CN112920787B - Cage-shaped amphiphilic nano-particle and preparation method and application thereof - Google Patents
Cage-shaped amphiphilic nano-particle and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cage-shaped amphiphilic nano particle and a preparation method and application thereof, wherein the preparation process of the cage-shaped amphiphilic nano particle comprises the following steps: adding octamercaptopropyl silsesquioxane and N-alkyl-2-butenamic acid (prepared by reacting maleic anhydride and alkylamine) into dichloromethane serving as a solvent, adding a photoinitiator, introducing nitrogen to remove oxygen above a container, and sealing under ultraviolet light to react to obtain the cage-shaped amphiphilic nanoparticles. The invention adopts octa-mercaptopropyl silsesquioxane as the nano-core and has the following advantages: the octamercaptopropyl silsesquioxane is small in size and has good dispersion stability; the octamercaptopropyl silsesquioxane has eight active sites, can be modified in a targeted manner, and has a clear product structure and good reproducibility; the amphiphilic nano-particle with hydrophilic inner core and hydrophobic outer shell is easily prepared by taking N-alkyl-2-butenamide acid as a modified monomer and utilizing the 'click' reaction of mercapto-olefin.
Description
Technical Field
The invention relates to a cage-shaped amphiphilic nano particle and a preparation method and application thereof.
Background
The Jamin effect generated by the foam in the stratum can greatly improve the apparent viscosity of the fluid and increase the swept area; meanwhile, the foaming agent used as a surfactant also has the effects of reducing the oil-water interfacial tension, changing the rock wettability and the like. The unique property of the foam enables a foam flooding technology to become a key technology for further improving the recovery ratio of the oil deposit after the oil deposit development and the chemical flooding in the middle and later periods. The foam quality is a key factor for determining the foam flooding efficiency, and the search for a high-efficiency foaming and stable foam system is a key task for developing the foam flooding technology.
Inorganic nano-particles are used as foam stabilizers, and can generate a synergistic effect with surfactant molecules under certain conditions, so that the foam stability is remarkably improved. Commonly used nanoparticles include silica, montmorillonite, aluminum hydroxide, fly ash, ferroferric oxide, calcium carbonate, and the like. By utilizing the charge characteristics of the surfaces of the nano particles, a nano particle reinforced foam system can be constructed by the nano particle reinforced foam system and the surfactant with opposite charges. For example, nano-silica is compounded with Cetyl Trimethyl Ammonium Bromide (CTAB), a surfactant is adsorbed on the surface of the nano-particles, and hydrophilic nano-particles are converted into hydrophobic particles to generate a good foam stabilizing effect; the nano aluminum hydroxide and Sodium Dodecyl Sulfate (SDS) are compounded, a layer of alkyl chain of a surfactant covers the nano particles, and the hydrophilicity of the particles is weakened to generate a better foam stabilizing effect. In addition, the surface properties of the nanoparticles can also be changed to enhance foam stability by utilizing the hydrogen bonding interaction between the hydroxyl groups on the surface of the nanoparticles and the nonionic surfactant. However, such nano-scale foam stabilization systems based on electrostatic and hydrogen bonding are susceptible to failure from external factors. Particularly, under the oil reservoir condition, metal cations in water can generate a charge shielding effect, the oil reservoir temperature can weaken the hydrogen bond effect, and the adsorption balance of the surfactant on the particle surface can be changed, so that the surface property of the particle is influenced. Therefore, it is difficult to effectively control the properties of the foam system only by the form of physical adsorption, and the research on chemical modification of nanoparticles is gradually gaining attention. The surface modification of nanoparticles is mainly based on a dehydration condensation reaction between a silane coupling agent and hydroxyl groups on the surface of the particles. The nano-particles formed based on the chemical reaction have strong adaptability to the external environment, and are an effective way for further improving the foam stabilizing performance of the nano-particles.
At present, the method for modifying nano particles based on coupling agent has the following two limitations: 1) the silane coupling agent has limited types, so that the functional modification of the nano-particles is limited; 2) due to the random distribution of hydroxyl on the surface of the nano-particles, functional units of the silane coupling agent are randomly distributed on the surface of the nano-particles in the modification process, so that the structure of the nano-particles is uncontrollable and the reproducibility is poor.
Disclosure of Invention
The invention mainly overcomes the defects in the prior art and provides the cage-shaped amphiphilic nano-particles for improving the stability of the foam for oil displacement and the preparation method and the application thereof; the cage-shaped amphiphilic nano-particle with carboxyl and amido as hydrophilic units and long-chain alkyl as hydrophobic units is synthesized simply and efficiently by taking octamercaptopropyl silsesquioxane as a nano-core through a 'click' reaction of mercapto-alkene.
The technical scheme provided by the invention for solving the technical problems is as follows: a cage-shaped amphiphilic nanoparticle, which has the following structural formula:
in the formula: r1is-CH2CH2CH2-；R2Is hydrophobic alkyl chain with carbon number of 1-18.
The preparation process of the cage-shaped amphiphilic nano-particles comprises the following steps: adding octamercaptopropyl silsesquioxane and N-alkyl-2-butenamic acid (prepared by reacting maleic anhydride and alkylamine) into dichloromethane serving as a solvent, adding a photoinitiator, introducing nitrogen to remove oxygen above a container, and sealing under ultraviolet light to react to obtain the cage-shaped amphiphilic nanoparticles. The reaction principle is as follows:
in the formula: r1is-CH2CH2CH2-；R2Is hydrophobic alkyl chain with carbon number of 1-18.
A preparation method of cage-shaped amphiphilic nanoparticles comprises the following steps:
a. adding octamercaptopropyl silsesquioxane, N-alkyl-2-butenamic acid and a photoinitiator into dichloromethane serving as a solvent;
b. introducing nitrogen to remove oxygen above the solution;
c. then sealing and reacting under ultraviolet light;
d. and after the reaction is finished, pouring the solution into cyclohexane to obtain white powder, namely the cage-shaped amphiphilic nano particles.
The further technical scheme is that the molar ratio of the octamercaptopropyl silsesquioxane to the N-alkyl-2-butenamic acid is 1: 8.
The further technical scheme is that the molar ratio of the addition amount of the photoinitiator to the N-alkyl-2-butenamic acid is in the range of 1-10%.
The further technical scheme is that the mass concentration of the N-alkyl-2-butene amide acid is 5-20%.
The further technical proposal is that the photoinitiator is 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone or 2, 2-dimethoxy-2-phenyl acetophenone.
The further technical scheme is that the N-alkyl-2-butenamide acid is prepared by reacting maleic anhydride and alkylamine.
The further technical scheme is that the reaction time in the step c is 1-6h, and the reaction temperature is 15-30 ℃.
The further technical scheme is that the specific process in the step d is as follows: and after the reaction is finished, concentrating the product, then pouring the product into cyclohexane for precipitation, filtering and drying to obtain white powder, wherein the white powder is the cage-shaped amphiphilic nano particles.
The application of the cage-shaped amphiphilic nano particles in a foam stabilizer is characterized in that the cage-shaped amphiphilic nano particles are the cage-shaped amphiphilic nano particles or the cage-shaped amphiphilic nano particles prepared by the preparation method of the cage-shaped amphiphilic nano particles.
The invention has the following beneficial effects: the invention adopts octa-mercaptopropyl silsesquioxane as the nano-core and has the following advantages: the octamercaptopropyl silsesquioxane is small in size and has good dispersion stability; the octamercaptopropyl silsesquioxane has eight active sites, can be modified in a targeted manner, and has a clear product structure and good reproducibility; the amphiphilic nano-particle with hydrophilic inner core and hydrophobic outer shell is easily prepared by taking N-alkyl-2-butenamide acid as a modified monomer and utilizing the 'click' reaction of mercapto-olefin.
A preparation method of cage-shaped amphiphilic nano-particles comprises the steps of dissolving a monomer obtained by reacting maleic anhydride with alkylamine and octa-mercaptopropyl silsesquioxane in dichloromethane according to a certain proportion, introducing nitrogen to remove oxygen, adding an initiator, and preparing the cage-shaped amphiphilic nano-particles through a mercapto-alkene click reaction. The method has the advantages of reliable principle, simple operation, definite structure of the prepared nano-particles, good reproducibility and wide application prospect.
The cage-shaped amphiphilic nano-particles are intended to be used as a foam stabilizer, improve the stability of foam for oil displacement and have wide application prospect.
Drawings
FIG. 1 is an infrared spectrum of cage amphiphilic nanoparticles;
FIG. 2 is a photograph of a nanoparticle reinforced foam system;
FIG. 3 is a micrograph of a nanoparticle-reinforced foam system;
FIG. 4 is a graph of the effect of nanoparticle concentration on foam performance.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
Octamercaptopropylsilsesquioxane (5.08g), N-phenethyl-2-butenamic acid (8.76g) and 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone (0.18g) were weighed out and dissolved in 100mL of dichloromethane; placing the solution in a beaker, introducing nitrogen to remove air in the beaker, and sealing; placing the mixture under an ultraviolet light initiating device, and reacting for 4 hours; after the reaction is finished, the product is concentrated and then poured into cyclohexane for precipitation, and white powder is obtained after filtration and drying.
Example 2
Octamercaptopropylsilsesquioxane (5.08g), N-phenethyl-2-butenamic acid (8.2g) and 2, 2-dimethoxy-2-phenylacetophenone (0.21g) were weighed out and dissolved in 100mL of dichloromethane; placing the solution in a beaker, introducing nitrogen to remove air in the beaker, and sealing; placing the mixture under an ultraviolet light initiating device, and reacting for 4 hours; after the reaction is finished, the product is concentrated and then poured into cyclohexane for precipitation, and white powder is obtained after filtration and drying.
The cage-shaped amphiphilic nanoparticles prepared in example 1 were subjected to an infrared light experiment, and the infrared spectrum of the cage-shaped amphiphilic nanoparticles prepared in example 1 is shown in fig. 1.
It can be seen from the figure that: 3425cm-1Stretching vibration peak at position of hydroxyl group, 3263cm-1Treated as secondary amidesN-H stretching vibration absorption peak, 2923cm-11712cm from stretching vibration peak of methylene-1And 1637cm-1The characteristic absorption peaks of carbonyl groups in carboxylic acid and amido are shown in the specification, 1425-1583cm-1The characteristic peak in the range is attributed to benzene ring skeleton vibration, 1116cm-1The peak is the characteristic peak of Si-O-Si in the nanometer particle skeleton.
The characteristic peaks show that the nanoparticles contain characteristic units of octamercaptopropyl silsesquioxane and N-phenethyl-2-butenamide acid, and the product structure is clear.
Testing of the foam stabilizing Properties of the cage-shaped amphiphilic nanoparticles prepared in example 1
Preparing the nano particles obtained in the example 1 into a dispersion liquid with a certain concentration, adding a certain amount of sodium dodecyl sulfate and sodium chloride, and performing ultrasonic dispersion for 30min to obtain a nano enhanced foam system with the concentration of the sodium dodecyl sulfate of 5000mg/L and the concentration of the sodium chloride of 10000 mg/L.
The stability of the nanoreinforced foam was observed by hand shaking at room temperature. From fig. 2 (the left bottle in the figure is a blank sample, and the right bottle in the figure is a nano-enhanced foam system with the nano-particle concentration of 1000 mg/L), it can be seen that the foam stability of the nano-particle enhanced foam system is obviously better than that of the blank sample, and the cage-shaped amphiphilic nano-particles are proved to have better foam stabilizing effect.
The foam morphology was observed under a microscope at room temperature with a magnification of 40. Wherein it can be seen in fig. 3 that the foam size of the nanoparticle reinforced foam system is more uniform; under the same light intensity condition, the liquid film has darker color, which shows that the nano particles are uniformly dispersed in the liquid film, and the improvement of the foam stability is facilitated.
The effect of different concentrations of nanoparticles on the foam properties was evaluated using a Roche foam tester at 50 ℃. As can be seen from FIG. 4, the foam volume reaches a maximum value at a nanoparticle concentration of 1000 mg/L; thereafter, as the particle concentration increases, the foam volume gradually decreases; within the scope of the experiments, an increase in the concentration of nanoparticles was found to be advantageous for improving the foam stability, as indicated by a continuous increase in the foam half-life.
Although the present invention has been described with reference to the above embodiments, it should be understood that the present invention is not limited to the above embodiments, and those skilled in the art can make various changes and modifications without departing from the scope of the present invention.
Claims (8)
1. A cage-shaped amphiphilic nanoparticle, characterized in that the structural formula is as follows:
in the formula: r1is-CH2CH2CH2-；R2Is phenethyl.
2. A method for preparing the amphiphilic cage nanoparticles of claim 1, comprising the steps of:
a. adding octa-mercaptopropyl silsesquioxane, N-phenethyl-2-butenamic acid and a photoinitiator into dichloromethane serving as a solvent;
b. introducing nitrogen to remove oxygen above the solution;
c. then sealing and reacting under ultraviolet light;
d. and after the reaction is finished, pouring the solution into cyclohexane to obtain white powder, namely the cage-shaped amphiphilic nano particles.
3. The method for preparing amphiphilic cage nanoparticles as claimed in claim 2, wherein the molar ratio of octamercaptopropyl silsesquioxane to N-phenethyl-2-butenamic acid is 1: 8; the molar ratio of the addition amount of the photoinitiator to the N-phenethyl-2-butenamic acid is in the range of 1-10%.
4. The method for preparing amphiphilic cage-shaped nanoparticles as claimed in claim 2, wherein the mass concentration of N-phenethyl-2-butenamic acid is 5% -20%.
5. The method for preparing the amphiphilic cage nanoparticle as claimed in claim 2, wherein the photoinitiator is 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone or 2, 2-dimethoxy-2-phenylacetophenone.
6. The method for preparing amphiphilic cage nanoparticles as claimed in claim 2, wherein the reaction time in step c is 1-6h and the reaction temperature is 15-30 ℃.
7. The method for preparing cage-shaped amphiphilic nanoparticles as claimed in claim 2, wherein the specific process in the step d is as follows: and after the reaction is finished, concentrating the product, then pouring the product into cyclohexane for precipitation, filtering and drying to obtain white powder, wherein the white powder is the cage-shaped amphiphilic nano particles.
8. Use of amphiphilic cage nanoparticles as defined in claim 1 or as prepared by the process for the preparation of amphiphilic cage nanoparticles as defined in any one of claims 2 to 7 in a foam stabiliser.
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| US9428383B2 (en) * | 2011-08-19 | 2016-08-30 | Baker Hughes Incorporated | Amphiphilic nanoparticle, composition comprising same and method of controlling oil spill using amphiphilic nanoparticle |
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| US6605351B1 (en) * | 1997-09-27 | 2003-08-12 | Gerd Rossmy | Amphiphilic particles or molecules with predominantly hydrophilic and predominantly hydrophobic domains distributed anisotropically on their surface |
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