WO2011088743A1

WO2011088743A1 - Flake material having different properties on its front and back sides and preparing method thereof

Info

Publication number: WO2011088743A1
Application number: PCT/CN2011/000081
Authority: WO
Inventors: 杨振忠; 梁福鑫; 刘继广
Original assignee: 中国科学院化学研究所
Priority date: 2010-01-21
Filing date: 2011-01-19
Publication date: 2011-07-28
Also published as: CN102133802B; CN102133802A

Abstract

Disclosed are flake materials having different properties on its front and back sides (also known as Janus structure) and the preparing method thereof. In the preparing method, hollow sphere of non-organic, organic and non-organic/organic composite material is formed by materializing the oil-water boundary of emulsion, that is, by means of chemical reaction or physical absorption occurred at the interface between disperse phase and continuous phase of the emulsion, so as to prepare inner and outer surface structure of a spherical shell or construct different micro hollow spheres. Said flakes with Janus structure can then be obtained by cracking. A widely adaptive method for massive preparing the flakes with Janus structure is also provided. The flake material of this invention is of great practical value in many fields due to its different composition and properties on the front and back sides.

Description

Sheet material having different properties on front and back surfaces and preparation method thereof

The invention belongs to the technical field of materials, and relates to a sheet material having different properties on the front and back surfaces and a preparation method thereof.

Background technique

Controllable preparation with special microstructured materials has always been an important part of new material research. Since 1991, when De Gennes first used Janus to express the different chemical properties of the surface of inorganic particles, the study of microscopic particles with dual properties on the surface has become a research hotspot in the field of special microstructure materials. Micro- or nano-particles (Janus) with dual properties (hydrophilic/hydrophobic) on the surface impart different or even opposite properties (polar/non-polar, positive/negative charge, etc.) to micro or nano particles. The Janus sheet material with different properties on the reverse surface will provide an effective way to solve the bottleneck of the application of micro-nano materials, which is functional and dispersive of nano-materials. More importantly, it will produce new properties and play an important role in promoting the development of new materials. effect. The development of a dual-integrated particle (Janus) has become a hot topic in recent years.

As early as a century ago, Pickering discovered that solid particles have a stabilizing oil/water emulsion [S. U.

Pickering. J. Chem. Soc. 1907, 91, 2001-2021.], such an emulsion is referred to as a Pickering emulsion. Unlike the emulsifying mechanism of traditional surfactants and polymer emulsifiers, although solid particles do not reduce the interfacial tension [E. Vignati, R. Piazza, TP Lockhart. Langmuir 2003, 19, 6650-6656.], the solid particles have High emulsifying ability and excellent stability of the Pickering emulsion, which is related to the type and size of the particles [BP Binks, S. 0. Lumsdon. Langmuir 2001, 17, 4540-4547]. If a part of the surface of the solid particles can be made hydrophilic while the other part is simultaneously lipophilic, the Pickering property of the solid particles can be combined with the ability to reduce the surface tension, which greatly enhances the emulsifying ability and emulsion stability. In the 1990s, people began to study micro- or nano-particles (Janus) with dual properties (hydrophilic/hydrophobic) on the surface. The results show that Janus particles can better reduce surface tension at the oil-water interface compared to Pickering particles [BP Binks, PDI Fletcher. Langmuir 2001, 17, 4708-4710], playing a better emulsification [N. Glaser, DJ Adams, A. Boker, G. Krausch. Langmuir 2006, 22, 5227-5229.].

On the basis of Janus granules, in recent years, attention has been paid to sheet-like structural materials having different properties (Janus) on the front and back surfaces. This is because the spherical particles have spherical symmetry, and the Janus structure sheet material will exhibit significant anisotropy, which is easy to orient, and can play multiple synergistic effects, such as enhancement, reflected light and heat radiation, and improved gas barrier properties. Etc., therefore, it has potential application prospects in oil-water emulsifiers, surfactants, foam stabilizers, wetness, anti-fog materials, barrier materials and the like. For example, the Janus structure sheet material is blended with two polymers which are compatible with the materials on both sides of the sheet in a certain processing mode, and the inorganic material is obtained. Imitation shell structure or imitation fish scale structure alternately organic layered [ZY Tang, NA Kotov, S. Magonov, B. Ozturk. Nature mater, 2003, 2, 413-418; P. Podsiadlo, AK Kaushik and NA Kotov Science, 2007, 318, 80-83; LJ Bonderer, AR Studart, LJ Gauckler. Science, 2008, 319, 1069-1073; E. Munch, ME Launey and RO Ritchie. Science, 2008, 322, 1516-1520], and this layered hybrid structural material not only improves the mechanical properties of the material, but also alternates the hybridization of the two organic layers into a material. Functionalization provides a wider range of spaces, such as the choice of hydrophobic and oleophobic organic materials to provide a layered material with high barrier properties. Such materials, which can improve the mechanical properties of materials (such as strengthening and toughening) and material functionalization (such as barrier properties), will play an important role in the controllable preparation of high-strength, high-toughness biomimetic materials and noise-reducing damping materials.

At present, the relevant research is in its infancy, and there are few reports. Existing preparation methods [JR Link, MJ Sailor. PNAS. 2003, 100, 10607-10610; JR Dorvee, AM Derfus, SN Bhatia, MJ Sailor. Nature Mater. 2004, 3, 896-899] have great limitations Sexuality, in principle, determines that it is difficult to prepare in batches. Although the Janus structural sheet material exhibits unique properties and attractive application prospects, the controllable preparation and mass preparation of the sheet material composition and structure remain unresolved, which is also the biggest bottleneck for its application.

Invention disclosure

It is an object of the present invention to provide a sheet material having different properties on the front and back surfaces and a method of producing the same. The Janus structure sheet material is widely composed and may be composed of an inorganic material or an organic material, or even composed of an inorganic material and an organic material, and the Janus structure sheet material may have a pore structure or may have no pores. structure. The Janus structure sheet material is not only tunable in composition and properties, but also has a controllable microstructure and size. The Janus structure sheet material having different compositions, structures and properties can be designed according to practical application requirements. The Janus structure sheet material has a thickness greater than 5 nm and less than 50 μm _{; and} the Janus structure sheet material has a size greater than 50 nm and less than 500 μm. The composition ratio of the sides of the Janus structure sheet material is adjustable from 1:100 to 100:1. The different surfaces of the Janus structure sheet material have different responses to electricity, magnetism, light, etc., and thus can be used in the material field; the Janus structure sheet material has an emulsification property in an organic, inorganic dispersed phase or a different organic dispersed phase. And the inorganic sheet composite has a different orientation at the interface.

The present invention provides a Janus structure sheet material having different properties on the front and back surfaces, including a substrate and a different material composition on the front and back surfaces of the substrate; wherein the material on the front surface of the substrate is at least one a layer; the material on the reverse surface of the substrate is at least one layer;

The material on the front and back surfaces of the substrate is selected from any one of two types of materials: a material obtained by compounding an inorganic material with an organic chemical group, and an organic material.

In the above-mentioned front and back surface having different properties of the Janus structure sheet material, the inorganic material is selected from the group consisting of Si0 ₂ ,

Ti0 _{_{_2,}} Sn0 _2, Zr0 ₂ and A1 ₂ 0 ₃ at least one; structural formula of the organic chemical groups are RC _n H _2n, where, n = an integer of 0~ 121, R is - OH, - H ₂ , HS-, - SCN, - HCO H ₂ , CI-, H ₂ (CH ₂ ) ₂ H-, (CH ₃ ) ₂ -C(Br)-C(0)- H -, -S0 ₃ -Ph-SOCl ₂ , -Ph-S0 ₃ , 2, 3-epoxypropoxy, methacryloyloxy, (CH ₂ ) ₃ -S _x -, -(CH ₂ ) _n CH ₃ , CH ₂ =CH- or Ph- _;

In the (CH ₂ ) ₃ -S _X -, an integer of x = 1 to 4; in the -(CH ₂ ) _n CH ₃ , an integer of n = 0 to 127; the organic material is selected from the group consisting of urea-formaldehyde resins, Melamine resin, polyacrylonitrile, epoxy resin, phenolic resin, polyamide, polyurea, polysulfonamide, polyurethane, polyester, polyoxypropylene, polydimethylsilane, polyisobutylene polystyrene, polybutadiene , polyisoprene, gum arabic, sodium alginate, agar, sodium polyphosphate, sodium polysilicate, Carboxymethylcellulose, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolysate of ethylene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene methyl ether-maleic anhydride copolymer a sodium salt hydrolyzate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid copolymerized with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile And the resulting copolymer, polyvinylbenzene sulfonic acid and polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin or casein recombination reaction to form a polymer and sodium polyvinylbenzene sulfonate and polyvinylpyridin A polymer formed by re-coagulation of bromo, polyvinylpyrrolidone, gelatin or casein. In the present invention, the copolymer of acrylic acid or methacrylic acid and styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile refers specifically to Any of the following copolymers: a copolymer of acrylic acid as a comonomer copolymerized with any of the following comonomers: styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, Copolymers of isobutylene, acrylate, methacrylate and acrylonitrile; or methacrylic acid as a comonomer copolymerized with any of the following comonomers: styrene, ethylene, vinyl alcohol, vinyl acetate , methacrylamide, isobutylene, acrylate, methacrylate and acrylonitrile. The polymer formed by the polycondensation reaction of the polyvinylbenzenesulfonic acid with polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin or casein specifically refers to any one of the following copolymers: polyvinylbenzene A polymer formed by a re-coagulation reaction of a sulfonic acid with any of the following polymers: polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin, and casein. A polymer formed by a polycondensation reaction of sodium polyvinylbenzenesulfonate with any of the following polymers: polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin, and casein.

The above-mentioned front and back surfaces have different properties of the Janus structure sheet material, the thickness is 5 ηηη - 50 μιη, and the length and width are both 50 ηιη - 500 μιη _; the material on the front surface of the substrate and the bottom surface of the substrate are The weight ratio of the material on the substrate is 1:100-100:1; the Janus structure sheet material having different properties on the front and back surfaces has a porous structure; the porous structure has a pore diameter of 1 to 50 nm.

The method for preparing the above-mentioned front and back surfaces having different properties of the sheet material is obtained by materializing the emulsion oil-water interface, that is, by chemical reaction or physical adsorption at the interface between the discontinuous phase droplets and the continuous phase of the emulsion. The method forms a layer of inorganic material, organic material and inorganic and organic composite material, and the spherical shell layer may be continuous or discontinuous. For continuous shells, they can be ground into pieces. The size of the fragments can be achieved by controlling the grinding process. The thickness of the fragments can be achieved by controlling the concentration of the reactants. For non-continuous shells, the shell can be used directly as a shell. The above-mentioned sheet material is used, and it can be further used for grinding. The thickness and size of the sheet are related to conditions such as the concentration of the reactant.

The preparation process of the Janus structure sheet material having the dual properties described above may be prepared in a one-step process or a multi-step process. The multi-step preparation method refers to further reacting or depositing other substances on the inner surface, or the outer surface, or the inner and outer surfaces of the shell layer after forming the primary shell layer, thereby obtaining a sheet-like material having different inner and outer surface properties. The following describes in detail various methods 1 to 6 of the present invention for preparing Janus structure sheet materials having different properties on the front and back surfaces:

The method 1 is as follows: 1) or step Γ):

Step 1): dispersing a dispersed phase composed of a dispersed phase reactant, a coupling agent and a non-polar solvent under an action of an emulsifier in a continuous phase composed of a continuous phase reactant and a polar solvent to form an emulsion. Under the condition of pH 2-10, an acid or a base is added, and the reactant dissolved in the continuous phase and the dispersed phase is dispersed in the dispersion. The phase reacts with the interface of the continuous phase to directly form a Janus structure sheet material having different properties on the front and back surfaces; wherein the viscosity of the non-polar solvent in the dispersed phase is lower than that in the continuous phase a viscosity of the polar solvent, a volume ratio of the dispersed phase to the continuous phase is less than 5 and more than 0.5, and a reaction temperature is not lower than a melting point of the non-polar solvent and the polar solvent, and is not higher than a boiling point of the non-polar solvent and the polar solvent;

Step Γ): dispersing a dispersed phase composed of a dispersed phase reactant, a coupling agent and a non-polar solvent under an action of an emulsifier in a continuous phase composed of a continuous phase reactant and a polar solvent to form an emulsion. An acid or a base is added under the condition of a pH of 2-10, and the reactant dissolved in the continuous phase and the dispersed phase reacts at the interface of the dispersed phase and the continuous phase, on the surface of the dispersed phase droplet Forming a core-shell structure product having a continuous shell layer of a Janus structure, removing the core in the core-shell structure product having the continuous shell layer of the Janus structure, and pulverizing to obtain a Janus structure sheet material having different properties on the front and back surfaces; The viscosity of the non-polar solvent in the dispersed phase is higher than the viscosity of the polar solvent in the continuous phase, and the volume ratio of the dispersed phase to the continuous phase is greater than 0 and less than 5, and the temperature of the reaction is not Lower than the melting point of the non-polar solvent and the polar solvent, and not higher than the boiling points of the non-polar solvent and the polar solvent;

The method 2 includes the following steps:

The ABC triblock copolymer is placed in an emulsion, and the A chain segment and the C segment of the ABC triblock copolymer are respectively distributed toward the aqueous phase and the oil phase under the induction of the dispersed phase and the continuous phase solvent, in the ultraviolet Under the condition of light irradiation or temperature of 50-100 ° C, the B segment in the ABC triblock copolymer undergoes in-situ polymerization at the interface of the emulsion, and the B segment is obtained as the intermediate layer of the shell, A a hollow microsphere having a Janus structural shell layer on both sides of the middle layer of the shell layer respectively, and pulverizing to obtain a Janus structure sheet material having different properties on the front and back surfaces;

The method 3 includes the following steps 1) to 2):

Wherein the step 1) is any one of the following steps a) to b):

Step a): dissolving the radical polymerization monomer dissolved in the non-polar solvent in a non-polar solvent under the action of an emulsifier as a dispersed phase dispersed in the pole of the monomer or prepolymer in which the polycondensation reaction is dissolved Forming an emulsion in a continuous phase composed of a solvent, the initiator being dissolved in the dispersed phase solvent or the continuous phase solvent;

Step b): Dispersing a dispersed phase composed of a polar solvent in which a polycondensation reaction monomer or a prepolymer is dissolved in a non-polar solvent-soluble radical polymerization monomer under the action of an emulsifier Forming an emulsion in the continuity of the polar solvent, the initiator being dissolved in the phase of the dispersed phase solvent or the continuous phase solvent;

Step 2): if the decomposition temperature of the initiator is lower than the temperature of the polycondensation reaction, the radical polymerization reaction monomer is first subjected to radical polymerization to obtain a primary shell layer, and then the unpolymerized polycondensation sheet is initiated. The body or prepolymer undergoes a polycondensation reaction outside the primary shell layer to form hollow microspheres having a Janus structure shell layer, and after pulverization, a Janus structure sheet material having different properties on the front and back surfaces is obtained; if the initiator is decomposed When the temperature is higher than the temperature of the polycondensation reaction, the monomer or prepolymer which initiates the polycondensation reaction is subjected to a polycondensation reaction to obtain a primary shell layer; and the unrepolymerized radical reactive monomer is further induced in the primary shell layer. A radical polymerization reaction occurs on the inner side to form hollow microspheres having a Janus structural shell layer, and after pulverization, a Janus structure sheet material having different properties on the front and back surfaces is obtained.

The method 4 includes the following steps 1) to 2): Wherein the step 1) is any one of the following steps a) to (f): Step a): dissolving the inorganic reactant in a non-polar solvent as a dispersed phase under the action of an emulsifier Forming an emulsion in a continuous phase composed of a polar solvent in which a monomer or prepolymer of a polycondensation reaction is dissolved;

Step b): dispersing a polar solvent in which the polycondensation reaction monomer or prepolymer is dissolved as a dispersed phase in a continuous phase composed of a nonpolar solvent in which an inorganic reactant is dissolved, by an emulsifier Emulsion

Step c): dissolving the inorganic reactant in a non-polar solvent under the action of an emulsifier as a dispersed phase dispersed in a radical polymerization polymerization of a radically polymerizable monomer dissolved in a polar solvent and dissolved in a polar solvent Forming an emulsion in a continuous phase composed of a solvent and a polar solvent;

Step d): Dispersing a dispersed phase composed of a radical polymerizable monomer dissolved in a polar solvent, a radical polymerization initiator dissolved in a polar solvent, and a polar solvent in the dissolved inorganic reactant under the action of an emulsifier Forming an emulsion in a continuous phase composed of a non-polar solvent;

Step e): dissolving the inorganic reactant, the radical polymerizable monomer dissolved in the non-polar solvent, and the radical polymerization initiator dissolved in the non-polar solvent in a non-polar solvent as a dispersion under the action of an emulsifier The phase is dispersed in a continuous phase composed of a polar solvent to form an emulsion;

Step 0: Dispersing a polar solvent as a dispersed phase under the action of an emulsifier, radical polymerization of a radically polymerizable monomer dissolved in an inorganic reactant, dissolved in a nonpolar solvent, and dissolved in a nonpolar solvent Forming an emulsion in a continuous phase composed of a non-polar solvent of an initiator;

Step 2): first, the inorganic reactant is subjected to a sol-gel reaction at the interface between the dispersed phase and the continuous phase to obtain a primary shell layer, and then the monomer or prepolymer of the polycondensation reaction which is not polymerized is in the primary shell. A polycondensation reaction occurs on the outer side of the layer to form hollow microspheres having a Janus structural shell layer, and after pulverization, a Janus structure sheet material having different properties on the front and back surfaces is obtained.

The method 5 includes the following steps 1) to 3):

Wherein the step 1) is any one of the following steps a) to d):

Step a): dispersing the dispersed phase solvent in the continuous phase solvent to form an emulsion under the action of an emulsifier, adding a monomer or a resin prepolymer dissolved in the continuous phase solvent to carry out a polycondensation reaction, in the dispersed phase and Forming a water-insoluble polycondensate of a crosslinked three-dimensional network structure at a continuous phase interface, that is, forming a primary shell layer;

Step b): dispersing the dispersed phase reactant in the solvent of the dispersed phase in the solvent of the continuous phase to form an emulsion under the action of the emulsifier, adding a continuous phase reactant dissolved in the solvent of the continuous phase, the dispersed phase The reactant and the continuous phase reactant undergo polycondensation or polyaddition reaction at the interface between the dispersed phase and the continuous phase to form a primary shell layer; Step c): Dissolving the dispersed phase radical polymerizable monomer under the action of an emulsifier Dispersing a solvent in a dispersion phase to form an emulsion in a continuous phase solvent, the initiator is dissolved in a dispersed phase and/or a continuous phase, and the initiator initiates radical polymerization of the dispersed phase radical polymerization monomer to form a polymer. The polymer is phase-separated and deposited at the interface between the dispersed phase and the continuous phase to form a crosslinked three-dimensional network polymer shell layer, that is, a primary shell layer;

Step d): dispersing the dispersed phase organic solvent in which the dispersed phase polymer is dissolved in the continuous phase solvent to form an emulsion under the action of an emulsifier, wherein the continuous phase solvent is dissolved in the opposite phase to the dispersed phase polymer a charge continuous phase polymer, the dispersed phase polymer and the continuous phase polymer electrostatically attract at the interface between the dispersed phase and the continuous phase to form a primary shell layer; The step 2) is the following steps a') or b') _:

Step a') _: adding a prepolymer of a monomer or a resin dissolved in the continuous phase solvent to the reaction system of the step 1) to carry out a polycondensation reaction, forming a new shell on the outer side of the primary shell layer a layer forming hollow microspheres having a Janus structural shell;

Step b') _: further adding a polymer having an opposite charge to the polymer obtained in the step 1) to the reaction system of the step 1), so that the polymer obtained in the step 1) is opposite to the one described The charged polymer undergoes electrostatic attraction, forming a new shell layer outside the primary shell layer to form hollow microspheres having a Janus shell layer;

Step 3): pulverizing the hollow microspheres having the Janus structural shell layer obtained in the step 2) to obtain the Janus structure sheet material having different properties on the front and back surfaces;

The method 6 includes the following steps 1) to 2):

Wherein the step 1) is any one of the following steps a) to b):

Step a): dissolving the radical polymerizable monomer dissolved in the non-polar solvent and the radical polymerization initiator dissolved in the non-polar solvent in a non-polar solvent as a dispersed phase by the action of the emulsifier Forming an emulsion in a dispersed phase composed of a radical polymerizable monomer dissolved in a polar solvent, a radical polymerization initiator dissolved in a polar solvent, and a polar solvent;

Step b): dissolving the radical polymerizable monomer dissolved in the polar solvent and the radical polymerization initiator dissolved in the polar solvent in a polar solvent as a dispersed phase by dispersing in the action of the emulsifier Forming an emulsion in a dispersed phase composed of a radical polymerizable monomer of a polar solvent, a radical polymerization initiator dissolved in a non-polar solvent, and a non-polar solvent;

Step 2): The step 1) raising the temperature of the reaction system causes the radical polymerizable monomer dissolved in the polar solvent to be polymerized at the emulsion interface to obtain hollow spheres having different compositions and properties on both sides, crushing or The Janus structure sheet material having different properties on the front and back surfaces is obtained without pulverization.

among them,

In the first method, the structure of the dispersed phase reactant is X _n MR _m , preferably ethyl orthosilicate; wherein M is Si, Ti, Sn, A1 or Zr; X is Na, Mg or K , n is 0, 1 or 2; R is Cl, OS0 ₄ , OCH ₃ , OCH ₂ CH ₃ , OCH(CH ₃ ) ₂ , OCH ₂ CH ₂ CH ₂ CH ₃ or S0 ₄ , m is 1, 2, 3 Or 4; the non-polar solvent is selected from at least one of an aromatic hydrocarbon, a paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, an aliphatic hydrocarbon, and ethyl acetate, preferably toluene; the coupling Agent

(C ₂ H ₅ 0)3-Si-(CH ₂ ) ₃ -S _x -(CH ₂ ) ₃ -Si-(OC ₂ H ₅ ) ₃ or

H _2n -M(R ₂ ) _P (R ₃ ) _2-P; wherein M is Si, Ti, Sn, Zr or Al; m, n, p and x are integers, 0 n 127, preferably n is 0 An integer of -17, 0 m 3, 0^p^2; l ^x^4; R ₂ and R ₃ are each selected from Cl, CH ₃ , OC _x H _2x+1 or OC ₂ H ₄ OCH ₃ ; In OC _x H _2x+1 , x = an integer of 1-20, preferably x is an integer from 1 to 4; the selected from H, fatty alkyl, phenyl, vinyl, amino, CN, HCO H ₂ Cl, H ₂ (CH ₂ ) ₂ H 2, 3-epoxypropoxy, methacryloxy or decyl; the emulsifier is selected from the sodium salt hydrolyzate of styrene-maleic anhydride copolymer, ethylene-ma a sodium salt hydrolyzate of an anhydride copolymer, a sodium salt hydrolyzate of a vinyl methyl ether-maleic anhydride copolymer, a sodium salt hydrolyzate of an isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid and styrene, Copolymerization of ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile Copolymer, polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, OP-5, OP-10, Span20, Span60, Span80, Tween20, Tween60, Tween80, Triton X-100, dodecyl At least one of sodium sulfate, sodium lauryl sulfonate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, and sodium dioctyl sulfonate; the emulsifier The amount is 1% to 20%, specifically 1%-15%, 5-15%, 5-10%, 10-20%, 5%, 8%, 10%, 15% or 20% of the weight of the initial emulsion; The acid is selected from at least one of hydrochloric acid, sulfuric acid and nitric acid, and the base is selected from at least one of sodium hydroxide, potassium hydroxide and ammonia; the dispersed phase reactant and the continuous phase reactant both account for the reaction The percentage of the total weight of the system is greater than 0 and less than 80%, specifically 10-20%, 10-30%, 20-40% 30-60% or 40-50%.

In the method 2, wherein, in the ABC triblock copolymer, the A block is a hydrophilic polymer segment selected from the group consisting of polyoxyethylene, polymaleic anhydride, polymethyl methacrylate and polyacrylic acid. At least one of; B block is a reactive olefin or alkyne polymer segment selected from polyacetylene, polybutadiene or polyisoprene; C block is a hydrophobic polymer segment, selected At least one of polyoxypropylene, polyoxybutylene, polystyrene, polyolefin, and polysiloxane; in the emulsion, the solvent as the dispersed phase and the continuous phase are respectively selected from mutually incompatible polarities a solvent and a non-polar solvent; wherein the non-polar solvent is at least one selected from the group consisting of aromatic hydrocarbons, paraffin wax, n-hexane, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, aliphatic hydrocarbons and ethyl acetate; The polar solvent is at least one selected from the group consisting of water, ethylene glycol, propylene glycol, glycerin, tetrahydrofuran, and N,N-dimethylformamide; and the ultraviolet light irradiation step has a time of 5 to 60 minutes.

In the third method, the monomer or prepolymer of the polycondensation reaction is selected from the group consisting of acrylonitrile, vinyl acetate, urea resin (urea-formaldehyde prepolymer), melamine resin (melamine-formaldehyde prepolymer), phenolic Resin (phenol-formaldehyde prepolymer), melamine modified urea-formaldehyde resin, polyethylene glycol modified urea-formaldehyde resin, polypropylene glycol modified urea-formaldehyde resin, polyethylene glycol modified melamine resin with molecular weight of 200-2000, molecular weight 200-2000 polypropylene glycol modified melamine resin, polyvinyl alcohol modified urea formaldehyde resin, resorcin modified urea resin, hydroquinone modified urea formaldehyde resin, phenol modified urea resin, phenol and melamine copolymerization Modified urea-formaldehyde resin, polyvinyl alcohol and melamine copolymer modified urea-formaldehyde resin, resorcinol and melamine copolymer modified urea-formaldehyde resin, resorcinol and polyvinyl alcohol copolymer modified urea-formaldehyde resin, resorcinol modified melamine resin And at least one of a polyvinyl alcohol-modified melamine resin; the initiator is selected from the group consisting of lithium persulfate-triethylaluminum, lithium persulfate-triethylboron, lithium persulfate-triethyllead, Hydrogen peroxide-ferrous salt, persulphate-sodium bisulfite, dibenzoyl peroxide, even diisobutyronitrile, persulphate, dicumyl peroxide, cumene hydroperoxide and tert-butyl iso At least one of propylbenzene; the emulsifier is selected from the group consisting of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer, a sodium salt hydrolyzate of an ethylene-maleic anhydride copolymer, and a vinyl methyl ether-butylene a sodium salt hydrolyzate of an acid anhydride copolymer, a sodium salt hydrolyzate of an isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, Copolymer obtained by copolymerization of methacrylate or acrylonitrile, polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, OP-5, OP-10, Span20, Span60, Span80, Tween20, Tween60, Tween80, Triton At least X-100, sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, and sodium dioctyl sulfonate One kind; the emulsifier is used in an amount of 1% to 20% by weight of the initial emulsion Specifically, it is 1%-15%, 5-15%, 5-10%, 10-20%, 5%, 8%, 10%, 15% or 20%; the non-polar solvent is selected from the group consisting of aromatic hydrocarbons, At least one of paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, aliphatic hydrocarbons and ethyl acetate, preferably octadecane; The radical polymerization monomer of the non-polar solvent is selected from the group consisting of styrene, butadiene, isoprene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate, Isobutyl methacrylate, ethyl cinnamate acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, propylene oxide, vinyl butyl ester, isobutylene or vinyl acetate, divinyl At least one of benzene, ethylene glycol dimethacrylate and diallyl terephthalate; the polar solvent is selected from the group consisting of water, ethylene glycol, propylene glycol, glycerol, tetrahydrofuran and N, N At least one of dimethylformamide; a molar ratio of the monomer of the radical polymerization reaction to the initiator: 10: 1-1000: 1; preferably 50: 1: 500: 1; The temperature of the radical polymerization reaction is 20-90 ° C, the reaction time is 0.5-72 hours, preferably 2-16 hours; the temperature of the polycondensation reaction is 60-90 ° C, and the reaction time is 0.5-72 hours. , preferably 2-16 hours;

In the fourth method, the inorganic reactant has a structural formula of X _n MR _m: wherein M is Si, Ti,

Sn, A1 or Zr; X is Na, Mg or K, n is 0, 1 or 2; R is Cl, OS0 ₄ , OCH ₃ , OCH ₂ CH ₃ , OCH(CH ₃ ) ₂ , OCH ₂ CH ₂ CH ₂ CH ₃ or S0 ₄ , m is 1, 2, 3 or 4; or

(C ₂ H ₅ 0) ₃ -Si-(CH ₂ ) ₃ -S _x -(CH ₂ ) ₃ -Si-(OC ₂ H ₅ ) ₃ ,

H _2n -M(R ₂ ) _P (R ₃ ) _2-P: wherein M is Si, Ti, Sn, Zr or Al; m, n, p and x are integers, 0 n 127, preferably n is 0 An integer of -17, 0 ^m^3 , 0^p^2; l ^x^4 _; R ₂ and R ₃ are all selected from Cl, CH ₃ , OC _x H _2x+1 or OC ₂ H ₄ OCH ₃ One or more of the above; in the OC _x H _2x+1 , an integer of x = 1-20, preferably X is an integer of 1-4; the selected from the group consisting of H, a fatty alkyl group, a phenyl group, a vinyl group, Amino, CN, NHCONH ₂ , Cl, NH ₂ (CH ₂ ) ₂ NH, 2, 3-epoxypropoxy, methacryloxy or decyl; the monomer or prepolymer of the polycondensation reaction is selected from Urea-formaldehyde (urea-formaldehyde prepolymer), melamine resin (melamine-formaldehyde prepolymer), phenolic resin (phenol-formaldehyde prepolymer), melamine modified urea-formaldehyde resin, polyethylene glycol modified urea-formaldehyde resin , polypropylene glycol modified urea-formaldehyde resin, polyethylene glycol modified melamine resin with molecular weight of 200~2000, polypropylene glycol modified melamine resin with molecular weight of 200~2000, polyvinyl alcohol modified urea-formaldehyde resin, m-benzene Diphenol modified urea-formaldehyde resin, hydroquinone modified urea-formaldehyde tree , phenol modified urea-formaldehyde resin, phenol and melamine copolymer modified urea-formaldehyde resin, polyvinyl alcohol and melamine copolymer modified urea-formaldehyde resin, resorcinol and melamine copolymer modified urea-formaldehyde resin, resorcinol and polyvinyl alcohol copolymerization modified urea-formaldehyde At least one of a resin, a resorcinol-modified melamine resin, and a polyvinyl alcohol-modified melamine resin; the radically polymerizable monomer dissolved in the non-polar solvent is selected from the group consisting of styrene, butadiene, and Pentadiene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, methacrylic acid, ethyl cinnamate, methyl acrylate, Ethyl acrylate, butyl acrylate, tert-butyl acrylate, propylene oxide, dimethyl silane, vinyl butyl acrylate, isobutylene or vinyl acetate, divinyl benzene, ethylene glycol dimethacrylate and p-phenylene At least one of diallyl formate; the radical polymerization initiator dissolved in the non-polar solvent is selected from the group consisting of azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, and Hydrogen cumene hydroperoxide, dodecyl peroxide, isopropyl diperoxide and isopropyl ester, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide / N, N-dimethylaniline redox initiation system, At least one of a naphthate and a dibenzoyl peroxide redox initiating system; the non-polar solvent is selected from the group consisting of aromatic hydrocarbons, paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, and aliphatic hydrocarbons And at least one of ethyl acetate; the radically polymerizable monomer dissolved in the polar solvent is at least one selected from the group consisting of acrylamide, acrylic acid, methacrylic acid, vinyl alcohol, and N-methylol acrylamide; The radical polymerization initiator in the polar solvent is selected from the group consisting of potassium persulfate, ammonium persulfate, persulfate and thiosulfate or sulfite redox initiation system, persulfate At least one of redox initiation systems consisting of a fatty amine or a fatty diamine; the polar solvent being selected from the group consisting of water, ethylene glycol, propylene glycol, glycerol, tetrahydrofuran, and N, N-dimethylformamide At least one of the emulsifiers is selected from the group consisting of sodium salt hydrolysates of styrene-maleic anhydride copolymers, sodium salt hydrolysates of ethylene-maleic anhydride copolymers, and ethylene methyl ether-maleic anhydride copolymers. Sodium salt hydrolysate, sodium salt hydrolysate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate Or a copolymer of acrylonitrile copolymerized, polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, OP-5, OP-10, Span20, Span60, Span80, Tween20, Tween60, Tween80, Triton X-100, At least one of sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, and sodium dioctyl sulfonate; The emulsifier is used in an amount of 1% by weight of the initial emulsion. 20%, specifically 1%-15%, 5-15%, 5-10%, 10-20%, 5%, 8%, 10%, 15% or 20%; in the polycondensation reaction, the temperature is 60 -90 ° C, preferably 70 ° C, the reaction time is 0.5-72 hours, preferably 2-16 hours; the molar ratio of the monomer of the radical polymerization reaction to the initiator is 10: 1-1000 : 1; preferably 50: 1: 500: 1; the temperature of the radical polymerization is 20-90 ° C, and the reaction time is 0.5-72 hours, preferably 2-16 hours.

In the method 5, the prepolymer of the monomer or the resin dissolved in the continuous phase solvent in the step 1) a) is selected from the group consisting of acrylonitrile, vinyl acetate, urea formaldehyde resin (urea-formaldehyde prepolymer), Melamine resin (melamine-formaldehyde prepolymer), phenolic resin (phenol-formaldehyde prepolymer), melamine modified urea-formaldehyde resin, polyethylene glycol modified urea-formaldehyde resin, polypropylene glycol modified urea-formaldehyde resin, molecular weight 200~2000 Polyethylene glycol modified melamine resin, polypropylene glycol modified melamine resin with molecular weight of 200~2000, polyvinyl alcohol modified urea formaldehyde resin, resorcin modified urea resin, hydroquinone modification Urea-formaldehyde resin, phenol-modified urea-formaldehyde resin, phenol and melamine copolymerization modified urea-formaldehyde resin, polyvinyl alcohol and melamine copolymerization modified urea-formaldehyde resin, resorcinol and melamine copolymerization modified urea-formaldehyde resin, resorcinol and polyvinyl alcohol copolymerization At least one of a urea resin, a resorcinol modified melamine resin, and a polyvinyl alcohol modified melamine resin;

The continuous phase reactant and the dispersed phase reactant in step 1) b) are each selected from the group consisting of diamines, polyamines, glycols, polyols, dihydric phenols, polyhydric phenols, dibasic acid chlorides, polyacid chlorides, and binary At least one of a sulfonyl chloride, a polysulfonyl chloride, a diisocyanate, a polyisocyanate, a bischloroformate, an epoxy resin prepolymer, and an organosiloxane prepolymer;

The dispersed phase free radical polymerizable monomer in the step 1) c) is selected from the group consisting of styrene, butadiene, isoprene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid. Tert-butyl ester, isobutyl methacrylate, ethyl cinnamic acid acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, propylene oxide, dimethyl silane, vinyl butyl ester At least one of isobutylene or vinyl acetate, divinylbenzene, ethylene glycol dimethacrylate and diallyl terephthalate;

The dispersed phase polymer and the continuous phase polymer forming the primary shell layer in step 1) d) are each selected from the group consisting of polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin, casein, gum arabic, sodium alginate, agar, Sodium polyphosphate, sodium polysilicate, carboxymethyl cellulose, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene-maleic anhydride copolymer, vinyl methyl ether-butylene Sodium salt hydrolysate of dianhydride copolymer, sodium salt hydrolyzate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate , methacrylate or acrylonitrile copolymerization At least one of a copolymer, polyvinylbenzenesulfonic acid (sodium), polyvinylpyridinium bromide, and polyvinylpyrrolidone;

The monomer or resin prepolymer dissolved in the continuous phase solvent in step 2) a') is selected from the group consisting of acrylonitrile, vinyl acetate, urea formaldehyde resin (urea-formaldehyde prepolymer), melamine resin (melamine). Formaldehyde prepolymer), phenolic resin (phenol-formaldehyde prepolymer), melamine modified urea-formaldehyde resin, polyethylene glycol modified urea-formaldehyde resin, polypropylene glycol modified urea-formaldehyde resin, polyethylene glycol modified molecular weight of 200~ 2000 melamine resin, polypropylene glycol modified melamine resin with molecular weight of 200~2000, polyvinyl alcohol modified urea-formaldehyde resin, resorcinol modified urea-formaldehyde resin, hydroquinone modified urea-formaldehyde resin, phenol modification Urea-formaldehyde resin, phenol and melamine copolymerization modified urea-formaldehyde resin, polyvinyl alcohol and melamine copolymerization modified urea-formaldehyde resin, resorcinol and melamine copolymerization modified urea-formaldehyde resin, resorcinol and polyvinyl alcohol copolymerization modified urea-formaldehyde resin, m-benzene At least one of a diphenol-modified melamine resin and a polyvinyl alcohol-modified melamine resin;

The polymer having opposite charge to the polymer obtained in the step 2) b) is selected from the group consisting of polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin, casein, gum arabic, sodium alginate, agar , sodium polyphosphate, sodium polysilicate, carboxymethyl cellulose, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene-maleic anhydride copolymer, vinyl methyl ether-cis-butane Sodium salt hydrolysate of enedic anhydride copolymer, sodium salt hydrolysate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylic acid a copolymer obtained by copolymerization of an ester, a methacrylate or an acrylonitrile, at least one of polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, polyvinylpyridinium bromide and polyvinylpyrrolidone;

In the polycondensation reaction in the step 1) a), the temperature is 60-90 ° C, preferably 70 ° C, the time is 0.5-72 hours, preferably 2-16 hours, the pH is 2-10, and the stirring speed is 50- 16000r/min, preferably 150-12000r/min; in the polycondensation or polyaddition reaction in step 1) b), the molar ratio of the reactive phase reactant to the continuous phase reactant reactive functional group is 1:1; Is 60-90 ° C, preferably 70 ° C, time is 0.5-72 hours, preferably 2-16 hours, stirring speed is 50-16000r / min, preferably 150-12000r / min;

In the radical polymerization reaction in the step 1) c), the molar fraction ratio of the dispersed phase radical polymerizable monomer to the initiator is 10: 1-1000: 1; preferably 50: 1-500: 1 , the temperature is 20-90 ° C, the time is 0.5-72 hours, preferably 2-16 hours;

Step 1) The pH of the reaction system described in d) is 2-10;

In the polycondensation reaction in the step 2) a'), the temperature is 60-90 ° C, preferably 70 ° C, the time is 0.5-72 hours, preferably 2-16 hours, the pH is 2-10, and the stirring speed is 50. - 16000r / min, preferably 150-12000r / min; the pH of the reaction system described in step 2) b') is 2-10;

The emulsifier is selected from the group consisting of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer, a sodium salt hydrolyzate of an ethylene-maleic anhydride copolymer, and a sodium salt hydrolyzate of a vinyl methyl ether-maleic anhydride copolymer. a sodium salt hydrolyzate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid copolymerized with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile Copolymer, polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, OP-5, OP-10, Span20, Span60, Span80, Tween20, Tween60, Tween80, Triton X-100, dodecyl At least one of sodium sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, and sodium dioctyl sulfonate; the emulsifier The amount is from 1% to 20% by weight of the initial emulsion, specifically 1%-15%, 5-15%, 5-10%, 10-20%, 5%, 8%, 10%, 15% or 20% ;

The dispersed phase solvent is at least one selected from the group consisting of aromatic hydrocarbons, paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, aliphatic hydrocarbons and ethyl acetate;

The continuous phase solvent is at least one selected from the group consisting of water, ethylene glycol, propylene glycol, glycerin, tetrahydrofuran, and N, N-dimethylformamide.

In the method 6, the radical polymerizable monomer dissolved in the non-polar solvent is selected from the group consisting of styrene, butadiene, isoprene, methyl methacrylate, ethyl methacrylate, and methacrylic acid Ester, tert-butyl methacrylate, isobutyl methacrylate, methacrylic acid, ethyl cinnamate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, propylene oxide, dimethyl At least one of silane, vinyl butyl ester, isobutylene or vinyl acetate, divinyl benzene, ethylene glycol dimethacrylate and diallyl terephthalate; said dissolving in a non-polar solvent The radical polymerization initiator is selected from the group consisting of azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, cumene hydroperoxide, dodecyl peroxide, peroxydicarbonate and isopropyl ester, At least one of dicyclohexyl peroxydicarbonate, dibenzoyl peroxide/N,N-dimethylaniline redox initiation system, naphthate and dibenzoyl peroxide redox initiation system; The non-polar solvent is selected from the group consisting of aromatic hydrocarbons and stones. At least one of carbon tetrachloride, chloroform, cyclohexane, dichloromethane, an aliphatic hydrocarbon, and ethyl acetate; the radically polymerizable monomer dissolved in a polar solvent is selected from the group consisting of acrylamide, hydrazine, hydrazine- At least one of dimethyl bis acrylamide, acrylic acid, methacrylic acid, vinyl alcohol, hydrazine-hydroxymethyl acrylamide; the radical polymerization initiator dissolved in a polar solvent is selected from the group consisting of potassium persulfate and sulfuric acid Iron, ammonium persulfate, a mixture of persulfate and thiosulfate, a mixture of persulfate and sulfite, a mixture of persulfate and fatty amine or a persulfate and fatty diamine At least one of the components of the composition, preferably at least one of potassium persulfate and ferrous sulfate; the polar solvent is selected from the group consisting of water, ethylene glycol, propylene glycol, glycerol, tetrahydrofuran and hydrazine, hydrazine-dimethyl At least one of the formamides is preferably water; the emulsifier is selected from the group consisting of sodium salt hydrolysates of styrene-maleic anhydride copolymers, sodium salt hydrolysates of ethylene-maleic anhydride copolymers, vinyl methyl ethers - Maleic anhydride Sodium salt hydrolysate of polymer, sodium salt hydrolysate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, nail Copolymer obtained by copolymerization of acrylate or acrylonitrile, polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, cesium-5, ΟΡ-10, Span20 Span60, Span80, Tween20, Tween60, Tween80, Triton X- 100, sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide (CTAB) and sodium dioctyl sulfonate At least one; the emulsifier is used in an amount of 1% to 20% by weight of the initial emulsion, specifically 1% to 15%, 5-15%, 5-10%, 10-20%, 5%, 8%, 10%, 15% or 20%; the molar fraction ratio of the radical polymerizable monomer to the radical polymerization initiator is 10: 1-1000: 1; preferably 50: 1: 500: 1; The temperature of the radical polymerization is 20-90 ° C, and the reaction time is 0.5-72 hours, preferably 2-16 hours; the radical polymerizable monomer is Concentration of the solution in the system from 0.01% to 90%, preferably 0.1% to 30%.

In the above method 1 to method 6, the complex coacervation reaction utilizes electrostatic attraction between two or more water-soluble polymer molecules having opposite charges, and the formed agglomerates are phase-separated in the aqueous phase and A method of depositing at the interface and forming a polymer after cross-linking and solidification. In each of the above methods, the thickness of the Janus structure sheet material can be controlled by changing the amount of the reactant. The pulverization method is various commonly used pulverization methods. Can The size of the Janus structure sheet material can be adjusted from 50 nm to 500 μm by controlling the ball mill or colloid mill grinding time and the grinding method, preferably 50 ηηη to 100 μηη. The emulsion includes a type emulsion of a normal phase emulsion, an inverse emulsion, a microemulsion, a reverse phase microemulsion, and the like. The low temperature grinding temperature ranges from 0 °C to 170 °C.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a silica prepared on Example 1 of the present invention having an amine group on one side and a phenyl group on the other side.

Scanning electron micrograph of Janus sheet material.

Figure 2 is a scanning electron micrograph of a Janus sheet material of a silicon dioxide having an epoxy group on one side and a phenyl group on the other side prepared in Example 2 of the present invention.

3 is a photograph showing the emulsification performance of a sheet material of Janus structure having different properties on both sides prepared in Example 3 of the present invention. The left side is a system without a Janus sheet, and the right side is a system emulsified after adding a Janus sheet. .

4 is a scanning electron micrograph of a sheet material of Janus structure having different properties on both sides prepared in Example 3 of the present invention, and the embedded figure is the sulfonated polystyrene pellet adsorbed on the Janus aramid side of Example 3. Scanning electron micrograph of a 30 nm) Janus structure sheet material.

Fig. 5 is a scanning electron micrograph of a porous Janus structure sheet material prepared in Example 4 of the present invention, and the inlaid photograph is a transmission photograph of the porous Janus structure sheet material of Example 4 of the present invention.

Fig. 6 is a transmission electron micrograph of a porous Janus structure sheet material prepared in Example 5 of the present invention. Fig. 7 is a scanning electron micrograph of an organic Janus structure sheet material having an amine group on one side and a pentadecyl group on the other side prepared in Example 6 of the present invention.

Figure 8 is a scanning electron micrograph of a urea-formaldehyde resin/polystyrene Janus sheet material prepared in Example 8 of the present invention.

Figure 9 is a scanning electron micrograph of a silica/melamine resin Janus sheet material prepared in Example 11 of the present invention.

Figure 10 is a scanning electron micrograph of a polystyrene/silica Janus sheet material prepared in Example 14 of the present invention.

Figure 11 is a scanning electron micrograph of a polydivinylbenzene/silica Janus sheet material Janus sheet material prepared in Example 15 of the present invention.

Figure 12 is a scanning electron micrograph of a uric acid/melamine resin Janus sheet material prepared in Example 16 of the present invention.

Figure 13 is a scanning electron micrograph of a polyethylene glycol modified urea-formaldehyde resin/gelatin Janus sheet material prepared in Example 17 of the present invention.

Figure 14 is a scanning electron micrograph of a polyurethane/urea resin Janus sheet material prepared in Example 18 of the present invention.

Figure 15 is a scanning electron micrograph of an epoxy resin/polyvinylpyrrolidone Janus sheet material prepared in Example 19 of the present invention.

Figure 16 is a scanning electron micrograph of a polystyrene/urea resin Janus sheet material prepared in Example 20 of the present invention.

Figure 17 is a scanning of the polydivinylbenzene/gelatin Janus sheet material prepared in Example 21 of the present invention. Electron micrograph.

Figure 18 is a scanning electron micrograph of gelatin / sodium alginate Janus sheet material prepared in Example 22 of the present invention.

Figure 19 is a scanning electron micrograph of a polyacrylamide/polystyrene Janus sheet material prepared in Example 23 of the present invention.

Figure 20 is a scanning electron micrograph of a polymethyl methacrylate/polystyrene layered material modified with a silica sheet material prepared in Example 1 of the present invention.

Figure 21 is a polarizing microscope photograph of the emulsion prepared from the Janus sheet material provided in Example 1. Figure 22 is a photograph of a silica Janus sheet having an amine group on one side and a phenyl group on the other side in the oil-water separation process in Example 1 of the present invention.

The best way to implement the invention

The invention is further illustrated by the following specific examples, but the invention is not limited to the following examples. The concentrations described in the following examples are all mass percent concentrations unless otherwise specified. The compounds described in the following examples are commercially available from commercially available sources unless otherwise stated. Wherein, the ethylene-maleic anhydride copolymer has a weight average molecular weight of 200 to 20,000 in the sodium salt hydrolyzate of the ethylene-maleic anhydride copolymer, and is commercially available from Aldrich as CAS: 31959-78-1, vinyl methyl In the sodium salt hydrolyzate of the ether-maleic anhydride copolymer, the ethylene methyl ether-maleic anhydride copolymer has a weight average molecular weight of 600 to 300,000, which is commercially available from Aldrich, CAS: 25087-06-3. In the sodium salt hydrolysate of isobutylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer can be prepared according to the following literature method: Deng Cuiping, Yan Yincheng, Research on copolymerization of isobutylene-maleic anhydride, Petrochemical, 1990, 11, 739-744, the average weight of the copolymer of acrylic acid or methacrylic acid copolymerized with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile The molecular weight is 500-100,000, which can be purchased directly from commercial sources, or prepared according to the methods in the following literature or books: Chen Jun, Ren Tianrui, Yu Songrui, etc., Acrylic Copolymer Synthesis and dispersion of powders, Journal of Process Engineering, 2009, 6, 1204-1209; Yanrui Xuan, water-soluble polymer, Chemical Industry Press, 1998, pages 179-222.

Example 1. Using Method 1 to prepare a silica with a amide group on one side and a phenyl group on the other side Janus sheet material

Take 10g of reactant tetraethyl orthosilicate, 2g of coupling agent aminopropyltriethoxysilane and lg coupling agent phenyltriethoxysilane to 25g of non-polar solvent toluene, fully mixed as oil phase . 2.5 g of emulsifier sodium lauryl sulfate was added to 50 g of polar solvent water, and the pH was adjusted to 3 with 2 mol/L hydrochloric acid as an aqueous phase; the oil phase was added to the aqueous phase, and high-speed shear emulsification was used. The machine was emulsified by shearing at 100 rpm for 10 min, and the obtained emulsion was transferred to a three-necked flask in a water bath at 70 ° C, and mechanically stirred for 12 hours to discharge, directly obtaining an amine group on one side and a phenyl side on the other side. Different Janus structure sheet materials. An electron micrograph of the material is shown in Figure 1. The material has a thickness of 200-400 nm and a length and a width of 2-10 μm _; the weight ratio of the material on the front surface of the substrate to the aminopropyl group and the material on the opposite surface of the substrate (which is a phenyl group) is 2: 1; The material has a porous structure with a pore diameter of 5-7 nm.

The Janus structure sheet material having the amine side on one side and the other side of the phenyl group on the other side can be used to emulsify paraffin wax (melting point 52-54 ° C) / water system to prepare the preparation. Paraffin The continuous phase, the water is the emulsion of the continuous phase, the specific method is as follows: 20 g of paraffin is heated to 70 ° C to melt, 0.5 g of the Janus piece with an amine group on one side and a phenyl group on the other side The material was added to 50 mL of water at 70 ° C and dispersed uniformly. The melted paraffin is added to the above aqueous solution, and is strongly sheared at 12000 r/min for 5 min to obtain a paraffin wax as a discontinuous phase, and water is a continuous phase emulsion. FIG. 21 is a polarizing microscope photograph of the emulsion, and the Janus sheet is seen from the figure. The material acts as an emulsifier.

Using this example, a sheet of Janus structure having an amine group on one side and a different side on the other side of the phenyl group can be used to induce the preparation of polymethyl methacrylate (PMMA) / polystyrene (PS). The layered material is as follows: 180 g of polymethyl methacrylate (weight average molecular weight of 80,000 to 150,000), 180 g of polystyrene (weight average molecular weight of 100,000 to 200,000), and 40 g of the obtained sheet prepared in this example The material was added to a twin-screw mixer, and kneaded at 50 ° C for 10 min at 210 ° C, and then extruded to obtain a silica sheet-like material modified polymethyl methacrylate / polystyrene. Layered material. The layered material structure is a polymethyl methacrylate / silica / polystyrene / silica alternating layer structure. An electron micrograph of the material is shown in Figure 20.

The Janus structure sheet material with the amine side on one side and the other side of the phenyl group on the other side can be used for the separation of oil and water by the method. The specific method is as follows: Take 0.2g of the preparation sheet prepared in this example. The material was emulsified into 10 ml of toluene and 5 mL of water to form a stable emulsion. The aqueous phase was dyed orange with methyl orange to distinguish the oil-water two phases. The continuous phase water was able to flow out through the glass sand, and the toluene was prepared in this example. The droplet formed under the action of the stabilization, due to its large size, cannot flow through the pores at the bottom of the glass sand, still in the separation column, and then the glass jar is used to smash the Janus sheet stable oil droplets in the separation column, and the toluene can pass through the glass. The bottom of the sand flows out, and the Janus piece remains in the separation column, thereby achieving separation of the oil-water two phases of the emulsion and recovery of the Janus piece. The results obtained are shown in Figure 22. The oil-water two-phase separation of the Janus stable emulsion makes the Janus tablet more advantageous than molecular emulsifiers in tertiary oil recovery, wastewater treatment, and splash cleaning.

Example 2 Method 1 Preparation of silica with epoxy group and phenyl group Janus sheet material

1) 6g of reactant tetraethyl orthosilicate, 0.5g of coupling agent epoxypropyltrimethoxysilane, 0.5g of coupling agent phenyltriethoxysilane, 6g of emulsifier Span80 and lg emulsifier Tween80 are added to 60 g of non-polar solvent toluene was mixed well and used as an oil phase. 50 g of polar solvent water was taken as the aqueous phase.

2) Adding the aqueous phase to the oil phase, using a high-speed shear emulsifier to shear emulsification at 100 rpm for 2 min, transferring the obtained inverse emulsion to a three-necked flask in a water bath of 80 ° C, and mechanically stirring the reaction for 24 hours to directly obtain The one side has an epoxy group, and the other side has a Janus structure sheet material having different properties on both sides of the phenyl group. An electron micrograph of the material is shown in Figure 2. The material has a thickness of 100-300 and a width of l-ΙΟμιη; the weight ratio of the material (which is an epoxy group) on the front surface of the substrate to the material (which is a phenyl group) on the reverse surface of the substrate is 1 : 1

Example 3 Method 1 Preparation of a silica with an amine group on one side and a phenyl group on the other side Janus sheet material

1) Take 5g of reactant tetraethyl orthosilicate, lg coupling agent aminotrimethoxysilane and lg coupling agent phenyltrimethoxysilane to 25g of 70 ° C non-polar solvent paraffin (melting point 52-54 ° In C), it was thoroughly mixed at 70 ° C for 4 hours as an oil phase. Taking 15 _§ 10% of the sodium salt hydrolyzate solution of the styrene-maleic anhydride copolymer As an emulsifier, it was added to 75 g of polar solvent water, and its pH was adjusted to 2 with 2 mol/L hydrochloric acid, and heated to 70 V as an aqueous phase.

2) The oil phase was added to the water phase, and the emulsion was shear emulsified at 100 ° C for 10 min at 70 ° C using a high-speed shear emulsifier. The obtained emulsion was transferred to a three-necked flask in a 70 ° C water bath, and mechanically stirred for 12 hours. material. The emulsion was diluted with water, ground by a colloid mill, and washed with water and hexane repeatedly to remove the surfactant and paraffin, thereby obtaining an amine group on one side and a phenyl Janus structure sheet on the other side. Electron micrographs of this material are shown in Figures 3 and 4. The material has a thickness of 50-100 nm, a length and a width of 200 ηιη - 5 μιη _; a material on the front surface of the substrate (which is an amine propyl group) and a weight of a material (which is a phenyl group) on the reverse surface of the substrate. The ratio is 1:1.

The sodium salt hydrolyzate aqueous solution of the styrene-maleic anhydride copolymer used in this example was prepared as follows: 100 mL of toluene was added to a three-necked flask, oxygen was removed by nitrogen for 30 min, and 10 g of styrene and 10 g of maleic anhydride were added. The mixture was stirred and dissolved at room temperature, and O. lg azobisisobutyronitrile was added as an initiator, and the reaction was carried out at 90 ° C for 3 h. The product was washed with suction at room temperature, and the obtained white powder was vacuum dried at 60 ° C to obtain a styrene-maleic anhydride copolymer; 10 g of the styrene-maleic anhydride copolymer was placed in a single-mouth bottle, and 5 g of hydrogen was added. Sodium oxide and 90 mL of deionized water, magnetically stirred and hydrolyzed at 90 ° C for 4-6 h to obtain a pale yellow transparent viscous solution to obtain a hydrolyzed aqueous solution of styrene-maleic anhydride copolymer (HSMA aqueous solution), ie styrene - An aqueous solution of a sodium salt hydrolyzate of a maleic anhydride copolymer having a mass percent concentration of 10%.

Example 4: Using Method 1 to prepare a porous silica with an amine group on one side and a phenyl group on the other side Janus sheet material

1) Take 5g of reactant tetraethyl orthosilicate, lg coupling agent aminotrimethoxysilane and lg coupling agent phenyltriethoxysilane to paraffin wax (melting point 52-54°) at 70 °C in non-polar solvent In C), mix well at 70 ° C for 4 hours as an oil phase. 15 g of 10% by weight of a sodium salt hydrolyzate aqueous solution of styrene-maleic anhydride copolymer was added as an emulsifier to 75 g of polar solvent water, and the pH was adjusted to 7 with 2 mol/L hydrochloric acid, and heated to 70 ° C. As the water phase. Among them, an aqueous solution of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer was prepared in accordance with the method provided in Example 3.

2) The oil phase was added to the water phase, and the emulsion was shear emulsified at 100 ° C for 10 min at 70 ° C using a high-speed shear emulsifier. The obtained emulsion was transferred to a three-necked flask in a 70 ° C water bath, and mechanically stirred for 12 hours. material. The emulsion was diluted with water, ground by a colloid mill, washed three times with water and hexane, and refluxed with ethanol as a solvent for 24 hours to remove the surfactant, and the side provided by the present invention was provided with an amine group and the other side was provided with benzene. A porous silica Janus structure sheet material. An electron micrograph of the material is shown in Figure 5. The material has a thickness of 200-500 nm, a length and a width of l-ΙΟμιη; a material on the front surface of the substrate (which is an amine propyl group) and a weight of a material (which is a phenyl group) on the reverse surface of the substrate. The ratio is 1:1.

Example 5, using Method 1 to prepare porous silica with an amine group on one side and octadecyl on the other side Janus sheet material =

1) Take 3g of reactant tetraethyl orthosilicate, lg coupling agent aminotriethoxysilane and 0.5g coupling agent octadecyltriethoxysilane to be added to the non-polar solvent toluene, and mix well Oil phase. 2.5 g of an emulsifier sodium lauryl sulfate was added to 50 g of polar solvent water, and the pH was adjusted to 2 with 2 mol/L hydrochloric acid as an aqueous phase. 2) Adding the oil phase to the water phase, using a high-speed shear emulsifier to shear emulsification at 100 rpm for 10 min, transferring the obtained emulsion to a three-necked flask in a 70 ° C water bath, mechanically stirring the reaction for 12 hours, and directly obtaining two The Janus structure sheet material with different side properties has a sheet thickness of 200 nm.

The above-mentioned sheet material was repeatedly washed with water and ethanol, and the surfactant was washed away to obtain a porous Janus structure sheet material. An electron micrograph of the material is shown in Figure 6. The material has a thickness of 50-80 nm, a length and a width of 300 ηιη - 5 μιη; a material on the front surface of the substrate (which is an amine propyl group) and a material on the reverse surface of the substrate (which is an octadecyl group). The weight ratio is 2:1; the material has a porous structure with a pore diameter of 5-7 nm.

Example 6. An organic Janus structure sheet material having a polyoxypropylene segment on one side and a polyethylene glycol segment on the other side was prepared by the second method.

0.2g polyethylene glycol-polybutadiene-polyoxypropylene triblock copolymer (weight average molecular weight 500-20000, polyoxypropylene is a hydrophobic segment, polyethylene glycol is a hydrophilic segment, polybutan The olefin is a reactive segment) dispersed in 100 mL of deionized water to obtain an aqueous solution of a glycol-butadiene-polyoxypropylene triblock copolymer, and 20 mL of decane is added to the above aqueous solution, followed by emulsification for 10 min to obtain The emulsion was stabilized, and the emulsion was irradiated with ultraviolet light for 30 minutes to obtain hollow microspheres of Janus structure. The emulsion was freeze-dried and then ground into a sheet at a low temperature to obtain a polyoxypropylene segment on one side and a polyethylene glycol chain on the other side. Segment of the organic Janus structure sheet material. An electron micrograph of the material is shown in Figure 7. The material has a thickness of 30-200 nm and a length and a width of 200 ηιη - 5 μιη _; the weight ratio of the material (which is polyethylene glycol) on the front surface of the substrate to the material (polyoxypropylene) on the reverse surface of the substrate is 1 : 1.

Example 7. An organic Janus structure sheet material having a polystyrene chain on one side and a polymethyl methacrylate chain on the other side was prepared by the second method.

0.1 styrene-butadiene-methyl methacrylate amphiphilic triblock graft polymer (weight average molecular weight 2000-0000, CAS: 25053-09-2, purchased from Sigma, where hydrophilic polymer The segment is polymethyl methacrylate, the reactive olefin or alkyne polymer segment is polybutadiene, the hydrophobic polymer segment is the polystyrene segment in the block copolymer) dissolved in 50mL In the non-polar solvent n-hexane, 10 mL of a 0.01% by weight aqueous solution of potassium persulfate was added to the above solution, and emulsified by ultrasonication for 10 min to obtain a stable emulsion, and the temperature was raised to 70 ° C. After 8 h of reaction, the Janus structure was hollow. Microspheres. The emulsion was freeze-dried and then ground at a low temperature to obtain a Janus structure sheet material having a polystyrene chain on one side and a polymethyl methacrylate chain on the other side. The material has a thickness of 20-50 nm, a length and a width of 100 ηιη - 2 μιη _{; a} weight of the material on the front surface of the substrate (polystyrene) and a material on the opposite surface of the substrate (polymethyl methacrylate). The ratio is 1:1.

Example 8. Preparation of urea-formaldehyde resin by method three / polystyrene Janus sheet material

1) Take 10g of free radical polymerization monomer styrene and 5g of free radical polymerization monomer divinylbenzene is added to 100g of non-polar solvent octadecane, mixed uniformly and then added to O. lg initiator potassium persulfate , O. lg initiator sodium hydrogen sulfite, 10 g emulsifier tween 80 and 200 g of a 5% polycondensation reaction prepolymer urea-formaldehyde prepolymer aqueous solution mixture, at room temperature High-speed shear emulsification lOmin, the emulsion was transferred to a three-necked flask equipped with a reflux condenser in a constant temperature water bath at 30 ° C, mechanically stirred uniformly, and the pH of the system was adjusted to 5 with 1 M hydrochloric acid;

2)。 O. lg initiator used in the reaction of the reaction system was carried out at 30 ° C for 12 h under the protection of nitrogen. The potassium persulfate and the O. lg initiator sodium bisulphite initiate a free radical polymerization reaction to obtain a styrene polymer, and then raise the reaction temperature to 70 ° C to cause the urea-formaldehyde prepolymer to undergo a polycondensation reaction, and continue the reaction for 8 hours. The emulsion was cooled by ice water, suction filtered, and vacuum dried to obtain a urea-formaldehyde resin/polystyrene composite polymer hollow microsphere. The hollow microspheres were ground to a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the urea-formaldehyde resin/polystyrene composite. An electron micrograph of the material is shown in Figure 8. The material has a thickness of 30-60 nm, a length and a width of 500 ηιη - 5 μιη _; a weight ratio of a material (which is polystyrene) on the front surface of the substrate to a material (a urethane resin) on the reverse surface of the substrate is 3 : 2.

In the method, the urea-formaldehyde prepolymer aqueous solution is prepared according to the following method: 240 g of urea and 500 g of a 37% by mass aqueous formaldehyde solution are added to a three-necked flask equipped with a reflux condenser, and mechanically dissolved and dissolved. Adding triethanolamine to adjust the pH of the system to 8, heating to 70 ° C, holding the reaction for 1 h to obtain a viscous liquid, and adding 1000 g of water to dilute to obtain a stable urea-formaldehyde prepolymer aqueous solution.

Example 9. Preparation of melamine resin by using Method 3 / Polybutadiene Janus sheet material

1) taking 10g of free radical polymerization monomer butadiene and 5g of free radical polymerization monomer divinylbenzene is added to 100g of non-polar solvent n-hexane, mixed uniformly and then added to the potassium persulfate by O. lg initiator , O. lg initiator sodium hydrogen sulfite, 5 g emulsifier sodium lauryl sulfate and 200 g of a 5% by weight polycondensation prepolymer melamine-formaldehyde prepolymer aqueous solution, in The system was emulsified at high speed for 10 min at room temperature, and the emulsion was transferred to a three-necked flask equipped with a reflux condenser in a constant temperature water bath at 30 ° C, and mechanically stirred uniformly. Adjust the pH of the system to 5 with 1M hydrochloric acid;

2) Under the protection of nitrogen, the reaction system of step 1) is reacted at 30 ° C for 12 h, using O. lg initiator potassium persulfate and O. lg initiator sodium hydrogen sulfite to initiate free radical polymerization to obtain polybutadiene. Polymer, then raise the reaction temperature to 70 ° C, the melamine-formaldehyde prepolymer is polycondensed, continue the reaction for 8h, the emulsion is cooled by ice water, suction filtration, vacuum drying, to obtain melamine resin / polybutadiene Composite polymer hollow microspheres. The hollow microspheres are ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the melamine resin/polybutadiene composite. The material has a thickness of 20-100 nm and a length and a width of 100 ηιη - 2 μιη _; the weight ratio of the material on the front surface of the substrate (which is a melamine resin) to the material on the reverse surface of the substrate (which is polybutadiene) is 3: 2.

In the method, the melamine-formaldehyde prepolymer aqueous solution is prepared according to the following method: 110 g of melamine and 500 g of 37% aqueous formaldehyde solution are added to a three-necked flask equipped with a reflux condenser, mechanically stirred to dissolve, and triethanolamine is added to adjust the pH of the system. 8, heated to 70 ° C, the reaction was incubated for 1 h to obtain a viscous liquid, and then diluted with 1000 g of water to obtain a stable aqueous solution of melamine-formaldehyde prepolymer.

Example 10 Preparation of Polystyrene / Urea Resin by Method 3 Janus Sheet Material

1) Take 10g of free radical polymerization monomer styrene and O. lg initiator butyl benzoate peroxide added to 100g of non-polar solvent toluene, mixed uniformly and then added to 5g emulsifier Tween80 and 200g mass% In a mixture of 5% polycondensation prepolymer urea-formaldehyde prepolymer aqueous solution, the system was emulsified at high speed for 10 min at room temperature, and the emulsion was transferred to a 50 ° C constant temperature water bath with reflux condensation. In the three-necked tube of the tube, the machine is evenly stirred. Adjust the pH of the system to 4 with 1M hydrochloric acid;

2) Under the protection of nitrogen, react at 50 °C for 2 h, the polycondensation reaction of urea-formaldehyde prepolymer is carried out, then the reaction temperature is raised to 90 °C, and the initiator is initiated by free radical polymerization of tert-butyl peroxybenzoate. Polystyrene Compound, continue to react for 8h. The emulsion was cooled by ice water, suction filtered, and vacuum dried to obtain a polystyrene/urea resin composite polymer hollow microsphere. The hollow microspheres are ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polystyrene/urea resin composite. In this method, the urea-formaldehyde prepolymer aqueous solution used was prepared in accordance with the method of Example 6. The material has a thickness of 20-60 nm and a length and a width of 100-800 nm; the weight ratio of the material (which is polystyrene) on the front surface of the substrate to the material (for the urethane resin) on the reverse surface of the substrate is 1 : 1.

Example 11 Preparation of Silica/Melamine Resin by Method 4 Janus Sheet Material

1) 2 g of the inorganic reactant tetraethyl orthosilicate and 0.5 g of the inorganic reactant aminopropyltriethoxysilane were added to 100 g of non-polar solvent toluene, uniformly mixed and added to 8 g of emulsifier Triton X-100 and 200g of a 5% polycondensation prepolymer melamine-formaldehyde prepolymer aqueous solution mixture was mixed at room temperature for 10 min at high speed, and the emulsion was transferred to a constant temperature water bath at 25 °C. In a three-necked flask equipped with a reflux condenser, the machine was evenly stirred. The pH of the system was adjusted to 5 with 1M hydrochloric acid;

2) Under the protection of nitrogen, react at 25 °C for 8h, then increase the reaction temperature to 70 °C, the polycondensation reaction of melamine-formaldehyde prepolymer is carried out, continue the reaction for 8h, and the emulsion is cooled by ice water and then filtered. Vacuum Drying gives a silica/melamine resin composite hollow microsphere. The hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the silica/melamine resin composite. An electron micrograph of the material is shown in Figure 9. In this method, a melamine-formaldehyde prepolymer aqueous solution was prepared in accordance with the method of Example 7. The material has a thickness of 100-500 nm, a length and a width of 300 ηιη - 5 μιη _; a material on the front surface of the substrate (which is silica) and a material on the reverse surface of the substrate (the weight ratio of the melamine resin is 1: 10.

Example 12: Preparation of Titanium Dioxide / Urea Resin by Method 4 Janus Sheet Material

1) Take 5g of inorganic reactant tetrabutyl titanate and 0.5g of inorganic reactant aminopropyltriethoxysilane, add to 50g of non-polar solvent decane, mix well and add to the mass of 5g emulsifier OplO and 100g In a mixture of 5% polycondensation prepolymer urea-formaldehyde prepolymer aqueous solution, the system was emulsified at high speed for 10 min at room temperature, and the emulsion was transferred to a constant temperature water bath at 25 °C. The three bottles of the reflux condenser were mechanically stirred uniformly, and the pH of the system was adjusted to 5 with 1 M hydrochloric acid;

2) Under the protection of nitrogen, react at 25 °C for 8h, then increase the reaction temperature to 70 °C, and make the urea-formaldehyde prepolymer undergo polycondensation reaction, continue the reaction for 8h, then use the ice water to cool down, then filter, vacuum Drying, that is, a titanium dioxide/urea resin composite hollow microsphere is obtained. The hollow microspheres are ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the titanium dioxide/urea resin composite. In this method, a urea-formaldehyde prepolymer aqueous solution was prepared in accordance with the method provided in Example 6. The material has a thickness of 50-200 nm and a length and a width of 400 ηιη - 10 μιη _; the weight ratio of the material (which is titanium dioxide) on the front surface of the substrate to the material (for the urethane resin) on the reverse surface of the substrate is 1:3. .

Example 13. Preparation of Silica/Urea Resin by Method 4 Janus Sheet Material

1) Take 5g of inorganic reactant tetraethyl orthosilicate and lg inorganic reactant aminopropyltriethoxysilane to

50 g of non-polar solvent cyclohexane, uniformly mixed and added to a mixture of 5 g of emulsifier OplO and 100 g of a 5% polycondensation prepolymer urea-formaldehyde prepolymer aqueous solution. At room temperature, the system is emulsified at high speed for 10 minutes, and the emulsion is transferred to a 25 ° C constant temperature water bath equipped with a reflux condenser. In the three-necked bottle, the machine is evenly stirred, and the pH of the emulsion system is adjusted to 6 with 1M hydrochloric acid;

2) Under the protection of nitrogen, react at 25 °C for 8h, then increase the reaction temperature to 70 °C, and make the urea-formaldehyde prepolymer undergo polycondensation reaction, continue the reaction for 8h, then use the ice water to cool down, then filter, vacuum Drying gave silica/urea resin composite hollow microspheres. The hollow microspheres were ground to a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the silica/urea resin composite. In this method, urea

- Aqueous formaldehyde prepolymer aqueous solution was prepared according to the method provided in Example 6. The material has a thickness of 60-380 nm, a length and a width of 500 ηιη - 10 μιη _; a weight ratio of a material (as silica) on the front surface of the substrate to a material (for urea-formaldehyde resin) on the reverse surface of the substrate is 2: 5.

Example 14. Preparation of Silica/Polystyrene by Method 4 Janus Sheet Material

1) taking 5g of inorganic reactant tetraethyl orthosilicate, lg inorganic reactant aminopropyltrimethoxysilane, 3g of free-radical polymerizable monomer styrene into 10g of non-polar solvent toluene, fully mixed as an oil phase; Taking 80 g of water and 5 g of sodium lauryl sulfate as an aqueous phase;

2) Add the aqueous phase to the oil phase, use a high-speed shear emulsifier to shear emulsifie at 12000 rpm for 2 min to form an emulsion, mechanically stir at room temperature for 8 h, then transfer to a three-neck bottle in a water bath at 80 ° C for mechanical agitation. The reaction was continued for 8 hours. The emulsion was cooled with ice water, filtered under vacuum, dried in a vacuum, and then ground at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polystyrene/silica composite. An electron micrograph of the material is shown in Figure 10. The material has a thickness of 100-400 nm and a length and a width of l-ΙΟμιη; the weight ratio of the material (which is silicon dioxide) on the front surface of the substrate to the material (polystyrene) on the reverse surface of the substrate is 2 : 5.

Example 15. Preparation of Silica/Polydivinylbenzene by Method 4 Janus Sheet Material

1) Take 3g of inorganic reactant tetraethyl orthosilicate, lg inorganic reactant aminopropyltrimethoxysilane, 2g of free-radically polymerizable monomer styrene, add to 20g of non-polar solvent decane, mix well and use as oil phase Take 100g water and 5g OplO as the water phase;

2) Add the aqueous phase to the oil phase, use a high-speed shear emulsifier to shear emulsifie at 12000 rpm for 2 min to form an emulsion, mechanically stir at room temperature for 8 h, then transfer to a three-neck bottle in a 70 ° C water bath for mechanical agitation. The reaction was continued for 2 hours. The emulsion was cooled with ice water, filtered under vacuum, dried in a vacuum, and then ground to a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polydivinyl phenylene/silica composite. An electron micrograph of the material is shown in Figure 11. The material has a thickness of 40-200 nm, a length and a width of 300 ηιη - 8 μιη _; a weight ratio of a material (which is silicon dioxide) on the front surface of the substrate to a material (polydivinylbenzene) on the reverse surface of the substrate. It is 1:1.

Example 16: Preparation of Urea/Melamine Resin by Method 5 Janus Sheet Material

1) 2 g of a 10% by mass aqueous solution of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer is used as an emulsifier, added to 20 g of continuous phase solvent water, and the pH is adjusted to 5 with 1 M hydrochloric acid, and 10 g is added. Disperse the solvent solvent n-hexane, use a high-speed shear emulsifier to shear emulsified lOmin at 12000r/min, transfer the obtained emulsion to a three-necked bottle in a 50°C water bath, and mix it with mechanical agitation, then take 20g of mass concentration to 5 % of the aqueous solution of the resin prepolymer urea-formaldehyde prepolymer dissolved in the continuous phase solvent water, dissolved in 2 g of sodium chloride, adjusted to pH 6 with 1 M hydrochloric acid, slowly dropped into the above emulsion, lOmin was added dropwise After completion, 50 ° C constant temperature polycondensation reaction for 1 h, slowly adjust the pH of the system to 3.5 with 1M hydrochloric acid, continue the polycondensation reaction for 4 h, in dispersion a water-insoluble polycondensate of a crosslinked three-dimensional network structure is formed at the interface between the phase and the continuous phase to obtain a primary shell layer;

2) further adding 20 g of a 5% by mass aqueous solution of a resin prepolymer melamine-formaldehyde prepolymer dissolved in a continuous phase solvent water to the reaction system of the step 1), and adding 2 g of sodium chloride to dissolve therein, It is slowly dripped into the above emulsion, and the addition is completed in 2 minutes, and the polycondensation reaction is carried out at 50 ° C for 6 hours. The emulsion is cooled by ice water, filtered under vacuum, and dried under vacuum to obtain a hollow microsphere of urea/melamine composite polymer;

3) The hollow microspheres obtained in the step 2) are ground into pieces at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the urea/melamine composite. An electron micrograph of the material is shown in Figure 12. The material has a thickness of 30-100 nm, a length and a width of 200 ηιη - 10 μιη _; a weight ratio of a material on the front surface of the substrate (for urea-formaldehyde resin) to a material on the opposite surface of the substrate (melamine resin) is 1: 1.

In this method, the sodium salt hydrolyzate aqueous solution of the styrene-maleic anhydride copolymer used is prepared according to the method provided in Example 4, and the melamine-formaldehyde prepolymer aqueous solution is prepared according to the method provided in Example 5. A urea-formaldehyde prepolymer aqueous solution was prepared according to the method provided in Example 6.

Example 17. Preparation of Polyethylene Glycol Modified Urea Resin by Method 5 / Gelatin Janus Sheet Material

1) Take 0.5g of emulsifier sodium lauryl sulfate, add to 20g of continuous phase solvent water, adjust the pH value to 4 with 1M hydrochloric acid, add 10g of paraffin wax with a melting point of 25-28 °C in the dispersed phase solvent, and make the system temperature maintain at

50 ° C, using a high-speed shear emulsifier at 12000r / min shear emulsification for 5min, the resulting emulsion was transferred to a three-necked bottle in a 50 ° C water bath, mechanically stirred until the emulsion was obtained, taking 20g of mass concentration of 3 % prepolymer of a resin dissolved in continuous phase solvent water, polyethylene glycol modified urea-formaldehyde prepolymer aqueous solution, dissolved in 2g of sodium chloride, adjusted to pH 6 with 1M hydrochloric acid, slowly drip Into the above emulsion, lOmin is added dropwise, constant temperature polycondensation reaction at 50 °C for 1 h, slowly adjust the pH of the system to 3.5 with 1M hydrochloric acid, continue the polycondensation reaction for 6 h, and form a cross-linked three-dimensional network at the interface between the dispersed phase and the continuous phase. a water-soluble polycondensate, that is, a primary shell layer;

2) taking 0.2 g of the oppositely charged polymer gelatin dissolved in 20 g of secondary water at 50 ° C, and adding the gelatin aqueous solution to the three-necked bottle of the above step 1) to uniformly mix with the emulsion; Slowly adding a 10% aqueous solution of acetic acid to adjust the pH of the system to 3, at which time the gelatin molecule and the sodium lauryl sulfate recombine at the oil-water interface to form a shell layer, and continue the condensation reaction for 1 hour; The system is placed in an ice water bath, and then added with 2 mL of 37% aqueous formaldehyde solution for 3 h. The polycondensate obtained in step 1) and the gelatin molecule are electrostatically attracted, and a new shell layer is formed on the outer side of the primary shell layer obtained in the step 1). The capsule shell layer is initially cross-linked and solidified, and then the emulsion is suction filtered and vacuum dried to obtain a polyethylene glycol-modified urine aldehyde resin/gelatin composite polymer hollow microsphere. The hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polyethylene glycol modified urethane tree/gelatin composite. An electron micrograph of the material is shown in Figure 13. The material has a thickness of 50 nm to 200 nm, a length and a width of 200 ηηη - 5 μιη _; a material on the front surface of the substrate (polyethylene glycol modified urethane resin) and a material on the reverse surface of the substrate (gelatin) The weight ratio is 3:1.

Wherein, the polyethylene glycol modified urea-formaldehyde prepolymer aqueous solution used is prepared as follows: 240 g of urea, 50 g of polyethylene glycol and 450 g of 37% aqueous formaldehyde solution are added to a three-necked flask equipped with a reflux condenser. , mechanical stirring and dissolution, adding triethanolamine to adjust the pH value of 8, to 70 ° C, the reaction reaction for 1 h to obtain a viscous liquid, and then adding 1000 g of water to dilute, to obtain a stable polyethylene glycol modified urea-formaldehyde prepolymerization Aqueous solution.

Example 18, Preparation of Polyurethane / Urea-Formaldehyde Resin by Method 5 Janus Sheet Material

1) 20 g of the dispersed phase reactant toluene diisocyanate and 10 g of the dispersed phase reactant xylene diisocyanate are added to 200 g of the dispersed phase solvent melting point 50 to 52 ° C in paraffin, mixed uniformly and then added to 10 g of emulsifier tween 80 and In a mixture of 600g continuous phase solvent water, the system was emulsified at high speed at 12000r/min for 10min at 70°C, and then transferred to a three-neck bottle in a constant temperature water bath at 70 °C, mechanically stirred. To the emulsion, slowly adding 20 g of the continuous phase reactant triethylenetetramine and reacting for 1 h;

2) Then, 400 g of a urea-formaldehyde prepolymer having a resin prepolymer concentration of 5% in a continuous phase solvent water was added dropwise to the system, and the pH of the solution was adjusted to 3 with 1 M hydrochloric acid, and the reaction was continued for 5 hours. Thereafter, the emulsion was cooled with ice water, suction filtered, and vacuum dried to obtain a polyurethane/urea resin composite polymer hollow microsphere. The hollow microspheres were ground to a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polyurethane/urea resin composite. An electron micrograph of the material is shown in Figure 14. Wherein the urea-formaldehyde prepolymer aqueous solution was prepared according to the method provided in Example 6. The thickness of the material is

30-100 nm, both length and width are 500 ηιη-10 μιη _; the weight ratio of the material (which is a urethane resin) on the front surface of the substrate to the material (which is a urea-formaldehyde resin) on the reverse surface of the substrate is 3:2.

Example 19 Preparation of Epoxy Resin / Polyvinylpyrrolidone by Method 5 Janus Sheet Material

1) 20 g of the dispersed phase reactant epoxy resin (weight average molecular weight 340-3000) was added to 100 g of the dispersed phase solvent cyclohexane, and after mixing, it was added to 10 g of 10% styrene as an emulsifier. An aqueous solution of maleic anhydride copolymer, a mixture of lg continuous phase reactant ethylenediamine (molar ratio of reactive functional groups of epoxy resin and ethylenediamine: 1:1) and 590 g of water, at 60 ° C The system was emulsified at 400 r/min for 5 min at high speed, then the emulsion was transferred to a three-necked flask in a 60 ° C constant temperature water bath, mechanically stirred, and the dispersed phase reactant and continuous phase reactant were in the dispersed phase and the continuous phase. A polycondensation reaction occurs at the interface for 8 hours, and the reaction is completed to form a primary shell layer;

2) 0.5 g of the first shell polymer obtained in the step 1) and the oppositely charged polymer polyvinylpyrrolidone (weight average molecular weight 6000-98000) are dissolved in 20 g of water at 50 ° C, and the aqueous solution is added dropwise to the above steps.

1) The three-necked bottle is mixed with the emulsion evenly; then slowly add a 10% by mass aqueous solution of acetic acid to the system to adjust the pH of the system to 4, at this time polyvinylpyrrolidone and styrene-ma The aqueous solution of the anhydride anhydride copolymer undergoes a re-agglomeration reaction at the oil-water interface due to electrostatic attraction. A new shell layer is formed on the outer side of the primary shell layer obtained in the step 1), and the condensation reaction is continued for 1 hour; the system is placed in an ice water bath, and then 2 mL is added. A 37% aqueous solution of formaldehyde was reacted for 3 hours to crosslink and cure the capsule shell. The emulsion was cooled by ice water, filtered, and vacuum dried to obtain an epoxy resin/polyvinylpyrrolidone composite polymer hollow microsphere. The hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the epoxy resin/polyvinylpyrrolidone composite. An electron micrograph of the material is shown in Figure 15. Among them, an aqueous solution of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer was prepared in accordance with the method provided in Example 3. The material has a thickness of 30-200 nm, a length and a width of 300 ηιη - 10 μιη _; a weight ratio of a material (which is an epoxy resin) on the front surface of the substrate to a material (for polyvinylpyrrolidone) on the reverse surface of the substrate is 40 : 1.

Example 20 Preparation of Polystyrene / Urea-Formaldehyde Resin by Method 5 Janus Sheet Material

1) Take 10g of dispersed phase radical polymerizable monomer styrene and 5g of dispersed phase radical polymerizable monomer divinyl Benzene was added to 100 g of the dispersed phase solvent octadecane, mixed uniformly, and added to a mixture of 10 g of emulsifier tweenSO and 290 g of water, and the system was heated at a speed of 12000 r/min in a constant temperature water bath at 70 °C. The emulsion was transferred and emulsified for 10 min, and the emulsion was transferred to a three-necked flask equipped with a reflux condenser in a constant temperature water bath at 70 ° C, and mechanically uniformly stirred. To the emulsion was added dropwise O. lg initiator potassium persulfate (dispersed phase radical polymerization) A 20g aqueous solution having a mass ratio of monomeric styrene to divinylbenzene and an initiator of 150:1), reacted at 70 ° C for 8 hours under the protection of nitrogen, the initiator initiates free radical polymerization of the dispersed phase The monomer undergoes radical polymerization to form a polymer, and the polymer is phase-separated and deposited at the interface between the dispersed phase and the continuous phase to form a crosslinked three-dimensional network polymer shell, that is, a primary shell layer;

2) Then, to the reaction system obtained in the step 1), 200 g of a resin prepolymer urea-formaldehyde prepolymer aqueous solution dissolved in a continuous phase solvent water of 5% by weight is added dropwise, and the pH of the solution is adjusted to 3 with 1 M hydrochloric acid. The polycondensation reaction is continued for 4 hours, and a new shell layer is formed on the outer side of the primary shell layer obtained in the step 1). The emulsion is cooled by ice water, suction filtered, and vacuum dried to obtain a polystyrene/urea resin composite polymer hollow microsphere. . The hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polystyrene/urea resin composite. Among them, a urea-formaldehyde prepolymer aqueous solution was prepared in accordance with the method provided in Example 6. An electron micrograph of the material is shown in Figure 16. The material has a thickness of 50-300 nm, a length and a width of 500 ηιη - 15 μιη _; a weight ratio of a material (which is polystyrene) on the front surface of the substrate to a material (which is a urea-formaldehyde resin) on the reverse surface of the substrate is 3: 2.

Example 21: Preparation of Polydivinylbenzene / Gelatin by Method 5 Janus Sheet Material

1) Take lg disperse phase free radical polymerization monomer divinylbenzene is added to 10g of the dispersed phase solvent octadecanoic acid, mix well and then add it to 30g water containing lg emulsifier sodium lauryl sulfate, at 50 The system was emulsified by high-speed water bath at °C for 10 min at a speed of 12000 r/min. The emulsion was transferred to a three-necked flask equipped with a reflux condenser in a constant temperature water bath at 70 ° C. The machine was uniformly stirred and added to the emulsion. 5 g of an aqueous solution containing 0.5 g of potassium persulfate under the protection of nitrogen at 70 ° C for 5 h, the initiator initiates radical polymerization of the free-radical polymerization monomer of the dispersed phase to form a polymer, which produces a phase Separating and depositing at the interface between the dispersed phase and the continuous phase to form a crosslinked three-dimensional network polymer shell layer, that is, a primary shell layer;

2) 0.2 g of the oppositely charged polymer gelatin is dissolved in 20 g of secondary water at 50 ° C, and the gelatin aqueous solution is added dropwise to the three-necked bottle of the above step 1) to be uniformly mixed with the emulsion; Slowly adding 10% aqueous solution of acetic acid to adjust the pH of the system to 3. The gelatin molecule and sodium lauryl sulfate form a complex coacervation reaction at the oil-water interface due to electrostatic attraction at the outer side of the primary shell obtained in step 1). The new shell layer, continue to coagulate reaction lh; the system is placed in an ice water bath, and then added 2mL 37% aqueous formaldehyde solution for 3h, the capsule shell layer cross-linking solidified, the emulsion is cooled by ice water, suction filtration, vacuum drying , obtaining polydivinylbenzene/gelatin composite polymer hollow microspheres. The hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polydivinylbenzene/gelatin composite. An electron micrograph of the material is shown in Figure 17. The material has a thickness of 30-100 nm, a length and a width of 500 ηιη - 5 μιη _; a weight ratio of a material (for polydivinylbenzene ₎ on the front surface of the substrate to a material (for gelatin) on the reverse surface of the substrate is 5 : 1.

Example 22: Preparation of gelatin / sodium alginate using Method 5 Janus sheet material

1) 10 g of a 10% by mass concentration of a hydrolyzate sodium salt of a styrene-maleic anhydride copolymer (this water) The aqueous solution of the emulsifier and the dispersed phase reactant is added to 80 g of the continuous phase solvent water to be uniformly mixed, and 20 g of the paraffin wax having a melting point of 50 to 52 ° C of the dispersed phase solvent is added thereto, and the high-speed shear emulsifier is used for 12000 rpm. /min speed emulsified lOmin to obtain a uniform and stable emulsion, transferred to a three-necked bottle in a constant temperature water bath of 70 ° C, mechanically stirred; take lg continuous phase polymer gelatin dissolved in 70g of secondary water at 70 ° C, The gelatin aqueous solution is added dropwise to the above three-necked bottle to be uniformly mixed with the emulsion; and the aqueous solution of 10% by mass of acetic acid is slowly added dropwise to the system to adjust the pH of the system to 3, and the gelatin molecule and The hydrolyzate molecule of the styrene-maleic anhydride copolymer recombines at the oil-water interface due to electrostatic attraction to form a shell layer of the microcapsule, and continues to coagulate for 1 h to form a primary shell layer;

2) Then take lg of the oppositely charged polymer sodium alginate dissolved in 20g of water at 70 ° C, the aqueous solution is added dropwise to the three-necked bottle of the above step 1), and it is evenly mixed with the emulsion; Slowly add 10% aqueous ammonia solution to adjust the pH value of the system to 10, and continue the coagulation reaction for 1 h. At this time, the agglomeration reaction of sodium alginate and gelatin due to electrostatic attraction will form a new shell on the outer side of the primary shell obtained in step 1). The system was placed in an ice water bath, then 1 mL of 37% aqueous formaldehyde solution was added and reacted for 3 hours to preliminarily crosslink and cure the capsule shell. The emulsion was cooled with ice water, suction filtered, and vacuum dried to obtain a gelatin/alginate nanocomposite hollow microsphere. The hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the gelatin/alginate nano composite. An electron micrograph of the material is shown in Figure 18. The material has a thickness of 30-150 nm, a length and a width of 500 ηιη - 5 μιη _; a weight ratio of a material (as gelatin) on the front surface of the substrate to a material (in the form of sodium alginate) on the opposite surface of the substrate is 1:1. .

In this method, an aqueous solution of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer used was prepared in accordance with the method provided in Example 3.

Example 23, Preparation of Polyacrylamide by Method Six / Polystyrene Janus Sheet Material

1) 2 g of a radical polymerizable monomer acrylamide monomer dissolved in polar solvent water, 0.3 g of a free radical polymerization initiator ferrous sulfate dissolved in a polar solvent water, added to 50 g of polar solvent water, and sufficiently mixed Aqueous phase; take 2g of free radical polymerizable monomer styrene dissolved in non-polar solvent decane, 5g emulsifier Span80, lg free radical polymerization initiator cumene dissolved in non-polar solvent decane Dissolved in 200 g of decane as an oil phase; the aqueous phase was added to the oil phase, and emulsified by shearing at 12000 rpm for 2 min using a high speed shear emulsifier to form an emulsion;

2) The emulsion obtained in step 1) is reacted under mechanical stirring in a 40 ° C water bath for 12 h, and then the emulsion is cooled by ice water, suction filtered, vacuum dried, and the polyacrylamide/polystyrene composite is directly obtained. A Janus structure sheet material having different compositions on both sides. An electron micrograph of the material is shown in Figure 19. The material has a thickness of 50-200 nm and a length and a width of 1-15 μm _; the weight ratio of the material (as polyacrylamide) on the front surface of the substrate to the material (polystyrene) on the reverse surface of the substrate is 1 : 1.

Example 24, Preparation of Crosslinked Polyacrylamide/Crosslinked Polystyrene Janus Sheet Material by Method 6 1) Take 5 g of free radical polymerizable monomer acrylamide dissolved in polar solvent water, 0.5 g dissolved in polar solvent water Free radical polymerization initiator ferrous sulfate, O. lg free radical polymerizable monomer in polar solvent water Ν, Ν-dimethyl bis acrylamide, lg emulsifier cetyl trimethyl bromide ( CTAB) was added to 200g of polar solvent water and mixed well as an aqueous phase; 2g of free radical polymerizable monomer divinylbenzene dissolved in non-polar solvent decane, 2g dissolved in non-polar solvent decane Free radical polymerization monomer styrene, 2g soluble in non-polar The free radical polymerization initiator in solvent decane is dissolved in 50 g of non-polar solvent decane as an oil phase; the aqueous phase is added to the oil phase, and the emulsion is sheared at 12000 rpm using a high-speed shear emulsifier. 2min, forming an emulsion; 2) The emulsion obtained in step 1) is reacted under mechanical stirring in a 40 ° C water bath for 6 h, and the emulsion is cooled with ice water, suction filtered, and vacuum dried to obtain crosslinked polyacrylamide/crosslinking. The front and back sides of the polystyrene composite have different compositions of Janus structure sheet materials. The material has a thickness of 50-200 nm, a length and a width of 500 ηιη - 10 μιη; a material on the front surface of the substrate (which is a cross-linked polyacrylamide) and a material on the opposite surface of the substrate (which is a cross-linked polystyrene) The weight ratio is 5:2.

Example 25: Preparation of Polymethyl Methacrylate / Polyvinyl Alcohol by Method Six Janus Sheet Material

1) 10 g of a radical polymerization monomer methyl methacrylate dissolved in a non-polar solvent toluene, O. lg is dissolved in a non-polar solvent toluene, a free radical polymerization initiator azobisisobutyronitrile is added to 60 g In the non-polar solvent toluene, fully mixed as an oil phase; take 5g of free radical polymerizable monomer vinyl alcohol dissolved in polar solvent water, 2g of emulsifier sodium dodecylbenzene sulfonate, O. lg dissolved in polarity The free radical polymerization initiator in solvent water is dissolved in 150 g of polar solvent water to form an aqueous phase; the oil phase is added to the aqueous phase, and the emulsion is sheared and emulsified at 12000 rpm for 5 minutes using a high speed shear emulsifier to form an emulsion; 2) Step 1) The obtained emulsion is reacted under a mechanical stirring in a water bath at 70 ° C for 8 hours, and the emulsion is cooled by ice water, suction filtered, and vacuum dried to directly obtain the front and back sides of the polymethyl methacrylate/polyvinyl alcohol composite. Different composition of the Janus structure sheet material. The material has a thickness of 50-300 nm, a length and a width of 500 ηιη - 10 μιη _{; a} weight of the material on the front surface of the substrate (polymethyl methacrylate) and a material on the opposite surface of the substrate (polyvinyl alcohol). The ratio is 2: 1.

Industrial application

The invention prepares the spherical shell by materializing the emulsion oil-water interface, that is, forming inorganic materials, organic materials and inorganic and organic composite hollow microspheres by chemical reaction or physical adsorption at the interface between the discontinuous phase and the continuous phase of the emulsion. Hollow microspheres having different inner and outer surface structures or compositions; the shell layer may be continuous or discontinuous. For continuous shells, they can be ground into pieces. The size of the fragments can be achieved by controlling the grinding process. The thickness of the fragments can be achieved by controlling the concentration of the reactants. For non-continuous shells, the shell can be used directly as a shell. The above-mentioned sheet material is used, and it can be further used for grinding. The thickness and size of the sheet are related to conditions such as the concentration of the reactant. Such a sheet material can also be prepared as a Janus structure sheet material having a cell structure, and both sides of the sheet material have different cell structures due to differences in structure and composition. The method is a universal preparation method for preparing a sheet material having different properties on the front and back surfaces on a large scale.

The Janus sheet material provided by the invention has important application value in many fields due to its different composition and properties on both sides. For example, Janus sheet replaces ordinary polymer inorganic filler and polymer blending compatibilizer, and Janus sheet material can simultaneously combine inorganic filler and polymer blending compatibilizer, which is beneficial to the formation of layered polymer, and It plays a role in increasing polymer compatibility and enhancing toughening. In addition, due to the difference in hydrophilic and lipophilic properties on both sides, Janus sheet material can also be used to prepare emulsions instead of traditional surfactants as emulsifiers, and because Janus sheet materials are different from molecular surfactants, Janus sheet materials can be used as emulsifiers. Special types of emulsions such as ultra-concentrated emulsions are obtained, which are of great significance in practical application and theoretical research.

Claims

Rights request

1. A Janus structure sheet material having different properties on the front and back surfaces, comprising a substrate and a different material composition on the front and back surfaces of the substrate; wherein: the material on the front surface of the substrate is at least one a layer; the material on the reverse surface of the substrate is at least one layer;

2, the material according to claim 1, wherein: said inorganic material is selected from _{_{_{Si0 2, Ti0 2, Sn0 2}}} , Zr0 2 and at least one of A1 ₂ 0 _3;

The structural formula of the organic chemical group is RC _n H _2n , wherein an integer of n=0 to 121, R is -OH,

- H ₂ , HS -, -SCN - HCO H ₂ Cl-, H ₂ (CH ₂ ) ₂ H- (CH ₃ ) ₂ -C(Br)-C(0)- H- -S0 ₃ , -Ph- SOCl ₂ , -Ph-S0 ₃ , 2, 3-epoxypropoxy, methacryloxy, (CH ₂ ) ₃ -S _x -, -(CH ₂ ) _n CH ₃ , CH ₂ =CH- Or Ph-;

In the (CH ₂ ) ₃ -S _X -, an integer of x = 1 to 4; in the -(CH ₂ ) _n CH ₃ , an integer of n = 0 to 127, preferably an integer of 0-17;

The organic material is selected from the group consisting of urea-formaldehyde resin, melamine resin, polyacrylonitrile, epoxy resin, phenolic resin, polyamide, polyurea, polysulfonamide, polyurethane, polyester, polyoxypropylene, polydimethylsilane, poly Isobutylene polystyrene, polybutadiene, polyisoprene, gum arabic, sodium alginate, agar, sodium polyphosphate, sodium polysilicate, carboxymethyl cellulose, sodium styrene-maleic anhydride copolymer a salt hydrolyzate, a sodium salt hydrolyzate of an ethylene-maleic anhydride copolymer, a sodium salt hydrolyzate of a vinyl methyl ether-maleic anhydride copolymer, a sodium salt hydrolyzate of an isobutylene-maleic anhydride copolymer, acrylic acid or Copolymer of methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile, polyvinylbenzenesulfonic acid and polyvinylpyridine a polymer formed by re-coagulation of butyl bromide, polyvinylpyrrolidone, gelatin or casein, sodium polyvinyl benzene sulfonate, polyvinylpyridinium bromide, polyvinylpyrrolidone, Complex coacervation polymer produced by a reaction occurring gum or casein.

The material according to claim 1 or 2, wherein: the JA JS structure sheet material having different properties on the front and back surfaces has a thickness of 5 ηηη - 50 μιη, and a length and a width of 50 ηιη - 500 μιη, specifically 100 ι η η 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Weight ratio 1: 100-100: 1, specifically 10-90: 90-10, 20-80: 80-20, 30-70: 70-30, 40-60: 60-40 or 50: 50; The Janus structure sheet material having different properties on the front and back surfaces has a porous structure; the porous structure has a pore diameter of 1 to 50 nm.

A method for producing a Janus structured sheet material having different properties on the front and back surfaces according to any one of claims 1 to 3, which is any one of methods 1 to 6, wherein:

The method 1 is as follows: 1) or step Γ):

Step 1): dispersing a dispersed phase composed of a dispersed phase reactant, a coupling agent and a non-polar solvent under an action of an emulsifier in a continuous phase composed of a continuous phase reactant and a polar solvent to form an emulsion. pH value An acid or a base is added under the condition of 2-10, and the reactant dissolved in the continuous phase and the dispersed phase reacts at the interface of the dispersed phase and the continuous phase, and the direct formation of the front and back surfaces has different properties. a Janus structure sheet material; wherein a viscosity of the non-polar solvent in the dispersed phase is lower than a viscosity of the polar solvent in the continuous phase, and a volume ratio of the dispersed phase to the continuous phase is less than 5 is greater than 0.5, the temperature of the reaction is not lower than the melting point of the non-polar solvent and the polar solvent, and not higher than the boiling point of the non-polar solvent and the polar solvent;

The method 2 includes the following steps:

The method 3 includes the following steps 1) to 2):

Wherein the step 1) is any one of the following steps a) to b):

Step 2): if the decomposition temperature of the initiator is lower than the temperature of the polycondensation reaction, the radical polymerization reaction monomer is first subjected to radical polymerization to obtain a primary shell layer, and then the unpolymerized polycondensation sheet is initiated. The body or prepolymer undergoes a polycondensation reaction outside the primary shell layer to form hollow microspheres having a Janus structure shell layer, and after pulverization, a Janus structure sheet material having different properties on the front and back surfaces is obtained; if the initiator is decomposed When the temperature is higher than the temperature of the polycondensation reaction, the monomer or prepolymer which initiates the polycondensation reaction is subjected to a polycondensation reaction to obtain a primary shell layer; and the unrepolymerized radical reactive monomer is further induced in the primary shell layer. A radical polymerization reaction occurs on the inner side to form hollow microspheres having a Janus structural shell layer, and after pulverization, a Janus structure sheet material having different properties on the front and back surfaces is obtained. The method 4 includes the following steps 1) to 2):

Wherein, the step 1) is any one of the following steps a) to f):

Step a): dissolving the inorganic reactant in a non-polar solvent under the action of an emulsifier; forming a dispersion in a continuous phase composed of a polar solvent in which the dispersed phase is dispersed in the monomer or prepolymer in which the polycondensation reaction is dissolved;

Step f): Dispersing a polar solvent as a dispersed phase in a radically polymerized monomer dissolved in an inorganic reactant, dissolved in a nonpolar solvent, and free radical dissolved in a nonpolar solvent under the action of an emulsifier Forming an emulsion in a continuous phase composed of a non-polar solvent of a polymerization initiator;

The method 5 includes the following steps 1) to 3):

Wherein the step 1) is any one of the following steps a) to d):

Step d): dispersing the dispersed phase organic solvent in which the dispersed phase polymer is dissolved in the continuous phase solvent to form an emulsion under the action of an emulsifier, wherein the continuous phase solvent is dissolved in the opposite phase to the dispersed phase polymer a charged continuous phase polymer, the dispersed phase polymer and the continuous phase polymer at the interface of the dispersed phase and the continuous phase Electrostatic attraction occurs to form a primary shell layer;

The step 2) is the following steps a') or b') _:

The method 6 includes the following steps 1) to 2):

Wherein the step 1) is any one of the following steps a) to b):

The method according to claim 4, wherein in the method 1, the structural formula of the dispersed phase reactant is X _n MR _m , preferably tetraethyl orthosilicate; wherein M is Si, Ti, Sn, A1 or Zr; X is Na, Mg or K, n is 0, 1 or 2; R is Cl, OS0 ₄ , OCH ₃ , OCH ₂ CH ₃ , OCH(CH ₃ ) ₂ , OCH ₂ CH ₂ CH ₂ CH ₃ or S0 ₄ , m is 1, 2, 3 or 4; the non-polar solvent is selected from the group consisting of aromatic hydrocarbons, paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, aliphatic hydrocarbons and acetic acid At least one of ethyl esters, preferably toluene; the coupling agent is

(C ₂ H ₅ 0) ₃ -Si-(CH ₂ ) ₃ -S _x -(CH ₂ ) ₃ -Si-(OC ₂ H ₅ ) ₃ or RiC„H _2n -M(R ₂ )p(R ₃ Wherein M is Si, Ti, Sn, Zr or Al; m, n, p and x are integers, 0^η^ 127, preferably n is an integer from 0-17, 0 m 3, 0 ^p^2 _; l ^x^4 _; R ₂ and R ₃ are each selected from Cl, CH ₃ , OC _x H _2x+1 or OC ₂ H ₄ OCH _{3 ; in} the OC _x H _2x+1 , x= An integer of from 1 to 20, preferably x is an integer from 1 to 4; the selected from the group consisting of H, aliphatic alkyl, phenyl, vinyl, amino, CN, HCO H ₂ , Cl, H ₂ (CH ₂ ) ₂ H 2 a 3-glycidoxy group, a methacryloyloxy group or a decyl group; the emulsifier is selected from the group consisting of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer, and a sodium salt hydrolysate of an ethylene-maleic anhydride copolymer. a sodium salt hydrolyzate of a vinyl methyl ether-maleic anhydride copolymer, a sodium salt hydrolyzate of an isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, Methacrylamide, isobutyl Copolymer obtained by copolymerization of olefin, acrylate, methacrylate or acrylonitrile, polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, OP-5, OP-10, Span20, Span60, Span80, Tween20, Tween 60, Tween 80, Triton X-100, sodium lauryl sulfate, sodium lauryl sulfonate, sodium dodecylbenzene sulfonate, cetyltrimethylammonium bromide and dioctyl sulfonate At least one of sodium; the emulsifier is used in an amount of 1% to 20% by weight of the initial emulsion, specifically 1% to 15%, 5-15%, 5-10%, 10-20%, 5% And 8%, 10%, 15% or 20%; the acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid and nitric acid, and the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonia water; The percentage of the total weight of the reaction phase reactant and the continuous phase reactant in the reaction system is greater than 0 and less than 80%, specifically 10-20%, 10-30%, 20-40% 30-60% or 40-50 In the method 2, wherein, in the ABC triblock copolymer, the A block is a hydrophilic polymer segment selected from the group consisting of polyoxyethylene, polymaleic anhydride, polymethyl methacrylate, and poly Propylene At least one of; B block is a reactive olefin or alkyne polymer segment selected from polyacetylene, polybutadiene or polyisoprene; C block is a hydrophobic polymer segment, And at least one selected from the group consisting of polyoxypropylene, polyoxybutylene, polystyrene, polyolefin, and polysiloxane; wherein the solvent as the dispersed phase and the continuous phase in the emulsion is respectively selected from mutually incompatible polar groups a solvent and a non-polar solvent; wherein the non-polar solvent is at least one selected from the group consisting of aromatic hydrocarbons, paraffin wax, n-hexane, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, aliphatic hydrocarbons and ethyl acetate; The polar solvent is at least one selected from the group consisting of water, ethylene glycol, propylene glycol, glycerin, tetrahydrofuran, and N, N-dimethylformamide; and the ultraviolet light irradiation step is 5 to 60 minutes. ;

In the third method, the monomer or prepolymer of the polycondensation reaction is selected from the group consisting of acrylonitrile, vinyl acetate, urea formaldehyde resin, melamine resin, phenolic resin, melamine modified urea-formaldehyde resin, and polyethylene glycol modified urea-formaldehyde resin. , polypropylene glycol modified urea-formaldehyde resin, polyethylene glycol modified melamine resin with molecular weight of 200-2000, polypropylene glycol modified melamine resin with molecular weight of 200-2000, polyvinyl alcohol modified urea-formaldehyde resin, m-benzene Diphenol modified urea-formaldehyde resin, hydroquinone modified urea-formaldehyde resin, phenol-modified urea-formaldehyde resin, phenol and melamine copolymer modified urea-formaldehyde resin, polyvinyl alcohol and melamine copolymer modified urea-formaldehyde resin, resorcinol and melamine copolymerization At least one of a urea-formaldehyde resin, a resorcinol, and a polyvinyl alcohol copolymer-modified urea-formaldehyde resin, a resorcinol-modified melamine resin, and a polyvinyl alcohol-modified melamine resin; the initiator is selected from the group consisting of lithium persulfate - triethyl aluminum, lithium persulfate - triethyl boron, lithium persulfate - triethyl lead, hydrogen peroxide - ferrous salt, persulfate - sodium hydrogen sulfite, dibenzoyl peroxide, even two At least one of butyronitrile, persulfate, dicumyl peroxide, cumene hydroperoxide, and tert-butyl cumene; the emulsifier is selected from the sodium salt hydrolyzate of a styrene-maleic anhydride copolymer a sodium salt hydrolyzate of an ethylene-maleic anhydride copolymer, a sodium salt hydrolyzate of a vinyl methyl ether-maleic anhydride copolymer, a sodium salt hydrolyzate of an isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid Copolymer copolymerized with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile, polyvinylbenzenesulfonic acid, polyvinylbenzenesulfonic acid Sodium, OP-5, OP-10, Span20, Span60, Span80, Tween20, Tween60, Tween80, Triton X-100, sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate At least one of cetyltrimethylammonium bromide and sodium dioctyl sulfonate; the emulsifier is used in an amount of from 1% to 20% by weight of the initial emulsion, specifically from 1% to 15% 5-15%, 5-10%, 10-20%, 5%, 8%, 10%, 15% or 20%; The solvent is at least one selected from the group consisting of aromatic hydrocarbons, paraffin wax, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, aliphatic hydrocarbons and ethyl acetate, preferably octadecane; The radical polymerization monomer is selected from the group consisting of styrene, butadiene, isoprene, Methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, ethyl cinnamate methacrylate, methyl acrylate, ethyl acrylate, acrylic acid At least one of butyl ester, tert-butyl acrylate, propylene oxide, vinyl butyl acrylate, isobutylene or vinyl acetate, divinyl benzene, ethylene glycol dimethacrylate and diallyl terephthalate The polar solvent is selected from at least one of water, ethylene glycol, propylene glycol, glycerin, tetrahydrofuran, and N, N-dimethylformamide; the monomer of the radical polymerization reaction and the initiation The molar ratio of the agent is 10: 1-1000: 1; preferably 50: 1: 500: 1; the temperature of the radical polymerization is 20-90 ° C, and the reaction time is 0.5-72 hours, preferably 2 -16 hours; the temperature of the polycondensation reaction is 60-90 ° C, and the reaction time is 0.5-72 hours, preferably 2-16 hours; in the fourth method, the inorganic reactant has the structural formula X _n MR _m: where M is Si, Ti, Sn, A1 or Zr; X is Na, Mg or K, n is 0, 1 or 2; R is Cl, OS0 ₄ , OCH ₃ , OCH ₂ CH ₃ , OCH(CH ₃ ) ₂ , OCH ₂ CH ₂ CH ₂ CH ₃ or S0 ₄ , m is 1, 2, 3 or 4; or

(C ₂ H ₅ 0)3-Si-(CH ₂ )3-S _x -(CH ₂ )3-Si-(OC ₂ H ₅ ) ₃ RiC _n H _2n -M(R ₂ ) _p (R ₃ ) _2- p: where M is Si, Ti, Sn, Zr or Al; m, n, p and x are integers, 0 n 127, preferably n is an integer from 0 to 17, 0 m 3, 0^p^ 2; l ^x^4; R ₂ and R ₃ are each selected from one or more of Cl, CH ₃ , OC _x H _2x+1 or OC ₂ H ₄ OCH ₃ ; the OC _x H _2x+1 Wherein x is an integer from 1 to 20, preferably X is an integer from 1 to 4; the selected from the group consisting of H, aliphatic alkyl, phenyl, vinyl, amino, CN, NHCONH ₂ , Cl, NH ₂ (CH ₂ ) ₂ NH, 2, 3-epoxypropoxy, methacryloxy or fluorenyl; the monomer or prepolymer of the polycondensation reaction is selected from the group consisting of urea formaldehyde, melamine resin, phenolic resin, melamine modification Urea-formaldehyde resin, polyethylene glycol modified urea-formaldehyde resin, polypropylene glycol modified urea-formaldehyde resin, polyethylene glycol modified melamine resin with molecular weight of 200~2000, polypropylene glycol modified melamine with molecular weight of 200~2000 Resin, polyvinyl alcohol modified urea-formaldehyde resin, resorcinol-modified urea-formaldehyde resin, hydroquinone-modified urea-formaldehyde resin, phenol-modified urea-formaldehyde tree , phenol and melamine copolymerization modified urea-formaldehyde resin, polyvinyl alcohol and melamine copolymerization modified urea-formaldehyde resin, resorcinol and melamine copolymerization modified urea-formaldehyde resin, resorcinol and polyvinyl alcohol copolymerization modified urea-formaldehyde resin, resorcinol At least one of a modified melamine resin and a polyvinyl alcohol-modified melamine resin; the radically polymerizable monomer dissolved in the non-polar solvent is selected from the group consisting of styrene, butadiene, isoprene, methyl Methyl acrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, methacrylic acid, ethyl cinnamate, methyl acrylate, ethyl acrylate, butyl acrylate Ester, tert-butyl acrylate, propylene oxide, dimethyl silane, vinyl butyl acrylate, isobutylene or vinyl acetate, divinyl benzene, ethylene glycol dimethacrylate and diallyl terephthalate At least one of; the radical polymerization initiator dissolved in the non-polar solvent is selected from the group consisting of azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, cumene hydroperoxide, and oxygen Dodecyl, peroxydicarbonate and isopropyl ester, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide/N,N-dimethylaniline redox initiation system, naphthate and diphenyl peroxide At least one of a formyl redox initiation system; the non-polar solvent is selected from at least one of an aromatic hydrocarbon, a paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, an aliphatic hydrocarbon, and ethyl acetate. The radically polymerizable monomer dissolved in a polar solvent is at least one selected from the group consisting of acrylamide, acrylic acid, methacrylic acid, vinyl alcohol, and N-methylol acrylamide; The radical polymerization initiator is selected from the group consisting of potassium persulfate, ammonium persulfate, a redox initiation system consisting of a persulfate and a thiosulfate or a sulfite, a redox initiation consisting of a persulfate with a fatty amine or a fatty diamine. At least one of the systems; the polar solvent is at least one selected from the group consisting of water, ethylene glycol, propylene glycol, glycerol, tetrahydrofuran, and N, N-dimethylformamide The emulsifier is selected from the group consisting of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer, a sodium salt hydrolyzate of an ethylene-maleic anhydride copolymer, and a sodium salt hydrolyzate of a vinyl methyl ether-maleic anhydride copolymer. a sodium salt hydrolyzate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid copolymerized with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile Copolymer, polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, OP-5, OP-10, Span20, Span60, Span80, Tween20, Tween60, Tween80, Triton X-100, dodecyl At least one of sodium sulfate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, and sodium dioctylsulfonate; the emulsifier The amount is from 1% to 20% by weight of the initial emulsion, specifically 1%-15%, 5-15%, 5-10%, 10-20%, 5%, 8%, 10%, 15% or 20%; In the polycondensation reaction, the temperature is 60-90 ° C, preferably 70 ° C, and the reaction time is 0.5-72 hours, preferably 2-16 hours; The molar ratio of the monomer of the radical polymerization reaction to the initiator is 10: 1-1000: 1; preferably 50: 1: 500: 1; the temperature of the radical polymerization reaction is 20-90 ° C, The reaction time is from 0.5 to 72 hours, preferably from 2 to 16 hours. In the method 5, in the step a), the prepolymer of the monomer or resin dissolved in the continuous phase solvent is selected from the group consisting of acrylonitrile, vinyl acetate, urea formaldehyde resin, melamine resin, phenolic resin, melamine modified Urea-formaldehyde, polyethylene glycol modified urea-formaldehyde resin, polypropylene glycol modified urea-formaldehyde resin, polyethylene glycol modified melamine resin with molecular weight of 200~2000, polypropylene glycol modified with molecular weight of 200~2000 Melamine resin, polyvinyl alcohol modified urea-formaldehyde resin, resorcinol-modified urea-formaldehyde resin, hydroquinone-modified urea-formaldehyde resin, phenol-modified urea-formaldehyde resin, phenol and melamine copolymerized urea-formaldehyde resin, polyvinyl alcohol and Melamine copolymerization modified urea-formaldehyde resin, resorcinol and melamine copolymerization modified urea-formaldehyde resin, resorcinol and polyvinyl alcohol copolymerization modified urea-formaldehyde resin, resorcinol-modified melamine resin and polyvinyl alcohol-modified melamine At least one of the resins;

In step b), the continuous phase reactant and the dispersed phase reactant are each selected from the group consisting of a diamine, a polyamine, a glycol, a polyol, a dihydric phenol, a polyhydric phenol, a dibasic acid chloride, a polyacid chloride, a disulfide. At least one of an acid chloride, a polysulfonyl chloride, a diisocyanate, a polyisocyanate, a bischloroformate, an epoxy resin prepolymer, and an organosiloxane prepolymer;

In the step c), the dispersed phase radical polymerizable monomer is selected from the group consisting of styrene, butadiene, isoprene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid. Butyl ester, isobutyl methacrylate, ethyl cinnamic acid acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, propylene oxide, dimethyl silane, vinyl butyl ester, At least one of isobutylene or vinyl acetate, divinylbenzene, ethylene glycol dimethacrylate and diallyl terephthalate;

In the step d), the dispersed phase polymer and the continuous phase polymer forming the primary shell layer are selected from the group consisting of polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin, casein, gum arabic, sodium alginate, agar, poly Sodium phosphate, sodium polysilicate, carboxymethyl cellulose, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene-maleic anhydride copolymer, vinyl methyl ether-butylene a sodium salt hydrolyzate of an acid anhydride copolymer, a sodium salt hydrolyzate of an isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, a copolymer obtained by copolymerizing methacrylate or acrylonitrile, at least one of polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, polyvinylpyridinium bromide and polyvinylpyrrolidone; In the step a'), the monomer or resin prepolymer dissolved in the continuous phase solvent is selected from the group consisting of acrylonitrile, vinyl acetate, urea formaldehyde resin, melamine resin, phenolic resin, melamine modified urea resin, polyethyl b Diol modified urea-formaldehyde resin, polypropylene glycol modified urea-formaldehyde resin, polyethylene glycol modified melamine tree with molecular weight of 200~2000, polypropylene glycol modified melamine resin with molecular weight of 200~2000, polyethylene Alcohol-modified urea-formaldehyde resin, resorcinol-modified urea-formaldehyde resin, hydroquinone-modified urea-formaldehyde resin, phenol-modified urea-formaldehyde resin, phenol and melamine copolymerization modified urea-formaldehyde resin, polyvinyl alcohol and melamine copolymerization modified urea-formaldehyde resin, Hydroquinone and melamine copolymerized at least one of urea-formaldehyde resin, resorcinol and polyvinyl alcohol copolymer-modified urea-formaldehyde resin, resorcinol-modified melamine resin and polyvinyl alcohol-modified melamine resin;

In the step b'), the polymer having an opposite charge to the polymer obtained in the step 1) is selected from the group consisting of polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin, casein, gum arabic, sodium alginate, agar, Sodium polyphosphate, sodium polysilicate, carboxymethyl cellulose, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene-maleic anhydride copolymer, vinyl methyl ether-butylene Sodium salt hydrolysate of dianhydride copolymer, sodium salt hydrolyzate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate a copolymer obtained by copolymerizing methacrylate or acrylonitrile, at least one of polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, polyvinylpyridinium bromide and polyvinylpyrrolidone;

Step a) In the polycondensation reaction, the temperature is 60-90 ° C, preferably 70 ° C, the time is 0.5-72 hours, preferably 2-16 hours, the pH is 2-10, and the stirring speed is 50-16000r/min. Preferably, in the polycondensation or polyaddition reaction of step b), the molar ratio of the reactive phase reactant to the continuous phase reactant reactive functional group is 1:1; the temperature is 60-90 ° C , preferably 70 ° C, the time is 0.5-72 hours, preferably 2-16 hours, the stirring speed is 50-16000r / min, preferably 150-12000r / min;

In the radical polymerization reaction in the step c), the molar fraction ratio of the dispersed phase radical polymerizable monomer to the initiator is 10: 1-1000: 1; preferably 50: 1-500: 1, temperature 20-90 ° C, time is 0.5-72 hours, preferably 2-16 hours;

In step d), the pH of the reaction system is 2-10;

Step a') In the polycondensation reaction, the temperature is 60-90 ° C, preferably 70 ° C, the time is 0.5-72 hours, preferably 2-16 hours, the pH is 2-10, and the stirring speed is 50-16000r/ Min, preferably 150-12000r/min; step b') the pH of the reaction system is 2-10;

The emulsifier is selected from the group consisting of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer, a sodium salt hydrolyzate of an ethylene-maleic anhydride copolymer, and a sodium salt hydrolyzate of a vinyl methyl ether-maleic anhydride copolymer. a sodium salt hydrolyzate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid copolymerized with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile Copolymer, polyvinylbenzenesulfonic acid, sodium polyvinylbenzenesulfonate, OP-5, OP-10, Span20, Span60, Span80, Tween20, Tween60, Tween80, Triton X-100, dodecyl At least one of sodium sulfate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, and sodium dioctylsulfonate; the emulsifier The amount is from 1% to 20% by weight of the initial emulsion, specifically 1%-15%, 5-15%, 5-10%, 10-20%, 5%, 8%, 10%, 15% or 20%;

The dispersed phase solvent is selected from the group consisting of aromatic hydrocarbons, paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, and fat. At least one of an aliphatic hydrocarbon and an ethyl acetate;

The continuous phase solvent is selected from at least one of water, ethylene glycol, propylene glycol, glycerin, tetrahydrofuran and N, N-dimethylformamide; in the method 6, the solution is dissolved in a non-polar solvent The radical polymerizable monomer is selected from the group consisting of styrene, butadiene, isoprene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate, and butyl methacrylate. Ester, methacrylic acid, ethyl cinnamate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, propylene oxide, dimethyl silane, vinyl butyl acrylate, isobutylene or vinyl acetate, At least one of vinyl benzene, ethylene glycol dimethacrylate, and diallyl terephthalate; the radical polymerization initiator dissolved in the non-polar solvent is selected from the group consisting of azobisisobutyronitrile, Azobisisoheptanenitrile, dibenzoyl peroxide, cumene hydroperoxide, dodecyl peroxide, isopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, diphenyl peroxide Acyl/N, N-dimethylaniline redox At least one of a hair system, a naphthate and a dibenzoyl peroxide redox initiating system; the non-polar solvent is selected from the group consisting of aromatic hydrocarbons, paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane At least one of an aliphatic hydrocarbon and an ethyl acetate; the radically polymerizable monomer dissolved in a polar solvent is selected from the group consisting of acrylamide, hydrazine, hydrazine-dimethylbisacrylamide, acrylic acid, methacrylic acid, and vinyl alcohol. At least one of hydrazine-hydroxymethyl acrylamide; the radical polymerization initiator dissolved in a polar solvent is selected from the group consisting of potassium persulfate, ferrous sulfate, ammonium persulfate, and persulfate and thiosulfate a mixture of the composition, a mixture of persulfate and sulfite, a mixture of persulfate and fatty amine or a mixture of persulfate and fatty diamine, preferably potassium persulfate and sulfuric acid At least one of ferrous iron; the polar solvent is at least one selected from the group consisting of water, ethylene glycol, propylene glycol, glycerol, tetrahydrofuran, and hydrazine, hydrazine-dimethylformamide, preferably water; Agent selected from benzene Sodium salt hydrolysate of ethylene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene methyl ether-maleic anhydride copolymer, isobutylene-maleic anhydride copolymerization Copolymer of sodium salt hydrolysate, acrylic acid or methacrylic acid copolymerized with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile, poly Vinyl benzene sulfonic acid, sodium polyvinylbenzene sulfonate, hydrazine-5, hydrazine-10, Span20 Span60, Span80, Tween20, Tween60, Tween80, Triton X-100, sodium lauryl sulfate, dodecyl sulfonate At least one of sodium, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide (CTAB) and sodium dioctyl sulfonate; the emulsifier is used as the initial emulsion weight 1% to 20%, specifically 1%-15%, 5-15%, 5-10%, 10-20%, 5%, 8%, 10%, 15% or 20%; the radical polymerization The molar fraction ratio of the monomer to the radical polymerization initiator is 10: 1-1000: 1; preferably 50: 1: 500: 1; The temperature of the radical polymerization reaction is 20-90 ° C, the reaction time is 0.5-72 hours, preferably 2-16 hours; the concentration of the radical polymerizable monomer in the emulsion system is 0.01%-90%, preferably 0.1%-30%.