Asymmetric Gemini surfactant, preparation method and application thereof

Abstract

The present invention is applicable to the field of oil recovery, and provides an asymmetric Gemini surfactant, a preparation method and an application thereof. The asymmetric Gemini surfactant provided by the present invention has a lower critical micelle concentration, can form micelle aggregates at low concentrations, and has the potential for micelle drive or microemulsion drive; relative to single-chain surfactants with the same carbon chain length, it has a stronger ability to reduce surface tension and oil-water interfacial tension. It can reduce oil-water interfacial tension under alkali-free or alkaline conditions, improve oil recovery efficiency, and has great application potential in the field of chemical drive to enhance oil recovery; the asymmetric Gemini surfactant has three charge sites, good solubility, can be combined with a variety of counterions, has strong salt resistance, will not undergo phase separation precipitation, and is easy to prepare and use; the asymmetric Gemini surfactant can achieve matching with various types of crude oil by adjusting its own structure, and has a wide range of applications.

Description

Technical Field

[0001] The invention belongs to the field of oil recovery, and particularly relates to an asymmetric Gemini surfactant, a preparation method and application thereof. Background Art

[0002] Surfactant molecules are amphiphilic molecules composed of a hydrophilic head group and a hydrophobic chain. In the bulk phase and at the interface (oil-water interface, solid-liquid interface, gas-liquid interface), surfactant molecules will form an ordered assembly through intermolecular interactions. These assembly structures and molecular arrangements give surfactants a series of unique properties, such as unique rheology, reduced surface tension, improved wettability, etc. Therefore, surfactants are widely used in the fields of detergents, food, medicine, printing and dyeing, tertiary oil recovery, etc.

[0003] Gemini surfactants are a new type of surfactants that are generally composed of at least two hydrophilic head groups and two hydrophobic groups connected by a linking group at or near the hydrophilic head group. Gemini surfactants have a special structure in which two hydrophilic groups are chemically bonded together by a linking group, which not only enhances the hydrophobic interaction between the hydrophobic groups, but also greatly weakens the repulsive effect between the ionic hydrophilic groups due to the limitation of the linking group. At the same time, the chemical bond between the two ionic head groups does not destroy their hydrophilicity. Therefore, compared with traditional single-head and single-tail surfactants, Gemini surfactants exhibit more unique physical and chemical properties. Compared with traditional single-chain surfactants, Gemini surfactants have extremely low CMC, strong ability to reduce surface tension, multiple aggregation forms, special phase behavior and rheological properties.

[0004] In the field of tertiary oil recovery, oil recovery surfactants such as heavy alkylbenzene sulfonates and petroleum sulfonates have been widely used. However, due to insufficient raw material supply and weak resistance to high mineralization, the existing sulfonate oil recovery surfactants cannot fully meet production needs. Other oil recovery surfactants usually require long hydrophobic chains to match the crude oil components, which brings about problems such as solubility and cost. Gemini surfactants can achieve matching with crude oil components without increasing the length of the hydrophobic chain by adjusting their own structure, such as the length of the connecting group, and significantly reduce the oil-water interfacial tension. The unique structure and properties of Gemini surfactants make it one of the research directions of oil recovery surfactant research.

[0005] In recent years, researchers have conducted exploratory research on the development of Gemini surfactants for oil recovery and developed several Gemini surfactants for oil recovery. For example, patent CN110683991A discloses a Gemini ionic liquid surfactant and its synthesis method. The interfacial tension between the weak-base composite oil recovery system of the Gemini ionic liquid surfactant and Daqing crude oil is 10-3 to 10-1 mN / m. Patent CN110746955A discloses a dialkyl dipolyoxyethylene ether-based urea Gemini surfactant for oil recovery. The surfactant has excellent interfacial tension reduction performance in a wide pH range and reduces the oil-water interfacial tension to ultra-low under alkali-free conditions. Patent CN 102219897A discloses an N, N-bis-fatty phthalyl diamine dimethyl propionic acid dipolyoxyethylene ether disulfonate Gemini surfactant, which still has a strong ability to reduce interfacial tension under high temperature and high salt conditions, solving the problem of low oil recovery efficiency of oil recovery agents under high temperature and high salt conditions and alkali damage to formations in ternary composite flooding. However, the synthesis methods of most Gemini surfactants are relatively complicated, which affects the yield of the final product and affects the promotion and application of the product in oil fields. Summary of the invention

[0006] In view of the above problems, on the one hand, the present invention discloses an asymmetric Gemini surfactant, the molecular structure of which is as follows:

[0007] ALB

[0008] L is CmH2m, CmH2m-2 (m=0~6) or CmH2m-6, m=6~8; A is N+R1R2R3X-; B is NR4R5.

[0009] Furthermore, R1 and R4 in A and B are hydrophilic groups with the same or different structures, selected from -CH2CO2-Na+, -CH2CH2CO2-Na+, -COCH=CHCO2-Na+, -COCH2CH2CO2-Na+, -CH2CH2SO3-Na+, -CH2CH2CH2SO3-Na+, -CH2CH(OH)CH2SO3-Na+, -CH2CH2CH2CH2SO3-Na+, containing sulfonic acid or carboxylic acid groups; R2 and R5 are long-chain hydrophobic groups of the same or different lengths, including long-chain alkanes -CnH2n+1, long-chain olefins -CnH2n-1 or long-chain alkyl aromatics -CnH2n-5, where n=6 to 18; R3 is -CH3, -CH2CH3, -CH2CH2CH3, -C6H5.

[0010] On the other hand, a method for preparing an asymmetric Gemini surfactant comprises:

[0011] Add halogenated hydrocarbon R3Y or R5Y or a mixture of R3Y and R5Y to the monosubstituted fatty diamine to react and obtain an intermediate

[0012]

[0013] Add R2X or R4X or a mixture of R2X and R4X to the intermediate solution to react, and obtain the final product, which is an asymmetric Gemini surfactant.

[0014]

[0015] Furthermore, the step of adding halogenated hydrocarbon R3Y or R5Y or a mixture of R3Y and R5Y to the monosubstituted fatty diamine to react to obtain the intermediate specifically comprises: dissolving the monosubstituted fatty diamine in an organic solvent; heating under reflux, adding the halogenated hydrocarbon R3Y / R5Y dropwise to the monosubstituted fatty diamine, and monitoring by TLC until the monosubstituted fatty diamine is completely dissolved and reacted; and then washing, filtering and purifying the product to obtain the intermediate.

[0016] Furthermore, the mass ratio of the monosubstituted fatty diamine to the halogenated hydrocarbon R3Y or R5Y or the mixture of R3Y and R5Y is 1:(2.0-2.5).

[0017] Furthermore, the halogenated hydrocarbon R3Y or R5Y or a mixture of R3Y and R5Y is added to the monosubstituted fatty diamine for reaction at a temperature of 60 to 120°C.

[0018] Furthermore, the halogenated hydrocarbons include chloroalkanes and brominated alkanes.

[0019] Further, the monosubstituted fatty diamine is any one of N-methylethylenediamine, N-ethylethylenediamine, N-phenylethylenediamine, N-methylpropylenediamine, N-ethylpropylenediamine, N-phenylpropylenediamine, N-methylbutylenediamine, N-ethylbutylenediamine, N-phenylbutylenediamine, N-methylpentanediamine, N-ethylpentanediamine, N-phenylpentanediamine, N-methylhexanediamine, N-ethylhexanediamine, and N-phenylhexanediamine.

[0020] Furthermore, the step of adding R2X or R4X or a mixture of R2X and R4X to the intermediate solution for reaction to obtain the final product, which is an asymmetric Gemini surfactant, specifically includes: dissolving the synthetic intermediate in an organic solvent; then adding R2X or R4X or a mixture of R2X and R4X, heating and refluxing, and monitoring the conversion of the raw intermediate by TLC; after the reaction is complete, washing, filtering, and purifying the product to obtain the final product.

[0021] Furthermore, the mass ratio of the intermediate to R2X or R4X or the mixture of R2X and R4X is 1:(2.2-5).

[0022] Furthermore, R2X or R4X or a mixture of R2X and R4X is added to the intermediate solution for reaction at a temperature of 70 to 140°C.

[0023] Furthermore, the pH value range of the reaction between the intermediate and R2X or R4X or the mixture of R2X and R4X is maintained at 7-13.

[0024] Further, the R2X / R4X is any one of sodium 2-chloroacetate, sodium 2-bromoacetate, sodium 3-chloropropionate, sodium 4-chlorobutyrate, maleic anhydride, succinic anhydride, sodium 3-chloro-2-hydroxypropanesulfonate, sodium 2-chloroethylsulfonate, sodium 2-bromoethylsulfonate, sodium 3-chloropropylsulfonate, sodium 3-bromopropylsulfonate, propane sultone, and butane sultone.

[0025] On the other hand, an application of an asymmetric Gemini surfactant is provided, wherein the asymmetric Gemini surfactant is used in the field of oil extraction. When used, the asymmetric Gemini surfactant is used in the form of a composition, and the types of the composition include a ternary composite flooding composition, an alkali-free binary composite flooding composition, and a surfactant flooding composition.

[0026] Furthermore, the components of the alkali-free binary composite flooding composition include: 0.05wt% to 0.30wt% of Gemini surfactant, 0.05wt% to 0.30wt% of polymer, and the balance of water.

[0027] Furthermore, the components of the ternary composite flooding composition include: 0.03wt% to 3.0wt% of alkaline substances, 0.05wt% to 0.30wt% of Gemini surfactants, 0.05wt% to 0.30wt% of polymers, and the balance of water.

[0028] Furthermore, the polymer is a hydrophobic associating polymer, a star-shaped temperature-resistant and salt-resistant polymer or a partially hydrolyzed polyacrylamide polymer.

[0029] Furthermore, the average molecular weight of the polymer is 3 million to 35 million.

[0030] Furthermore, the alkaline substance includes one or a combination of trimethylamine, triethylamine, tetrasodium ethylenediaminetetraacetate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium tetraborate, and sodium phosphate.

[0031] In addition, an application of an asymmetric Gemini surfactant is provided, wherein the asymmetric Gemini surfactant is used in a low permeability oil reservoir. When used, the asymmetric Gemini surfactant is used in the form of a composition, and the type of the composition is a surfactant flooding composition.

[0032] Furthermore, the components of the surfactant flooding composition include: 0.05wt% to 0.30wt% of Gemini surfactant, and the balance of water.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The asymmetric Gemini surfactant provided by the present invention has a lower critical micelle concentration and can form micelle aggregates at low concentrations, thus having the potential for micelle flooding or microemulsion flooding.

[0035] (2) The asymmetric Gemini surfactant provided by the present invention has a stronger ability to reduce surface tension and oil-water interfacial tension than single-chain surfactants with the same carbon chain length. It can reduce oil-water interfacial tension and improve oil recovery efficiency under alkali-free or alkaline conditions, and has great application potential in the field of chemical flooding to enhance oil recovery.

[0036] (3) The asymmetric Gemini surfactant provided by the present invention has three charge sites, good solubility, can combine with a variety of counterions, has strong salt resistance, will not undergo phase separation precipitation, and is easy to prepare and use.

[0037] (4) The asymmetric Gemini surfactant provided by the present invention can be matched with various types of crude oil by adjusting its own structure and has a wide range of applications;

[0038] (5) The asymmetric Gemini surfactant provided by the present invention has few synthesis steps and only requires two steps of reaction. The raw materials for production are cheap and readily available, the yield is high, the cost is low, and it is easy to achieve large-scale industrial production of the product, thereby promoting the industrial promotion and application of Gemini surfactants in the field of tertiary oil recovery.

[0039] Other features and advantages of the present invention will be described in the following description, and partly become apparent from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention can be realized and obtained by the structures pointed out in the description, claims and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0041] Figure 1 is the nuclear magnetic resonance spectrum of 12-2-1-12 of Example 1;

[0042] Figure 2 is the mass spectrum of 12-2-1-12 of Example 1;

[0043] Figure 3 The 12-2-1-12-(CO 2 - ) 2 Mass spectrum of

[0044] Figure 4 is the nuclear magnetic resonance spectrum of 12-3-1-12 of Example 3;

[0045] Figure 5 is the mass spectrum of 12-3-1-12 of Example 3;

[0046] Figure 6 It is 12-3-1-12-(CO 2 - ) 2 NMR spectrum of

[0047] Figure 7 It is 12-3-1-12-(CO 2 - ) 2 Mass spectrum of

[0048] Figure 8 It is 12-2-1-12-(SO 3 - ) 2 Mass spectrum of

[0049] Fig. 9 It is 12-2-1-12-(SO 3 - ) 2 NMR spectrum of

[0050] Fig.10 It is 12-3-1-12-(SO 3 - ) 2 Mass spectrum of

[0051] Fig.11 It is 12-3-1-12-(SO 3 - ) 2 NMR spectrum of

[0052] Fig.12 is the mass spectrum of 16-3-1-16 of Example 9;

[0053] Fig.13 is the nuclear magnetic resonance spectrum of 16-3-1-16 in Example 9;

[0054] Fig.14 It is 16-3-1-16-(SO 3 - ) 2 Mass spectrum of

[0055] Fig.15 It is 16-3-1-16-(SO 3 - ) 2 NMR spectrum of

[0056] Fig.16 It is 12-2-1-12-(SO 3 - ) 2 Surface tension comparison chart with sodium dodecyl sulfate;

[0057] Fig.17 It is 12-2-1-12-(CO 2 - ) 2 Interfacial tension test diagram of solution and Changqing crude oil under different concentration conditions;

[0058] Fig.18 It is 12-2-1-12-(CO 2 - ) 2 Interfacial tension test diagram between alkali-free binary composite system solution and Changqing crude oil;

[0059] Fig.19 It is 12-3-1-12-(CO 2 - ) 2 Interfacial tension between binary composite system solution and Changqing crude oil at different adsorption times;

[0060] Fig. 20 It is 12-3-1-12-(CO 2 - ) 2 Interfacial tension test diagram between the ternary composite system solution and Daqing crude oil under different alkali concentration conditions. DETAILED DESCRIPTION

[0061] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0062] The present invention synthesizes an asymmetric Gemini surfactant, and the molecular structure is as follows:

[0063] ALB

[0064] L is C m H 2m , C m H 2m-2 (m=0~6) or C m H 2m-6 , m = 6 to 8; A is N + R 1 R 2 R 3 X - ; B is NR 4 R 5 .

[0065] The R of A and B 1 , R 4 is a hydrophilic group having the same or different structure, selected from -CH 2 CO 2 - Na + 、-CH 2 CH 2 CO 2 - Na + 、-COCH=CHCO 2 - Na + 、-COCH 2 CH 2 CO 2 - Na + 、-CH 2 CH 2 SO 3 - Na + 、-CH 2 CH 2 CH 2 SO 3 - Na + 、-CH2 CH(OH)CH 2 SO 3 - Na + 、-CH 2 CH 2 CH 2 CH 2 SO 3 - Na + etc.; R 2 , R 5 are long-chain hydrophobic groups of the same or different lengths, including long-chain alkane-C n H 2n+1 、Long chain olefins-C n H 2n-1 Or long chain alkyl aromatics-C n H 2n-5 , n=6~18; R 3 -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 , -C 6 H 5 .

[0066] The main steps for synthesizing the above asymmetric Gemini surfactants are:

[0067] Add halogenated hydrocarbon R3Y or R5Y or a mixture of R3Y and R5Y to the monosubstituted fatty diamine to react and obtain an intermediate

[0068]

[0069] Add R2X or R4X or a mixture of R2X and R4X to the intermediate solution to react, and obtain the final product, which is an asymmetric Gemini surfactant.

[0070]

[0071] Embodiment 1:

[0072] A Gemini surfactant, wherein X - =Br - , m=2,n=12,R 2 =-CH 2 COO - Na + .

[0073] 1) Preparation and characterization of intermediate 12-2-1-12:

[0074] N-methylethylenediamine (1M) was added to a three-necked flask, and anhydrous methanol was used as solvent. n-dodecyl bromide (2.1M) was added dropwise. The temperature was raised to reflux, and the reaction was continued for more than 48 hours. TLC was used to monitor whether the raw material N-methylethylenediamine was completely reacted (dichloromethane / methanol = 9 / 1). A large amount of white solid precipitated from the reaction system. n-hexane was added and filtered. The obtained solid was washed with ethyl acetate and n-hexane for many times, and recrystallized with ethyl acetate and ethanol (4:1) for three times to obtain a white (slightly yellowish) solid, which was the hydrobromide salt of the product. The product was dissolved in 20% NaOH solution, extracted with ethyl acetate, and the organic phase was dried with anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol: 10 / 1, 4 / 1) to obtain a pure product. The NMR spectrum and mass spectrum of 12-2-1-12 are shown in the following figure. Figure 1 and Figure 2 shown.

[0075] 1 H NMR (400 MHz, CDCl 3 ):δ=0.861-0.902(t,6H,CH 3 ),1.264-1.458(m,38H,CH 3 –(CH 2 ) 10 –CH 2 –N-CH 2 -CH 2 -N(H)-CH 2 -(CH 2 ) 9 -CH 3 ).1.801-1.855(m,2H,CH 3 –(CH 2 ) 9 –CH 2 –CH 2 –N),2.415(s,3H,N-CH 3 ),2.956-3.001(m,4H,CH 3 -(CH 2 ) 10 –CH 2 –N(H)–CH 2 ).3.134(m,2H,N-CH 2 ).ESI–MS(HP1100LC–MSD):[M+H + ] / (C 27 H 58 N 2 H) + :Calcd:411.4.Found:411.4.

[0076] 2)12-2-1-12-(COO - ) 2 Preparation and characterization:

[0077] 12-2-1-12 (1M) was added to a three-necked flask, 1-propanol was used as solvent, KI (0.1M) and sodium bromoacetate (2.2M) were added, the temperature was raised to reflux, and the reaction was continued for more than 24 hours. During the reaction, the pH value of the reaction system was kept between 9.5 and 11. The conversion of the raw material 12-2-1-12 was monitored by TLC (dichloromethane / methanol = 4 / 1). A white solid was obtained by filtration. Methanol and ethyl acetate were recrystallized several times to obtain a white solid. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product. 12-2-1-12-(CO 2 - ) 2 The mass spectrum of Figure 3 shown.

[0078] δ=0.877–0.922[t,6H,2CH 3 CH 2 ],1.179–1.389[m,36H,2CH 3 (CH 2 ) 9 CH 2 ],1.817[m,

[0079] 4H,2(CH 2 ) 9 CH 2 CH 2 N],3.247–3.349[m,3H,CH 3 N + ],3.541–3.626[m,4H,2(CH 2 ) 9 CH 2 CH 2 N],3.884[s,4H,2 - OOCCH 2 N],4.221[s,4H,NCH 2 CH 2 N],ESI–MS(HP1100LC–MSD):[M - ] / (C 31 H 61 N 2 O 4 ) - :Calcd:525.4.Found:525.4.

[0080] Embodiment 2:

[0081] An asymmetric Gemini surfactant, wherein X - =Br - , m=2,n=12,R 2 =-CH 2 COO - Na + .

[0082] 1) Preparation and characterization of intermediate 12-2-1-12:

[0083] N-methylethylenediamine (1M) was added to a three-necked flask, and anhydrous ethanol was used as a solvent. n-Dodecyl bromide (2.5M) was added dropwise. The temperature was raised to reflux, and the reaction was carried out for more than 48 hours. TLC was used to monitor whether the raw material N-methylethylenediamine was completely reacted (dichloromethane / methanol = 9 / 1); a large amount of white solid was precipitated in the reaction system, and n-hexane was added and filtered. The obtained solid was washed with ethyl acetate and n-hexane for many times, and recrystallized with acetone and methanol (4:1) for three times to obtain a white (slightly yellowish) solid, which was the hydrobromide of the product. The product was dissolved in a 20% NaOH solution, extracted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0084] 2)12-2-1-12-(COO - ) 2 Preparation and characterization:

[0085] 12-2-1-12 (1M) was added to a three-necked flask, n-butanol was used as solvent, KI (0.1M) and sodium bromoacetate (5M) were added, the temperature was raised to reflux, and the reaction was carried out for more than 24 hours. During the reaction, the pH value of the reaction system was maintained in the range of 10.5-11.5, and the conversion of the raw material 12-2-1-12 was monitored by TLC (dichloromethane / methanol = 4 / 1); a white solid was obtained by filtration; methanol and ethyl acetate were recrystallized several times to obtain a white solid, which was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product.

[0086] Example 3

[0087] An asymmetric Gemini surfactant, wherein X - =Br - , m=3,n=12,R 2 =-CH 2 COO - Na + .

[0088] 1) Preparation and characterization of intermediate 12-3-1-12:

[0089] N-methylpropylenediamine (1M) was added to a three-necked flask, and anhydrous ethanol was used as the solvent. n-Dodecyl bromide (2.2M) was added dropwise. The temperature was raised to reflux, and the reaction was continued for more than 48 hours. TLC was used to monitor whether the raw material N-methylpropylenediamine was completely reacted (dichloromethane / methanol = 9 / 1). After cooling, a large amount of white solid precipitated from the reaction system. The solid was filtered and washed with acetone for many times. The solid was recrystallized three times with acetone and methanol (4:1) to obtain a white (slightly yellowish) solid, which was the hydrobromide salt of the product. The product was dissolved in 20% NaOH solution, extracted with ethyl acetate, and the organic phase was dried with anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product. The NMR spectrum and mass spectrum of 12-3-1-12 are shown in the following figure. Figure 4 and Figure 5 shown.

[0090] 1 H NMR (400MHz, CDCl3): δ = 0.856-0.912 (t, 6H, CH 3 ),1.257-1.497(m,38H,CH 3 –(CH 2 ) 10 –CH 2 –N-CH 2 -CH 2 -N(H)-CH 2 -(CH 2 ) 9 -CH 3 ),1.557(m,2H,N–CH 2 –CH 2 –CH 2 –N),1.851-1.865(m,2H,CH 3 –(CH 2 ) 9 –CH 2 –CH 2 –N),2.416(s,3H,N-CH3),2.961-3.006(m,4H,CH 3 –(CH 2 ) 10 –CH 2 –N(H)–CH 2 ),3.133(m,2H,N-CH 2 ).ESI–MS(HP1100LC–MSD):[M+H + ] / (C 27 H 58 N 2 H) + :Calcd:425.4.Found:425.4.

[0091] 2)12-3-1-12-(COO - ) 2 Preparation and characterization:

[0092] The intermediate 12-3-1-12 (1M) was added to a three-necked flask, 1-propanol was used as solvent, KI (0.1M) and sodium bromoacetate (3M) were added, the temperature was raised to reflux, and the reaction was continued for more than 24 hours. TLC was used to monitor whether the raw material 12-3-1-12 was completely reacted (dichloromethane / methanol = 4 / 1); during the reaction, the pH value of the reaction system was maintained at 11-13, and a white solid was obtained by suction filtration; methanol and ethyl acetate were recrystallized several times to obtain a white solid, which was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product. 12-3-1-12-(CO 2 - ) 2 The NMR spectra and mass spectra of Figure 6 and Figure 7 shown.

[0093] δ=0.873–0.911[t,6H,2CH 3 CH 2 ],1.183–1.267[m,36H,2CH 3 (CH 2 ) 9 CH 2 ],1.573(m,

[0094] 2H,N–CH 2 –CH 2 –CH 2 –N),1.825[m,4H,2(CH 2 ) 9 CH 2 CH 2 N],3.239–3.324[m,3H,CH 3 N + ],3.548–3.619[m,4H,2(CH 2 ) 9 CH 2 CH 2 N],3.892[s,4H,2 - OOCCH 2 N],4.254[s,4H,NCH 2 CH 2 N],ESI–MS(HP1100LC–MSD):[M - ] / (C 31 H 61 N2 O 4 ) - :Calcd:539.5.Found:539.5.

[0095] Example 4

[0096] An asymmetric Gemini surfactant, wherein X - =Br - , m=3,n=12,R 2 =-CH 2 COO - Na + .

[0097] 1) Preparation and characterization of intermediate 12-3-1-12:

[0098] N-methylpropylenediamine (1M) was added to a three-necked flask, anhydrous methanol was used as solvent, n-dodecyl bromide (2.5M) was added dropwise, the temperature was raised to reflux, and the reaction was carried out for more than 48 hours. TLC was used to monitor whether the raw material N-methylpropylenediamine was completely reacted (dichloromethane / methanol = 9 / 1); after cooling, a large amount of white solid was precipitated in the reaction system, which was filtered, and the obtained solid was washed with ethyl acetate and n-hexane for many times, and recrystallized three times with ethyl acetate and ethanol (4:1) to obtain a white (slightly yellowish) solid, which was the hydrobromide of the product. The product was dissolved in 20% NaOH solution, extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0099] 2)12-3-1-12-(COO - ) 2 Preparation and characterization:

[0100] The intermediate 12-3-1-12 (1M) was added to a three-necked flask, 1-propanol was used as solvent, KI (0.1M) and sodium bromoacetate (5M) were added, the temperature was raised to reflux, and the reaction was carried out for more than 24 hours. TLC was used to monitor whether the reaction of the raw material 12-3-1-12 was complete (dichloromethane / methanol = 4 / 1); during the reaction, the pH value of the reaction system was maintained at 8.5-10, and a white solid was obtained by suction filtration; methanol and ethyl acetate were recrystallized several times to obtain a white solid, which was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0101] Embodiment 5:

[0102] An asymmetric sulfonic Gemini surfactant, wherein X - =Br - , m=2,n=12,R 2 =-CH 2 CH 2CH 2 SO 3 - Na + .

[0103] 1) Preparation and characterization of intermediate 12-2-1-12:

[0104] N-methylethylenediamine (1M) was added to a three-necked flask, and anhydrous ethanol was used as the solvent. n-dodecyl bromide (2.2M) was added dropwise. The temperature was raised to reflux, and the reaction was continued for more than 48 hours. TLC was used to monitor whether the raw material N-methylethylenediamine was completely reacted (dichloromethane / methanol = 9 / 1). A large amount of white solid precipitated from the reaction system. n-hexane was added and filtered. The obtained solid was washed with ethyl acetate and n-hexane for many times, and recrystallized with ethyl acetate and ethanol (4:1) for three times to obtain a white (slightly yellowish) solid, which was the hydrobromide of the product. The product was dissolved in 20% NaOH solution, extracted with ethyl acetate, and the organic phase was dried with anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain the pure product. 12-2-1-12-(SO 3 - ) 2 The mass spectrum and nuclear magnetic resonance spectrum of Figure 8 and Fig. 9 shown.

[0105] 1 H NMR (400 MHz, CDCl 3 ):δ=0.861-0.902(t,6H,CH 3 ),1.264-1.458(m,36H,CH 3 –(CH 2 ) 9 –CH 2 –CH 2 -N-CH 2 -CH 2 -N(H)-CH 2 –CH 2 -(CH 2 ) 9 -CH 3 ),1.544(m,2H,CH 3 –(CH 2 ) 9 –CH 2 –CH 2 –NH), 1.811-1.847(m,2H,CH 3 –(CH 2 ) 9 –CH 2 –CH 2 –N),2.415(s,3H,N-CH3 ),2.656(m,2H,CH 3 –(CH 2 ) 9 –CH 2 –CH 2 –N),2.956-3.001(m,4H,N–CH 2 -CH 2 -NH-CH 2 ).3.134(m,2H,N–CH 2 -CH 2 -NH).ESI–MS(HP1100LC–MSD):[M+H + ] / (C 27 H 58 N 2 H) + :Calcd:411.4.Found:411.4.Elementalanalysis:calculated for C 27 H 58 N 2 :C,78.95;H,14.23;N,6.82. Found:C,79.01;H,14.19;N,6.80.

[0106] 2)12-2-1-12-(SO 3 - ) 2 Preparation and characterization:

[0107] 12-2-1-12 (1M) was added to a three-necked flask, ethyl acetate was used as solvent, 1,3-propane sultone (3M) was added dropwise, the temperature was raised to reflux, and the reaction was continued for more than 24 hours. The conversion of the raw material 12-2-1-12 was monitored by TLC (dichloromethane / methanol = 4 / 1). During the reaction, the pH value of the reaction system was maintained at 9-10, and an off-white solid was obtained by suction filtration; methanol and ethyl acetate were recrystallized several times to obtain a white (slightly yellowish) solid, which was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0108] 1 H NMR (400MHz, CDCl3): δ = 0.834-0.893 (t, 6H, CH 3 ),1.263-1.444(m,36H,CH 3 -(CH 2 ) 9 -CH 2 -CH 2 -N-CH 2 -CH 2-N-CH 2 -(CH 2 ) 9 -CH 3 ),1.554(m,2H,CH 3 -(CH 2 ) 9 -CH 2 -CH 2 -N), 1.809-1.847(m,2H,CH 3 –(CH 2 ) 9 –CH 2 –CH 2 –N + ),2.558-2.635(t,4H,N–CH 2 –CH 2 –CH 2 –SO 3 – ),2.979-3.127(m,6H,N-(CH 2 ) 3 ),3.214(m,6H, + N-(CH 2 ) 3 ).3.557(s,3H,N-CH 3 ),3.797(t,4H,N–CH 2 –CH 2 –CH 2 –SO 3 – ),ESI–MS(HP1100LC–MSD):[M - ] / (C 33 H 69 N 2 O 6 S 2 ) - :Calcd:653.46.Found:653.46038.Elemental analysis:calculated for C 33 H 71 C1N 2 O 6 S 2 :C,57.32;H,10.35;N,4.05.Found:C,57.54;H,10.18;N,3.98.

[0109] Embodiment 6:

[0110] An asymmetric sulfonic Gemini surfactant, wherein X -=Br - , m=2,n=12,R 2 =-CH 2 CH 2 CH 2 SO 3 - Na + .

[0111] 1) Preparation and characterization of intermediate 12-2-1-12:

[0112] N-methylethylenediamine (1M) was added to a three-necked flask, and anhydrous ethanol was used as a solvent. n-Dodecyl bromide (2.3M) was added dropwise. The temperature was raised to reflux, and the reaction was carried out for more than 48 hours. TLC was used to monitor whether the raw material N-methylethylenediamine was completely reacted (dichloromethane / methanol = 9 / 1); a large amount of white solid was precipitated in the reaction system, and n-hexane was added, and the solid was filtered. The obtained solid was washed with ethyl acetate and n-hexane for many times, and recrystallized with ethyl acetate and ethanol (4:1) for three times to obtain a white (slightly yellowish) solid, which was the hydrobromide of the product. The product was dissolved in a 20% NaOH solution, extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0113] 2)12-2-1-12-(SO 3 - ) 2 Preparation and characterization:

[0114] 12-2-1-12 (1M) was added to a three-necked flask, butyl acetate was used as solvent, 1,3-propane sultone (5M) was added dropwise, the temperature was raised to reflux, and the reaction was continued for more than 24 hours. The conversion of the raw material 12-2-1-12 was monitored by TLC (dichloromethane / methanol = 4 / 1). During the reaction, the pH value of the reaction system was maintained at 9-10, and an off-white solid was obtained by suction filtration; methanol and ethyl acetate were recrystallized several times to obtain a white (slightly yellowish) solid, which was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0115] 1 H NMR (400MHz, CDCl3): δ=0.834-0.8993(t,6H,CH 3 ),1.263-1.465(m,38H,CH 3 –(CH 2 ) 10 –CH 2 –N-CH 2 -CH 2 -N-CH 2 -(CH 2 ) 9 -CH3 ),1.809-1.851(m,2H,CH 3 –(CH 2 ) 9 –CH 2 –CH 2 –N),2.553-2.678(t,4H,N–CH 2 –CH 2 –CH 2 –SO 3 – ),2.943-3.013(m,6H,N-(CH 2 ) 3 ),3.214(m,6H,CH3-N + -(CH 2 ) 3 ).3.364(s,3H,N-CH 3 ),3.416(t,4H,N–CH 2 –CH 2 –CH 2 –SO 3 – ),ESI–MS(HP1100LC–MSD):[M - ] / (C 33 H 69 N 2 O 6 S 2 ) - :Calcd:653.46.Found:653.46038.

[0116] Embodiment 7:

[0117] An asymmetric sulfonic Gemini surfactant, wherein X - =Br - , m=3,n=12,R 2 =-CH 2 CH 2 CH 2 SO 3 - Na + .

[0118] 1) Preparation and characterization of intermediate 12-3-1-12:

[0119] N-methylpropylenediamine (1M) was added to a three-necked flask, and n-butanol was used as a solvent. n-Dodecyl bromide (2.5M) was added dropwise. The temperature was raised to reflux, and the reaction was carried out for more than 48 hours. TLC was used to monitor whether the raw material N-methylpropylenediamine was completely reacted (dichloromethane / methanol = 9 / 1); a large amount of white solid was precipitated in the reaction system, and the obtained solid was filtered, and the obtained solid was washed with ethyl acetate and n-hexane for many times, and recrystallized with ethyl acetate and ethanol (4:1) for three times to obtain a white (slightly yellowish) solid, which was the hydrobromide of the product. The product was dissolved in a 20% NaOH solution, extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0120] 1 H NMR (400MHz, CDCl3): δ = 0.850-0.883 (t, 6H, CH 3 ),1.231-1.354(m,36H,CH 3 -(CH 2 ) 9 -CH 2 -CH 2 -N-CH 2 -CH 2 -CH 2 -NH-CH 2 -(CH 2 ) 9 -CH 3 ),1.781-1.841(m,2H,CH 3 -(CH 2 ) 9 -CH 2 -CH 2 -NH), 1.897-1.914 (m, 2H, CH 3 -(CH 2 ) 9 -CH 2 -CH 2 -N),2.090(s,1H,NH),2.610-2.663(m,2H,N-CH 2 -CH 2 -CH 2 -NH), 2.914(m,3H,N-CH 3 ),2.988-3.069(m,2H,CH 3 -(CH 2 ) 9 -CH 2 -CH 2 -NH-CH 2 ),3.173-3.193(m,2H,CH 3-(CH 2 ) 9 -CH 2 -CH 2 -N-CH 2 ),3.213-3.448(m,2H,NH-CH 2 -CH 2 -CH 2 -N), 3.466-3.574 (m, 2H, N-CH 2 -CH 2 -CH 2 -NH).ESI–MS(HP1100LC-MSD):[M+H + ] / (C 28 H 60 N 2 H) + :Calcd:425.4.Found:425.4.Elemental analysis:calculated for C 28 H 60 N 2 :C,79.17;H,14.24;N,6.59.Found:C,79.21;H,14.21;N,6.58.

[0121] 2)12-3-1-12-(SO 3 - ) 2 Preparation and characterization of

[0122] The intermediate 12-3-1-12 (1M) was added to a three-necked flask, butyl acetate was used as solvent, 1,3-propane sultone (3M) was added dropwise, the temperature was raised to reflux, and the reaction was continued for more than 24 hours. The conversion of the raw material 12-3-1-12 was monitored by TLC (dichloromethane / methanol = 4 / 1); during the reaction, the pH value of the reaction system was maintained at 9-10, and a white solid was obtained by filtration; methanol and ethyl acetate were recrystallized several times to obtain a white solid, which was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product. 12-3-1-12-(SO 3 - ) 2 The mass spectrum and nuclear magnetic resonance spectrum of Fig.10 and Fig.11 shown.

[0123] 1 H NMR (400MHz, CDCl3): δ = 0.858-0.892 (t, 6H, CH 3 ),1.246-1.368(m,36H,CH 3 -(CH2 ) 9 -CH 2 -CH 2- N-CH 2 -CH 2 -N-CH 2 -(CH 2 ) 9 -CH 3 ),1.519-1.558(m,2H,N-CH 2 -CH 2 -CH 2 -N),1.865-1.873(m,2H,CH 3 -(CH 2 ) 9 -CH 2 -CH 2 -N),2.132(m,2H,N-CH 2 -CH 2 -CH 2 -N + ),2.309(m,4H, + N-CH 2 -CH 2 -CH 2 -SO 3 - ),3.488-3.650(m,6H,N-(CH 2 ) 3 ),3.827(s,3H,-CH 3 ),4.327(m,6H, + N-(CH 2 ) 3 ),4.547-4.755(m,4H,CH 2 -CH 2 -SO 3 - ).ESI–MS(HP1100LC–MSD):[M - ] / (C 34 H 71 N 2 O 6 S 2 ) - :Calcd:667.5.Found:667.5.Elemental analysis:calculated for C 34 H 73 N 2 O 6 S 2Cl: C, 57.88; H, 10.43; N, 3.97; Found: C, 58.01; H, 10.26; N, 3.84.

[0124] Embodiment 8:

[0125] An asymmetric sulfonic Gemini surfactant, wherein X - =Br - , m=3,n=12,R 2 =-CH 2 CH 2 CH 2 SO 3 - Na + .

[0126] 1) Preparation and characterization of intermediate 12-3-1-12:

[0127] N-methylpropylenediamine (1M) was added to a three-necked flask, and anhydrous ethanol was used as a solvent. n-Dodecyl bromide (2.2M) was added dropwise. The temperature was raised to reflux, and the reaction was carried out for more than 48 hours. TLC was used to monitor whether the raw material N-methylpropylenediamine was completely reacted (dichloromethane / methanol = 9 / 1); after cooling, a large amount of white solid was precipitated in the reaction system, which was filtered, and the obtained solid was washed with ethyl acetate and n-hexane for many times, and recrystallized three times with ethyl acetate and ethanol (4:1) to obtain a white (slightly yellowish) solid, which was the hydrobromide of the product. The product was dissolved in a 20% NaOH solution, extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0128] 2)12-3-1-12-(SO 3 - ) 2 Preparation and characterization of

[0129] The intermediate 12-3-1-12 (1M) was added to a three-necked flask, ethyl acetate was used as solvent, 1,3-propane sultone (5M) was added dropwise, the temperature was raised to reflux, and the reaction was carried out for more than 24 hours. The conversion of the raw material 12-3-1-12 was monitored by TLC (dichloromethane / methanol = 4 / 1); during the reaction, the pH value of the reaction system was maintained at 9-10, and a white solid was obtained by filtration; methanol and ethyl acetate were recrystallized several times to obtain a white solid, which was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0130] Embodiment 9:

[0131] An asymmetric sulfonic Gemini surfactant, wherein X - =Br - , m=2,n=16,R2 =-CH 2 CH 2 CH 2 SO 3 - Na + .

[0132] 1) Preparation and characterization of intermediate 16-3-1-16:

[0133] N-methylpropylenediamine (1M) was added to a three-necked flask, and anhydrous ethanol was used as the solvent. Hexadecyl bromide (2.2M) was added dropwise. The temperature was raised to reflux, and the reaction was continued for more than 48 hours. TLC was used to monitor whether the raw material N-methylpropylenediamine was completely reacted (dichloromethane / methanol = 9 / 1). A large amount of white solid precipitated from the reaction system. n-hexane was added and filtered. The obtained solid was washed with ethyl acetate and n-hexane for many times, and recrystallized three times with ethyl acetate and ethanol (4:1) to obtain a white (slightly yellowish) solid, which was the hydrobromide salt of the product. The product was dissolved in 20% NaOH solution, extracted with ethyl acetate, and the organic phase was dried with anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product. The mass spectrum and nuclear magnetic resonance spectrum of 16-3-1-16 are shown in the following figure: Fig.12 and Fig.13 shown.

[0134] 1 H NMR (400MHz, CDCl3): δ=0.863-0.897(t,6H,CH 3 ),1.256-1.357(m,52H,CH 3 -(CH 2 ) 13 -CH 2 -CH 2 -NH-CH 2 -CH 2 -N-CH 2 -CH 2 -(CH 2 ) 13 -CH 3 ),1.504(m,2H,CH 3 -(CH 2 ) 13 -CH 2 -CH 2 -NH), 1.745(m,2H,CH 3 -(CH 2 ) 13 -CH 2 -CH 2 -NH), 2.003(m,2H,HN-CH 2 -CH2 -CH 2 -N), 2.664-2.776(m,2H,CH 2 -N-CH 2 -CH 2 -CH 2 -NH), 2.810-2.866(m,2H,N–CH 2 –CH 2 –CH 2 –NH), 3.387(s,3H,N-CH 3 ),3.463-3.505(m,2H,HN–CH 2 –CH 2 –CH 2 –N-CH 2 ),3.677-3.707(m,2H,HN–CH 2 –CH 2 –CH 2 –N).ESI–MS(HP1100LC–MSD):[M+H + ] / (C 36 H 77 N 2 ) + :Calcd:537.6.Found:537.6.

[0135] 2)16-3-1-16-(SO 3 - ) 2 Preparation and characterization:

[0136] 16-3-1-16 (1M) was added to a three-necked flask, ethyl acetate was used as solvent, 1,3-propane sultone (3M) was added dropwise, the temperature was raised to reflux, and the reaction was continued for more than 24 hours. The conversion of the raw material 16-3-1-16 was monitored by TLC (dichloromethane / methanol = 4 / 1). An off-white solid was obtained by suction filtration; methanol and ethyl acetate were recrystallized several times to obtain a white (slightly yellowish) solid, which was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product. 16-3-1-16-(SO 3 - ) 2 The mass spectrum and nuclear magnetic resonance spectrum of Fig.14 and Fig.15 shown.

[0137] 1 H NMR (400MHz, CDCl3): δ = 0.884-0.897 (t, 6H, CH 3 ),1.248-1.369(m,52H,CH 3 -(CH2 ) 13 -CH 2 -CH 2 -NH-CH 2 -CH 2 - + N(CH 3 ) 2 -CH 2 -CH 2 -(CH 2 ) 13 -CH 3 ),1.793(m,2H,CH 3 -(CH 2 ) 13 -CH 2 -CH 2 -N),1.889-1.945(m,2H,CH 3 -(CH 2 ) 13 -CH 2 -CH 2 -N + ),2.371(m,2H,N-CH 2 -CH 2 -CH 2 -N + ),2.647-2.684(m,2H,N-CH 2 -CH 2 -CH 2 -SO 3 - ),2.970-2.979(m,2H, + N-CH 2 -CH 2 -CH 2 -SO 3 - ),3.340(s,3H, + N-CH 3 ),3.386-3.428(m,6H,N-(CH 2 ) 3 ),3.997-4.037(m,6H, + N-(CH 2 ) 3 ),4.211-4.333(m,4H,CH 2 -CH 2 -SO 3 - ).ESI–MS(HP1100LC–MSD):[M + ] / (C 42 H89 N 2 O 6 S 2 ) + :Calcd:781.6.Found:781.6.

[0138] Embodiment 10:

[0139] An asymmetric sulfonic Gemini surfactant, wherein X - =Br - , m=2,n=16,R 2 =-CH 2 CH 2 CH 2 SO 3 - Na + .

[0140] 1) Preparation and characterization of intermediate 16-3-1-16:

[0141] N-methylethylenediamine (1M) was added to a three-necked flask, and anhydrous ethanol was used as a solvent. Hexadecyl bromide (2.5M) was added dropwise. The temperature was raised to reflux, and the reaction was carried out for more than 48 hours. TLC was used to monitor whether the raw material N-methylpropylenediamine was completely reacted (dichloromethane / methanol = 9 / 1); a large amount of white solid was precipitated in the reaction system, and n-hexane was added and filtered. The obtained solid was washed with ethyl acetate and n-hexane for many times, and recrystallized with ethyl acetate and ethanol (4:1) for three times to obtain a white (slightly yellowish) solid, which was the hydrobromide of the product. The product was dissolved in a 20% NaOH solution, extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The product was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product;

[0142] 2)16-3-1-16-(SO 3 - ) 2 Preparation and characterization:

[0143] 16-3-1-16 (1M) was added to a three-necked flask, butyl acetate was used as solvent, 1,3-propane sultone (5M) was added dropwise, the temperature was raised to reflux, and the reaction was continued for more than 24 hours. The conversion of the raw material 16-3-1-16 was monitored by TLC (dichloromethane / methanol = 4 / 1). An off-white solid was obtained by suction filtration; methanol and ethyl acetate were recrystallized several times to obtain a white (slightly yellowish) solid, which was further purified by column chromatography (dichloromethane / methanol 10 / 1, 4 / 1) to obtain a pure product.

[0144] Above Figure 1-Figure 15 The spectrum (nuclear magnetic resonance spectrum or mass spectrum) of the synthesized compound is given to confirm that the synthesized compound is the target compound.

[0145] Test Example 1

[0146] This test example tests the asymmetric sulfonic Gemini surfactant 12-2-1-12-(SO 3 - ) 2 Surface tension and critical micelle concentration.

[0147] The asymmetric sulfonated Gemini surfactant 12-2-1-12-(SO 3 - ) 2 Prepare surfactant solutions of different concentrations and then test 12-2-1-12-(SO 3 - ) 2 Surface tension of aqueous solution. Test temperature 25°C. The surface tension of sodium dodecyl sulfate (purity 99%) was tested in the same way as a comparison. The comparison results are as follows: Fig.16 shown.

[0148] Depend on Fig.16 It can be seen that the evaluated asymmetric sulfonic Gemini surfactant 12-2-1-12-(SO 3 - ) 2 Compared with sodium dodecyl sulfate, it has the effect of significantly reducing surface tension and critical micelle concentration. The critical micelle concentration reaches 0.03mmol / L, which is reduced by two orders of magnitude, and the surface tension is reduced to about 28mN / m.

[0149] Test Example 2

[0150] This test example tests the Gemini surfactant 12-2-1-12-(COO - ) 2 interface performance.

[0151] The interfacial tension test was conducted using a TX500C spinning drop interfacial tension meter at a test temperature of 55°C for 2 hours. The mass percentages of the surfactants were 0.05wt%, 0.1wt%, 0.2wt%, and 0.3wt%. The oil and water used were from Changqing No. 2 Plant, such as Fig.17 As shown in the figure, 12-2-1-12-(COO - ) 2 In the concentration range of 0.05wt% to 0.3wt%, the interfacial tension of the system reaches an ultra-low level and the interfacial performance is excellent, which indicates that the Gemini surfactant 12-2-1-12-(COO - ) 2 Has good performance.

[0152] The same method was used to test sodium dodecyl carboxylate, sodium dodecyl aminoacetate, and the symmetrical carboxyl Gemini surfactant 12-2-12-(COO - ) 2 The results are shown in Table 1. Sodium dodecyl carboxylate and sodium dodecyl aminoacetate were purchased with a purity of more than 99%. The symmetrically structured carboxyl Gemini surfactant 12-2-12-(COO - ) 2 It was synthesized in the laboratory. The synthesis steps are as follows: 0.76 g of methylethylenediamine was dissolved in a three-necked flask containing isopropanol, 5.30 g of n-dodecyl bromide was added, the temperature was raised and refluxed for 24 hours, TLC was used to monitor whether the raw material N-methylethylenediamine was completely reacted (dichloromethane / methanol = 9 / 1), and the solid was filtered off. The solid was washed with ether and n-hexane for many times, and recrystallized with ethanol and ethyl acetate for many times to obtain a white solid. The product was dissolved in 20% NaOH solution, extracted with ether, and column chromatography (chloroform / methanol 5 / 1) to further purify to obtain the intermediate; 3.96g of the intermediate was added to a three-necked flask containing isopropanol, and 3.5g of sodium chloroacetate was added, the temperature was raised to reflux, and the reaction was carried out for 48h. The conversion of the raw materials was monitored by TLC (dichloromethane / methanol = 3 / 1). After the reaction was complete, a white solid was obtained by suction filtration; methanol and ethyl acetate were recrystallized several times to obtain a white solid, which was further purified by column chromatography (dichloromethane / methanol 6 / 1) to obtain the product 12-3-12 (COO - ) 2 .

[0153] Table 1: Comparison of equilibrium interfacial tension of different surfactants

[0154] 0.05wt% 0.1wt% 0.2wt% 0.3wt% Sodium dodecyl carboxylate 0.73 0.68 0.71 0.70 Sodium dodecylaminoacetate 0.62 0.65 0.78 0.62 <![CDATA[12-2-12-(COO - ) 2 ]]> 0.072 0.068 0.055 0.056 <![CDATA[12-2-1-12-(COO - ) 2 ]]> 0.0074 0.0018 0.0015 0.0044

[0155] In the preparation of Gemini surfactant flooding system (including ternary flooding system and binary flooding system), an appropriate amount of commercial surfactant can be added as an oil displacement adjuvant to adjust the interfacial properties of the oil displacement system to match different crude oil compositions and formation water salinity. Some commercial nonionic surfactants such as alkyl polyoxyethylene ether, alkyl polyoxypropylene ether, alkyl glycoside, alkanolamide and other nonionic surfactants can be used as adjuvants to adjust the interfacial properties of the oil displacement system.

[0156] Test Example 3

[0157] This test example tests the Gemini surfactant 12-2-1-12-(COO - ) 2 The performance of binary systems.

[0158] Tested by TX500C 12-2-1-12-(COO - ) 2 The interfacial tension of the binary system. - ) 2 Prepare an alkali-free binary composite system solution and then test 12-2-1-12-(COO - ) 2 The interfacial tension between the alkali-free binary composite system solution and the crude oil of Changqing No. 2 Plant was tested at a temperature of 55°C. The results are as follows Fig.18 As shown. In the Gemini surfactant 12-2-1-12-(COO - ) 2 In the alkali-free binary composite system solution, the mass percentage of the surfactant is 0.05wt%, 0.1wt%, 0.2wt%, and 0.3wt%, and the molecular weight of the polymer is 16 million, and the mass percentage is 0.15wt%. Fig.18 It can be seen that the evaluated Gemini surfactant 12-2-1-12-(COO - ) 2 The alkali-free binary composite flooding compositions composed of polymers can achieve ultra-low interfacial tension with the Changqing No. 2 crude oil under alkali-free conditions, showing excellent interfacial properties.

[0159] Tested 12-2-1-12-(COO - ) 2 The anti-adsorption performance of the binary system. 100-200 mesh Changqing oil sand and Gemini surfactant 12-2-1-12-(COO - ) 2 The binary flooding formula system was added to a ground-mouth conical bottle with a stopper, sealed and placed in a constant temperature oscillating water bath at 55°C (Changqing oil layer temperature) for 24 hours. The conical bottle was taken out, the interfacial tension of the upper solution was measured, and then adsorption with new oil sand was continued. This was repeated until the interfacial tension could not reach an ultra-low level. The results are shown in the figure. Fig.19 As shown. It can be seen that the Gemini surfactant containing symmetrical carboxyl groups 12-2-1-12-(COO - ) 2 The binary flooding formula system still achieved ultra-low interfacial tension after six times of oil-water adsorption on Changqing No. 2 Plant, and its anti-adsorption performance was excellent.

[0160] The oil displacement efficiency of the Gemini surfactant composition of the present invention was evaluated by core flooding experiments. Table 2 shows the Gemini surfactant 12-2-1-12-(COO - ) 2The experimental results of binary composite flooding composition. The mass percentage of surfactant in the binary composite flooding composition is 0.30wt%; the polymer molecular weight is 16 million, the mass percentage is 0.15wt%, the oil and water used are the oil and water of Changqing No. 2 Plant, and the formation temperature is 55°C. The segment plug of the binary composite flooding system used is 0.5PV. From the experimental results, it can be seen that the Gemini surfactant binary composite flooding composition improves the recovery rate by more than 28%, indicating that the Gemini surfactant provided by the present invention has great advantages in the field of medium and low permeability binary composite flooding.

[0161] Table 2: Results of oil displacement experiments with Gemini surfactant 12-2-1-12-(COO-)2 binary composite flooding composition

[0162]

[0163] Test Example 4

[0164] This test example tests the Gemini surfactant 12-3-1-12-(COO - ) 2 The performance of the ternary system.

[0165] Gemini surfactant 12-3-1-12-(COO - ) 2 The formation water of Daqing No. 1 Plant was used to prepare a ternary system with different concentrations, and then the interfacial tension between the solution and the crude oil of Daqing No. 1 Plant was tested at a temperature of 45°C. The results are as follows: Fig. 20 As shown. In the Gemini surfactant 12-3-1-12-(COO - ) 2 In the ternary composite flooding composition system solution, the mass percentage of the surfactant is 0.3wt%, the mass percentage of sodium carbonate is 0.2wt%, 0.4wt%, 0.6wt%, 0.8wt%, 1.0wt%, 1.2wt%, and the molecular weight of the polymer is 25 million, and the mass percentage is 0.15wt%. Fig. 20 It can be seen that the evaluated Gemini surfactant 12-3-1-12-(COO - ) 2 The oil displacement system can achieve ultra-low interfacial tension with Daqing No. 1 crude oil under different alkali concentration conditions, showing excellent interfacial performance.

[0166] The oil displacement efficiency of the Gemini surfactant composition of the present invention was evaluated by core flooding experiments. Table 3 shows the Gemini surfactant 12-3-1-12-(COO - ) 2The experimental results of oil displacement of ternary composite flooding composition. The mass percentage of surfactant in the ternary composite flooding composition is 0.30wt%, the mass percentage of sodium carbonate is 1.0wt%, the molecular weight of polymer is 25 million, the mass percentage is 0.15wt%, the oil and water used are the oil and water of Daqing No. 1 Plant, and the formation temperature is 45°C. The segment plug of the ternary composite flooding system used is 0.5PV. From the experimental results, it can be seen that the Gemini surfactant ternary composite flooding composition improves the recovery rate by about 35%, indicating that the Gemini surfactant provided by the present invention has great advantages in the field of ternary composite flooding.

[0167] Table 3: Gemini surfactant 12-3-1-12-(COO - ) 2 Results of oil displacement experiment with ternary composite flooding combination

[0168]

[0169] The present invention prepares a carboxyl Gemini surfactant through a two-step reaction. The surfactant has a simple preparation process, has the advantages of high interfacial activity, high oil displacement efficiency, high oil washing efficiency, etc., and can meet the needs of different oil reservoirs by adjusting the structure, and has great application prospects in the field of tertiary oil recovery.

[0170] Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent substitutions for some of the technical features therein; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An asymmetric Gemini surfactant, characterized in that: The molecular structure is as follows: AL-B A is N + CH3CH2COO - Na + C 12 H 25 Br - , L is C2H4, B is NCH2COO - Na + C 12 H 25 ;or; A is N + CH3CH2COO - Na + C 12 H 25 Br - , L is C3H6, B is NCH2COO - Na + C 12 H 25 ;or; A is N + CH3CH2CH2CH2SO3 - Na + C 12 H 25 Br - , L is C2H4, B is NCH2CH2CH2SO3 - Na + C 12 H 25 ;or; A is N + CH3CH2CH2CH2SO3 - Na + C 12 H 25 Br - , L is C3H6, B is NCH2CH2CH2SO3 - Na + C 12 H 25 ;or; A is N + CH3CH2CH2CH2SO3 - Na + C 16 H 33 Br - , L is C2H4, B is NCH2CH2CH2SO3 - Na + C 16 H 33 .

2. A method for preparing an asymmetric Gemini surfactant as claimed in claim 1, characterized in that: The preparation method comprises: Adding a halogenated hydrocarbon to a monosubstituted fatty diamine for reaction, wherein the monosubstituted fatty diamine is N-methylethylenediamine or N-methylpropylenediamine, and the halogenated hydrocarbon is n-dodecyl bromide or n-hexadecyl bromide to obtain an intermediate; Sodium bromoacetate or 1,3-propane sultone is added to the intermediate solution to react, and the final product is an asymmetric Gemini surfactant.

3. The method for preparing an asymmetric Gemini surfactant according to claim 2, characterized in that: The method for obtaining the intermediate specifically comprises: dissolving the monosubstituted fatty diamine in an organic solvent; heating under reflux, dropping the halogenated hydrocarbon into the monosubstituted fatty diamine, and monitoring by TLC until the monosubstituted fatty diamine reacts completely; and then washing, filtering and purifying the product to obtain the intermediate.

4. The method for preparing an asymmetric Gemini surfactant according to claim 2, characterized in that: The amount ratio of the monosubstituted fatty diamine to the halogenated hydrocarbon is 1:2.0-2.

5.

5. The method for preparing an asymmetric Gemini surfactant according to claim 2, characterized in that: The halogenated hydrocarbon is added to the monosubstituted fatty diamine for reaction at a temperature of 60-120°C.

6. The method for preparing an asymmetric Gemini surfactant according to claim 2, characterized in that: The step of adding sodium bromoacetate or 1,3-propane sultone to the intermediate solution for reaction to obtain the final product, which is the asymmetric Gemini surfactant, specifically comprises: dissolving the synthetic intermediate in an organic solvent; then adding sodium bromoacetate or 1,3-propane sultone, heating and refluxing, and monitoring the conversion of the raw intermediate by TLC; after the reaction is complete, washing, filtering, and purifying the product to obtain the final product.

7. The method for preparing an asymmetric Gemini surfactant according to claim 2, characterized in that: The mass ratio of the intermediate to sodium bromoacetate or 1,3-propane sultone is 1:2.2-5.

8. The method for preparing an asymmetric Gemini surfactant according to claim 2, characterized in that: The sodium bromoacetate or 1,3-propane sultone is added to the intermediate solution for reaction at a temperature of 70-140°C.

9. The method for preparing an asymmetric Gemini surfactant according to claim 2, characterized in that: The pH value range of the reaction between the intermediate and sodium bromoacetate or 1,3-propane sultone is maintained at 7-13.

10. An application of an asymmetric Gemini surfactant, characterized in that: The asymmetric Gemini surfactant as claimed in claim 1 is used in the field of oil production. When used, the asymmetric Gemini surfactant is used in the form of a composition, and the types of the composition include a ternary composite flooding composition, an alkali-free binary composite flooding composition and a surfactant flooding composition.

11. The use of the asymmetric Gemini surfactant according to claim 10, characterized in that: The components of the alkali-free binary composite flooding composition include: 0.05wt%-0.30wt% of Gemini surfactant, 0.05wt%-0.30wt% of polymer, and the balance of water.

12. The use of the asymmetric Gemini surfactant according to claim 10, characterized in that: The components of the ternary composite flooding composition include: 0.03wt%~3.0wt% of alkaline substance, 0.05wt%~0.30wt% of Gemini surfactant, 0.05wt%~0.30wt% of polymer, and the balance of water.

13. The use of the asymmetric Gemini surfactant according to claim 11 or 12, characterized in that: The polymer is a hydrophobic associating polymer, a star-shaped temperature-resistant and salt-resistant polymer or a partially hydrolyzed polyacrylamide polymer.

14. The use of the asymmetric Gemini surfactant according to claim 13, characterized in that: The average molecular weight of the polymer is 3 million to 35 million.

15. The use of the asymmetric Gemini surfactant according to claim 12, characterized in that: The alkaline substance includes one or a combination of trimethylamine, triethylamine, tetrasodium ethylenediaminetetraacetate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium tetraborate, and sodium phosphate.

16. An application of an asymmetric Gemini surfactant, characterized in that: The asymmetric Gemini surfactant as claimed in claim 1 is used in a low permeability oil reservoir. When used, the asymmetric Gemini surfactant is used in the form of a composition, and the type of the composition is a surfactant flooding composition.

17. Use of the asymmetric Gemini surfactant according to claim 10 or 16, characterized in that: The components of the surfactant flooding composition include: 0.05wt% to 0.30wt% of Gemini surfactant, and the balance of water.

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