, strengthens the combination between the hydrophobic hydrocarbon chains, and makes it easier for Gemini surfactants to aggregate into micelles. Therefore, compared with traditional surfactants with comparable hydrocarbon chain lengths, the critical micelle concentration of Gemini surfactants is much lower, so the use concentration can be greatly reduced, making it more suitable for use as emulsifiers and dispersants.

(2) It is easier to adsorb on the gas/liquid interface, and the arrangement is more compact, thereby effectively reducing the surface tension of the aqueous solution. In many occasions, it is an excellent wetting agent.

(3) It has a very low Kraft point and good water solubility.

(4) Good solubilization and strong solubilizing ability for organic matter.

(5) It has unique rheology and viscoelasticity.

(6) The synergistic effect between Gemini surfactant and other surfactants is more likely. For ionic Gemini surfactants, the ion head group has twice the charge, so that small solid particles can be stably dispersed and suspended in water, and there may be stronger interactions with other types of surfactants (Since the synergistic effect of a surfactant with other surfactants depends to a large extent on the strength of the interaction between the hydrophilic groups of the two surfactants).

In addition, Gemini surfactants with asymmetric molecular structure, especially when they have two different head groups, exhibit novel self-organization properties and become the focus of current attention. However, at present, Gemini surfactants, especially asymmetric Gemini surfactants, are difficult to synthesize and have high production costs, which seriously hinder the popularization and application of Gemini surfactants.

Contents of the invention

One of the objects of the present invention is to provide an asymmetric Gemini surfactant.

The second object of the present invention is to provide a preparation method of the asymmetric Gemini surfactant.

The third object of the present invention is to provide the purposes of this asymmetric Gemini surfactant.

Four of object of the present invention is to provide a kind of system that comprises this asymmetric Gemini surfactant, this system can form low or ultra-low interfacial tension ( 10 ^-3 mN/m), which can be applied in the tertiary oil recovery of oil fields.

A kind of asymmetric Gemini surfactant provided by the present invention

Express it as C _m CO ₂ XpC _n SO ₃ Y.

The asymmetrical Gemini surfactant C _m CO ₂ XpC _n SO ₃ Y synthesized by the present invention is characterized in that the molecule contains two traditional surfactants with a single head and a single tail, which are connected by phenoxy groups, and the two hydrophilic The groups are respectively sulfonate and carboxylate or carboxylate, and its structural formula is:

Among them: m=6~30, n=0~30; X=H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , or the groups mentioned above or a mixture of ions; Y is Li ⁺ , Na ⁺ or K ⁺ , NH ₄ ⁺ ions or a mixture of the above ions.

Among them, the preferred scheme is: m=10-15; n=0-15.

The invention provides two preparation methods _{of asymmetric} Gemimi surfactant _{CmCO2XpCnSO3Y :}

method one:

The synthesis of the asymmetric Gemini surfactant C _m CO ₂ XpC _n SO ₃ Y of the present invention is completed by the following steps in turn:

(1) Synthesis of α-alkyphenoxy carboxylate

Among them: m=6～30, n=0～30; R=H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ ;

Get α-bromocarboxylate, alkylphenol with carbon number 0～30 and alkali in the reactor, α-bromocarboxylate: alkylphenol: the molar ratio of alkali is 1～1.2:1:1 ~2; Dissolve the above mixture in a mixed solvent of N, N'-dimethylformamide or dimethyl sulfoxide and benzene or toluene, wherein, N, N'-dimethylformamide or dimethyl sulfoxide The volume ratio of sulfone to benzene or toluene is 1 to 5:1, heat up to boiling under stirring, reflux to separate water, stop heating after no water comes out, filter the reaction solution after cooling, transfer the filtrate to a separatory funnel, add water to separate Liquid, the separated organic phase was dried with a desiccant, evaporated to remove the organic solvent, and subjected to vacuum distillation to obtain α-alkphenoxy carboxylate.

The base is K ₂ CO ₃ , Na ₂ CO ₃ , KHCO ₃ , NaHCO ₃ , NaOH or KOH.

The desiccant is anhydrous magnesium sulfate, anhydrous calcium chloride, anhydrous calcium sulfate, anhydrous sodium sulfate and the like.

(2) Sulfonation of α-alkylphenoxy carboxylates

Among them: m=6~30, n=0~30; X=H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , Li ⁺ , Na ₊ , K ⁺ , NH ₄ ⁺ , or the groups mentioned above or a mixture of ions; Y is Li ⁺ , Na ⁺ or K ⁺ in alkali metal ions, NH ₄ ⁺ ions or a mixture of the above-mentioned ions.

Take α-alkphenoxy carboxylate in a reactor filled with 1,2-dichloroethane or methylene chloride or chloroform, and add a sulfonating agent dropwise to the reactor under stirring, wherein the sulfonating agent is chlorine Sulfonic acid or oleum, the molar ratio of α-alkphenoxy carboxylate to sulfonating agent (calculated as oleum converted to SO ₃ ) is 1:1 to 1:2. During the dropwise addition, use an ice-water bath to lower the temperature of the reaction solution to below 10°C. After the sulfonating agent is added dropwise, remove the ice-water bath and continue the reaction at room temperature for 1.5 to 8 hours, then slowly pour the reaction solution into cold water. Transfer to a separatory funnel, separate the organic phase and wash with water until neutral. The organic phase was evaporated to remove the solvent, then dissolved in water, neutralized by adding alkali, and then evaporated to remove the water, the obtained solid was extracted with ethanol or methanol, filtered, and the filtrate was evaporated to remove the solvent to obtain the target product asymmetric Gemini surfactant C _m CO ₂ XpC _n SO ₃ y.

The base is LiOH, LiHCO ₃ , Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ , NaHCO ₃ , KOH, K ₂ CO ₃ , or KHCO ₃ , ammonia water or a mixture thereof.

Method Two:

The synthesis of the asymmetric Gemini surfactant C _m CO ₂ XpC _n SO ₃ Y of the present invention is completed by the following steps in turn:

(1) Synthesis of α-alkyphenoxy carboxylate

Among them: m=6～30, n=0～30; R=H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ ;

Get α-bromocarboxylate, alkylphenol with carbon number 0～30 and alkali in the reactor, α-bromocarboxylate: alkylphenol: the molar ratio of alkali is 1～1.2:1:1 ~2; Dissolve the above mixture in a mixed solvent of N, N'-dimethylformamide or dimethyl sulfoxide and benzene or toluene, wherein, N, N'-dimethylformamide or dimethyl sulfoxide The volume ratio of sulfone to benzene or toluene is 1 to 5:1, heat up to boiling under stirring, reflux to separate water, stop heating after no water comes out, filter the reaction solution after cooling, transfer the filtrate to a separatory funnel, add water to separate Liquid, the separated organic phase was dried with a desiccant, evaporated to remove the organic solvent, and subjected to vacuum distillation to obtain α-alkphenoxy carboxylate.

The base is K ₂ CO ₃ , Na ₂ CO ₃ , KHCO ₃ , NaHCO ₃ , NaOH or KOH.

The desiccant is anhydrous magnesium sulfate, anhydrous calcium chloride, anhydrous calcium sulfate, anhydrous sodium sulfate and the like.

(2) Hydrolysis of α-alkylphenoxycarboxylate

Among them: m=6～30, n=0～30;

Get α-alkphenoxy carboxylate and dissolve in ethanol or methanol, add the aqueous solution of alkali wherein, the mol ratio of used α-alkphenoxy carboxylic acid: alkali is 1: 1～2; The temperature of reaction mixture is raised To reflux, the reaction solution becomes clear, indicating that the reaction is complete, stop heating, wait for the system to cool, add dilute hydrochloric acid or dilute sulfuric acid to it until the pH value of the reaction solution is 2 to 6, stir overnight, filter with suction, wash the solid with water and dry it, that is In α-alkphenoxy carboxylic acid.

The base is K ₂ CO ₃ , Na ₂ CO ₃ , NaOH or KOH.

(3) Sulfonation of α-alkylphenoxycarboxylic acid

Among them: m=6~30, n=0~30; X=H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , or the groups mentioned above or any mixture of ions; Y is Li ⁺ , Na ⁺ or K ⁺ of alkali metal ions, NH ₄ ⁺ ions or any mixture of the above-mentioned ions.

Take α-alkphenoxy carboxylic acid in a reactor filled with 1,2-dichloroethane or dichloromethane or chloroform, and add sulfonating agent dropwise to the reactor under stirring, wherein the sulfonating agent is chlorosulfur Acid or oleum, the molar ratio of α-alkphenoxy carboxylate to sulfonating agent (calculated as oleum converted to SO ₃ ) is 1:1 to 1:2. During the dropwise addition, use an ice-water bath to lower the temperature of the reaction solution to below 10°C. After the sulfonating agent is added dropwise, remove the ice-water bath and continue the reaction at room temperature for 1.5 to 8 hours, then slowly pour the reaction solution into cold water. Transfer to a separatory funnel, separate the organic phase and wash with water until neutral. The organic phase was evaporated to remove the solvent and then dissolved in water, neutralized by adding alkali and then evaporated to remove the water. The resulting solid was extracted with ethanol or methanol, filtered and the filtrate was evaporated to obtain the target product C _m CO ₂ XpC _n SO ₃ Y.

The base is LiOH, LiHCO ₃ , Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ , NaHCO ₃ , KOH, K ₂ CO ₃ , or KHCO ₃ , ammonia water or a mixture thereof.

The preparation method of the asymmetric Gemini surfactant C _m CO ₂ XpC _n SO ₃ Y provided by the invention has simple process and high yield; its molecular structure contains two hydrophobic groups and two hydrophilic groups, and has excellent Solubility and high surface activity; ^-COO- in the hydrophilic group can complex high-valent cations, such as Ca ²⁺ , Mg ^{2+ ,} etc., and another hydrophilic group -SO ^3- still acts as a surfactant The role of the surfactant greatly improves the surface activity and hard water resistance of the surfactant, and their alkali resistance and foaming properties are also very good. Therefore, this type of surfactant can be used as an emulsifier and wetting agent for pesticides, as a wetting agent and detergent for metal cleaning, as a collector and foaming agent for ore flotation, as a penetrating agent, homogeneous Dyeing agent and antistatic agent for silk dyeing and finishing, as solubilizer and softener for leather treatment, also used as corrosion inhibitor, lubricant, fuel additive, foaming agent, fiber cleaning agent, antistatic agent and antirust One of the raw materials of the additive formula.

The asymmetric Gemini surfactant C _m CO ₂ XpC _n SO ₃ Y provided by the invention has high surface activity and can be used in tertiary oil recovery by compounding with auxiliary agents. Wherein, the concentration of the asymmetric Gemini surfactant C _m CO ₂ XpC _n SO ₃ Y in the system is 100mg/L～10000mg/L; the auxiliary agent is alkali, anionic surfactant, nonionic Surfactants, amphoteric surfactants, fatty acids, fatty alcohols, partially hydrolyzed polyacrylamide polymers, polyacrylic acid polymers, polysaccharide polymers, hydrophobic association copolymers, xanthan gum, chelating agents, etc. or their The mixture; the base is LiOH, LiHCO ₃ , Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ , NaHCO ₃ , KOH, K ₂ CO ₃ , or KHCO ₃ , ammonia water or their mixture; the anion surface Active agents include fatty acid salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, petroleum sulfonates, lignosulfonates, alkyl sulfates, phosphate ester salts or mixtures thereof ; Described nonionic surfactant comprises fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol polyoxyethylene ether, polyoxyethylene alkyl amine, polyoxyethylene alkyl acyl alcohol amine, alkyl polyoxyethylene Glucoside or their mixtures; the amphoteric surfactants include imidazoline derivatives, betaine derivatives, aminopropionic acid derivatives, taurine derivatives or their mixtures.

Description of drawings

Fig. 1. The ¹ H NMR spectrum (heavy water) of C ₁₂ CO ₂ C ₂ H ₅ -pC ₄ SO ₃ Na of Example 1 of the present invention.

Fig. 2. ESI-MS spectrum of C ₁₂ CO ₂ C ₂ H ₅ -pC ₄ SO ₃ Na in Example 1 of the present invention.

Fig. 3. The ¹ H NMR spectrum (heavy water) of C ₁₂ CO ₂ Na-pC ₀ SO ₃ Na of Example 2 of the present invention.

Fig. 4. C ₁₂ CO ₂ Na-pC ₀ SO ₃ Na aqueous solution γ-1gC curve of Example 2 of the present invention (experimental temperature 30°C).

Figure 5. ¹ H NMR spectrum (heavy water) of C ₁₂ CO ₂ HpC ₈ SO ₃ NH ₄ of Example 3 of the present invention

Fig. 6. ¹ H NMR spectrum (heavy water) of C ₁₂ CO ₂ HpC ₈ SO ₃ Na of Example 5 of the present invention.

Figure 7. The dynamic interfacial tension between the C ₁₂ CO ₂ HpC ₈ SO ₃ Na 0.5wt% aqueous solution of Example 5 of the present invention and Chengdong crude oil from Shengli Oilfield (the water is simulated Chengdong groundwater, and the salinity is 6257mg/L) .

Fig. 8. C ₁₂ CO ₂ Na-pC ₉ SO ₃ Na aqueous solution γ-1gC curve of Example 6 of the present invention (experimental temperature 30°C).

Figure 9. The dynamic interfacial tension between the C ₁₂ CO ₂ Na-pC ₉ SO ₃ Na 0.3wt% aqueous solution of Example 6 of the present invention and Chengdong crude oil from Shengli Oilfield in the presence of 0.2wt% Na ₂ CO ₃ (water is simulated Chengdong Groundwater, salinity 6257mg/L).

Figure 10. Foaming performance and foam stabilizing performance of the C ₁₂ CO ₂ Na-pC ₉ SO ₃ Na aqueous solution of Example 6 of the present invention.

Detailed ways

Below by embodiment the present invention will be further described, and its purpose is only to understand content of the present invention better and unrestricted protection scope of the present invention:

Example 1

The first step: get α-bromotetradecanoic acid ethyl ester, p-tert-butylphenol and potassium carbonate in a three-necked flask, the mol ratio of α-bromotetradecanoic acid ethyl ester: p-tert-butylphenol: potassium carbonate 1.1:1:1.5; dissolve the above mixture in a mixed solvent of N,N'-dimethylformamide:toluene with a volume ratio of 3:1, heat up to boiling under stirring, reflux to separate water, and wait for no water to come out Then stop heating, filter the reaction solution after cooling, transfer the filtrate to a separatory funnel, add water to separate the liquid, and dry the separated organic phase with anhydrous magnesium sulfate. After filtering, evaporate the organic solvent and carry out vacuum distillation to obtain α- Ethyl (p-tert-butyl)phenoxytetradecanoate.

The second step: take α-(p-tert-butyl)phenoxytetradecanoic acid ethyl ester in a three-necked flask filled with 1,2-dichloroethane, and add chlorosulfonic acid dropwise to the three-necked flask under stirring , The molar ratio of ethyl α-(p-tert-butyl)phenoxycarboxylate:chlorosulfonic acid was 1:1.2. During the dropwise addition process, the temperature of the reaction solution was lowered to below 10°C with an ice-water bath. After the dropwise addition of chlorosulfonic acid, the ice-water bath was removed, and the reaction was continued at room temperature for 4.5 hours, then the reaction solution was slowly poured into cold water, and transferred to Using a separatory funnel, the organic phase was separated and washed with water until neutral. The organic phase was evaporated to remove the solvent, dissolved in water, neutralized by adding sodium bicarbonate to pH = 8, and then evaporated to remove the water, the obtained solid was extracted with ethanol, filtered and the filtrate was evaporated to obtain the target product C ₁₂ CO ₂ C ₂ H ₅ - pC ₄ SO ₃ Na. Its ¹ H-NMR spectrum and ESI-MS spectrum are shown in Figure 1 and Figure 2, respectively.

Example 2

The first step: get α-bromotetradecanoic acid ethyl ester, phenol and salt of wormwood in the reactor, the mol ratio of α-bromoteristate ethyl ester: phenol: potassium carbonate is 1.1: 1: 1.5; Dissolve the mixture in a mixed solvent of N,N'-dimethylformamide:benzene with a volume ratio of 3:1, heat up to boiling with stirring, reflux to separate water, stop heating after no water is separated, and filter the reaction solution after cooling , the filtrate was transferred to a separatory funnel, water was added for liquid separation, the separated organic phase was dried with anhydrous calcium chloride, the organic solvent was evaporated after filtration, and the vacuum distillation was carried out to obtain ethyl α-phenoxytetradecanoate .

The second step: take α-phenoxytetradecanoic acid ethyl ester in a three-necked flask filled with 1,2-dichloroethane, add chlorosulfonic acid dropwise to the three-necked flask under stirring, α-phenoxy The ethyl carboxylate:chlorosulfonic acid molar ratio was 1:1.5. During the dropwise addition process, the temperature of the reaction solution was lowered to below 10°C with an ice-water bath. After the dropwise addition of chlorosulfonic acid, the ice-water bath was removed, and the reaction was continued at room temperature for 4.5 hours, then the reaction solution was slowly poured into cold water, and transferred to Using a separatory funnel, the organic phase was separated and washed with water until neutral. Dissolve the organic phase in water after distilling off the solvent, add sodium hydroxide 2.5 times the molar weight of α-phenoxytetradecanoic acid ethyl ester, heat to boiling, stop heating after reflux for 2 hours, add dilute hydrochloric acid to neutralize to pH = After 8, the water was distilled off, and the obtained solid was extracted with ethanol. After filtration, the filtrate was distilled to remove ethanol to obtain the target product C ₁₂ CO ₂ Na-pC ₀ SO ₃ Na. Its ¹ H-NMR spectrum is shown in Figure 3, and its aqueous solution γ-1gC curve is shown in Figure 4.

Example 3

The first step: get α-bromotetradecanoic acid ethyl ester, p-tert-butylphenol and potassium carbonate in a three-necked flask, the mol ratio of α-bromotetradecanoic acid ethyl ester: p-tert-butylphenol: potassium carbonate 1.1:1:1.5; dissolve the above mixture in a mixed solvent of N,N'-dimethylformamide:toluene with a volume ratio of 3:1, heat up to boiling under stirring, reflux to separate water, and wait for no water to come out Then stop heating, filter the reaction solution after cooling, transfer the filtrate to a separatory funnel, add water to separate the liquid, and dry the separated organic phase with anhydrous magnesium sulfate. After filtering, evaporate the organic solvent and carry out vacuum distillation to obtain α- Ethyl (p-tert-butyl)phenoxytetradecanoate.

The second step: take α-(p-tert-butyl)phenoxytetradecanoic acid ethyl ester and dissolve it in ethanol, add an aqueous solution of sodium hydroxide to it, and use α-(p-tert-butyl)phenoxytetradecanoic acid The molar ratio of ethyl ester: sodium hydroxide is 1: 1.5; the temperature of the reaction mixture is raised to reflux, the reaction liquid becomes clear, indicating that the reaction is complete, stop heating, and when the system is cooled, add dilute hydrochloric acid or dilute sulfuric acid dropwise to the pH of the reaction liquid The value is 2-6, stir overnight, filter with suction, wash the solid with water and dry to obtain α-(p-tert-butyl)phenoxytetradecanoic acid. The third step: take α-(p-tert-butyl)phenoxytetradecanoic acid in a three-necked flask filled with 1,2-dichloroethane, and add chlorosulfonic acid dropwise to the three-necked flask under stirring, α -(p-tert-butyl)phenoxytetradecanoic acid:chlorosulfonic acid molar ratio is 1:1.5. During the dropwise addition process, the temperature of the reaction solution was lowered to below 10°C with an ice-water bath. After the dropwise addition of chlorosulfonic acid, the ice-water bath was removed, and the reaction was continued at room temperature for 4.5 hours, then the reaction solution was slowly poured into cold water, and transferred to Using a separatory funnel, the organic phase was separated and washed with water until neutral. The organic phase was evaporated to remove the solvent, then dissolved in water, neutralized with excess ammonia water, and then evaporated to remove the _water . _The obtained solid _was extracted with _{ethanol .} The ¹ H-NMR spectrum of this product is shown in FIG. 5 .

Example 4

The first step: get α-bromotetradecanoic acid ethyl ester, p-octylphenol and potassium carbonate in the reactor, α-bromotetradecanoic acid ethyl ester: p-octylphenol: the mol ratio of potassium carbonate is 1.1: 1:1.5; dissolve the above mixture in a mixed solvent of N,N'-dimethylformamide:benzene with a volume ratio of 3:1, heat up to boiling under stirring, reflux to separate water, and stop heating after no water is separated , the reaction solution is filtered after cooling, the filtrate is transferred to a separatory funnel, and water is added to separate liquids, and the separated organic phase is dried with anhydrous magnesium sulfate, and the organic solvent is evaporated after filtration, and the underpressure distillation is carried out to obtain α-( base) ethyl phenoxytetradecanoate.

The second step: take α-(p-octyl)phenoxytetradecanoic acid ethyl ester and dissolve it in ethanol, add the aqueous solution of sodium hydroxide to it, the used α-(p-octyl)phenoxytetradecanoic acid ethyl ester : The molar ratio of sodium hydroxide is 1: 1.5; The reaction mixture is warmed up to reflux, the reaction solution becomes clear to indicate that the reaction is complete, stop heating, and when the system is cooled, dilute hydrochloric acid or dilute sulfuric acid is added dropwise thereto until the pH of the reaction solution is 2-6, stir overnight, filter with suction, wash the solid with water and dry to obtain α-(p-octyl)phenoxycarboxylic acid.

The third step: take α-(p-octyl)phenoxytetradecanoic acid in a three-necked flask filled with 1,2-dichloroethane, add chlorosulfonic acid dropwise to the three-necked flask under stirring, α- The molar ratio of (p-octyl)phenoxytetradecanoic acid:chlorosulfonic acid is 1:1.5. During the dropwise addition process, the temperature of the reaction solution was lowered to below 10°C with an ice-water bath. After the dropwise addition of chlorosulfonic acid, the ice-water bath was removed, and the reaction was continued at room temperature for 4.5 hours, then the reaction solution was slowly poured into cold water, and transferred to Using a separatory funnel, the organic phase was separated and washed with water until neutral. The organic phase was evaporated to remove the solvent, then dissolved in water, neutralized by adding excess NaHCO ₃ to neutrality, and then evaporated to remove the water, the obtained solid was extracted with ethanol, filtered, and the filtrate was evaporated to remove the ethanol to obtain the target product C ₁₂ CO ₂ HpC ₈ SO ₃ Na. The ¹ H-NMR spectrum of this product is shown in Figure 6, and the dynamic interfacial tension between its 0.5wt% aqueous solution (water is simulated Chengdong groundwater, salinity 6257 mg/L) and Chengdong crude oil from Shengli Oilfield is shown in Figure 7 shown.

Example 5

The first step: get α-bromotetradecanoic acid ethyl ester, p-nonylphenol and potassium carbonate in the reactor, α-bromoteristate ethyl ester: p-nonylphenol: the mol ratio of potassium carbonate is 1.1: 1:1.5; dissolve the above mixture in a mixed solvent of N,N'-dimethylformamide:benzene with a volume ratio of 3:1, heat up to boiling under stirring, reflux to separate water, and stop heating after no water is separated , the reaction solution is filtered after cooling, the filtrate is transferred to a separatory funnel, and water is added to separate liquids, and the organic phase separated is dried with anhydrous calcium chloride, and the organic solvent is evaporated after filtration, and the underpressure distillation is carried out to obtain α-( Nonyl)phenoxytetradecanoic acid ethyl ester.

The second step: get α-(p-nonyl)phenoxytetradecanoic acid ethyl ester in a three-necked flask filled with 1,2-dichloroethane, and add chlorosulfonic acid dropwise in the three-necked flask under stirring, The molar ratio of α-(p-nonyl)phenoxytetradecanoic acid ethyl ester:chlorosulfonic acid is 1:1.5. During the dropwise addition process, the temperature of the reaction solution was lowered to below 10°C with an ice-water bath. After the dropwise addition of chlorosulfonic acid, the ice-water bath was removed, and the reaction was continued at room temperature for 4.5 hours, then the reaction solution was slowly poured into cold water, and transferred to Using a separatory funnel, the organic phase was separated and washed with water until neutral. Dissolve the organic phase in water after distilling off the solvent, add sodium hydroxide 2.5 times the molar weight of α-phenoxytetradecanoic acid ethyl ester, heat to boiling, stop heating after reflux for 2 hours, add dilute hydrochloric acid to neutralize to pH = After 8, the water was evaporated, and the obtained solid was extracted with ethanol. After filtration, the filtrate was evaporated to remove the ethanol to obtain the target product C ₁₂ CO ₂ Na-pC ₉ SO ₃ Na. The γ-1gC curve of its aqueous solution is shown in Figure 8, and its 0.3wt% aqueous solution ( The water is simulated Chengdong groundwater, the salinity is 6257mg/L) in the presence of 0.2wt% Na ₂ CO ₃ and the dynamic interfacial tension of Chengdong crude oil from Shengli Oilfield is shown in Fig. 9, and the foaming performance and foam stabilizing performance of its aqueous solution are shown in Fig. 10.

Claims (6)

1, an asymmetric Gemini surfactant, is characterized in that its structural formula is as shown in (1):

In formula (I): m=6~30; n=0~30; X is selected from H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ One or a mixture of several; Y is one or a mixture of several selected from Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ . 2. An asymmetric Gemini surfactant as claimed in claim 1, characterized in that m=10-15; n=0-15. 3. A method for preparing the asymmetric Gemini surfactant as claimed in claim 1, characterized in that it is completed by the following steps successively: (1) Synthesis of α-alkyphenoxy carboxylate Get α-bromocarboxylate, alkylphenol and alkali with carbon number of 0～30 in the reactor, wherein α-bromocarboxylate: alkylphenol: the mol ratio of alkali is 1～1.2: 1: 1~2; Dissolve the above mixture in a mixed solvent of N,N'-dimethylformamide or dimethyl sulfoxide and benzene or toluene, wherein, N,N'-dimethylformamide or dimethyl The volume ratio of sulfoxide to benzene or toluene is 1 to 5:1, heat up to boiling under stirring, reflux to separate water, stop heating after no water is separated, filter the reaction solution after cooling, transfer the filtrate to a separatory funnel, add water to carry out Liquid separation, the separated organic phase is dried with a desiccant, and the organic solvent is evaporated, and the vacuum distillation is carried out to obtain α-alkphenoxy carboxylate; The base is K ₂ CO ₃ , Na ₂ CO ₃ , KHCO ₃ , NaHCO ₃ , NaOH or KOH; The desiccant is anhydrous magnesium sulfate, anhydrous calcium chloride, anhydrous calcium sulfate, anhydrous sodium sulfate; (2) Sulfonation of α-alkylphenoxy carboxylates Take α-alkphenoxy carboxylate in a reactor filled with 1,2-dichloroethane or dichloromethane or chloroform, add sulfonating agent dropwise to the reactor under stirring, α-alkphenoxy The molar ratio of carboxylate and sulfonating agent is 1:1～1:2; during the dropping process, use an ice-water bath to lower the temperature of the reaction solution to below 10°C. After adding the sulfonating agent dropwise, remove the ice-water bath, and Continue to react for 1.5 to 8 hours, then slowly pour the reaction solution into cold water, transfer it to a separatory funnel, separate the organic phase and wash it with water until neutral; dissolve the organic phase in water after removing the solvent, add alkali to neutralize Evaporate the water, extract the obtained solid with ethanol or methanol, and evaporate the solvent from the filtrate after filtration to obtain the target product Gemini surfactant; The base is LiOH, LiHCO ₃ , Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ , NaHCO ₃ , KOH, K ₂ CO ₃ , KHCO ₃ , ammonia water or their mixtures; The sulfonating agent is chlorosulfonic acid or oleum. 4. A method for preparing the asymmetric Gemini surfactant as claimed in claim 1, characterized in that it is completed by the following steps successively: (1) Synthesis of α-alkylphenoxy carboxylate: Get α-bromocarboxylate, alkylphenol with carbon number 0～30 and alkali in the reactor, α-bromocarboxylate: alkylphenol: the molar ratio of alkali is 1～1.2:1:1 ~2; Dissolve the above mixture in a mixed solvent of N, N'-dimethylformamide or dimethyl sulfoxide and benzene or toluene, wherein, N, N'-dimethylformamide or dimethyl sulfoxide The volume ratio of sulfone to benzene or toluene is 1 to 5:1, heat up to boiling under stirring, reflux to separate water, stop heating after no water comes out, filter the reaction solution after cooling, transfer the filtrate to a separatory funnel, add water to separate Liquid, the separated organic phase is dried with a desiccant and then evaporated to remove the organic solvent, and then distilled under reduced pressure to obtain α-alkphenoxy carboxylate; The base is K ₂ CO ₃ , Na ₂ CO ₃ , KHCO ₃ , NaHCO ₃ , NaOH or KOH; The desiccant is anhydrous magnesium sulfate, anhydrous calcium chloride, anhydrous calcium sulfate, anhydrous sodium sulfate; (2) Hydrolysis of α-alkylphenoxy carboxylate: Dissolve α-alkphenoxy carboxylate in ethanol or methanol, add alkali aqueous solution therein, the molar ratio of α-alkphenoxy carboxylic acid used: alkali is 1: 1～2; the temperature of reaction mixture is raised To reflux, the reaction solution becomes clear, indicating that the reaction is complete, stop heating, wait for the system to cool, add dilute hydrochloric acid or dilute sulfuric acid to it until the pH value of the reaction solution is 2 to 6, stir overnight, filter with suction, wash the solid with water and dry it, that is Get α-alkphenoxy carboxylic acid; The base is K ₂ CO ₃ , Na ₂ CO ₃ , NaOH or KOH; (3) Sulfonation of α-alkylphenoxycarboxylic acid Take α-alkphenoxy carboxylic acid in a reactor filled with 1,2-dichloroethane or dichloromethane or chloroform, add sulfonating agent dropwise to the reactor under stirring, α-alkphenoxy carboxylic acid The molar ratio of acid ester to sulfonating agent is 1:1~1:2; during the dropping process, use an ice-water bath to lower the temperature of the reaction solution below 10°C. After adding the sulfonating agent dropwise, remove the ice-water bath and continue at room temperature. React for 1.5 to 8 hours, then slowly pour the reaction solution into cold water, transfer to a separatory funnel, separate the organic phase and wash with water until neutral; the organic phase is evaporated to remove the solvent and then dissolved in water, neutralized by adding alkali and then evaporated water, the resulting solid is extracted with ethanol or methanol, and after filtration, the filtrate is evaporated to remove the solvent to obtain the target product Gemini surfactant; The base is LiOH, LiHCO ₃ , Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ , NaHCO ₃ , KOH, K ₂ CO ₃ , KHCO ₃ , ammonia water or their mixtures. 5. The application of the asymmetric Gemini surfactant as claimed in claim 1 in pesticides as emulsifier and wetting agent; as the application of wetting agent and detergent in metal cleaning process; as collector and foaming agent Application in ore flotation; application in silk dyeing and finishing as penetrant, leveling agent and antistatic agent; application in leather treatment as solubilizer and softener; and application in corrosion inhibitor, lubricant, fuel Application as one of the formula raw materials in additives, foaming agents, fiber cleaning agents, antistatic agents and antirust additives. 6. The application of the asymmetric Gemini surfactant as claimed in claim 1 as an oil displacement agent in tertiary oil recovery.

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