Magnetic multi-functional polymer-inorganic hybrid amphiphilic particles, and preparation method and application thereof

Abstract

The present application relates to sewage treatment technical field, provide a kind of magnetic multi-effect polymer inorganic hybrid amphiphilic particle and its preparation method and application.The particle includes magnetic Fe3O4 Particle core and the shell layer separated from the shell of the magnetic Fe3O4 Particle core, the shell layer is the hybrid shell layer of silica / titanium dioxide with micro-pore structure;The inner surface of the shell layer and the surface of magnetic Fe3O4 Particle core are grafted with poly (diethylaminoethyl methacrylate);The outer surface of the shell layer includes hydrophilic part and hydrophobic part, the hydrophilic part has amino group, the amino group is grafted polydopamine, and gallic acid is compounded on the polydopamine.The magnetic multi-effect polymer inorganic hybrid amphiphilic particle provided by the present application has excellent emulsifying performance, can realize oil-water separation;Meanwhile, it can selectively adsorb part of hydrolyzed polyacrylamide, and can efficiently treat oil-containing sewage containing part of hydrolyzed polyacrylamide in one step.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of sewage treatment, more particularly to a magnetic multi-effect polymer inorganic hybrid amphiphilic particle and a preparation method and application thereof. BACKGROUND

[0002] Partially hydrolyzed polyacrylamide (HPAM) is currently widely used in tertiary oil recovery of high water cut oilfields, and has good flocculation, thickening and drag reduction properties, which can effectively improve the recovery rate. However, the treatment of oil-containing sewage containing partially hydrolyzed polyacrylamide is more difficult than that of ordinary oil-containing sewage. The existing methods cannot achieve standard treatment of partially hydrolyzed polyacrylamide in oil-containing sewage in one step, and often require multiple methods and multiple steps to achieve standard treatment. In addition, due to the differences in oil wells and oil displacement operations, the pH value of the oil well displacement fluid changes greatly, and a large amount of sewage is acidic or alkaline, making it more difficult to treat.

[0003] Amphiphilic solid particle emulsifiers can achieve emulsification by reducing the interfacial tension of two phases, have high interfacial desorption energy, and can achieve efficient and stable emulsification of emulsions. The amphiphilic solid particles with magnetism can also make the emulsified droplets have magnetism, which facilitates the manipulation of the dispersed phase droplets. Therefore, by using magnetic amphiphilic solid particles, stable dispersed phase oil droplets can be obtained by emulsifying the oil phase in water, and then the oil droplets can be migrated and enriched under the control of an external magnetic field, thereby realizing oil-water separation and achieving the effect of treating oil-containing sewage. However, although the existing magnetic amphiphilic solid particle emulsifiers can successfully achieve oil-water separation when applied to treat partially hydrolyzed polyacrylamide-containing oil-containing sewage, they cannot simultaneously and efficiently remove partially hydrolyzed polyacrylamide in one step. SUMMARY

[0004] The present application aims to provide a magnetic multi-effect polymer inorganic hybrid amphiphilic particle and a preparation method thereof, to solve the technical problem in the prior art that partially hydrolyzed polyacrylamide-containing oil-containing sewage is difficult to treat in one step to meet the standard.

[0005] To achieve the above-mentioned purposes, the technical solution adopted by the present application is as follows:

[0006] In a first aspect, the present application provides a magnetic multi-effect polymer inorganic hybrid amphiphilic particle, which comprises a magnetic Fe3O4 particle core and a shell layer separated from the core-shell of the magnetic Fe3O4 particle core, the shell layer being a silica / titania hybrid shell layer with a micro-porous structure; the inner surface of the shell layer and the surface of the magnetic Fe3O4 particle core are grafted with poly (diethylaminoethyl methacrylate) (PDEAEMA); the outer surface of the shell layer comprises a hydrophilic portion and a hydrophobic portion, the hydrophilic portion has an amino group, the amino group is grafted with polydopamine, and the polydopamine is complexed with gallic acid.

[0007] It should be noted that the "micropore structure" mentioned in this invention includes intermolecular voids in the silica / titanium dioxide macromolecular framework and defects generated during the core-shell separation process between the silica / titanium dioxide hybrid shell and the magnetic Fe3O4 particle core, and even micropores and capillaries with a pore size of 0.5 to 50 nm.

[0008] The magnetic multifunctional polymer inorganic hybrid amphiphilic particles provided by this invention have a silicon dioxide / titanium dioxide hybrid shell coating the core of the magnetic Fe3O4 particles, which can protect the core of the magnetic Fe3O4 particles. Within a certain time and pH range, it can resist the corrosion of the core of the magnetic Fe3O4 particles by hydrochloric acid, sulfuric acid, nitric acid or various alkaline reagents, thus ensuring the industrial application of the magnetic particles.

[0009] The magnetic multifunctional polymer inorganic hybrid amphiphilic particles provided by this invention have an outer shell surface that includes both hydrophilic and hydrophobic portions, giving them amphiphilic properties. Compared with traditional homogeneous particles, they have more stable emulsification characteristics and can more stably and extensively emulsify oil and water phases to form stable oil-in-water emulsions, providing a stable basis for the manipulation of emulsion droplets.

[0010] The magnetic multifunctional polymer inorganic hybrid amphiphilic particles provided by this invention exhibit electrostatic and other interactions between the functional groups on the outer surface of the shell and partially hydrolyzed polyacrylamide, promoting the adsorption of partially hydrolyzed polyacrylamide on the outer surface of the shell. Furthermore, the polydopamine grafted onto the amino group of the hydrophilic portion and the gallic acid complexed on the polydopamine through strong hydrogen bonding both contain polyhydroxy structures, exhibiting adhesiveness. This further enhances the adhesion and hydrogen bonding of the amphiphilic particles to the partially hydrolyzed polyacrylamide, thus improving the removal efficiency of partially hydrolyzed polyacrylamide from wastewater. Simultaneously, after achieving the adsorption and adhesion of partially hydrolyzed polyacrylamide, the wetting effect of the internal structure of the hybrid amphiphilic particles on the partially hydrolyzed polyacrylamide adsorbed on the outer surface of the shell promotes the adsorption process of partially hydrolyzed polyacrylamide into the shell. Poly(diethylaminoethyl methacrylate) (PDEAEMA) grafted onto the inner surface of the shell and the core surface of the magnetic Fe3O4 particles forms a brush-like coating, increasing the specific surface area and enhancing the hydrogen bond density. The microporous structure of the shell provides channels for the migration and transport of partially hydrolyzed polyacrylamide, and the weakly acidic nature of the partially hydrolyzed polyacrylamide further facilitates its transfer and adsorption from the outer surface of the shell to the PDEAEMA inside, thus achieving the adsorption and migration capture of partially hydrolyzed polyacrylamide by PDEAEMA. The magnetic multifunctional polymer inorganic hybrid amphiphilic particles provided by this invention, through the combination of their internal and external structures, significantly improve the adsorption capacity and efficiency for partially hydrolyzed polyacrylamide.

[0011] And, PDEAEMA has pH sensitivity, which will show hydrophilic properties at low pH and hydrophobic properties at high pH, and this feature can achieve the repeated adsorption and desorption of PDEAEMA to partially hydrolyzed polyacrylamide, so that the magnetic multi-effect polymer inorganic hybrid amphiphilic particles can be reused, greatly reducing the material cost of wastewater treatment.

[0012] In addition, the used magnetic multi-effect polymer inorganic hybrid amphiphilic particles can be washed and extracted with a good solvent of partially hydrolyzed polyacrylamide (such as ethanol), and the adsorbed partially hydrolyzed polyacrylamide can also be removed, so as to realize the reuse of the magnetic multi-effect polymer inorganic hybrid amphiphilic particles.

[0013] According to some embodiments of the present application, the mass ratio of silica and titanium dioxide in the shell layer is 1:10-10:1.

[0014] According to some embodiments of the present application, the amino-containing silane coupling agent includes 3-aminopropyl triethoxysilane.

[0015] The modification of the outer surface of the shell layer with 3-aminopropyl triethoxysilane makes the hydrophilic part of the outer surface of the shell layer contain amino groups, which can interact weakly with the carboxyl-containing partially hydrolyzed polyacrylamide, thereby realizing the adsorption of the partially hydrolyzed polyacrylamide.

[0016] According to some embodiments of the present application, the hydrophobic part is obtained by modifying the outer surface of the shell layer with an alkyl-containing silane coupling agent.

[0017] According to some embodiments of the present application, the alkyl-containing silane coupling agent includes n-octyl triethoxysilane.

[0018] According to some embodiments of the present application, the area of the hydrophilic part accounts for 1 / 3-2 / 3 of the total area of the outer surface of the shell layer.

[0019] According to some embodiments of the present application, the particle size of the magnetic multi-effect polymer inorganic hybrid amphiphilic particles is 100nm

[0020] In a second aspect, the present application provides a preparation method of magnetic multi-effect polymer inorganic hybrid amphiphilic particles, comprising:

[0021] S1. dispersing magnetic Fe3O4 particles, tetraethyl orthosilicate and tetra-n-butyl titanate into an alcohol solvent to obtain Fe3O4@SiO2 / TiO2 particles;

[0022] S2. Disperse Fe3O4@SiO2 / TiO2 particles into water, add paraffin, heat to completely melt the paraffin, mix under stirring, filter after cooling, and obtain paraffin balls formed by embedding Fe3O4@SiO2 / TiO2 particles on the surface of paraffin;

[0023] S3. Disperse the paraffin balls into dimethyl sulfoxide, add amino-containing silane coupling agent, stir to react, and disperse the obtained solid particles into an alcohol solvent to obtain hydrophilic modified particles;

[0024] S4. Disperse the hydrophilic modified particles into ethanol, add alkyl-containing silane coupling agent, and stir to react, and obtain amphiphilic modified particles;

[0025] S5. Mix the amphiphilic modified particles with acetic acid for 8-12 h to obtain amphiphilic modified particles with separated core and shell;

[0026] S6. Disperse the amphiphilic modified particles with separated core and shell into an alcohol solvent, add 4-(chloromethyl)phenyl trimethoxysilane to modify; and then add diethylaminoethyl methacrylate to graft, to obtain particles grafted with polydiethylaminoethyl methacrylate;

[0027] S7. Disperse the particles grafted with polydiethylaminoethyl methacrylate into a solvent, add dopamine to react for the first time; then add gallic acid to react for the second time, and obtain the magnetic multi-functional polymer inorganic hybrid amphiphilic particles after the reaction.

[0028] The preparation method of the magnetic multi-effect polymer inorganic hybrid amphiphilic particles provided by the application is as follows: taking magnetic Fe3O4 particles as carriers, tetraethyl orthosilicate and tetra-n-butyl titanate are used to realize hydrolysis on the surface of the magnetic Fe3O4 particles, and through a sol-gel process, the magnetic Fe3O4 particles are coated to form a core-shell structure of effective silicon / titanium-embedded iron. Then, using paraffin with a phase transition temperature of 52 DEG C as an oil phase, and using Fe3O4@SiO2 / TiO2 particles as solid particle emulsifiers, the oil and water phases are emulsified when the temperature is higher than the phase transition temperature of the paraffin, to form a stable water-in-paraffin emulsion. After the emulsion is cooled, the paraffin phase is solidified and separated from the water phase, to obtain paraffin balls in which Fe3O4@SiO2 / TiO2 particles are embedded on the surface of the paraffin, and part of the Fe3O4@SiO2 / TiO2 particles are embedded in the paraffin and part of the Fe3O4@SiO2 / TiO2 particles are exposed outside the paraffin. Then, the outer surface of the Fe3O4@SiO2 / TiO2 particles exposed outside the paraffin is modified to be hydrophilic, the paraffin is removed, and the part of the Fe3O4@SiO2 / TiO2 particles which was protected by the paraffin is exposed, and the outer surface of the part is modified to be hydrophobic, to obtain the amphiphilic particles with the outer surface including both hydrophilic and hydrophobic parts. Then, acid etching treatment is performed to reduce the size of the magnetic Fe3O4 particles, separate the magnetic Fe3O4 particles from the shell layer, and form a hollow structure between the core-shell structures. Further, 4-(chloromethyl)phenyl trimethoxysilane is used to modify benzyl chloride 【4-(chloromethyl)phenyl】 on the surface of the magnetic Fe3O4 particles and the inner surface of the shell layer. The benzyl chloride has high activity and can be grafted with poly (diethylaminoethyl methacrylate) (PDEAEMA) through ATRP (atom transfer radical polymerization). Finally, the particles are reacted with dopamine to graft polydopamine on the outer surface of the shell layer, and then gallic acid is compounded on the polydopamine through strong hydrogen bonding, to obtain the magnetic multi-effect polymer inorganic hybrid amphiphilic particles.

[0029] In the application, tetraethyl orthosilicate and tetra-n-butyl titanate are used to realize hydrolysis on the surface of the magnetic Fe3O4 particles, and through a sol-gel process, a relatively dense silica / titanium hybrid shell layer structure is formed on the surface of the magnetic Fe3O4 particles to protect the magnetic Fe3O4 particles inside, which can resist corrosion of hydrochloric acid, sulfuric acid, nitric acid or various alkaline reagents within a certain time and within a certain PH range, and ensure the industrial application of the magnetic particles. Moreover, the silica / titanium hybrid shell layer in the application is a polymer formed by hydrolysis and condensation of tetraethyl orthosilicate and tetra-n-butyl titanate, although the formed silica / titanium hybrid shell layer is relatively dense, but in the sol-gel process of hydrolysis of tetraethyl orthosilicate and tetra-n-butyl titanate, the macromolecular skeleton formed by condensation reaction still has intermolecular space, which ensures the smooth progress of the subsequent acid etching treatment, 4-(chloromethyl)phenyl trimethoxysilane modification and PDEAEMA grafting process.

[0030] In the present application, the magnetic Fe3O4 particles are reduced in size by acid etching treatment, resulting in core-shell separation. This process further causes defects in the shell layer, even micro- or capillary pores, which together with the intermolecular space in the shell layer form a micro-pore structure to provide a channel for the transport of partially hydrolyzed polyacrylamide into the shell layer.

[0031] In the present application, the acid etching treatment reagent is acetic acid, which can slow down the etching process, ensure controllable etching process, and make the inner core surface of the magnetic Fe3O4 particles smoother. If hydrochloric acid, sulfuric acid, or the like is used, it is difficult to control the etching process, and it is easy to cause excessive etching, resulting in too weak magnetic particles or even complete disappearance.

[0032] According to some embodiments of the present application, the alcohol solvent includes at least one of methanol, ethanol, propanol, butanol, isopropanol, and cyclohexanol.

[0033] According to some embodiments of the present application, the stirring speed in step S2 is 1000-5000 rpm.

[0034] In the present application, the stirring speed in step S2 directly affects the emulsification process of the particle emulsifier (Fe3O4@SiO2 / TiO2 particles), and directly leads to the stability of the particle emulsifier to the emulsion interface. When the stirring speed is less than 1000 rpm, the stirring speed is too low, the particle emulsifier is difficult to deliver to the interface, and the interface cannot be stabilized, and the emulsion is easy to break; when the stirring speed is greater than 5000 rpm, the stirring speed is too high, the particle emulsifier is forced to be pulled at the interface, and the interface is easy to be unstable, and the emulsion is easy to break. Therefore, in order to ensure emulsification and interface stability, the stirring speed in step S2 is preferably controlled at 1000-5000 rpm.

[0035] According to some embodiments of the present application, the stirring time in step S2 is 3-5 min.

[0036] According to some embodiments of the present application, the amino-containing silane coupling agent includes 3-aminopropyl triethoxysilane.

[0037] The local hydrophilic modification of the outer surface of the Fe3O4@SiO2 / TiO2 particles by 3-aminopropyl triethoxysilane in dimethyl sulfoxide is realized by a sol-gel composite process on the outer surface of the Fe3O4@SiO2 / TiO2 particles exposed to paraffin, which modifies the amino group on one side of the outer surface of the Fe3O4@SiO2 / TiO2 particles, thereby realizing the adsorption of partially hydrolyzed polyacrylamide.

[0038] According to some embodiments of the present application, the alkyl-containing silane coupling agent includes n-octyl triethoxysilane.

[0039] The local hydrophobicity modification of the outer surface of the Fe3O4@SiO2 / TiO2 particles by using n-octyl triethoxysilane is to remove the paraffin by using an alcohol solvent, to expose the part of the Fe3O4@SiO2 / TiO2 particles embedded in the paraffin and protected, and to realize the sol-gel composite on the surface of the Fe3O4@SiO2 / TiO2 particles by the hydrolysis process of the n-octyl triethoxysilane from the exposed part of the Fe3O4@SiO2 / TiO2 particles embedded in the paraffin, and to modify the n-octyl on the other side of the outer surface of the Fe3O4@SiO2 / TiO2 particles.

[0040] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles, tetraethyl orthosilicate and tetra-n-butyl titanate is 1:(0.1-1):(0.1-1).

[0041] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and the paraffin is 1:(10-200).

[0042] According to some embodiments of the present application, the mass ratio of the paraffin and the water is 1:(2-10).

[0043] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and the amino-containing silane coupling agent is 1:(0.001-0.01).

[0044] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and the alkyl-containing silane coupling agent is 1:(0.001-0.01).

[0045] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and 4-(chloromethyl)phenyl trimethoxysilane is 1:(0.001-0.01).

[0046] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and diethylaminoethyl methacrylate is 1:(0.02-0.1).

[0047] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and dopamine is 1:(0.001-0.01).

[0048] According to some embodiments of the present application, the mass ratio of the magnetic Fe3O4 particles and gallic acid is 1:(0.001-0.01).

[0049] According to some embodiments of the present application, the particle size of the magnetic Fe3O4 particles is 100-500 nm.

[0050] According to some embodiments of the present application, the ratio of the particle size of the magnetic Fe3O4 particles and the core of the magnetic Fe3O4 particles is 100:(10-99).

[0051] In the present application, if the ratio of the particle size of the magnetic Fe3O4 particles and the core of the magnetic Fe3O4 particles is less than 100:99, it means that the gap between the shell and the core of the magnetic Fe3O4 particles is too small, which will affect the adsorption capacity of the magnetic multi-functional polymer inorganic hybrid amphiphilic particles to partially hydrolyzed polyacrylamide; if the ratio of the particle size of the magnetic Fe3O4 particles and the core of the magnetic Fe3O4 particles is greater than 100:10, it means that the size of the core of the magnetic Fe3O4 particles is too small, which will cause serious magnetic decay and make it difficult to realize the magnetic manipulation of the external magnetic field.

[0052] According to some embodiments of the present application, the grafting reaction comprises: dissolving cuprous chloride and 2,2-bipyridine in a solvent, adding the modified amphiphilic modified particles after the modification reaction treatment and diethylaminoethyl methacrylate, and stirring the reaction under a nitrogen atmosphere and at 60-100°C.

[0053] According to some embodiments of the present application, the solvent used in the grafting reaction comprises at least one of water, tetrahydrofuran (THF), and N,N-dimethylformamide (DMF).

[0054] According to some embodiments of the present application, the solvent used for dispersing the particles of the grafted poly(diethylaminoethyl methacrylate) comprises at least one of water, tetrahydrofuran (THF), and N,N-dimethylformamide (DMF).

[0055] According to some embodiments of the present application, the stirring reaction time in step S3 is 5-6h.

[0056] According to some embodiments of the present application, the stirring reaction time in step S4 is 5-6h.

[0057] According to some embodiments of the present application, the magnetic Fe3O4 particles and tetra-n-butyl titanate are dispersed in an alcohol solvent by ultrasonic and stirring for 12-24h, preferably, the ultrasonic frequency is 60-80Hz and / or the stirring speed is 50-100rpm.

[0058] According to some embodiments of the present application, the Fe3O4@SiO2 / TiO2 particles are dispersed in water by ultrasonic and stirring, preferably, the ultrasonic frequency is 60-80Hz and / or the stirring speed is 50-100rpm.

[0059] According to some embodiments of the present application, the paraffin balls are dispersed in dimethyl sulfoxide by stirring, preferably, the stirring speed is 50-100rpm.

[0060] According to some embodiments of the present application, the dispersing of the hydrophilic modified particles into the alcohol solvent is performed by ultrasonic and stirring, preferably, the ultrasonic frequency is 60-80 Hz and / or the stirring speed is 200-300 rpm.

[0061] According to some embodiments of the present application, the mixing of the amphiphilic modified particles with acetic acid for 8-12 h comprises: dispersing the amphiphilic modified particles in water, adding acetic acid, and mixing by ultrasonic and stirring for 8-12 h, preferably, the ultrasonic frequency is 60-80 Hz and / or the stirring speed is 50-100 rpm.

[0062] In a third aspect, the present application provides a magnetic multi-functional polymer-inorganic hybrid amphiphilic particle, which is prepared by the method of the second aspect.

[0063] In a fourth aspect, the present application provides an application of the magnetic multi-functional polymer-inorganic hybrid amphiphilic particle of the first aspect or the magnetic multi-functional polymer-inorganic hybrid amphiphilic particle of the third aspect in treating oil-containing wastewater containing partially hydrolyzed polyacrylamide.

[0064] The present application has at least the following beneficial effects:

[0065] (1) The magnetic multi-functional polymer-inorganic hybrid amphiphilic particle provided by the present application has uniform particle size and wide size distribution window, and can achieve sub-micron / micron distribution.

[0066] (2) The magnetic multi-functional polymer-inorganic hybrid amphiphilic particle provided by the present application has excellent emulsifying performance. The liquid droplets emulsified by the magnetic multi-functional polymer-inorganic hybrid amphiphilic particle can be controlled by an external magnetic field, realizing the enrichment and migration of oil droplets, and thus realizing oil-water separation.

[0067] (3) The magnetic multi-functional polymer-inorganic hybrid amphiphilic particle provided by the present application can treat oil-containing wastewater containing partially hydrolyzed polyacrylamide in one step with high efficiency through the combination of the internal and external structures of the particle.

[0068] (4) The magnetic multi-functional polymer-inorganic hybrid amphiphilic particle provided by the present application can be repeatedly used, and the adsorption capacity for partially hydrolyzed polyacrylamide does not decrease significantly, which can greatly reduce the material cost of wastewater treatment.

[0069] (5) The structure of the magnetic multi-functional polymer-inorganic hybrid amphiphilic particle provided by the present application, i.e., the silica / titanium dioxide hybrid shell layer covering the magnetic Fe3O4 particle core, can protect the magnetic Fe3O4 particle core, improve the acid and alkali resistance of the hybrid amphiphilic particle, and make it applicable to treat wastewater with more complex composition.

[0070] (6) The preparation method of the magnetic multi-effect polymer inorganic hybrid amphiphilic particles is simple in process, low in raw material cost and easy to obtain, and can realize industrialized ton-level batch production. DETAILED DESCRIPTION

[0071] In order to make the technical problems to be solved by the present application, technical solutions and beneficial effects more clear and explicit, the present application will be further described in detail below in combination with specific examples. It should be understood that the specific examples described herein are only used to illustrate the present patent in detail, and do not limit the protection scope of the present application in any way.

[0072] Unless defined, the technical terms used in the following examples have the same meanings as generally understood by those skilled in the art to which the present application belongs. The reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples can be purchased on the market or obtained by existing methods; the reagent amount, unless otherwise specified, is the reagent amount in conventional experimental operation; and the experimental method, unless otherwise specified, is a conventional method.

[0073] Example 1

[0074] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, and 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate were added, with 60 Hz ultrasonic and 100 rpm overhead stirring, to promote the dispersion of the magnetic Fe3O4 particles. The ultrasonic and stirring were maintained for 12 h, and Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0075] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, and 60 Hz ultrasonic and 100 rpm overhead stirring were additionally added to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. The water temperature was raised to 80℃, 20 g of paraffin (phase change temperature of 52℃) was added, and the stirring was continued until the paraffin was completely melted. The ultrasonic was turned off and the stirring speed was increased to 2000 rpm for 3 min. The stirring and heating were stopped, and the sample was cooled to room temperature. The solidified paraffin balls were filtered out and separated from the water. The paraffin balls were dispersed on filter paper and naturally air-dried to obtain paraffin ball powder formed by Fe3O4@SiO2 / TiO2 particles embedded in the surface of paraffin.

[0076] S3. The paraffin wax ball powder was dispersed in 100 mL of dimethyl sulfoxide, and the dispersion was stirred slowly by a overhead stirrer at a speed of 50 rpm. 20 mg of 3- aminopropyltriethoxysilane was added to the dispersion, and the stirring was continued for 6 h. The paraffin wax ball powder was separated from the solvent by an external magnetic field, and was dried naturally. The paraffin wax ball powder was dispersed in 100 mL of ethanol, and the paraffin wax was dissolved. The solid particles were separated by an external magnetic field, and Fe3O4@SiO2 / TiO2-NH2 particles with one side surface modified with amino groups were obtained.

[0077] S4. The Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, and the dispersion was stirred by a overhead stirrer at a speed of 300 rpm, while 60 Hz ultrasound was added. 20 mg of n-octylpropyltriethoxysilane was added to the dispersion, and the stirring was continued for 6 h. The solid particles were separated by an external magnetic field, and were dried naturally to obtain C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0078] C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0079] S5. The C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of water, and 2 mL of acetic acid was added. The dispersion was stirred by a overhead stirrer for 10 h at a speed of 100 rpm, while 60 Hz ultrasound was added. C8-Fe3O4@SiO2 / TiO2-NH2 particles with core-shell separation were obtained.

[0080] S6. The C8-Fe3O4@SiO2 / TiO2-NH2 particles with core-shell separation were dispersed in 100 mL of ethanol, and 10 mg of 4-(chloromethyl)phenyltrimethoxysilane was added. The stirring was continued for 12 h at a speed of 100 rpm. C8-Fe3O4@SiO2 / TiO2-NH2 particles with modification treatment were obtained. 0.02 g of cuprous chloride and 0.02 g of 2,2-bipyridine were dissolved in 50 mL of DMF, and the above C8-Fe3O4@SiO2 / TiO2-NH2 particles with modification treatment were added. 0.1 g of DEAEMA was added, and N2 was introduced to remove oxygen for 30 min. The temperature was increased to 80 °C, and the stirring was continued for 3 h at a speed of 100 rpm. Particles with grafted poly(diethylaminoethyl methacrylate) were obtained.

[0081] S7. The particles with grafted poly(diethylaminoethyl methacrylate) were dispersed in a solvent, and 20 mg of dopamine was added. The reaction was stirred for 6 h. Then, 20 mg of gallic acid was added, and the reaction was stirred for 6 h. After the reaction, magnetic multi-functional polymer inorganic hybrid amphiphilic particles were obtained.

[0082] Example 2

[0083] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, while 0.3 g of tetraethyl orthosilicate and 0.3 g of tetra-n-butyl titanate were added, with the addition of 60 Hz ultrasonic and 100 rpm overhead stirring, keeping the ultrasonic and stirring to promote the dispersion of the magnetic Fe3O4 particles, for 12 h, and Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0084] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, while the ultrasonic and 100 rpm overhead stirring were added, keeping the ultrasonic and stirring to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. The water temperature was raised to 80 °C, 40 g of paraffin wax (phase transition temperature of 52 °C) was added, and stirring was continued until the paraffin wax was completely melted. The ultrasonic was turned off and the stirring speed was increased to 1000 rpm, and stirring was continued for 5 min. The stirring and heating were stopped, and the sample was cooled to room temperature, and the solidified paraffin wax balls were filtered out and separated from the water. The paraffin wax balls were dispersed on filter paper and naturally air-dried to obtain paraffin wax ball powder with Fe3O4@SiO2 / TiO2 particles embedded in the surface of the paraffin wax.

[0085] S3. The paraffin wax ball powder was dispersed in 100 mL of dimethyl sulfoxide, and the dispersion was slowly stirred with an overhead stirrer at a speed of 50 rpm. 3 mg of 3- aminopropyltriethoxysilane was added to the dispersion, and stirring was continued for 6 h. The paraffin wax ball powder and the solvent were separated using an external magnetic field, and the paraffin wax ball powder was air-dried in a natural state. The paraffin wax ball powder was again dispersed in 100 mL of ethanol, and the paraffin wax was dissolved. The solid particles were separated using an external magnetic field, and Fe3O4@SiO2 / TiO2-NH2 particles with amino-modified surfaces on one side were obtained.

[0086] S4. The Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, and the dispersion was stirred with an overhead stirrer at a speed of 300 rpm, while 60 Hz ultrasonic was added. 3 mg of n-octylpropyltriethoxysilane was added to the dispersion, and stirring was continued for 6 h. The solid particles were separated using an external magnetic field, and air-dried in a natural state to obtain

[0087] C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0088] S5. The C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of water, and 2 mL of acetic acid was added. The dispersion was stirred with an overhead stirrer for 10 h at a speed of 100 rpm, while 60 Hz ultrasonic was added, and C8-Fe3O4@SiO2 / TiO2-NH2 particles with core-shell separation were obtained.

[0089] S6. The core-shell separated C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, 3 mg of 4-(chloromethyl)phenyl trimethoxysilane was added, and stirred at 100 rpm for 12 h to obtain modified C8-Fe3O4@SiO2 / TiO2-NH2 particles; 0.02 g of cuprous chloride and 0.02 g of 2,2-bipyridine were dissolved in 50 mL of DMF, the above modified C8-Fe3O4@SiO2 / TiO2-NH2 particles were added, 0.04 g of DEAEMA was added, and N2 was introduced to remove oxygen for 30 min, and the temperature was raised to 80°C, and stirred at 100 rpm for 3 h to obtain particles grafted with poly (diethylaminoethyl methacrylate) ;

[0090] S7. The particles grafted with poly (diethylaminoethyl methacrylate) were dispersed in a solvent, 3 mg of dopamine was added, and stirred for 6 h, then 3 mg of gallic acid was added, and stirred for 6 h, and the magnetic multi-functional polymer inorganic hybrid amphiphilic particles were obtained after the reaction was completed.

[0091] Example 3

[0092] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, 2 g of tetraethyl orthosilicate and 2 g of titanium tetrabutoxide were added, 60 Hz ultrasonic and 100 rpm overhead stirring were added, and the dispersion of the magnetic Fe3O4 particles was promoted by maintaining the ultrasonic and stirring for 12 h, and Fe3O4@SiO2 / TiO2 particles were separated.

[0093] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, 60 Hz ultrasonic and 100 rpm overhead stirring were added, and the dispersion of the Fe3O4@SiO2 / TiO2 particles was promoted by maintaining the ultrasonic and stirring. The water temperature was raised to 80°C, 20 g of paraffin (phase change temperature of 52°C) was added, and the stirring was continued until the paraffin was completely melted. The ultrasonic was turned off and the stirring speed was increased to 5000 rpm, and the stirring was continued for 4 min. The stirring and heating were stopped, the sample was cooled to room temperature, and the solidified paraffin balls were filtered out and separated from the water. The paraffin balls were dispersed on filter paper and naturally air-dried to obtain paraffin ball powder formed by Fe3O4@SiO2 / TiO2 particles embedded in the surface of paraffin.

[0094] S3. The paraffin wax ball powder was dispersed in 100 mL of dimethyl sulfoxide, and the dispersion was stirred slowly by a overhead stirrer at a speed of 50 rpm. 10 mg of 3- aminopropyltriethoxysilane was added to the dispersion, and the stirring was continued for 6 h. The paraffin wax ball powder was separated from the solvent by an external magnetic field, and was dried naturally. The paraffin wax ball powder was dispersed in 100 mL of ethanol, and the paraffin wax was dissolved. The solid particles were separated by an external magnetic field, and Fe3O4@SiO2 / TiO2-NH2 particles with one side surface modified with amino groups were obtained.

[0095] S4. The Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, and the dispersion was stirred by a overhead stirrer at a speed of 300 rpm, while 60 Hz ultrasound was added. 10 mg of n-octylpropyltriethoxysilane was added to the dispersion, and the stirring was continued for 6 h. The solid particles were separated by an external magnetic field, and were dried naturally to obtain C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0096] C8-Fe3O4@SiO2 / TiO2-NH2 particles.

[0097] S5. The C8-Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of water, and 2 mL of acetic acid was added. The dispersion was stirred by a overhead stirrer for 10 h at a speed of 100 rpm, while 60 Hz ultrasound was added to obtain C8-Fe3O4@SiO2 / TiO2-NH2 particles with core-shell separation;

[0098] S6. The C8-Fe3O4@SiO2 / TiO2-NH2 particles with core-shell separation were dispersed in 100 mL of ethanol, and 15 mg of 4-(chloromethyl)phenyltrimethoxysilane was added. The stirring was continued for 12 h at a speed of 100 rpm to obtain C8-Fe3O4@SiO2 / TiO2-NH2 particles with modification treatment. 0.02 g of cuprous chloride and 0.02 g of 2,2-bipyridine were dissolved in 50 mL of DMF, and the above C8-Fe3O4@SiO2 / TiO2-NH2 particles with modification treatment were added. 0.2 g of DEAEMA was added, and N2 was introduced to remove oxygen for 30 min. The temperature was increased to 80 °C, and the stirring was continued for 3 h at a speed of 100 rpm to obtain particles grafted with poly (methacrylic acid diethylaminoethyl ester).

[0099] S7. The particles grafted with poly (methacrylic acid diethylaminoethyl ester) were dispersed in a solvent, and 10 mg of dopamine was added. The reaction was stirred for 6 h. Then, 10 mg of gallic acid was added, and the reaction was stirred for 6 h. After the reaction was completed, magnetic multi-functional polymer inorganic hybrid amphiphilic particles were obtained.

[0100] Example 4

[0101] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, while 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate were added, 60 Hz ultrasound and 100 rpm overhead stirring were added, the ultrasound and stirring were kept to promote the dispersion of the magnetic Fe3O4 particles, and the process was continued for 12 h, and Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0102] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, while 60 Hz ultrasound and 100 rpm overhead stirring were added, the ultrasound and stirring were kept to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. The water temperature was raised to 80 °C, 20 g of paraffin wax (phase transition temperature of 52 °C) was added, and the stirring was continued until the paraffin wax was completely melted. The ultrasound was turned off and the stirring speed was increased to 500 rpm.

[0103] Due to the low stirring speed, the particles could not be delivered to the oil-water interface by mechanical force, the silicon / titanium coated magnetic particles could not be stably arranged on the oil-water interface, the oil-water two phases could not be stably emulsified, and the water phase and the oil phase were still two phases, so the silicon / titanium coated magnetic particle embedded paraffin wax powder could not be prepared.

[0104] Example 5

[0105] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, while 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate were added, 60 Hz ultrasound and 100 rpm overhead stirring were added, the ultrasound and stirring were kept to promote the dispersion of the magnetic Fe3O4 particles, and the process was continued for 12 h, and Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0106] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, while 60 Hz ultrasound and 100 rpm overhead stirring were added, the ultrasound and stirring were kept to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. The water temperature was raised to 80 °C, 20 g of paraffin wax (phase transition temperature of 52 °C) was added, and the stirring was continued until the paraffin wax was completely melted. The ultrasound was turned off and the stirring speed was increased to 6000 rpm.

[0107] Due to the high stirring speed, although the silicon / titanium coated magnetic particles were delivered to the oil-water interface by mechanical force to achieve emulsification, the fast mechanical stirring caused the particles to be stripped from the interface, the interface was destabilized, demulsification occurred, and the silicon / titanium coated magnetic particle embedded paraffin wax powder could not be prepared.

[0108] Comparative Example 1

[0109] S1. 2 g of magnetic Fe3O4 particles (0.2 pm in size) were dispersed in 200 mL of ethanol, while 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate were added, with 60 Hz ultrasonic and 100 rpm overhead stirring, to promote the dispersion of the magnetic Fe3O4 particles, for 12 h. The Fe3O4@SiO2 / TiO2 particles were separated.

[0110] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 200 mL of water, while 60 Hz ultrasonic and 100 rpm overhead stirring were added, to promote the dispersion of the Fe3O4@SiO2 / TiO2 particles. The water temperature was raised to 80 °C, and 20 g of paraffin wax (phase transition temperature of 52 °C) was added, and stirring was continued until the paraffin wax was completely melted. The ultrasonic was turned off and the stirring speed was increased to 2000 rpm, and stirring was continued for 3 min. The stirring and heating were stopped, and the sample was cooled to room temperature, and the solidified paraffin wax balls were filtered out and separated from the water. The paraffin wax balls were dispersed on filter paper and naturally air-dried, to obtain paraffin wax ball powder with Fe3O4@SiO2 / TiO2 particles embedded in the surface of the paraffin wax.

[0111] S3. The paraffin wax ball powder was dispersed in 100 mL of dimethyl sulfoxide, and the dispersion was slowly stirred using an overhead stirrer at a speed of 50 rpm. 20 mg of 3- aminopropyltriethoxysilane was added to the dispersion, and stirring was continued for 6 h. The paraffin wax ball powder and the solvent were separated using an external magnetic field, and the paraffin wax ball powder was air-dried in a natural state. The paraffin wax ball powder was again dispersed in 100 mL of ethanol, and the paraffin wax was dissolved, and the solid particles were separated using an external magnetic field, to obtain Fe3O4@SiO2 / TiO2-NH2 particles with amino groups modified on one side of the surface.

[0112] S4. The Fe3O4@SiO2 / TiO2-NH2 particles were dispersed in 100 mL of ethanol, and the dispersion was stirred using an overhead stirrer at a speed of 300 rpm, while 60 Hz ultrasonic was added. 20 mg of n-octylpropyltriethoxysilane was added to the dispersion, and stirring was continued for 6 h. The solid particles were separated using an external magnetic field, to obtain C8-Fe3O4@SiO2-NH2 particles.

[0113] S5. The C8-Fe3O4@SiO2-NH2 particles were dispersed in a solvent, 20 mg of dopamine was added, and the reaction was stirred for 6 h, and then 20 mg of gallic acid was added, and the reaction was stirred for 6 h, to obtain the particles.

[0114] Comparative Example 2

[0115] S1. 2 g of magnetic Fe3O4 particles (particle size of 0.2 μm) were dispersed in 200 mL of ethanol, while 1 g of tetraethyl orthosilicate and 1 g of tetra-n-butyl titanate were added, 60 Hz ultrasound and 100 rpm overhead stirring were added to promote the dispersion of the magnetic Fe3O4 particles, and the ultrasound and stirring were maintained for 12 h. Fe3O4@SiO2 / TiO2 particles were obtained by separation.

[0116] S2. The Fe3O4@SiO2 / TiO2 particles were dispersed in 100 mL of water, 2 mL of acetic acid was added, and the dispersion was stirred for 10 h at a speed of 100 rpm using an overhead stirrer, while 60 Hz ultrasound was added to obtain core-shell separated Fe3O4@SiO2 / TiO2 particles.

[0117] S3. The core-shell separated Fe3O4@SiO2 / TiO2 particles were dispersed in 100 mL of ethanol, 10 mg of 4-(chloromethyl)phenyltrimethoxysilane was added, and stirring was performed at 100 rpm for 12 h to obtain modified Fe3O4@SiO2 / TiO2 particles. 0.02 g of cuprous chloride and 0.02 g of 2,2-bipyridine were dissolved in 50 mL of DMF, the above modified Fe3O4@SiO2 / TiO2 particles were added, 0.1 g of DEAEMA was added, and N2 was introduced to remove oxygen for 30 min. The temperature was raised to 80°C, and stirring was performed at 100 rpm for 3 h. After the reaction was completed, the particles were obtained.

[0118] Comparative Example 3

[0119] The particles were prepared according to the preparation method of Example 1, except that acetic acid was replaced with an equal volume of dilute hydrochloric acid (PH 6).

[0120] Comparative Example 4

[0121] The particles were prepared according to the preparation method of Example 1, except that acetic acid was replaced with an equal volume of sulfuric acid.

[0122] Performance Evaluation

[0123] (1) The particle size of the particles of each example and comparative example was measured by scanning electron microscopy, and the results are shown in the following table:

[0124] Group Particle diameter (nm) Example 1 320 Example 2 224 Example 3 320 Comparative Example 1 320 Comparative Example 2 240 Comparative Example 3 320 Comparative Example 4 320

[0125] (2) Wastewater treatment effect

[0126] 1 kg of each of the particles prepared in the examples and the comparative examples was added to 10 t of oil-containing wastewater containing partially hydrolyzed polyacrylamide (COD value: 2020, oil content: 52.3 mg / L, partially hydrolyzed polyacrylamide content: 103.05 mg / L), and the oil-containing wastewater was emulsified by using a shearing machine to stir at 1000 rpm for 1 min; then the migration and enrichment of the oil droplets emulsified by the magnetic particles were achieved by external magnetic field control. The treated wastewater was detected, and the detection methods are shown in the following table:

[0127]

[0128]

[0129] The detection results are shown in the following table:

[0130]

[0131] (Three) Recycling performance

[0132] The magnetic multi-functional polymer inorganic hybrid amphiphilic particles were washed and regenerated by using a solvent method, so as to realize the recycling of the magnetic multi-functional polymer inorganic hybrid amphiphilic particles. The specific treatment method includes: collecting the magnetic multi-functional polymer inorganic hybrid amphiphilic particles prepared in Example 1 after wastewater treatment, washing with ethanol, and the mass ratio of ethanol to the amphiphilic particles is 10:1; after washing, the particles are treated by freeze-drying to obtain regenerated particles.

[0133] The particles after regeneration are used to repeat the treatment process of the oil-containing wastewater containing partially hydrolyzed polyacrylamide in (Two), and the indicators of the treated wastewater are similar to the treatment effect of the magnetic multi-functional polymer inorganic hybrid amphiphilic particles of Example 1 in the first wastewater treatment. The recycling number of the magnetic multi-functional polymer inorganic hybrid amphiphilic particles can reach more than 100 times, and the removal effects of COD, oil and partially hydrolyzed polyacrylamide will not be significantly deteriorated.

[0134] It should be noted that the above examples are only used to explain the present application and do not constitute any limitation on the present application. The present application is described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified as specified within the scope of the claims of the present application, and the present application can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications with the same function.

Claims

1. A magnetic multi-effect polymer-inorganic hybrid amphiphilic particle, characterized in that, The magnetic multi-effect polymer inorganic hybrid amphiphilic particle comprises a magnetic Fe3O4 particle core and a shell layer separated from the magnetic Fe3O4 particle core, and the shell layer is a silica / titania hybrid shell layer with a fine pore structure; the inner surface of the shell layer and the surface of the magnetic Fe3O4 particle core are grafted with poly (diethylaminoethyl methacrylate); the outer surface of the shell layer comprises a hydrophilic part and a hydrophobic part, the hydrophilic part has an amino group, the amino group is grafted with polydopamine, and the polydopamine is complexed with gallic acid.

2. The magnetic multi-effect polymeric inorganic hybrid amphiphilic particles according to claim 1, wherein, The amino group on the hydrophilic part is obtained by modifying the outer surface of the shell layer with an amino-containing silane coupling agent; And / or, the hydrophobic part is obtained by modifying the outer surface of the shell layer with an alkyl-containing silane coupling agent.

3. The magnetic multi-effect polymeric inorganic hybrid amphiphilic particle according to claim 2, wherein, The amino-containing silane coupling agent comprises 3-aminopropyl triethoxysilane; And / or, the alkyl-containing silane coupling agent comprises n-octyl triethoxysilane.

4. The magnetic multi-effect polymeric inorganic hybrid amphiphilic particle according to any one of claims 1-3, wherein, The particle size of the magnetic multi-effect polymer inorganic hybrid amphiphilic particle is 100 nm < r ≤ 1000 nm.

5. A method for preparing magnetic multi-effect polymer-inorganic hybrid amphiphilic particles, characterized by, Comprise: S1. Disperse the magnetic Fe3O4 particles, tetraethyl orthosilicate and tetra-n-butyl titanate into an alcohol solvent to obtain Fe3O4@SiO2 / TiO2 particles; S2. Disperse the Fe3O4@SiO2 / TiO2 particles into water, add paraffin, heat to completely melt the paraffin, stir and mix, cool, and then filter to obtain paraffin balls formed by embedding the surface of the Fe3O4@SiO2 / TiO2 particles in paraffin; S3. Disperse the paraffin balls into dimethyl sulfoxide, add an amino-containing silane coupling agent, stir and react, disperse the obtained solid particles into an alcohol solvent to obtain hydrophilic modified particles; S4. Disperse the hydrophilic modified particles into ethanol, add an alkyl-containing silane coupling agent, stir and react to obtain amphiphilic modified particles; S5. Mix the amphiphilic modified particles with acetic acid for 8-12 hours to obtain core-shell separated amphiphilic modified particles; S6. Disperse the core-shell separated amphiphilic modified particles into an alcohol solvent, add 4-(chloromethyl)phenyl trimethoxysilane to modify; then graft with diethylaminoethyl methacrylate to obtain particles grafted with polydiethylaminoethyl methacrylate; S7. Disperse the particles grafted with polydiethylaminoethyl methacrylate into a solvent, add dopamine to perform a first stirring reaction; then add gallic acid to perform a second stirring reaction, and obtain the magnetic multi-effect polymer inorganic hybrid amphiphilic particle after the reaction is completed.

6. The production method according to claim 5, wherein The stirring and mixing speed in step S2 is 1000-5000 rpm; And / or, the amino-containing silane coupling agent comprises 3-aminopropyl triethoxysilane; And / or, the alkyl-containing silane coupling agent comprises n-octyl triethoxysilane.

7. The production method according to claim 6, wherein The stirring and mixing time in step S2 is 3-5 min.

8. The production method according to any one of claims 5 to 7, characterized by, The mass ratio of the magnetic Fe3O4 particles, tetraethyl orthosilicate and tetra-n-butyl titanate is 1:(0.1-1):(0.1-1); And / or, the mass ratio of the magnetic Fe3O4 particles and paraffin is 1:(10-200). And / or, the mass ratio of the magnetic Fe3O4 particles and the amino-containing silane coupling agent is 1: (0.001-0.01); And / or, the mass ratio of the magnetic Fe3O4 particles and the alkyl-containing silane coupling agent is 1: (0.001-0.01); And / or, the mass ratio of the magnetic Fe3O4 particles and 4- (chloromethyl) phenyl trimethoxysilane is 1: (0.001-0.01); And / or, the mass ratio of the magnetic Fe3O4 particles and diethylaminoethyl methacrylate is 1: (0.02~0.1); And / or, the mass ratio of the magnetic Fe3O4 particles and dopamine is 1: (0.001-0.01); And / or, the mass ratio of the magnetic Fe3O4 particles and gallic acid is 1: (0.001-0.01).

9. The production method according to any one of claims 5 to 7, characterized by, The particle size of the magnetic Fe3O4 particles is 100~500nm; And / or, the particle size ratio of the magnetic Fe3O4 particles and the magnetic Fe3O4 particle core is 100: (10~99).

10. The production method according to any one of claims 5 to 7, characterized by, The grafting reaction comprises: dissolving cuprous chloride and 2,2-bipyridine in a solvent, adding the amphiphilic modified particles after modification reaction treatment and diethylaminoethyl methacrylate, stirring and reacting under the conditions of nitrogen atmosphere and 60~100℃.

11. A magnetic multi-functional polymer inorganic hybrid amphiphilic particle, prepared by the preparation method of any one of claims 5-10.

12. The use of the magnetic multi-functional polymer inorganic hybrid amphiphilic particle of any one of claims 1-4 or the magnetic multi-functional polymer inorganic hybrid amphiphilic particle of claim 11 in the treatment of oil-containing wastewater containing partially hydrolyzed polyacrylamide.

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