CN116332853A - Nitrogen heterocyclic Gemini ionic liquid surfactant, synthesis method thereof and oil displacement system - Google Patents

Nitrogen heterocyclic Gemini ionic liquid surfactant, synthesis method thereof and oil displacement system Download PDF

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CN116332853A
CN116332853A CN202310076490.2A CN202310076490A CN116332853A CN 116332853 A CN116332853 A CN 116332853A CN 202310076490 A CN202310076490 A CN 202310076490A CN 116332853 A CN116332853 A CN 116332853A
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ionic liquid
liquid surfactant
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牛瑞霞
龙彪
宋华
张健伟
李�杰
何珺瑶
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Northeast Petroleum University
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Abstract

An azacyclo Gemini ionic liquid surfactant for weak base oil extraction system, a synthesis method thereof and an oil displacement system, wherein the synthesis steps comprise: (a) Taking alcohol as a solvent in the presence of an acid binding agent, and carrying out microwave reaction on an azacyclic compound and dihaloalkane to obtain diazacyclylalkane; (b) Dissolving diazacyclylalkane and haloalkane in alcohol, and carrying out microwave reaction to obtain a halogenated Gemini ionic liquid surfactant; (c) Further, the halogen Gemini is separated fromThe sub-liquid surfactant is mixed with non-halogen anion salt and dissolved in water, and the non-halogen Gemini ionic liquid surfactant is obtained through microwave reaction. The synthesis technology does not need a catalyst, does not need a toxic organic solvent, has high reaction efficiency and is easy to purify a product. The prepared surfactant can be used as an emulsifier or a wetting agent to be singly or compositely used with other auxiliary agents for crude oil extraction in the tertiary oil recovery field, and the interfacial tension between the prepared weak base binary compound oil displacement system and Daqing crude oil is 10 ‑3 ～10 ‑1 mN/m has potential industrial application prospect.

Description

Nitrogen heterocyclic Gemini ionic liquid surfactant, synthesis method thereof and oil displacement system
Technical field:
the invention relates to the field of novel oil displacement surfactants for tertiary oil recovery in oil fields, in particular to a Gemini ionic liquid surfactant, a synthesis method thereof and an oil displacement system.
The background technology is as follows:
the ionic liquid type surfactant is a novel functional ionic liquid, and the ionic liquid has amphiphilicity and good surface activity by introducing a long hydrophobic alkyl chain to a parent of the ionic liquid capable of designing a green solvent, so that the ionic liquid becomes a novel surfactant. The surfactant has both the amphiphilicity of the surfactant and the designability of the ionic liquid, and can have brand-new physical and chemical properties by changing the composition of organic cations and anions in the molecular structure of the surfactant, so the surfactant is also called as a designable surfactant. The Gemini ionic liquid surfactant combines the advantages of the traditional Gemini surfactant and the single carbon chain long chain ionic liquid, and has a plurality of unique properties due to the existence of heterocyclic hydrophilic head groups, and the addition of the ionic liquid has proved to be helpful for reducing the oil-water interfacial tension, improving the oil displacement performance of a strong base-free oil displacement system, and being hopeful to solve the strong base problem in the tertiary oil recovery process of the current oil field, has larger application potential in the tertiary oil recovery field of the oil field, and brings great attention to related scientific researchers at home and abroad.
The synthesis of ionic liquid type surfactant is one of the important directions of research, and is also the basis and key link of industrialization. At present, two common methods for synthesizing the Gemini ionic liquid surfactant are as follows: (1) The two hydrophilic head groups are connected by a connecting group, and then the hydrophobic group is connected by the hydrophilic head group. (2) Two monomer ionic liquid surfactants are synthesized first and then connected directly to the chemical bond of hydrophilic head group via the connecting radical. For example, quaglioto P in 2003 adopts a first strategy, firstly, methyl pyridine is used as a raw material, the raw material reacts with dibromoalkane at the temperature of minus 20 ℃ under the catalysis of BuLi to obtain bipyridyl alkane, and then the bipyridyl alkane reacts with dodecyl methane sulfonate at the temperature of 140 ℃ to introduce a hydrophobic alkyl chain. In 2007, baltazar and the like adopted a first strategy, imidazole and dibromoalkane as raw materials, DMSO and toluene as solvents, reacted for 2 hours at 120 ℃ in the presence of an alkali solution to obtain diimidazolyl alkane, and then reacted with bromododecane to introduce a hydrophobic hydrocarbon group. In 2008 Ao et al, imidazole, acrylonitrile and halogenated alkane are taken as raw materials to prepare N-alkyl imidazole through about 34 hours in 3 steps, and then the N-alkyl imidazole and dibromobutane react for 24 hours at 60-65 ℃ to obtain the Gemini imidazole brominated ionic liquid with the alkyl chain length of 10-14. In 2007 Zhou et al, alpha-alkylpyridine and dibromobutane are taken as raw materials, and a reflux reaction is carried out for 72 hours to synthesize the Gemini pyridine brominated ionic liquid with the alkyl chain length of 8-12. The prior art adopts a traditional solvent reflux method, a large amount of organic solvent or catalyst is needed in the reaction process, and the reaction period is generally tens of hours or even days. In addition, the yields of the obtained intermediate and the target surfactant are low, and the separation and purification of the product are difficult.
The existing synthesis method of the Gemini ionic liquid surfactant has common problems, such as harsh synthesis conditions (a large amount of toxic organic solvents are needed), poor environmental protection, low selectivity, long reaction time and the like, and limits the industrialized popularization and application of the Gemini ionic liquid surfactant. Therefore, there is a need to develop a new efficient synthesis route which is easy to operate and high in safety, so that the production limit bottleneck of the existing technology is improved, products with stable efficient synthesis performance are synthesized, the application field of the ionic liquid surfactant is expanded, a strong base-free oil displacement formula system is developed, and the development requirement of the petroleum exploitation industry is met.
The invention comprises the following steps:
aiming at the problems of long reaction period, large amount of organic solvents required to be used and the like in the synthesis method of the Gemini ionic liquid surfactant in the background art, the invention aims to provide a method for synthesizing the Gemini ionic liquid surfactant by microwave radiation and an oil displacement system thereof. The synthesis method has the characteristics of simple operation, no catalyst participation, no use of toxic organic solvents, high reaction efficiency, high safety, easy purification of products and the like.
The invention relates to a Gemini ionic liquid surfactant, which has the following structural general formula:
Figure BDA0004066354600000021
wherein: r is R 1 Is H or saturated hydrocarbon radical containing 1-4 carbon atoms, R 2 Is a saturated hydrocarbon group containing 8 to 16 carbon atoms; x is an organic ion unit including, but not limited to: CH (CH) 3 COO - 、CF 3 COO - 、C 6 H 6 SO 3 - 、C 12 H 25 SO 3 - 、C 12 H 25 C 6 H 6 SO 3 - 、C 10 H 7 SO 3 - 。
The method for synthesizing the Gemini ionic liquid surfactant comprises the following steps:
(1) Nucleophilic substitution bridging reaction of an azacyclic compound with a dihaloalkane: dissolving an azaheterocyclic compound and dihaloalkane in an organic solvent according to a molar ratio of 2-3.5:1, adding an inorganic alkaline water solution with a concentration of 20-60 wt%, placing the mixture in a microwave chemical reactor, magnetically stirring the mixture for microwave radiation, controlling the microwave power to be 300-600W, reacting at 30-70 ℃ for 3-9 min, standing the obtained reaction solution for layering, collecting an upper organic phase, and performing reduced pressure distillation to obtain an intermediate diazacyclylalkane;
(2) Quaternization of diazacyclylalkanes: putting the intermediate diazacyclylalkane prepared in the step (1) and halogenated alkane into a microwave reaction flask according to a ratio of 1:2-2.5, adding an organic solvent, controlling the microwave power to be 300-600W, reacting at 45-60 ℃ for 4-6 min to obtain a halogenated Gemini ionic liquid surfactant crude product, performing reduced pressure distillation on the halogenated crude product, vacuum drying, recrystallizing for 3 times, and vacuum drying at room temperature to obtain the white Gemini ionic liquid surfactant, wherein X in the general formula is Cl - 、Br - 、I - Preparing the halogen Gemini ionic liquid surfactant by using plasma anions, wherein X in the general formula is CH 3 COO - 、CF 3 COO - 、C 6 H 6 SO 3 - 、C 12 H 25 SO 3 - 、C 12 H 25 C 6 H 6 SO 3 - 、C 10 H 7 SO 3 - And (3) preparing the non-halogeno Gemini ionic liquid surfactant by using plasma.
If the non-halogeno Gemini ionic liquid surfactant prepared in the step (2) is adopted, the halogeno anion exchange reaction in the step (3) is required to be continued: mixing the Gemini ionic liquid surfactant prepared in the step (2) with non-halogen anion salt according to a molar ratio of 1:2, stirring, adding water with 2-5 times of the total mass of reactants, controlling microwave power to 400W, reacting for 5-10 min at 60-110 ℃, carrying out anion exchange, recrystallizing the obtained crude product for 3 times, and vacuum drying at room temperature to obtain the white powdery or pasty non-halogen Gemini ionic liquid surfactant.
As a further improvement of the present invention, the non-halogen anion salt in the step (3) is sodium benzenesulfonate, sodium acetate, sodium naphthalenesulfonate, sodium dodecylbenzenesulfonate, etc.
As a further improvement of the present invention, the aza-cycle compound in step (1) is imidazole and its derivatives, and imidazole derivatives specifically include benzimidazole, methyl, ethyl, propyl, butyl-substituted 2-alkylimidazole, and methyl, ethyl, propyl, butyl-substituted 2-alkylbenzimidazole.
As a further improvement of the invention, the dihaloalkanes described in step (1) are symmetrical halo-substituted alkanes, including chloro-, bromo-and iodo-alkanes, having carbon chain lengths of 2,4,6,8.
As a further improvement of the invention, the inorganic alkaline water solution in the step (1) is one or more of sodium hydroxide water solution, potassium hydroxide water solution and ammonia water, and the concentration range is 20-60 wt%.
As a further improvement of the invention, the haloalkane in the step (2) has an alkyl chain length of C 8 ～C 16 Brominated alkanes, chlorinated alkanes and iodinated alkanes.
As a further improvement of the invention, the organic solvent in the step (1) is one or more of ethanol, isopropanol and n-butanol in any proportion.
The oil displacement system containing the Gemini ionic liquid surfactant is composed of the following components: the concentration of the Gemini ionic liquid surfactant is 0.1-0.3 wt%, the concentration of weak base is 0.6-1.2 wt%, and the rest is simulated water.
As a further improvement of the invention, the simulated water is prepared water with the mineralization degree of 400-8000mg/L under the simulated crude oil stratum.
As a further improvement of the invention, the weak base is Na 2 CO 3 Or NaHCO 3 。
Due to the adoption of the technical scheme, the invention has the following advantages compared with the existing synthesis process of the Gemini ionic liquid surfactant and the existing oil displacement system:
(1) The Gemini ionic liquid surfactant is synthesized in an auxiliary mode by adopting a microwave radiation technology, the operation is simple, the synthesis efficiency is high, the reaction is easy to control, and meanwhile, the product is easy to purify;
(2) The solvent used in the synthesis process is short-chain alcohols and water, so that the high-efficiency reaction of a homogeneous system is ensured, and the environment is protected, and the reaction process is safer;
(3) The weak base binary oil displacement system containing the Gemini ionic liquid surfactant can reduce the interfacial tension between Daqing crude oil and the oil displacement system to 10 -3 ～10 -1 mN/m has potential application value in the tertiary oil recovery field.
Description of the drawings:
FIG. 1 is an infrared spectrum analysis of intermediate diimidazolyl ethane synthesized in example 1;
FIG. 2 is a schematic illustration of a bromoimidazole Gemini ionic liquid surfactant [ C ] as described in example 1 14 -2-C 14 Im]Br 2 Is a spectrum of an infrared spectrum analysis;
FIG. 3 is a schematic illustration of a bromoimidazole Gemini ionic liquid surfactant [ C ] as described in example 2 8 -2-C 8 Im]Br 2 Is a nuclear magnetic resonance hydrogen spectrogram of (2);
FIG. 4 is a series of bromoimidazolyl Gemini ionic liquid surfactants [ C ] as described in example 3 n -2-C n Im]Br 2 Is a surface tension map of (1);
FIG. 5 is a series of bromoimidazolyl Gemini ionic liquid surfactants [ C ] as described in example 3 n -2-C n Im]Br 2 Formulated Na 2 CO 3 The concentration of (alkali) is 1.2%, the concentration of the surfactant is 0.1%, and the oil-water interface Zhang Litu between the oil displacement system and Daqing crude oil is provided;
FIG. 6 is a schematic illustration of a sulfonate-based Gemini ionic liquid surfactant [ C ] as described in example 4 12 -2-C 12 Im][C 6 H 6 SO 3 ] 2 Is an infrared spectrum of (c).
The specific embodiment is as follows:
the invention relates to a Gemini ionic liquid surfactant, which has the following structural general formula:
Figure BDA0004066354600000041
wherein: r is R 1 Is H or saturated hydrocarbon radical containing 1-4 carbon atoms, R 2 Is a saturated hydrocarbon group containing 8 to 16 carbon atoms;x is an organic ion unit including, but not limited to: CH (CH) 3 COO - 、CF 3 COO - 、C 6 H 6 SO 3 - 、C 12 H 25 SO 3 - 、C 12 H 25 C 6 H 6 SO 3 - 、C 10 H 7 SO 3 - 。
The method for synthesizing the Gemini ionic liquid surfactant comprises the following steps:
(1) Nucleophilic substitution bridging reaction of an azacyclic compound with a dihaloalkane: dissolving an azaheterocyclic compound and dihaloalkane in an organic solvent according to a molar ratio of 2-3.5:1, adding an inorganic alkaline water solution with a concentration of 20-60 wt%, placing the mixture in a microwave chemical reactor, magnetically stirring the mixture for microwave radiation, controlling the microwave power to be 300-600W, reacting at 30-70 ℃ for 3-9 min, standing the obtained reaction solution for layering, collecting an upper organic phase, and performing reduced pressure distillation to obtain an intermediate diazacyclylalkane;
(2) Quaternization of diazacyclylalkanes: putting the intermediate diazacyclylalkane prepared in the step (1) and halogenated alkane into a microwave reaction flask according to a ratio of 1:2-2.5, adding an organic solvent, controlling the microwave power to be 300-600W, reacting at 45-60 ℃ for 4-6 min to obtain a halogenated Gemini ionic liquid surfactant crude product, performing reduced pressure distillation on the halogenated crude product, vacuum drying, recrystallizing for 3 times, and vacuum drying at room temperature to obtain the white Gemini ionic liquid surfactant, wherein X in the general formula is Cl - 、Br - 、I - Preparing the halogen Gemini ionic liquid surfactant by using plasma anions, wherein X in the general formula is CH 3 COO - 、CF 3 COO - 、C 6 H 6 SO 3 - 、C 12 H 25 SO 3 - 、C 12 H 25 C 6 H 6 SO 3 - 、C 10 H 7 SO 3 - And (3) preparing the non-halogeno Gemini ionic liquid surfactant by using plasma.
If the non-halogeno Gemini ionic liquid surfactant prepared in the step (2) is adopted, the halogeno anion exchange reaction in the step (3) is required to be continued: mixing the Gemini ionic liquid surfactant prepared in the step (2) with non-halogen anion salt according to a molar ratio of 1:2, stirring, adding water with 2-5 times of the total mass of reactants, controlling microwave power to 400W, reacting for 5-10 min at 60-110 ℃, carrying out anion exchange, recrystallizing the obtained crude product for 3 times, and vacuum drying at room temperature to obtain the white powdery or pasty non-halogen Gemini ionic liquid surfactant.
The non-halogen anion salt in the step (3) is sodium benzenesulfonate, sodium acetate, sodium naphthalenesulfonate, sodium dodecylbenzenesulfonate, etc.
The nitrogen heterocyclic compound in the step (1) is imidazole and derivatives thereof, and the imidazole derivatives specifically comprise benzimidazole, methyl, ethyl, propyl and butyl substituted 2-alkyl imidazole and methyl, ethyl, propyl and butyl substituted 2-alkyl benzimidazole.
The dihaloalkane in the step (1) is symmetrical halogen substituted alkane, including chlorine, bromine and iodo alkane, and the carbon chain length is 2,4,6 and 8.
The inorganic alkaline water solution in the step (1) is one or the combination of more than one of sodium hydroxide water solution, potassium hydroxide water solution and ammonia water in any proportion, and the concentration range is 20-60 wt%.
The haloalkane in the step (2) is alkyl chain with length of C 8 ～C 16 Brominated alkanes, chlorinated alkanes and iodinated alkanes.
The organic solvent in the step (1) is one or more of ethanol, isopropanol and n-butanol in any proportion.
The oil displacement system containing the Gemini ionic liquid surfactant is composed of the following components: the concentration of the Gemini ionic liquid surfactant is 0.1-0.3 wt%, the concentration of weak base is 0.6-1.2 wt%, and the rest is simulated water.
The simulated water is prepared water with the mineralization degree of 400-8000mg/L under the simulated crude oil stratum.
The weak baseIs Na (Na) 2 CO 3 Or NaHCO 3 。
The formation temperature of the oil displacement system is 45 ℃.
Example 1:
bromoimidazolyl Gemini ionic liquid surfactant [ C ] 14 -2-C 14 Im]Br 2 The microwave-assisted synthesis method of (2) is as follows:
(1) Synthesis of intermediate diimidazolyl ethane: imidazole (0.032 mol) and 1, 2-dibromoethane (0.01 mol) are added into a special reaction bottle of a 250mL microwave reactor, 50% NaOH aqueous solution and 24mL isopropanol are added, a reflux condenser is arranged, and the mixture is uniformly mixed under magnetic stirring. After the reaction is finished, pouring the reaction liquid into a separating funnel for standing and layering, collecting upper organic phase liquid, distilling under reduced pressure to remove solvent, and vacuum drying for 24h at room temperature to obtain white diimidazole ethane solid with the yield of 63.8%. The infrared spectrum of the intermediate diimidazolyl ethane is shown in figure 1. As can be seen from fig. 1, 2998, 2914cm -1 The attribution is imidazole ring and bridging CH between two imidazole rings 2 C-H stretching vibration peak of (2) and compared with imidazole, the intensity of the two peaks is enhanced due to the introduction of two imidazole groups, 1651cm -1 The position ascription is imidazole ring C=N stretching vibration peak, 1436cm -1 The position belonging to the imidazole ring C=C telescopic vibration peak is 1313cm -1 The position is an imidazole ring C-N telescopic vibration characteristic absorption peak, 954 cm and 702cm -1 The position is attributed to the C-H bending vibration peak. 3120cm -1 No obvious characteristic absorption peak of N-H bond appears on the left and right sides, which indicates that nucleophilic substitution reaction is generated between N-H on imidazole ring and dibromoethane;
(2)[C 14 -2-C 14 Im]Br 2 is synthesized by the following steps: the intermediate obtained in the above step was added to a 100mL round bottom flask according to the intermediate: the molar ratio of bromoalkane is 1:2.1, bromotetradecane and a proper amount of isopropanol are added, a condensation reflux device is connected, the microwave power is 300W, the reaction temperature is 53 ℃, and the reaction is carried out for 6min under the action of magnetic stirring. The solvent was distilled off under reduced pressure to give a milky viscous liquid. The crude product obtained is then taken up in ethyl acetateRecrystallizing in solvent for 3 times, vacuum drying at room temperature for 24h to obtain target product [ C ] 14 -2-C 14 Im]Br 2 The yield thereof was found to be 93.4%. The infrared spectrum of the product is shown in FIG. 2, and as can be seen from FIG. 2, the introduction of tetradecyl hydrophobic chain leads to 2920, 2850cm -1 The characteristic peak is obviously enhanced, and the attribution is CH 3 And CH (CH) 2 C-H stretching vibration characteristic peak of 1562cm -1 The position is attributed to an imidazole ring C=N telescopic vibration peak of 1466cm -1 The left and right attributions are CH 3 And CH (CH) 2 C-H bending vibration characteristic peak of (2) 1163cm -1 The characteristic absorption peak of the imidazole ring C-N stretching vibration belongs to the left and right, and the introduction of long-chain hydrocarbon groups can lead the characteristic peak of the groups on the imidazole ring to have obvious blue shift phenomenon.
The specific operation method of the recrystallization is as follows:
respectively taking 10mL of methanol, ethanol, acetone, dichloromethane, petroleum ether and ethyl acetate in a small beaker, respectively adding 1g of [ C n -2-C n Im]Br 2 Stirring and dissolving. The results of crystallization of the various solvents are shown in the table.
TABLE 1C n -2-C n Im]Br 2 Crystallization in solvents
Figure BDA0004066354600000061
Through solvent screening, the recrystallization effect in ethyl acetate is finally considered to be better. And (3) carrying out suction filtration on a sample in the frozen ethyl acetate, preparing a hot saturated solution of the obtained filter cake by using ethyl acetate as a solvent, and carrying out quick suction filtration after freezing for 12 hours. This operation was repeated three times, and the finally obtained product was dried in vacuo for 24 hours to obtain a white powdery solid. Since the polarity of the product changes with the change in alkyl chain length, the solvent composition needs to be appropriately adjusted according to the actual situation.
Example 2:
bromoimidazolyl Gemini ionic liquid surfactant [ C ] 8 -2-C 8 Im]Br 2 The microwave-assisted synthesis method of (2) is as follows:
the intermediate described in example 1 above was added to a 100mL round bottom flask as an intermediate: the molar ratio of the bromooctane is 1:2.3, 30mL of isopropanol is added, a condensing reflux device is connected, the microwave power is 350W, the reaction temperature is 45 ℃, and the reaction is carried out for 5min under the action of magnetic stirring. The solvent was distilled off under reduced pressure to give a milky white liquid. Then recrystallizing the obtained crude product in ethyl acetate-cyclohexane (V: V=9:1) for 3 times, and vacuum drying at room temperature for 24 hours to obtain the target product [ C ] 8 -2-C 8 Im]Br 2 The quaternization yield was 97.6%. The nuclear magnetic resonance hydrogen spectrum structure analysis of the product is shown in fig. 3, delta (ppm): 9.45 (s, 2H), 7.89 (d, 4H), 4.20 (t, 4H), 3.94 (t, 4H), 1.80 (t, 4H), 1.67 (m, 4H), 1.23 (m, 16H), 0.85 (t, 6H).
Example 3:
chloroimidazolyl Gemini ionic liquid surfactant [ C ] 12 -2-C 12 Im]Cl 2 The microwave-assisted synthesis method of (2) is as follows:
the intermediate described in example 1 above was added to a 100mL round bottom flask as an intermediate: the mol ratio of the chlorohexadecane is 1:2.5, C is added 16 H 33 Cl,50mL of isopropanol/n-butanol (V: V=1:1), a condensation reflux device was connected, the microwave power was 600W, the reaction temperature was 60 ℃, and the reaction was performed for 6min under the magnetic stirring. The solvent was distilled off under reduced pressure to give a milky white liquid. Then recrystallizing the obtained crude product in ethyl acetate-cyclohexane (V: V=9:1) for 3 times, and vacuum drying at room temperature for 24 hours to obtain the target product [ C ] 16 -2-C 16 Im]Cl 2 The quaternization yield was 92.1%.
Example 4:
chloroimidazolyl Gemini ionic liquid surfactant [ C ] 10 -8-C 10 Im]Cl 2 The microwave-assisted synthesis method of (2) is as follows:
(1) Synthesis of intermediate diimidazolyl octane: imidazole (0.035 mol) and 1, 2-dibromooctane (0.01 mol) were added to a 250mL reactor special for a microwave reactor, followed by addition of 60% aqueous KOH and 40mL n-butanol, followed by installation of a reflux condenser, and mixing was carried out under magnetic stirring. After the reaction is finished, pouring the reaction liquid into a separating funnel for standing and layering, collecting upper organic phase liquid, distilling under reduced pressure to remove solvent, and drying in vacuum for 24h at room temperature to obtain diimidazolyl octane white solid with the yield of 60.1%.
(2)[C 10 -8-C 10 Im]Cl 2 Is synthesized by the following steps: the intermediate obtained in the above step was added to a 100mL round bottom flask according to the intermediate: the molar ratio of chlorinated alkane is 1:2.2, chlorinated decane and a proper amount of n-butanol are added, a condensation reflux device is connected, the microwave power is 400W, the reaction temperature is 55 ℃, and the reaction is carried out for 5min under the action of magnetic stirring. The solvent was distilled off under reduced pressure to give a milky viscous liquid. Then recrystallizing the obtained crude product in ethyl acetate solvent for 3 times, and vacuum drying at room temperature for 24h to obtain the target product [ C ] 10 -8-C 10 Im]Cl 2 The yield thereof was found to be 92.6%.
Example 5:
iodinated imidazolyl Gemini ionic liquid surfactant [ C ] 12 -8-C 12 Im]I 2 The microwave-assisted synthesis method of (2) is as follows:
the intermediate described in example 4 above was added to a 100mL round bottom flask as an intermediate: the molar ratio of the halogenated alkane is 1:2.5, and C is added in 12 H 25 I,50mL of isopropanol/n-butanol (V: V=1:1), a condensation reflux device is connected, the microwave power is 600W, the reaction temperature is 60 ℃, and the magnetic stirring reaction is carried out for 6min. After the solvent was distilled off under reduced pressure, it was recrystallized 3 times from ethyl acetate-cyclohexane (V: v=4:1), and dried under vacuum at room temperature for 24 hours to give the objective product [ C 12 -8-C 12 Im]I 2 The quaternization yield was 91.3%.
Example 6:
bromobutyl imidazolyl Gemini ionic liquid surfactant [ C ] 12 -2-C 12 -Bu-Im]Br 2 The microwave-assisted synthesis method of (2) is as follows:
(1) Synthesis of bis (2-butylimidazolyl) ethane: to a 250mL reactor special for microwave reactor, 2-butylimidazole (0.035 mol) and 1, 2-dibromoethane (0.01 mol) were added, followed by 50% aqueous KOH and 50mL n-butanol, and a reflux condenser was installed and mixed uniformly under magnetic stirring. After the reaction is finished, pouring the reaction liquid into a separating funnel for standing and layering, collecting upper organic phase liquid, distilling under reduced pressure to remove solvent, and vacuum drying for 24h at room temperature to obtain white solid of bis (2-butylimidazolyl) ethane with the yield of 64.2%.
Figure BDA0004066354600000081
(2)[C 12 -2-C 12 -Bu-Im]Br 2 Is synthesized by the following steps: the intermediate obtained in the above step was added to a 100mL round bottom flask according to the intermediate: the molar ratio of bromoalkane is 1:2.4, bromododecane and a proper amount of isopropanol are added, a condensation reflux device is connected, the microwave power is 400W, the reaction temperature is 50 ℃, and the reaction is carried out for 5min under the action of magnetic stirring. The solvent was distilled off under reduced pressure to give a milky viscous liquid. Then recrystallizing the obtained crude product in ethyl acetate solvent for 3 times, and vacuum drying at room temperature for 24h to obtain the target product [ C ] 12 -2-C 12 -Bu-Im]Br 2 The yield thereof was found to be 94.5%.
Example 7:
bromobutyl imidazolyl Gemini ionic liquid surfactant [ C ] 10 -4-C 10 -Et-Im]Br 2 The microwave-assisted synthesis method of (2) is as follows:
(1) Synthesis of bis (2-ethylimidazolyl) butane: to a 250mL reactor special for microwave reactor, 2-ethylimidazole (0.035 mol) and 1, 2-dibromobutane (0.01 mol) were added, followed by addition of 20% aqueous KOH and 50mL n-butanol, and a reflux condenser was installed and allowed to mix uniformly under magnetic stirring. After the reaction is finished, pouring the reaction liquid into a separating funnel for standing and layering, collecting upper organic phase liquid, distilling under reduced pressure to remove solvent, and vacuum drying for 24h at room temperature to obtain white solid of bis (2-ethylimidazolyl) butane, wherein the yield is 55.2%.
(2)[C 10 -4-C 10 -Et-Im]Br 2 Is combined with (a)The method comprises the following steps: the intermediate obtained in the above step was added to a 100mL round bottom flask according to the intermediate: bromoalkane molar ratio is 1:2.4, bromodecane and proper amount of isopropanol are added, a condensation reflux device is connected, microwave power is 400W, reaction temperature is 50 ℃, and reaction is carried out for 4min under the action of magnetic stirring. The solvent was distilled off under reduced pressure to give a milky viscous liquid. Then recrystallizing the obtained crude product in ethyl acetate solvent for 3 times, and vacuum drying at room temperature for 24h to obtain the target product [ C ] 10 -4-C 10 -Et-Im]Br 2 The yield thereof was found to be 91.1%.
Example 8:
bromomethyl benzimidazolyl Gemini ionic liquid surfactant [ C 16 -4-C 16 -Me-BI]Br 2 The microwave-assisted synthesis method of (2) is as follows:
(1) Synthesis of bis (2-methylbenzimidazolyl) butane: to a 250mL reactor special for microwave reactor, 2-methylbenzimidazole (0.035 mol) and 1, 2-dibromobutane (0.01 mol) were added, followed by 60% aqueous KOH and 60mL n-butanol, and a reflux condenser was installed to mix them uniformly under magnetic stirring. After the reaction is finished, pouring the reaction liquid into a separating funnel for standing and layering, collecting upper organic phase liquid, distilling under reduced pressure to remove solvent, and vacuum drying for 24h at room temperature to obtain white solid of bis (2-methylbenzimidazolyl) butane with the yield of 65.8%.
Figure BDA0004066354600000091
(2)[C 16 -4-C 16 -Me-BI]Br 2 Is synthesized by the following steps: the intermediate obtained in the above step was added to a 100mL round bottom flask according to the intermediate: the molar ratio of bromoalkane is 1:2.4, bromohexadecane and 60mL isopropanol are added, a condensation reflux device is connected, the microwave power is 400W, the reaction temperature is 50 ℃, and the reaction is carried out for 6min under the action of magnetic stirring. The solvent was distilled off under reduced pressure to give a milky viscous liquid. Then recrystallizing the obtained crude product in ethyl acetate solvent for 3 times, and vacuum drying at room temperature for 24hObtaining the target product [ C ] 16 -4-C 16 -Me-BI]Br 2 The yield thereof was found to be 92.5%.
Example 9:
surface/interfacial activity of serial bromoimidazolyl Gemini ionic liquid surfactants
The surface tension of the aqueous solution of the serial bromoimidazolyl Gemini ionic liquid surfactants is measured by adopting a full-automatic surface tension meter at 25 ℃, and the interfacial tension between a prepared weak base binary system and Daqing crude oil is evaluated, wherein the specific measurement results are respectively shown in fig. 4 and 5, and fig. 4 shows a serial product [ C n -2-C n Im]Br 2 (n=8, 10, 12, 14) critical micelle concentration of 2.04×10 -5 ～9.55×10 -4 The mol/L and the corresponding surface tension is 24.89-32.27 mN/m, which indicates that the product with the double-sub structure has good surface activity and can effectively reduce the surface tension of water. FIG. 5 illustrates that the interfacial tension between Daqing crude oil and water can be effectively reduced, and the lowest instantaneous interfacial tension can be reduced to 0.251mN/m after the product and sodium carbonate are prepared into a weak base binary system. Based on the mixture, the weak base binary system comprises the following components:
[C n -2-C n Im]Br 2 ：0.1wt％；
Na 2 CO 3 ：1.2wt％；
simulated water (formation water preparation: four-factory sewage, mineralization 5726.76 mg/L): 98.7wt%.
The measurement conditions are as follows: TX500C type rotary drop interfacial tension meter
Temperature: 45 DEG C
Crude oil: daqing four-factory dehydrated and degassed crude oil for oil extraction
Example 10:
sulfonate imidazolyl Gemini ionic liquid surfactant [ C ] 12 -2-C 12 Im][C 6 H 6 SO 3 ] 2 Microwave-assisted synthesis of (c)
(1) Synthesis of intermediate diimidazolyl octane: imidazole (0.02 mol) and 1, 2-dibromoethane (0.01 mol) are added into a special reaction bottle of a 250mL microwave reactor, 50% NaOH aqueous solution and 24mL isopropanol are added, a reflux condenser is arranged, the reaction is carried out under magnetic stirring, the microwave power is 600W, the reaction temperature is 45 ℃, the reaction time is 4min, and the white diimidazolyl ethane solid is obtained, and is purified according to the method of the example 1, and the yield is 65.2%.
(2)[C 12 -2-C 12 Im]Br 2 Is synthesized by the following steps: adding the white diimidazole ethane solid obtained in the above steps into a 100mL round bottom flask, adding 0.02mol bromododecane and isopropanol solution, placing the flask into a microwave reactor, connecting a condensing reflux device, reacting for 6min at 50 ℃ under the action of magnetic stirring at 300W microwave power, purifying according to the method described in example 1 to obtain [ C 12 -2-C 12 Im]Br 2 The yield thereof was found to be 98.4%.
(3)[C 12 -2-C 12 Im][C 6 H 6 SO 3 ] 2 Is synthesized by the following steps: 6.6g (0.01 mol) of intermediate [ C 12 -2-C 12 Im]Br 2 And 3.6g (0.01 mol) of sodium benzenesulfonate was added to a 250mL single neck round bottom flask, and distilled water was added in an amount of about 3 times the total mass of the reactants (30 mL), followed by reaction at 105℃for 10min at 400W of microwave power. After the reaction was completed, a pale yellow viscous substance (crude product) was obtained. After the crude product was cooled to room temperature, it was poured into a separatory funnel. Extracting and separating the product by using n-pentane, evaporating the solvent, and recrystallizing the target product for 3 times by using a cyclohexane/ethyl acetate mixed solvent to obtain [ C ] 12 -2-C 12 Im][C 6 H 6 SO 3 ] 2 The yield thereof was found to be 94.5%. Product [ C 12 -2-C 12 Im][C 6 H 6 SO 3 ] 2 The IR spectrum of (B) is shown in FIG. 6, IR (500-4000 cm) -1 KBr pellet): 2924 2850[ upsilon (CH)]，1623[υ(C＝N)]，1208，1046[υ(S＝O)]，728[υ(CH 2 ) n ，n>4]The infrared spectrogram contains characteristic absorption peaks of imidazole ring, benzene ring, long-chain hydrocarbon group and sulfonic acid group.
Comparative example 11:
sulfonate imidazolyl Gemini ionic liquid surfactant [ C ] 12 -2-C 12 Im][C 6 H 6 SO 3 ] 2 Is conventionally synthesized by heating
(1) High-temperature heating synthesis of intermediate diimidazolyl ethane by DMSO solvent system
3.4g (0.05 mol) of imidazole, 10mL of toluene and 10mL of LDMSO are added into a 100mL three-neck flask, 8g of 50wt% NaOH aqueous solution is added after stirring uniformly, the temperature is raised to water in an azeotropic removal system, the mixture is reacted for 1h under magnetic stirring to generate imidazole sodium salt, then 5mL of LDMSO is added into a reaction bottle, 2.5g (0.025 mol) of dibromoethane is slowly added dropwise, the reaction is carried out for 2h at 120 ℃ after the dropwise addition, naBr precipitation is filtered when the reaction is finished, a solvent is distilled soon, the crude product is dissolved in dichloromethane, residual NaBr is filtered, and the mixture is dried in vacuum after distillation to obtain light yellow solid diimidazolyl ethane, wherein the yield is 68.5%.
(2) Quaternization reaction of acetonitrile solvent system to synthesize [ C 12 -2-C 12 Im]Br 2
Adding 4.1g (0.025 mol) of diimidazole ethane and 15mL of acetonitrile into a three-neck flask with a condensing tube and a constant pressure dropping funnel, slowly dropwise adding 6.8g (0.0275 mol) of bromododecane under the condition of stirring at room temperature, reacting for 48 hours at 75 ℃ under the protection of nitrogen, evaporating the solvent under reduced pressure after the reaction is finished, washing the product with ethyl acetate for 3 times, removing residual impurities such as reaction raw materials, recrystallizing with ethyl acetate solvent for 3 times, and drying in vacuum for 48 hours to obtain [ C) 12 -2-C 12 Im]Br 2 The yield thereof was found to be 92.7%.
(3) Synthesis of non-halogen Gemini ionic liquid surfactant [ C ] by anion exchange reaction 12 -2-C 12 Im][C 6 H 6 SO 3 ] 2
3.3g (0.005 mol) of intermediate [ C ] are weighed out 12 -2-C 12 Im]Br 2 And 1.8g (0.01 mol) of sodium benzenesulfonate, respectively, are dissolved in a minimum amount of water, mixed and added into a 100mL round bottom flask, stirred at room temperature for reaction for 24 hours, white precipitate appears, the precipitate is collected by filtration and dissolved in dichloromethane, excessive salt is removed, the mixture is recrystallized 3 times in a mixed solvent of n-hexane and ethyl acetate, and a white pasty solid [ C ] is obtained after vacuum drying 12 -2-C 12 Im][C 6 H 6 SO 3 ] 2 The yield thereof was found to be 87.3%.
Comparison of the implementation effect of the synthetic technique described in Table 2 with the conventional method
Figure BDA0004066354600000111
Note that: a-diimidazole ethane, B-halogeno Gemini surfactant, C-non-halogeno Gemini surfactant,
comparing with the embodiment 4 of the present technology, the implementation effects are shown in table 2, and it can be found that the microwave radiation technology of the present invention can facilitate the reaction under the condition that the reaction dosage of each step is the same, and the reaction time required under the condition of obtaining the same yield is greatly reduced, and more importantly, the reaction solvent used in the present technical scheme is isopropanol and water, which is safe and environment-friendly. In the traditional method, the water generated by the azeotropic removal reaction is carried by toluene in the A synthesis process, the operation is complex, and the use of a cancerogenic solvent toluene is involved; the reactants with different polarities are dissolved by using DMSO, but the DMSO has high boiling point, and the removal by using a conventional reduced pressure distillation method is time-consuming and labor-consuming, so that the post-treatment of the product is inconvenient.
Example 12:
sulfonate imidazolyl Gemini ionic liquid surfactant [ C ] 16 -2-C 16 Im][C 6 H 6 SO 3 ] 2 The microwave-assisted synthesis method of (2) is as follows:
0.01mol of the intermediate described in example 3 above and 0.02mol of sodium benzenesulfonate were weighed into a 250mL single-neck round bottom flask, and then 30mL of distilled water was added thereto, followed by reaction at 105℃for 10 minutes under microwave power 400W. After the reaction was completed, a pale yellow viscous substance (crude product) was obtained. After the crude product was cooled to room temperature, it was poured into a separatory funnel. Extracting and separating the product by using n-pentane, evaporating the solvent, and recrystallizing the target product for 3 times by using a cyclohexane/ethyl acetate mixed solvent to obtain [ C ] 16 -2-C 16 Im][C 6 H 6 SO 3 ] 2 The yield thereof was found to be 92.8%.
Example 13:
sulfonate imidazolyl Gemini ionic liquidBulk surfactant [ C ] 8 -4-C 8 Im][C 12 H 25 C 6 H 6 SO 3 ] 2 The microwave-assisted synthesis method of (2) is as follows:
(1) Synthesis of intermediate diimidazole butane: imidazole (0.035 mol) and 1, 2-dibromobutane (0.01 mol) were added to a 250mL reactor special for a microwave reactor, then 50% KOH aqueous solution and 40mL n-butanol were added, and a reflux condenser was installed to mix them uniformly under magnetic stirring. After the reaction is finished, pouring the reaction liquid into a separating funnel for standing and layering, collecting upper organic phase liquid, distilling under reduced pressure to remove solvent, and drying in vacuum for 24h at room temperature to obtain white solid of diimidazole butane with the yield of 63.5%.
(2)[C 8 -4-C 8 Im]Cl 2 Is synthesized by the following steps: the intermediate obtained in the above step was added to a 100mL round bottom flask according to the intermediate: the molar ratio of chlorinated alkane is 1:2.4, chlorinated octane and proper amount of n-butanol are added, a condensation reflux device is connected, the microwave power is 400W, the reaction temperature is 52 ℃, and the reaction is carried out for 6min under the action of magnetic stirring. The solvent was distilled off under reduced pressure to give a milky viscous liquid. Then recrystallizing the obtained crude product in ethyl acetate solvent for 3 times, and vacuum drying at room temperature for 24h to obtain [ C ] 8 -4-C 8 Im]Cl 2 The yield thereof was found to be 89.7%.
(2)[C 8 -4-C 8 Im][C 12 H 25 C 6 H 6 SO 3 ] 2 Is synthesized by the following steps: 5.76g (0.01 mol) of intermediate [ C ] are weighed out 8 -4-C 8 Im]Cl 2 And 6.96g (0.02 mol) of sodium dodecylbenzenesulfonate were added to a 250mL single neck round bottom flask, and distilled water was added approximately 2 times the total reactant mass (25 mL) and reacted at 105℃for 10min at 400W microwave power. After the reaction was completed, a pale yellow viscous substance (crude product) was obtained. After the crude product was cooled to room temperature, it was poured into a separatory funnel. Extracting and separating the product by using n-pentane, evaporating the solvent, and recrystallizing the target product by using ethyl acetate for 3 times to obtain [ C ] 8 -4-C 8 Im][C 12 H 25 C 6 H 6 SO 3 ] 2 The yield thereof was found to be 95.7%.
Example 14:
sulfonate imidazolyl Gemini ionic liquid surfactant [ C ] 8 -4-C 8 Im][C 10 H 7 SO 3 ] 2 The microwave-assisted synthesis method of (2) is as follows:
5.76g (0.01 mol) of the composition described in example 13 above are weighed out as [ C ] 8 -4-C 8 Im]Cl 2 And 4.6g (0.02 mol) of sodium naphthalene sulfonate, are added into a 250mL single-neck round-bottom flask, distilled water which is about 5 times the total reactant mass (50 mL) is added, and then the reaction is carried out for 10min at 105 ℃ under 400W of microwave power. Cooling the light yellow viscous crude product to room temperature, extracting and separating with n-pentane, evaporating the solvent, and recrystallizing the target product with cyclohexane/ethyl acetate mixed solvent for 3 times to obtain [ C ] 8 -4-C 8 Im][C 10 H 7 SO 3 ] 2 The yield thereof was found to be 93.6%.
Example 15:
sulfonate type imidazolyl Gemini ionic liquid surfactant [ C ] 8 -4-C 8 Im][C 12 H 25 C 6 H 6 SO 3 ] 2 Interfacial activity of (2)
At 45 ℃, using a TX-500C rotary drop interfacial tension meter, the [ C ] was determined 8 -4-C 8 Im][C 12 H 25 C 6 H 6 SO 3 ] 2 The interfacial tension between the weak base binary system and dehydrated and degassed crude oil of Daqing four oil extraction plants is evaluated, and the components of the weak base binary compound oil displacement agent are as follows:
[C 8 -4-C 8 Im][C 12 H 25 C 6 H 6 SO 3 ] 2 ：0.3wt％；
NaHCO 3 ：0.6～1.2wt％；
simulated water: 98.5 to 99.1wt percent (prepared stratum water: total mineralization 6910.28mg/L, wherein CO) 3 2- 468.16mg/L，HCO 3 - 3046.12mg/L，Cl - 1121.25mg/L，SO 4 2- 36.5mg/L，Ca 2+ 35.27mg/L，Mg 2+ 9.24mg/L，Na + 2193.74mg/L)
The results of the lowest and equilibrium interfacial tension measurements with crude oil are shown in the following table:
TABLE 3 determination of minimum and equilibrium interfacial tension between crude oils
Figure BDA0004066354600000131
As shown in Table 3, the results of interfacial tension measurement show [ C 8 -4-C 8 Im][C 12 H 25 C 6 H 6 SO 3 ] 2 After the sodium bicarbonate is prepared into a weak base binary system, the interfacial tension between Daqing crude oil and water can be effectively reduced in a wider alkali concentration range, and the lowest instantaneous interfacial tension can be reduced to 10 -4 mN/m, equilibrium interfacial tension as low as 1X 10 -3 mN/m, achieves the ultra-low interfacial tension range and has potential industrial application prospect.

Claims (5)

1. The nitrogen heterocycle Gemini ionic liquid surfactant is characterized by having a structural general formula:
Figure FDA0004066354590000011
wherein: r is R 1 Is H or saturated hydrocarbon radical containing 1-4 carbon atoms, R 2 Is a saturated hydrocarbon group containing 8 to 16 carbon atoms; x is an organic ion unit, and the organic ion unit is as follows: CH (CH) 3 COO - 、CF 3 COO - 、C 6 H 6 SO 3 - 、C 12 H 25 SO 3 - 、C 12 H 25 C 6 H 6 SO 3 - 、C 10 H 7 SO 3 - ；
The method for synthesizing the Gemini ionic liquid surfactant comprises the following steps:
(1) Nucleophilic substitution bridging reaction of an azacyclic compound with a dihaloalkane: dissolving an azaheterocyclic compound and dihaloalkane in an organic solvent according to a molar ratio of 2-3.5:1, adding an inorganic alkaline water solution with a concentration of 20-60 wt%, placing the mixture in a microwave chemical reactor, magnetically stirring the mixture for microwave radiation, controlling the microwave power to be 300-600W, reacting at 30-70 ℃ for 3-9 min, standing the obtained reaction solution for layering, collecting an upper organic phase, and performing reduced pressure distillation to obtain an intermediate diazacyclylalkane;
the nitrogen heterocyclic compound is imidazole and derivatives thereof, the imidazole derivatives are benzimidazole, and methyl, ethyl, propyl and butyl substituted 2-alkyl benzimidazole; the dihaloalkane is symmetrical halogen substituted alkane, in particular chlorine, bromine and iodo alkane, and the carbon chain length is 2,4,6 and 8;
(2) Quaternization of diazacyclylalkanes: putting the intermediate diazacyclylalkane prepared in the step (1) and halogenated alkane into a microwave reaction flask according to a ratio of 1:2-2.5, adding an organic solvent, controlling the microwave power to be 300-600W, reacting at 45-60 ℃ for 4-6 min to obtain a Gemini ionic liquid surfactant crude product, performing reduced pressure distillation on the crude product, performing vacuum drying, recrystallizing for 3 times, and performing vacuum drying at room temperature to obtain the white powdery Gemini ionic liquid surfactant;
(3) Halogen anion exchange reaction: mixing the Gemini ionic liquid surfactant prepared in the step (2) with non-halogen anion salt according to a molar ratio of 1:2, stirring, adding water with 2-5 times of the total mass of reactants, controlling microwave power to 400W, reacting for 5-10 min at 60-110 ℃, performing anion exchange, recrystallizing the obtained crude product for 3 times, and vacuum drying at room temperature to obtain white powdery or pasty Gemini ionic liquid surfactant;
the non-halogen anion salt is sodium benzenesulfonate, sodium acetate, sodium naphthalenesulfonate and sodium dodecylbenzenesulfonate.
2. The synthesis method of the nitrogen heterocyclic Gemini ionic liquid surfactant according to claim 1, wherein the inorganic alkaline aqueous solution in the step (1) is one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and ammonia water, and the concentration range of the inorganic alkaline aqueous solution is 20-60 wt%.
3. The method for synthesizing an azacyclo-Gemini ionic liquid surfactant according to claim 1, wherein the haloalkane in the step (2) has an alkyl chain length of C 8 ～C 16 Brominated alkanes, chlorinated alkanes and iodinated alkanes.
4. An oil displacement system containing the aza-ring Gemini ionic liquid surfactant according to claim 1, which is characterized by comprising the following components: the concentration of the Gemini ionic liquid surfactant is 0.1-0.3 wt%, the concentration of weak base is 0.6-1.2 wt%, and the rest is simulated water.
5. The oil displacement system of the nitrogen heterocyclic Gemini ionic liquid surfactant according to claim 1, wherein the simulated water is formulated water with the mineralization degree of 400-8000mg/L under the simulated crude oil stratum.
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