A magnetic fluorescent Janus particle / phenylpropylene polymer composite microsphere profile control agent and a preparation method thereof

Abstract

The application discloses a kind of magnetic fluorescent Janus particles / phenylpropylene polymer composite microspheres profile control agents and preparation method thereof, raw material selects rigid monomer styrene, increases the strength of polymer microspheres, with Fe3O4 As magnetic raw material, by template method, Janus particles with superparamagnetic and fluorescent are synthesized, magnetic fluorescent Janus nanoparticles are introduced into water-in-oil type phenylpropylene polymer microspheres profile control agent, by the fluorescent tracing effect of CQDs, green and environmental protection, multi-functional low-cost water-in-oil type phenylpropylene polymer microspheres profile control agent is prepared, realizes the dynamic monitoring and evaluation of polymer microspheres profile control process, so that profile control agent has superparamagnetic and realizes magnetic separation recovery to polymer microspheres in produced fluid, effectively improve the utilization of polymer microspheres, reduce the damage to formation.

Description

Technical Field

[0001] This invention relates to the field of oil and gas field development technology, and in particular to a magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator and its preparation method. Background Technology

[0002] In oil and gas field development, tertiary oil recovery technologies are crucial for improving oil extraction efficiency. Chemical flooding (CFD), utilizing chemical modifiers to efficiently develop residual oil in formations, effectively increases oil recovery rates and reduces extraction difficulty, making it the mainstream CFD technology. However, current CFDs used in oilfield tertiary oil recovery suffer from high costs, low efficiency, severe pollution, difficulty in monitoring the modifier process, and cumbersome recycling. To improve the performance of CFDs, this product first synthesizes a water-in-oil polystyrene butyl acrylate (SBR) polymer microsphere nano-modifier, achieving a combination of good elasticity and superior strength, reducing the application cost of traditional acrylamide polymer microspheres. Furthermore, Janus particles with magnetic fluorescence properties are introduced to prepare polymer microspheres with dual magnetic and fluorescent functions, realizing low-cost, multifunctional composite microspheres that are both monitorable underground and retrievable aboveground, providing a novel modifier for low-permeability oilfield development.

[0003] In existing research, acrylamide remains the main material for polymer microsphere-based oil displacement agents. Researchers have conducted modification and performance studies based on acrylamide polymer microspheres. Patent application CN202310475416.8 discloses a nano-silica-based self-permeable oil displacement agent and its preparation method. This oil displacement agent is prepared using a one-pot method, with acrylamide as the polymer body, and introducing sodium 3-allyloxy-2-hydroxy-1-propanesulfonate, 2-allyl-2-methyl-1,3-cyclopentanedione, N-allyl-N,N-bis(trimethylsilyl)amine, and N,N-diallyl-2,2,2-trifluoroacetamide to synthesize a nano-silica-based self-permeable oil displacement agent with low surface tension and low interfacial tension. Patent application CN202211444419.7 discloses a lignin-reinforced emulsion polymer gel modifier. This modifier uses polyacrylamide as the emulsion polymer and sodium lignin sulfonate as the reinforcing agent. The synthesized modifier exhibits good plugging effect, stability, and erosion resistance in the high-temperature and high-salinity reservoirs of the western South China Sea, and can significantly improve oilfield recovery. Although polyacrylamide-based polymer microspheres have good expansion and deformation properties, and their application properties such as temperature and salt resistance can be improved through modification, these microspheres are water-in-oil microspheres. The use of oil as a solvent in the synthesis process not only increases the cost of synthesis, transportation, and field application, but also causes environmental pollution. Furthermore, current polymer microspheres have relatively limited functionality. To endow polymer microspheres with fluorescent functionality as a modulator / demodulator, in 2018, Vol. 47, No. 005, *Petrochemical Technology*, Ma Guorui et al. addressed the problems of limited variety, poor thermal stability, and poor resistance to interference from pH and metal ions in groundwater by synthesizing aggregation-induced emission molecule tetra(4,4′,4″,4′″-allyloxy)tetraphenylethylene (ALTPE). Fluorescent polymer microspheres were then prepared by crosslinking and copolymerizing ALTPE with styrene and sodium vinylbenzenesulfonate using dispersion polymerization. In 2018, Vol. 558, *Colloids and Surfaces A*, Yang H et al., prepared a fluorescent polymer microsphere using allylrhodamine as a fluorescent dye. Using the proposed fluorescence stability index, they studied the stability influencing factors and stability mechanism of the fluorescent polymer microsphere modulator / demodulator system. To endow polymer microsphere modulators with magnetic functionality, in the 2020 issue of Petrochemical Technology, Volume 49, No. 3, Cao Mengjing et al. synthesized a magnetic nano-micro polymer microsphere with a particle size of about 300 nm. They investigated the temperature resistance, salt resistance, and blocking performance of the prepared magnetic nano-micro polymer microsphere and concluded that the magnetic nano-micro polymer microsphere has good temperature resistance and salt resistance.

[0004] In summary, the main problems with the existing technology are: (1) The variety of polymer microsphere modulators is limited, mainly focusing on acrylamide polymer microspheres. However, acrylamide polymer microspheres are water-in-oil microspheres, and the synthesis of water-in-oil microspheres mainly uses white oil as the reaction solvent; the use of large amounts of white oil leads to increased production costs and reduced environmental friendliness. (2) After polymer microspheres are injected into the formation, it is impossible to determine the location of the microspheres entering the reservoir, and the concentration of microspheres produced is not easy to detect. In order to effectively monitor and evaluate the polymer microspheres used for modulators, researchers currently mainly use fluorescent polymer microspheres synthesized with organic fluorescent dyes. However, organic dyes have many problems, including poor thermal stability, poor pH resistance, and poor salt tolerance. (3) The treatment of polymer microspheres in produced fluids is still in an immature stage, and it is impossible to separate them quickly and effectively, thereby causing irreversible damage to the formation, leading to environmental pollution and increasing the cost of oil extraction. Therefore, it is necessary to develop new multifunctional polymer microsphere modulators. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, the present invention aims to provide a magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator and its preparation method. Water is used as a solvent in the synthesis process to prepare a green, environmentally friendly, multifunctional, and low-cost water-in-oil type styrene-acrylic polymer microsphere modulator, enabling dynamic monitoring of the polymer microsphere modulator process. Furthermore, the introduction of magnetic nanoparticles gives the modulator superparamagnetism, allowing for magnetic separation and recovery of polymer microspheres entering the produced fluid, effectively improving the utilization rate of the polymer microspheres and reducing damage to the formation.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows:

[0007] A magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator, comprising the following raw material components by mass parts:

[0008] Sodium dodecyl sulfonate 32-35 parts, TMN-10 15-20 parts, n-butanol 50-55 parts, styrene 2770-2830 parts, butyl acrylate 6380-6440 parts, ammonium persulfate 285-305 parts, Fe3O4 58-62 parts, tetraethyl orthosilicate 210-220 parts, sliced ​​paraffin 1950-2050 parts, hexadecyltrimethylammonium bromide 8-11 parts, methanol 15800-15850 parts, KH550 95-105 parts, glucose 5-8 parts, potassium dihydrogen phosphate 235-243 parts, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC 65-70 parts, N-hydroxysuccinimide NHS 20-25 parts, deionized water 65330-66030 parts.

[0009] A method for preparing a magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator, characterized by the following steps:

[0010] Step 1: Weigh out 32-35 parts of sodium dodecyl sulfonate, 15-20 parts of TMN-1015, and 50-55 parts of n-butanol according to the mass fractions. Add 6370-6450 parts of deionized water to the reaction vessel containing the above substances to dissolve them completely, and obtain mixture I.

[0011] Weigh out 2770-2830 parts of styrene and 6380-6440 parts of ethyl acrylate to obtain mixture II;

[0012] After adding mixture II to mixture I, ultrasonic emulsify for 5-10 minutes to obtain a pre-emulsion.

[0013] Weigh 50-60 parts of ammonium persulfate, add 6370-6450 parts of deionized water, stir well, and label as initiator aqueous solution A;

[0014] Weigh out 235-245 parts of ammonium persulfate, add 11190-11230 parts of deionized water, stir well, and label it as initiator aqueous solution B;

[0015] The initiator aqueous solution A was placed in a water bath at 75-80℃. Under constant pressure, the pre-emulsion and the initiator aqueous solution B were added dropwise to the initiator aqueous solution A. At the same time, the initiator and the emulsion were mixed evenly by mechanical stirring. After the addition was completed, the reaction was continued in the water bath for 2-2.5 hours until a uniformly dispersed milky white emulsion was obtained. Then, it was cooled to room temperature and filtered to obtain styrene-acrylic microsphere emulsion.

[0016] Step 2: Weigh 5-8 parts of glucose and 235-243 parts of potassium dihydrogen phosphate, add 7950-8050 parts of deionized water, stir with a glass rod to dissolve at room temperature, then transfer to a PTFE-lined high-pressure reactor and purge with nitrogen to remove dissolved oxygen. Preheat the oven to 200-220°C. After the nitrogen is completely introduced, seal the chamber and place it in the preheated oven to react for 12-14 hours. After the reaction is complete, centrifuge and collect the yellow supernatant. Add 6450-6550 parts of anhydrous ethanol to produce a white precipitate. Let it stand and collect the supernatant to obtain the CQDs solution.

[0017] Step 3: Weigh 58-62 parts of Fe3O4, disperse it in 5950-6050 parts of deionized water, then add 11690-11750 parts of anhydrous ethanol, stir and ultrasonically disperse evenly, adjust the pH of the solution to 9-10 with ammonia, and add 210-220 parts of tetraethyl orthosilicate dropwise while stirring at 650-700 r / min, stirring at room temperature for 4-4.5 h; after stirring, wash with anhydrous ethanol by centrifugation, vacuum dry at 50-70℃ for 4-5 h, and then grind to obtain Fe3O4@SiO2;

[0018] The preparation of Fe3O4 is as follows: 210-220 parts of ferric chloride hexahydrate and 35-45 parts of sodium citrate are weighed into a reaction vessel, 4420-4450 parts of ethylene glycol are added, and the mixture is stirred thoroughly until completely dissolved. Then, 230-250 parts of anhydrous sodium acetate are added, and the mixture is mechanically stirred until homogeneous. The solution is transferred to a polytetrafluoroethylene-lined reactor and reacted at 190-210℃ for 10-12 hours. After the reaction is complete, the mixture is cooled to room temperature, washed several times with anhydrous ethanol, and centrifuged. After washing, the mixture is vacuum dried at 50-70℃ for 4-5 hours and then ground to obtain Fe3O4.

[0019] Step 4: Weigh 1950-2050 parts of sliced ​​paraffin and melt it in a water bath at 70-80℃; weigh 190-210 parts of Fe3O4@SiO2, add 8-11 parts of hexadecyltrimethylammonium bromide and 17950-18050 parts of deionized water, and sonicate until the solution is homogeneous; add the solution to a three-necked flask containing melted paraffin, control the mechanical stirring speed at 900-1000 r / min, stir at high speed for 1-1.5 h, then reduce the speed to 450-550 r / min, stop heating, and cool to room temperature; remove the finished product, wash it with deionized water by centrifugation, and then vacuum dry it at 50-70℃ to obtain paraffin-coated Fe3O4@SiO2;

[0020] Step 5: Weigh 15800-15850 parts of methanol and 7950-8050 parts of deionized water, add 95-105 parts of KH550, and stir until dissolved evenly; then add 2190-2210 parts of paraffin-coated Fe3O4@SiO2, and mechanically stir at room temperature for 10-12 hours at a speed of 150-170 r / min; after stirring, discard the filtrate and place the solid under vacuum at 40-50℃; after drying, add cyclohexane and stir at room temperature until paraffin precipitates, then discard the liquid. Repeat this step until no paraffin is visible in the liquid, and then place the solid under vacuum at 50-70℃ to obtain Fe3O4@SiO2-NH2 particles;

[0021] Step 6: Weigh 18-22 parts of Fe3O4@SiO2-NH2 particles and disperse them in phosphate buffer solution with pH 7.3-7.5. Sonicate until uniformly dispersed. Then add 65-70 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC, 20-25 parts of N-hydroxysuccinimide NHS and CQDs solution. React the mixed solution with reciprocating shaking at 35-40℃ for 24-26 hours. After standing, allow the precipitate to settle and collect it. Place the precipitate in a vacuum dryer at 50-70℃ to obtain Fe3O4@SiO2@CQDs Janus particles.

[0022] Step 7: Weigh 1-2 parts of Fe3O4@SiO2@CQDs Janus particles, add 1600-1700 parts of deionized water, sonicate until the solution is fully dissolved, then add the styrene-acrylic microsphere emulsion to the sonicated solution, and sonicate until homogeneous to obtain magnetic fluorescent styrene-acrylic microsphere emulsion, which is the magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] (1) The water-in-oil type styrene-acrylic polymer microspheres synthesized in this invention use water as a solvent, which can avoid the pollution caused by the use of white oil, and at the same time solve the problem of high cost caused by the use of a large amount of white oil.

[0025] (2) This invention synthesizes bifunctional Janus nanoparticles with magnetic and fluorescent properties and introduces them into styrene-acrylic polymer microspheres, endowing the polymer microspheres with multifunctionality, which is beneficial to realize dynamic monitoring and evaluation of the polymer microsphere displacement process and recycling after oil displacement.

[0026] (3) This invention uses CQDs as fluorescent raw materials, which overcomes the shortcomings of the current fluorescent polymer microspheres, such as poor resistance to interference from metal ions in groundwater caused by the introduction of organic fluorescent dyes.

[0027] (4) The present invention uses Fe3O4 as a magnetic raw material, which is beneficial to the recycling and reuse after oil displacement, improves the utilization rate of polymer microspheres, and reduces the use of synthetic raw materials and damage to the formation environment.

[0028] In summary, the main raw material for the synthesis of water-in-oil polymer microspheres in this invention is the rigid monomer styrene, which increases the strength of the polymer microspheres; CQDs are selected as fluorescent materials, which have the characteristics of easy preparation, good optical stability, and easy functionalization; Fe3O4 is used as a magnetic raw material, and Janus particles with superparamagnetism and fluorescence are synthesized by template method. The magnetic fluorescent Janus nanoparticles are introduced into the water-in-oil styrene-acrylic polymer microsphere modulator, and the fluorescence tracer effect of CQDs is used to realize the dynamic monitoring and evaluation of the polymer microsphere modulator process, overcoming the shortcomings of the current fluorescent polymer microspheres with poor resistance to interference from metal ions in groundwater caused by the introduction of organic fluorescent dyes. Attached Figure Description

[0029] Figure 1 These are TEM and HRTEM images of Fe3O4, in which... Figure 1 (a) in the image is a TEM image. Figure 1 (b) in the image is an HRTEM photograph.

[0030] Figure 2 These are TEM and HRTEM(b) images of CQDs particles, in which... Figure 2 (a) in the image is a TEM image. Figure 2 (b) in the image is an HRTEM photograph.

[0031] Figure 3 These are TEM images and hysteresis loops of Fe3O4@SiO2, among which... Figure 3 (a) in the image is a TEM image. Figure 3 (b) in the image is an HRTEM photograph.

[0032] Figure 4 TEM image of magnetic fluorescent Fe3O4@SiO2-CQDs Janus particles

[0033] Figure 5 The magnetic and fluorescent properties of Fe3O4@SiO2-CQDs Janus particles, among which, Figure 5 Image (a) shows the particles dispersed in deionized water as a uniform brown suspension. Figure 5 (b) is a schematic diagram showing the particles being adsorbed onto one side of the glass bottle when an external magnetic field is applied; Figure 5 (c) is a schematic diagram of the blue fluorescence reaction of a liquid attracted by a magnet when irradiated with an ultraviolet lamp.

[0034] Figure 6 SEM images of magnetic fluorescent Janus / styrene-acrylic composite microspheres, in which... Figure 6 Image (a) in the image is from Example 1. Figure 6 Image (b) in the image is from Example 2.

[0035] Figure 7 The figure shows the relationship between pressure (P) and injected fluid volume (PV). Curve 1 is the relationship curve for Example 1, and curve 2 is the relationship curve for Example 2. Detailed Implementation

[0036] The invention will now be described in detail using a core sample from an oilfield and in conjunction with the accompanying drawings.

[0037] Example 1

[0038] The raw material components in this embodiment, by mass parts, include:

[0039] Sodium dodecyl sulfonate 32 parts, TMN-1015 parts, n-butanol 50 parts, styrene 2770 parts, butyl acrylate 6380 parts, ammonium persulfate 285 parts, Fe3O4 58 parts, tetraethyl orthosilicate 210 parts, sliced ​​paraffin 1950 parts, hexadecyltrimethylammonium bromide 8 parts, methanol 15800 parts, KH 55095 parts, glucose 5 parts, potassium dihydrogen phosphate 235 parts, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC 65 parts, N-hydroxysuccinimide NHS 20 parts, deionized water 65330 parts.

[0040] The preparation method of this embodiment converts the raw material components into grams, referring to the amounts of each component added in the preparation method of the embodiment, and includes the following steps:

[0041] Step 1: Dissolve 0.160g sodium dodecyl sulfonate, 0.0750g TMN-10 and 0.250g n-butanol completely in 31.850g deionized water to obtain a transparent and homogeneous mixed aqueous phase.

[0042] 13.850g of styrene and 31.900g of butyl acrylate were mixed evenly to obtain a mixed oil phase. The mixed oil phase was added to the mixed aqueous phase, and ultrasonication and emulsification were performed for 8 minutes respectively to obtain a pre-emulsion.

[0043] Add 0.250g of ammonium persulfate to 31.850g of deionized water to obtain initiator aqueous solution A; add 1.175g of ammonium persulfate to 55.950g of deionized water to obtain deinitiator aqueous solution B.

[0044] The initiator aqueous solution A was transferred to a three-necked flask and placed in a 78°C water bath. The mixture was mechanically stirred for 10 minutes at 300 rpm. After stirring, the pre-emulsion and initiator aqueous solution B were simultaneously added dropwise to the three-necked flask through a constant-pressure dropping funnel (dropping rate 3 s / d). After the addition was complete, the mixture was kept at 78°C for 2.5 hours, cooled to room temperature, filtered, and the resulting styrene-acrylic microsphere emulsion was prepared for later use. Figure 1 ).

[0045] Step 2: Weigh 0.025g glucose and 1.175g potassium dihydrogen phosphate (molar ratio 1:36) into a beaker, add 39.750g deionized water, and dissolve by stirring with a glass rod at room temperature. Transfer the solution to a PTFE-lined high-pressure reactor, purge with N2 (1h), and cover the mouth of the vessel with plastic wrap to remove dissolved oxygen. Preheat the oven to 200℃. After the N2 has been introduced, seal the chamber and place it in the preheated oven to react for 14h. After the reaction is complete, centrifuge the product at 8000r / min for 30min, collect the yellow supernatant, add 32.25g anhydrous ethanol, and a white precipitate will form. After standing for 2h, collect the supernatant to obtain the CQDs solution. Figure 2 As shown in (a), the microstructure of the prepared CQDs at a scale of 20 nm clearly shows that the CQDs have a regular spherical structure and uniform particle size distribution. Figure 2 (b) shows the lattice fringes captured by a high-resolution transmission electron microscope (HRTEM). The fringes of the CQDs crystal are clearly visible at 10 nm, and the lattice spacing is measured to be 0.32 nm.

[0046] Step 3: Weigh 0.290 g of Fe3O4 and disperse it in a mixed solution of 58.450 g of anhydrous ethanol and 29.750 g of deionized water. Sonicate for 15-20 min. After sonication, adjust the pH of the solution to 9 with 25 wt% ammonia. Place the mixed solution in a 250 ml three-necked flask and fix it on a mechanical stirrer. While stirring, add 1.050 g of tetraethyl orthosilicate dropwise. Adjust the stirring speed to 650 r / min and stir at room temperature for 4 h. After the reaction is complete, centrifuge four times with anhydrous ethanol. After washing, vacuum dry at 60 °C for 5 h and then grind to obtain Fe3O4@SiO2. Figure 3 Image (a) shows a TEM image of Fe3O4@SiO2. The Fe3O4 nanoparticles have a uniformly thick shell of SiO2 on their surface, indicating successful preparation of Fe3O4@SiO2. To detect the magnetization of Fe3O4@SiO2, its hysteresis loop was characterized, and the results are shown below. Figure 3 As shown in (b) of the figure, Fe3O4@SiO2 exhibits a certain degree of magnetism. As illustrated in the inset, when a certain magnetic field is applied, Fe3O4@SiO2 is attracted and accumulates on one side of the glass bottle, causing the solution to become clear. When the external magnetic field is removed, Fe3O4@SiO2 disperses back into the solution, demonstrating that the SiO2 shell does not disrupt the structure and magnetism of the Fe3O4 nanoparticles.

[0047] The specific preparation method of Fe3O4 is as follows: 1.050g of ferric chloride hexahydrate and 0.175g of sodium citrate are completely dissolved in 22.100g of ethylene glycol. While stirring, 1.175g of anhydrous sodium acetate is added. After mixing evenly, the mixture is mechanically stirred at 650r / min for 30min. The solution is then transferred to a polytetrafluoroethylene-lined reactor and reacted at 200℃ for 11h. After the reaction is complete and cooled to room temperature, the solution is washed with anhydrous ethanol and centrifuged. After washing, it is vacuum dried at 60℃ for 5h and then ground to obtain Fe3O4. Figure 1 As can be seen in (a), the Fe3O4 nanoparticles are loosely clustered spherical, with internal particles being nanocrystals. The size distribution is relatively uniform, with an average particle size of about 150-170 nm. Figure 1 (b) in the figure shows the lattice fringes of Fe3O4 nanoparticles at high resolution. As can be seen from the figure, the lattice fringes of Fe3O4 nanoparticles are clearly visible, and the lattice spacing is 0.25 nm, which corresponds to the Fe3O4 (311) crystal plane.

[0048] Step 4: Weigh 9.750g of sliced ​​paraffin into a 250ml three-necked flask and melt it in a 75℃ water bath. Weigh 0.950g of Fe3O4@SiO2 into a beaker, add 0.040g of cetyltrimethylammonium bromide and 89.750g of deionized water, and sonicate for 10 minutes to mix the solution thoroughly.

[0049] The solution was added to a three-necked flask containing melted paraffin. The mechanical stirring speed was controlled at 1000 rpm for 1.5 hours, then reduced to 500 rpm, heating was stopped, and the mixture was allowed to cool to room temperature. The product was removed, washed with deionized water by centrifugation, and then vacuum dried at 60°C to obtain paraffin-coated Fe3O4@SiO2.

[0050] Step 5: Weigh 79.000g of methanol and 39.750g of deionized water into a beaker, add 0.475g of KH550, and stir until dissolved. Then add 10.750g of paraffin-coated Fe3O4@SiO2, and mechanically stir at room temperature for 10 hours at 170 r / min. After stirring, discard the filtrate and dry the solid under vacuum at 45℃. After drying, add a certain amount of cyclohexane and stir at room temperature until paraffin precipitates. Pour off the liquid, and repeat this step until no obvious paraffin is visible in the liquid. Then, dry the solid under vacuum at 60℃ to obtain Fe3O4@SiO2-NH2 particles.

[0051] Step Six: Weigh 0.090 g of Fe3O4@SiO2-NH2 particles and disperse them in 10 ml of phosphate buffer solution (pH 7.4). Sonicate the solution for 20 min until uniformly dispersed. Then add 0.325 g of EDC, 0.100 g of NHS, and 30 ml of CQDs solution to the sonicated solution. React the mixture at 37°C with reciprocating shaking for 25 h, then allow it to settle and precipitate. Collect the precipitate and vacuum dry it at 60°C to obtain Fe3O4@SiO2@CQDs Janus particles. Figure 4 The image shown is a TEM image of magnetic fluorescent Fe3O4@SiO2-CQDs Janus particles. The magnetic fluorescent Fe3O4@SiO2-CQDs Janus particles dispersed in deionized water form a homogeneous brown suspension, as shown in the image. Figure 5 As shown in (a); when a certain external magnetic field is applied, the particles are adsorbed onto one side of the glass bottle, as shown in (a). Figure 5 As shown in (b) of Figure 5, the liquid becomes clear; if the external magnetic field is removed, it disperses into a uniform brown suspension, indicating that the magnetic fluorescent Fe3O4@SiO2-CQDs Janus particles have good magnetism. When the suspension in (a) of Figure 5 is irradiated with a 365nm ultraviolet lamp, the light cannot pass through. However, when the liquid adsorbed by the magnet in (b) of Figure 5 is irradiated, the system again exhibits the blue fluorescence characteristic of CQDs, as shown in (c) of Figure 5, indicating that the fluorescence of CQDs still exists. The above results indicate that the Fe3O4@SiO2-CQDs Janus particles possess both magnetic and fluorescent properties.

[0052] Step 7: Add 0.005g of Fe3O4@SiO2-CQDs Janus particles and 8.000g of deionized water to a beaker, and sonicate for 30 minutes to fully dissolve the particles. Then add 10ml of styrene-acrylic microsphere emulsion to the sonicated solution, and sonicate for another 30 minutes to obtain magnetic fluorescent styrene-acrylic microspheres. Figure 6 (a) shows a SEM image of the magnetic fluorescent Janus / styrene-acrylic composite microspheres, which are in regular spherical shape.

[0053] Based on oilfield core samples, saturated water and saturated oil were injected into the cores, and water flooding, composite microsphere flooding, and subsequent water flooding were carried out in three stages by injecting water and composite microsphere flooding agent into the cores. The oil displacement performance was analyzed, such as... Figure 7 As shown in curve 1. Figure 7The figure shows the relationship between injection pressure (P) and injected fluid pore volume (PV). As can be seen from the figure, the pressure is relatively low and stable during the waterflooding stage. During the composite microsphere flooding stage, it can be seen that the injection pressure significantly increases after the injection of the synthesized composite microsphere modulator, and continues to increase, indicating that the microspheres have blocked the core pores, causing fluid flow redirection. In the subsequent waterflooding stage, the pressure is found to be higher than in the first stage, but shows a gradual upward trend. Based on... Figure 7 The pressure ratios of the three stages demonstrate that the microspheres have a sealing effect on the core and exhibit oil displacement properties.

[0054] Example 2

[0055] The raw material components in this embodiment, by mass parts, include:

[0056] Sodium dodecyl sulfonate 35 parts, TMN-10 20 parts, n-butanol 55 parts, styrene 2830 parts, butyl acrylate 6440 parts, ammonium persulfate 305 parts, Fe3O4 62 parts, tetraethyl orthosilicate 220 parts, sliced ​​paraffin 2050 parts, hexadecyltrimethylammonium bromide 11 parts, methanol 15850 parts, KH550 105 parts, glucose 8 parts, potassium dihydrogen phosphate 243 parts, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC 70 parts, N-hydroxysuccinimide NHS 25 parts, deionized water 66030 parts.

[0057] The preparation method of this embodiment converts the raw material components into grams, referring to the amounts of each component added in the preparation method of the embodiment, and includes the following steps:

[0058] Step 1: Dissolve 0.175g sodium dodecyl sulfonate, 0.100g TMN-10 and 0.275g n-butanol completely in 32.250g deionized water to obtain a transparent and homogeneous mixed aqueous phase.

[0059] 14.150g of styrene and 32.200g of butyl acrylate were mixed evenly to obtain a mixed oil phase. The mixed oil phase was added to the mixed aqueous phase, and ultrasonication and emulsification were performed for 10 minutes respectively to obtain a pre-emulsion.

[0060] Add 0.300g of ammonium persulfate to 32.250g of deionized water to obtain initiator aqueous solution A; add 1.225g of ammonium persulfate to 56.150g of deionized water to obtain deinitiator aqueous solution B.

[0061] The initiator aqueous solution A was transferred to a three-necked flask and placed in an 80°C water bath. The mixture was mechanically stirred for 10 minutes at a speed of 300 r / min. After stirring, the pre-emulsion and the initiator aqueous solution B were simultaneously added dropwise to the three-necked flask through a constant pressure dropping funnel (dropping rate 3 s / d). After the addition was complete, the mixture was kept at 80°C for 2 hours. After cooling to room temperature, the mixture was filtered to obtain a styrene-acrylic microsphere emulsion for later use.

[0062] Step 2: Weigh 0.040g glucose and 1.215g potassium dihydrogen phosphate into a beaker, add 40.250g deionized water, stir with a glass rod to dissolve at room temperature, transfer to a PTFE-lined high-pressure reactor, purge with N2 (1h), and cover the bottle mouth with plastic wrap to remove dissolved oxygen. Preheat the oven to 220℃. After N2 has been introduced, seal the chamber and place it in the preheated oven to react for 12h. After the reaction is complete, centrifuge the product at 8000r / min for 30min, collect the yellow supernatant, add 32.75g anhydrous ethanol, and a white precipitate is produced. After standing for 2h, collect the supernatant to obtain CQDs.

[0063] Step 3: Weigh 0.310g Fe3O4 and disperse it in a mixed solution of 58.750g anhydrous ethanol and 30.250g deionized water. Sonicate for 15-20min. After sonication, adjust the pH of the solution to 9.5 with 25wt% ammonia. Place the mixed solution in a 250ml three-necked flask and fix the flask on a mechanical stirrer. While stirring, add 1.100g tetraethyl orthosilicate dropwise. Adjust the stirring speed to 700r / min and stir at room temperature for 4h. After the reaction is complete, centrifuge four times with anhydrous ethanol. After washing, vacuum dry at 65℃ for 4h and then grind to obtain Fe3O4@SiO2.

[0064] The specific preparation method of Fe3O4 is as follows: 1.100g of ferric chloride hexahydrate and 0.225g of sodium citrate are weighed and completely dissolved in 22.250g of ethylene glycol. While stirring, 1.225g of anhydrous sodium acetate is added. After mixing evenly, the mixture is mechanically stirred at 650r / min for 30min. The solution is then transferred to a reaction vessel lined with polytetrafluoroethylene and reacted at 210℃ for 10h. After the reaction is completed and cooled to room temperature, the solution is washed with anhydrous ethanol and centrifuged. After washing, the solution is vacuum dried at 65℃ for 4h and then ground to obtain Fe3O4.

[0065] Step 4: Weigh 10.250g of sliced ​​paraffin into a 250ml three-necked flask and melt it in an 80℃ water bath. Weigh 1.050g of Fe3O4@SiO2 into a beaker, add 0.055g of cetyltrimethylammonium bromide and 90.250g of deionized water, and sonicate for 10 minutes to mix the solution thoroughly.

[0066] The solution was added to a three-necked flask containing melted paraffin. The mechanical stirring speed was controlled at 950 rpm for 1 hour, then reduced to 450 rpm, heating was stopped, and the mixture was allowed to cool to room temperature. The product was removed, washed with deionized water by centrifugation, and then vacuum dried at 60°C to obtain paraffin-coated Fe3O4@SiO2.

[0067] Step 5: Weigh 79.250g of methanol and 40.250g of deionized water into a beaker, add 0.525g of KH550, and stir until dissolved. Then add 11.250g of paraffin-coated Fe3O4@SiO2, and mechanically stir at room temperature for 12 hours at 150 r / min. After stirring, discard the filtrate and dry the solid under vacuum at 40℃. After drying, add a certain amount of cyclohexane and stir at room temperature until paraffin precipitates. Pour off the liquid, and repeat this step until no obvious paraffin is visible in the liquid. Then, dry the solid under vacuum at 65℃ to obtain Fe3O4@SiO2-NH2 particles.

[0068] Step Six: Weigh 0.110g of Fe3O4@SiO2-NH2 particles and disperse them in 10ml of phosphate buffer solution (pH 7.5). Sonicate the solution for 30min until uniformly dispersed. Then add 0.350g of EDC, 0.125g of NHS, and 30ml of CQDs solution to the sonicated solution. React the mixture at 40℃ with reciprocating shaking for 24h, then allow it to settle and precipitate. Collect the precipitate and vacuum dry it at 65℃ to obtain Fe3O4@SiO2@CQDs Janus particles.

[0069] Step 7: Add 0.010g of Fe3O4@SiO2-CQDs Janus particles and 8.500g of deionized water to a beaker, and sonicate for 30 minutes to fully dissolve the solution. Then add 10ml of styrene-acrylic microsphere emulsion to the sonicated solution, and sonicate for another 30 minutes to obtain magnetic fluorescent styrene-acrylic microspheres. Figure 6 (b) shows a SEM image of the magnetic fluorescent Janus / styrene-acrylic composite microspheres. The composite material is regularly spherical with a particle size of approximately 1-2 μm.

[0070] Based on oilfield core samples, saturated water and saturated oil were injected into the cores, and water flooding, composite microsphere flooding, and subsequent water flooding were carried out in three stages by injecting water and composite microsphere flooding agent into the cores. The oil displacement performance was analyzed, such as... Figure 7Curve 2 in the figure shows that during the waterflooding stage, the pressure is relatively low and stable. During the composite microsphere flooding stage, it can be seen that after injecting the synthesized composite microsphere modulator, the injection pressure significantly increases and continues to rise, indicating that the microspheres have blocked the core pores, causing the fluid flow to redirect. In the subsequent waterflooding stage, the pressure is found to be higher than in the first stage, but shows a gradual increase. According to... Figure 7 The pressure ratios of the three stages demonstrate that the microspheres have a sealing effect on the core and exhibit oil displacement properties.

[0071] Example 3

[0072] The raw material components in this embodiment, by mass parts, include:

[0073] Sodium dodecyl sulfonate 34 parts, TMN-1018 parts, n-butanol 53 parts, styrene 2800 parts, butyl acrylate 6400 parts, ammonium persulfate 295 parts, Fe3O4 60 parts, tetraethyl orthosilicate 215 parts, sliced ​​paraffin 2000 parts, hexadecyltrimethylammonium bromide 10 parts, methanol 15830 parts, KH550 100 parts, glucose 7 parts, potassium dihydrogen phosphate 240 parts, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC 68 parts, N-hydroxysuccinimide NHS 23 parts, deionized water 65330-66030 parts.

[0074] The preparation method of this embodiment converts the raw material components into grams, referring to the amounts of each component added in the preparation method of the embodiment, and includes the following steps:

[0075] Step 1: Dissolve 0.1750g sodium dodecyl sulfonate, 0.090g TMN-10 and 0.265g n-butanol completely in 32.150g deionized water to obtain a transparent and homogeneous mixed aqueous phase.

[0076] 14.000g of styrene and 32.000g of butyl acrylate were mixed evenly to obtain a mixed oil phase. The mixed oil phase was added to the mixed aqueous phase, and ultrasonication and emulsification were performed for 10 minutes respectively to obtain a pre-emulsion.

[0077] Add 0.275g of ammonium persulfate to 32.150g of deionized water to obtain initiator aqueous solution A; add 1.200g of ammonium persulfate to 56.050g of deionized water to obtain deinitiator aqueous solution B.

[0078] The initiator aqueous solution A was transferred to a three-necked flask and placed in an 80°C water bath. The mixture was mechanically stirred for 10 minutes at a speed of 300 r / min. After stirring, the pre-emulsion and the initiator aqueous solution B were simultaneously added dropwise to the three-necked flask through a constant pressure dropping funnel (dropping rate 3 s / d). After the addition was complete, the mixture was kept at 80°C for 2 hours. After cooling to room temperature, the mixture was filtered to obtain a styrene-acrylic microsphere emulsion for later use.

[0079] Step 2: Weigh 0.035g glucose and 1.200g potassium dihydrogen phosphate into a beaker, add 40.000g deionized water, stir with a glass rod at room temperature to dissolve, transfer to a PTFE-lined high-pressure reactor, purge with N2 (1h), and cover the bottle mouth with plastic wrap to remove dissolved oxygen. Preheat the oven to 220℃. After N2 has been introduced, seal the chamber and place it in the preheated oven to react for 12h. After the reaction is complete, centrifuge the product at 8000r / min for 30min, collect the yellow supernatant, add 32.55g anhydrous ethanol, and a white precipitate is produced. After standing for 2h, collect the supernatant to obtain CQDs.

[0080] Step 3: Weigh 0.300g Fe3O4 and disperse it in a mixed solution of 58.750g anhydrous ethanol and 30.000g deionized water. Sonicate for 15-20min. After sonication, adjust the pH of the solution to 9.5 with 25wt% ammonia. Place the mixed solution in a 250ml three-necked flask and fix the flask on a mechanical stirrer. While stirring, add 1.075g tetraethyl orthosilicate dropwise. Adjust the stirring speed to 700r / min and stir at room temperature for 4h. After the reaction is complete, centrifuge four times with anhydrous ethanol. After washing, vacuum dry at 65℃ for 4h and then grind to obtain Fe3O4@SiO2.

[0081] The specific preparation method of Fe3O4 is as follows: 1.075g of ferric chloride hexahydrate and 0.200g of sodium citrate are weighed and completely dissolved in 22.150g of ethylene glycol. While stirring, 1.200g of anhydrous sodium acetate is added. After mixing evenly, the mixture is mechanically stirred at 650r / min for 30min. The solution is then transferred to a reaction vessel lined with polytetrafluoroethylene and reacted at 210℃ for 10h. After the reaction is completed and cooled to room temperature, the solution is washed with anhydrous ethanol and centrifuged. After washing, the solution is vacuum dried at 65℃ for 4h and then ground to obtain Fe3O4.

[0082] Step 4: Weigh 10.000g of sliced ​​paraffin into a 250ml three-necked flask and melt it in an 80℃ water bath. Weigh 1.000g of Fe3O4@SiO2 into a beaker, add 0.050g of hexadecyltrimethylammonium bromide and 90.000g of deionized water, and sonicate for 10 minutes to mix the solution thoroughly.

[0083] The solution was added to a three-necked flask containing melted paraffin. The mechanical stirring speed was controlled at 950 rpm for 1 hour, then reduced to 450 rpm, heating was stopped, and the mixture was allowed to cool to room temperature. The product was removed, washed with deionized water by centrifugation, and then vacuum dried at 60°C to obtain paraffin-coated Fe3O4@SiO2.

[0084] Step 5: Weigh 79.150g of methanol and 40.000g of deionized water into a beaker, add 0.500g of KH550, and stir until dissolved. Then add 11.250g of paraffin-coated Fe3O4@SiO2, and mechanically stir at room temperature for 12 hours at 150 rpm. After stirring, discard the filtrate and dry the solid under vacuum at 40℃. After drying, add a certain amount of cyclohexane and stir at room temperature until paraffin precipitates. Pour off the liquid and repeat this step until no obvious paraffin is visible in the liquid. Then, dry the solid under vacuum at 65℃ to obtain Fe3O4@SiO2-NH2 particles.

[0085] Step Six: Weigh 0.100g of Fe3O4@SiO2-NH2 particles and disperse them in 10ml of phosphate buffer solution (pH 7.5). Sonicate the solution for 30min until uniformly dispersed. Then add 0.340g of EDC, 0.115g of NHS, and 30ml of CQDs solution to the sonicated solution. React the mixture at 40℃ with reciprocating shaking for 24h, then allow it to settle and precipitate. Collect the precipitate and vacuum dry it at 65℃ to obtain Fe3O4@SiO2@CQDs Janus particles.

[0086] Step 7: Add 0.007g Fe3O4@SiO2-CQDs Janus particles and 8.250g deionized water to a beaker, and sonicate for 30 minutes to fully dissolve the particles. Then add 10ml of styrene-acrylic microsphere emulsion to the sonicated solution, and sonicate for another 30 minutes to obtain magnetic fluorescent styrene-acrylic microspheres. Figure 6 (b) shows a SEM image of the magnetic fluorescent Janus / styrene-acrylic composite microspheres. The composite material is regularly spherical with a particle size of approximately 1-2 μm.

[0087] Thus, through implementation cases, it can be seen that the novel composite microspheres synthesized by introducing magnetic fluorescent Janus particles into water-in-oil styrene-acrylic polymer microspheres have modulating and driving properties, creating a new type of multifunctional polymer microsphere modulating and driving agent, overcoming the defects of traditional polymer microsphere modulating and driving processes such as difficulty in monitoring and troublesome recycling and treatment; water-in-oil microspheres overcome the defects of high cost and high pollution of acrylamide polymer microspheres using white oil as a solvent.

[0088] Explanation of the principles of the experimental method

[0089] In oil and gas field development, tertiary oil recovery technologies are crucial for improving oil extraction efficiency. Among these, chemical flooding (CFD) utilizes chemical modifiers to efficiently develop remaining oil in formations, effectively increasing oil recovery rates and reducing extraction difficulty, and has become the mainstream technology. However, current CFDs used in oilfield tertiary oil recovery are costly, inefficient, and cause significant pollution. Monitoring the modifier process and handling recycling are also challenging. Traditional water-in-oil microsphere synthesis primarily uses white oil as a reaction solvent; the large-scale use of white oil increases production costs and reduces environmental friendliness. Furthermore, after polymer microspheres are injected into the formation, the location of their entry into the reservoir cannot be determined, and the concentration of produced microspheres is difficult to detect. Effective methods for dynamic monitoring and evaluation of polymer microspheres used in modifiers have not been developed. Additionally, the treatment of polymer microspheres in produced fluids is still in its infancy, failing to quickly and effectively separate them, leading to environmental pollution and increased oil extraction costs. The proposed polymer microsphere flood control agent is a water-in-oil type polystyrene-butyl acrylate (SBR) polymer microsphere nanoflot flood control agent using water as a solvent. The main raw material for synthesis is rigid monomer styrene, which increases the strength of the polymer microspheres without complicating the synthesis process and microsphere structure. Carbon quantum dots (CQDs) are chosen as the fluorescent material due to their ease of preparation, good optical stability, and ease of functionalization. Using iron(III) oxide (Fe3O4) as the magnetic raw material, superparamagnetic and fluorescent Janus particles are synthesized via a template method. These magnetic fluorescent Janus nanoparticles are introduced into the water-in-oil SBR polymer microsphere flood control agent. Through the fluorescence tracer effect of CQDs, dynamic monitoring and evaluation of the polymer microsphere flood control process can be achieved, overcoming the shortcomings of current fluorescent polymer microspheres, such as poor resistance to interference from metal ions in groundwater caused by the introduction of organic fluorescent dyes. Simultaneously, the introduced magnetic nanoparticles give the flood control agent superparamagnetism, enabling magnetic separation and recovery of polymer microspheres entering the produced fluid, effectively improving the utilization rate of the polymer microspheres and reducing damage to the formation.

Claims

1. A method for preparing a magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator, characterized in that, The steps are as follows: Step 1: Weigh out 32-35 parts of sodium dodecyl sulfonate, 15-20 parts of TMN-10 and 50-55 parts of n-butanol according to the mass fractions. Add 6370-6450 parts of deionized water to the reaction vessel containing the above substances to dissolve them completely, and obtain mixture I. Weigh out 2770-2830 parts of styrene and 6380-6440 parts of ethyl acrylate to obtain mixture II; After adding mixture II to mixture I, ultrasonic emulsify for 5-10 minutes to obtain a pre-emulsion. Weigh 50-60 parts of ammonium persulfate, add 6370-6450 parts of deionized water, stir well, and label as initiator aqueous solution A; Weigh out 235-245 parts of ammonium persulfate, add 11190-11230 parts of deionized water, stir well, and label it as initiator aqueous solution B; The initiator aqueous solution A was placed in a water bath at 75-80 ℃. Under constant pressure, the pre-emulsion and the initiator aqueous solution B were added dropwise to the initiator aqueous solution A. At the same time, the initiator and the emulsion were mixed evenly by mechanical stirring. After the addition was completed, the reaction was continued in the water bath for 2-2.5 h until a uniformly dispersed milky white emulsion was obtained. Then, it was cooled to room temperature and filtered to obtain styrene-acrylic microsphere emulsion. Step 2: Weigh 5-8 parts of glucose and 235-243 parts of potassium dihydrogen phosphate, add 7950-8050 parts of deionized water, stir with a glass rod to dissolve at room temperature, transfer to a PTFE-lined high-pressure reactor and purge nitrogen to remove dissolved oxygen. Preheat the oven to 200-220 °C. After the nitrogen is completely introduced, seal the chamber and place it in the preheated oven to react for 12-14 hours. After the reaction is complete, centrifuge and collect the yellow supernatant. Add 6450-6550 parts of anhydrous ethanol to produce a white precipitate. Let it stand and collect the supernatant to obtain the CQDs solution. Step 3: Weigh 58-62 parts of Fe3O4, disperse it in 5950-6050 parts of deionized water, then add 11690-11750 parts of anhydrous ethanol, stir and ultrasonically disperse evenly, adjust the pH of the solution to 9-10 with ammonia, and add 210-220 parts of tetraethyl orthosilicate dropwise while stirring at 650-700 r / min, stirring at room temperature for 4-4.5 h; after stirring, wash with anhydrous ethanol by centrifugation, vacuum dry at 50-70 °C for 4-5 h, and then grind to obtain Fe3O4@SiO2; Step 4: Weigh 1950-2050 parts of sliced ​​paraffin and melt it in a water bath at 70-80 °C; weigh 190-210 parts of Fe3O4@SiO2, add 8-11 parts of hexadecyltrimethylammonium bromide and 17950-18050 parts of deionized water, and sonicate until the solution is homogeneous; add the solution to a three-necked flask containing the melted paraffin, control the mechanical stirring speed at 900-1000 r / min, stir at high speed for 1-1.5 h, then reduce the speed to 450-550 r / min, stop heating, and cool to room temperature; remove the finished product, wash it with deionized water by centrifugation, and then vacuum dry it at 50-70 °C to obtain paraffin-coated Fe3O4@SiO2; Step 5: Weigh 15800-15850 parts of methanol and 7950-8050 parts of deionized water, add 95-105 parts of KH550, and stir until dissolved evenly; then add 2190-2210 parts of paraffin-coated Fe3O4@SiO2, and mechanically stir at room temperature for 10-12 h at a speed of 150-170 r / min; after stirring, discard the filtrate, and place the solid under vacuum drying at 40-50 °C; after drying, add cyclohexane, and stir at room temperature until paraffin precipitates, then discard the liquid, and repeat this step until no paraffin is visible in the liquid, and then place the solid under vacuum drying at 50-70 °C to obtain Fe3O4@SiO2-NH2 particles; Step 6: Weigh 18-22 parts of Fe3O4@SiO2-NH2 particles and disperse them in phosphate buffer solution with pH=7.3-7.

5. Sonicate until uniformly dispersed. Then add 65-70 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC, 20-25 parts of N-hydroxysuccinimide NHS and CQDs solution. React the mixed solution with reciprocating shaking at 35-40 °C for 24-26 h. After standing to precipitate, collect the precipitate and vacuum dry it at 50-70 °C to obtain Fe3O4@SiO2@CQDs Janus particles. Step 7: Weigh 1-2 parts of Fe3O4@SiO2@CQDs Janus particles, add 1600-1700 parts of deionized water, sonicate until the solution is fully dissolved, then add the styrene-acrylic microsphere emulsion to the sonicated solution, and sonicate until homogeneous to obtain magnetic fluorescent styrene-acrylic microsphere emulsion, which is the magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator.

2. The method for preparing a magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator according to claim 1, characterized in that, The preparation of Fe3O4 in step three is specifically as follows: Weigh 210-220 parts of ferric chloride hexahydrate and 35-45 parts of sodium citrate into a reaction vessel, add 4420-4450 parts of ethylene glycol, stir thoroughly until completely dissolved, then add 230-250 parts of anhydrous sodium acetate, and mechanically stir until uniformly mixed. Transfer the solution to a polytetrafluoroethylene-lined reactor and react at 190-210 °C for 10-12 h. After the reaction is complete, cool to room temperature, wash several times with anhydrous ethanol and centrifuge. After washing, vacuum dry at 50-70 °C for 4-5 h and grind to obtain ferric oxide (Fe3O4).

3. A magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator obtained by the preparation method according to claim 1, characterized in that, Its raw material components, by mass parts, include: Sodium dodecyl sulfonate 32-35 parts, TMN-10 15-20 parts, n-butanol 50-55 parts, styrene 2770-2830 parts, butyl acrylate 6380-6440 parts, ammonium persulfate 285-305 parts, Fe3O4 58-62 parts, tetraethyl orthosilicate 210-220 parts, sliced ​​paraffin 1950-2050 parts, hexadecyltrimethylammonium bromide 8-11 parts, methanol 15800-15850 parts, KH 550 95-105 parts, glucose 5-8 parts, potassium dihydrogen phosphate 235-243 parts, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC 65-70 parts, N-hydroxysuccinimide NHS 20-25 parts, deionized water 65330-66030 parts.

4. The magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator according to claim 3, characterized in that, Its raw material components, by mass parts, include: Sodium dodecyl sulfonate 32 parts, TMN-10 15 parts, n-butanol 50 parts, styrene 2770 parts, butyl acrylate 6380 parts, ammonium persulfate 285 parts, Fe3O4 58 parts, tetraethyl orthosilicate 210 parts, sliced ​​paraffin 1950 parts, hexadecyltrimethylammonium bromide 8 parts, methanol 15800 parts, KH550 95 parts, glucose 5 parts, potassium dihydrogen phosphate 235 parts, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC 65 parts, N-hydroxysuccinimide NHS 20 parts, deionized water 65330 parts.

5. The magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator according to claim 3, characterized in that, Its raw material components, by mass parts, include: Sodium dodecyl sulfonate 35 parts, TMN-10 20 parts, n-butanol 55 parts, styrene 2830 parts, butyl acrylate 6440 parts, ammonium persulfate 305 parts, Fe3O4 62 parts, tetraethyl orthosilicate 220 parts, sliced ​​paraffin 2050 parts, hexadecyltrimethylammonium bromide 11 parts, methanol 15850 parts, KH550 105 parts, glucose 8 parts, potassium dihydrogen phosphate 243 parts, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC 70 parts, N-hydroxysuccinimide NHS 25 parts, deionized water 66030 parts.

6. The magnetic fluorescent Janus particle / styrene-acrylic polymer composite microsphere modulator according to claim 3, characterized in that, Its raw material components, by mass parts, include: Sodium dodecyl sulfonate 34 parts, TMN-10 18 parts, n-butanol 53 parts, styrene 2800 parts, butyl acrylate 6400 parts, ammonium persulfate 295 parts, Fe3O4 60 parts, tetraethyl orthosilicate 215 parts, sliced ​​paraffin 2000 parts, hexadecyltrimethylammonium bromide 10 parts, methanol 15830 parts, KH550 100 parts, glucose 7 parts, potassium dihydrogen phosphate 240 parts, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDC 68 parts, N-hydroxysuccinimide NHS 23 parts, deionized water 65330-66030 parts.

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