WO2008154839A1

WO2008154839A1 - A sheet composite material with dual surface properties and its preparation process

Info

Publication number: WO2008154839A1
Application number: PCT/CN2008/071230
Authority: WO
Inventors: Zhenzhong Yang; Jiguang Liu; Xiaozhong Qu; Huifang Xu
Original assignee: Institute Of Chemistry, Chinese Academy Of Science
Priority date: 2007-06-15
Filing date: 2008-06-06
Publication date: 2008-12-24
Also published as: CN101323713B; CN101323713A

Abstract

A sheet composite material with dual surface properties and its preparation process. The raw materials being used in the process are inorganic hollow microspheres, polymer composite spheres with inorganic shell combined on their surfaces, or polymer composite fibre with inorganic shell combined on its surface. The outer surface of the raw materials is modified, and broken into crumbs. The sheet material with one modified surface is obtained. Then, the new exposed surface is modified, the inorganic sheet material with two surfaces with different chemical properties is obtained. The inorganic sheet material includes inorganic sheet substrate and single-layer, two-layer or multi-layer chemical matter on the substrate. The chemical matters on the two substrate's surfaces are different.

Description

Sheet composite material with dual properties on surface and preparation method thereof

The invention belongs to the technical field of materials, and in particular relates to a sheet composite material having dual properties on a surface and a preparation method thereof. Background technique

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 hot topic. The preparation of particles with different chemical properties on the surface is very important for molecular identification and control of the self-assembly process. If one surface of the particle is hydrophilic and the other surface is lipophilic, the particle can be used as an oil-water emulsifier, a surfactant, a foam stabilizer, a wetting agent, etc., if the surface of the particle is bonded to magnetic, electrical, Light-responsive particles or chemical molecules that can be used in printer inks, medicine, and more.

The earliest de Gennes and his colleagues dipped half of the glass beads into the varnish so that half of the beads were covered with varnish and the other half remained on the original surface, then treated with a silicon germanium coupling agent, not covered with varnish. The surface is modified; however, this method is difficult to prepare nanoscale microscopic particles with dual properties, because when the particles are too small, it is difficult to ensure that all particles are only partially coated, and the varnish layer will easily flood the entire particle. It has been reported that the charged microspheres are dispersed at the water-air interface or the liquid-solid interface, or the microspheres are partially embedded in the paraffin medium, and then modified; these methods have only theoretical research value, due to the requirement of microscopic The particles must be monodispersed on the surface of the medium, which limits the large amount of preparation; in addition, various complicated treatment methods also bring great limitations. Summary of the invention

It is an object of the present invention to provide a sheet-like composite material having a dual nature of the surface, i.e., different surfaces having different chemical properties. The different surfaces of the sheet-like composite material have different responses to electricity, magnetism and light, and thus can be used in the field of materials; the sheet-like composite material has emulsification properties in an organic, inorganic dispersed phase or different organic dispersed phases, and the sheet The composites have different orientations at the interface.

A further object of the present invention is to provide a method for preparing the sheet-like composite material, which can not only prepare a large amount of sheet-like composite materials having different chemical compositions on both sides, but also can design and change inorganic sheet-like composite materials according to requirements. The composition and properties of the surface, that is, the molecular design and production of the sheet-like composite material having dual properties can be carried out according to actual needs.

The inorganic sheet-like composite material having dual properties on the surface provided by the invention comprises inorganic sheets Shaped substrate and two positioned on the substrate surface of the monolayer, bilayer or multilayer composite ² composite chemical substance, the chemical substance on the both surfaces of the substrate are not the same; the organic chemistry by a single chemical group a group consisting of nanoparticles bonded by an organic chemical group or a polymer bonded by an organic chemical group; the double-layered compound is a single layer structure of a polymer bonded by an organic chemical group, and a two-layer composite structure composed of a composite of nanoparticles or a polymer; the multi-layer composite chemical substance is a multilayer composite structure formed by repeatedly adsorbing a polymer on the basis of a polymer bonded by an organic chemical group. ; among them:

(a) in the nanoparticle bound by an organic chemical group, the organic chemical group has an opposite charge property to the nanoparticle;

(b) in the two-layer composite structure, the organic chemical groups of the adjacent layers have opposite charge properties to the polymer of the first layer, and the nanoparticles have the opposite relationship with the polymers of the first layer a charge property, or an opposite charge property between the polymer of the first layer and the polymer of the second layer;

(c) In the multilayer composite structure, the polymers of the adjacent two layers are different and have opposite charge properties.

In the multilayer composite structure, the number of composite layers is preferably not more than 20 layers, more preferably 3 to 10 layers. The multi-layer composite structure, such as: organic chemical group / polymer A / polymer B / polymer C layer composite.

The thickness of the sheet-like composite material of the present invention is preferably from more than 0 μm to less than or equal to ΙΟΟμηι, more preferably from 1 to 80 μm.

The structure of the substrate may be a single-layer inorganic substrate composed of the same inorganic substance, or may be a multilayer composite inorganic substrate composed of different inorganic substances, such as: Si0 ₂ /Ti0 ₂ /Si0 ₂ multilayered junction.

^The inorganic substance may include one or more of an oxide or a hydroxide of silicon, aluminum, titanium, magnesium, zirconium, iron, zinc, tin, calcium.

The inorganic substance may further comprise one or more of potassium, sodium, lithium oxides or hydroxides in an amount of not more than 50% by weight based on the total weight of the substrate.

The organic chemical group may be a chemical group as shown in Formula 1:

RC _n H _2n - (Formula 1)

In Equation 1, n is an integer from 0 to 24;

R is -H, -NH ₂ , HS -, -SCN, -NHCONH ₂ , CI-, NH ₂ (CH ₂ ) ₂ NH -, (CH ₃ ) ₂ -C(Br)-C(0)-NH - , -S0 ₃ , -Ph-SOCl ₂ , -Ph-S0 ₃ , 2,3-epoxypropoxy, methyl Acryloxy, (CH ₂ ) ₃ -S _x -, -CH ₃ , CH ₂ =CH- or Ph, wherein x is an integer from 1 to 4; when n = 0, R is not -H, -NH ₂ , CI- or -S0 ₃ .

Wherein Ph represents a phenyl group.

The chemical group as shown in Formula 1 includes two types of hydrophilic organic chemical groups and hydrophobic organic chemical groups: when R is -NH ₂ , HS-, -SCN, -NHCONH ₂ , CI-, NH ₂ (CH ₂ ₂ NH-, (CH ₃ ) ₂ -C(Br)-C(0)-NH -, -S0 ₃ , -Ph-SOCl ₂ , -Ph-S0 ₃ , 2,3-epoxypropoxy or In the case of a methacryloyloxy group, the chemical group represented by Formula 1 is a hydrophilic organic chemical group; when R is (CH ₂ :> ₃ -S _X - (x=1 to 4), -CH ₃ , When CH ₂ =CH- or Ph, the chemical group as shown in Formula 1 is a hydrophobic chemical group.

The nanoparticles may be one or more of metal nanoparticles, inorganic nanoparticles, and organic nanoparticles.

The metal nanoparticles may be selected from one or more of the nanoparticles of Au, Ag, Fe, Pd and Pt.

The inorganic nanoparticles may be selected from the group consisting of SiO ₂ , Ti _{2 2} , GeO, FeO, Fe ₃ 0 ₄ , Fe ₂ 0 ₃ , A1 ₂ 0 ₃ , Sn 0 ₂ , Cu(OH) ₂ , Eu ₂ 0 ₃ , MnFe _{2 .} One or more of 0 ₄ , CaC0 ₃ , CdS, CoO, NiO, ZnO, and CeO^ nanoparticles.

The organic nanoparticles may be selected from the group consisting of polyaniline, sulfonated polystyrene, polystyrene, styrene copolymer, polyacrylic acid, acrylate polymer, polylactic acid, chitin, and glucose nanoparticles. Or several.

The polymer may be a polyelectrolyte, polymethyl methacrylate, polystyrene and derivatives thereof or polyacrylonitrile; wherein the polyelectrolyte may be sodium polyacrylate, polyacrylic acid, polymethacrylic acid, polymalan Acid, polymaleic anhydride, polyacrylamide, polyaniline, polyvinyl alcohol, polyethylene glycol, sulfonated polystyrene, sodium polystyrene sulfonate, polydiallyldimethylammonium chloride, carboxymethyl Cellulose sodium, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polypyrrolidone, sodium alginate, hydroxymethyl starch, polydimethyldiallylammonium chloride or poly(terephthalic acid) Ethylene glycol ester.

The preparation method of the sheet composite material provided by the invention is characterized in that the inorganic hollow microspheres, the polymer composite spheres with the surface combined with the inorganic shell layer or the polymer composite fibers with the surface combined with the inorganic shell layer are used as raw materials, and the method comprises :

a. Inorganic hollow microspheres, polymer composite spheres having an inorganic shell layer bonded thereto or polymer composite fibers having an inorganic shell layer bonded thereto are contacted with chemical substance A to obtain inorganic substances modified by inorganic shells. Hollow microspheres, polymer composite spheres modified with an inorganic shell, or polymer composite fibers modified with an inorganic shell;

b. crushing the outer shell of the inorganic hollow microsphere modified by the inorganic shell obtained in step a, Or the inorganic shell obtained in the step a is separated from the polymer component by the modified polymer composite sphere or the inorganic shell modified polymer composite fiber, and the inorganic shell is broken, and then the inorganic fragments are collected;

c. contacting the inorganic fragments obtained in step c with the chemical substance B to obtain the sheet composite material,

Wherein the chemical substance A and the chemical substance B are different, and the chemical substance A and the chemical substance B each independently comprise a silicon germanium coupling agent, and selectively include perchloric acid, dichromate, permanganate, One or more of sulfuric acid, nanoparticles, polymers, and mixtures of nanoparticles and polymers.

In the preparation method provided by the present invention, in the step a, the inorganic hollow microspheres, the polymer composite spheres whose surface is bonded to the inorganic shell layer or the outer surface of the polymer composite fiber whose surface is bonded to the inorganic shell layer are modified. Obtaining inorganic hollow microspheres modified with an inorganic shell, polymer composite spheres modified with an inorganic shell or polymer composite fibers; in step b, the shell of the inorganic hollow microspheres modified with the inorganic shell is broken, Or separating the inorganic shell and the polymer component in the polymer composite sphere or the polymer composite fiber and breaking the inorganic shell, collecting the inorganic fragments, and the collected inorganic fragments have been modified in step a, newly exposed. The surface has not been modified; in step c, the newly exposed surface of the inorganic debris is modified to obtain a sheet composite having both surfaces modified, and used for modification in steps a and c The chemicals are different, so the two surfaces of the resulting sheet composite have different chemical properties.

The inorganic hollow microspheres, the polymer composite spheres whose surface is combined with the inorganic shell layer or the polymer composite fibers whose surface is combined with the inorganic shell layer may have a diameter of 6 mm _or less _; the shell layer and surface combination of the inorganic hollow microspheres The thickness of the inorganic composite shell of the polymer composite sphere of the inorganic shell layer or the polymer composite fiber of the surface-bound inorganic shell layer may be 100 μm or less.

The inorganic hollow microsphere shell, the shell of the polymer composite sphere surface-bonded with the inorganic shell layer or the shell of the polymer composite fiber surface-bonded with the inorganic shell layer is composed of the same inorganic substance, or A multilayer composite structure composed of different inorganic substances. The shell layer of the inorganic hollow microsphere, the polymer composite sphere whose surface is combined with the inorganic shell layer or the inorganic shell layer of the surface of the polymer composite fiber surface-bonded with the inorganic shell layer may contain silicon, aluminum, titanium, magnesium a mixture of one or more of zirconium, iron, zinc, tin, calcium oxides or hydroxides; the inorganic shell layer may further contain potassium, sodium, lithium oxides or hydroxides, etc. One or more of the mixtures in an amount less than 50% by weight of the inorganic shell.

The inorganic hollow microspheres may be commercially available pure hollow microspheres or synthetic pure inorganic hollow microspheres, and the spherical shell of the hollow microspheres should be sealed. Such as glass hollow microspheres, ceramic hollow spheres And pure inorganic hollow spheres prepared now. Specifically, it is prepared by referring to the following method:

The prepared precursor solution (mixed with 5 parts by weight of sodium dodecylbenzenesulfonate, 500 parts by weight of water, 1 part by weight of 2 mol/L of hydrochloric acid, 100 parts by weight of tetraethyl orthosilicate) Prepared in 30 minutes) In a liquid channel in a special bubble generating device with two inner and outer air flow channels and one liquid channel through a continuous liquid inlet device at a flow rate of 5 mL/min, at a flow rate of 40 L/h. A continuous single bubble is produced, which is solidified by a heat curing device blown into a 300 ° C air stream at a gas flow rate of 200 L/h, and solidified to form a hollow sphere.

The outer surface of the inorganic hollow microspheres, the polymer composite spheres bonded to the inorganic shell layer or the outer surface of the polymer composite fibers bonded to the inorganic shell layer may also be treated with nitric acid, hydrochloric acid or sulfuric acid before use.

The polymer composite spheres having the surface combined with the inorganic shell layer or the polymer composite fibers having the surface combined with the inorganic shell layer are commercially available or can be prepared according to literature methods (eg, Literature 47 (2006) 8360~8366. Or, a composite ball or a composite fiber in which the above inorganic shell layer is bonded is formed in the following manner. For example, the polymer ball or fiber containing a polar group on the surface is immersed in the SiO ₂ , Ti _{2 2} sol, and then taken out, wherein the appropriate immersion time can be selected according to the thickness of the desired inorganic layer, for example, the immersion time can be 1-1000 seconds; or immersing polymer spheres or fibers with polar groups on the surface in tetraethyl orthosilicate and/or butyl titanate solution, adding water (may also add a small amount of acid or base to improve hydrolysis) 1 wt%。 The concentration of the tetraethyl orthosilicate and the butyl titanate solution, the immersion time and the amount of water, for example, the concentration may be 0. 1 wt% - _20wt%; soaking time may be 1 second to 1 hour, and / or tetrabutyl titanate used in the amount of water per g of tetraethyl orthosilicate 0.5 g or less.

More specifically, the preparation method of the inorganic composite microspheres having the multi-layer composite structure inorganic shell, the polymer composite spheres bonded to the inorganic shell layer or the polymer composite fibers having the surface-bound inorganic shell layer can be referred to The following preparation method:

(a) Dispersing polymer microspheres having polar groups (such as sulfonic acid groups, amino groups, hydroxyl groups, etc.) on the surface in an ethanol solution according to a weight ratio of 0.1% to 1%, and adding ammonia water (volume of ammonia water) Preferably, the volume of the ethanol is from 1% to 10% by volume, and the inorganic shell precursor A is added dropwise to the above reaction system under stirring. The amount of the inorganic shell precursor A is generally the polymerization of the sulfonic acid group. 1/3 to 2 times (by weight) of the microspheres. The reaction temperature is preferably 10 to 40 ° C, more preferably room temperature, and the reaction time is preferably 4 to 8 hours, and centrifugal washing is performed to obtain an inorganic shell layer A/polystyrene composite ball. The prepared inorganic shell layer A/polystyrene composite microspheres are dispersed in the ethanol sol of the inorganic shell precursor B according to a weight ratio of 1% to 0.1%, wherein the inorganic shell precursor B The concentration of the reaction is 0. 01~0. 05M, the concentration of H ⁺ is 0. 03~0. 08M; 65 to 80 ° C, the reaction time is preferably 12 to 24 hours, after washing twice with absolute ethanol, a large amount of water is washed until the supernatant is neutral. The obtained product is a composite microsphere of an inorganic shell layer B/inorganic shell layer A/polystyrene which is composed of two inorganic shell layers. or

(b) The process of preparing the inorganic shell layer C by repeating the composite microspheres of the inorganic shell layer B/inorganic shell layer A/polystyrene obtained in the step (a). A three-layer inorganic shell composite inorganic shell C/inorganic shell B/inorganic shell A/polystyrene composite microsphere was obtained. Or

(c) dispersing the polymer microspheres in an ethanol solution according to a weight ratio of 0.1% to 10%, adding an acid (the volume of the acid is preferably 1% to 20% by volume of the ethanol), and the inorganic shell is stirred under stirring The layer precursor is added dropwise to the above reaction system, and the amount of the inorganic shell precursor is generally 1/20 to 1 times that of the polymer microspheres. The reaction temperature is preferably room temperature, the reaction time is preferably 4 to 8 hours, and then spray-dried to obtain an inorganic shell/polymer composite sphere. The acid refers to a protic acid such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid or formic acid.

In the preparation method of the inorganic composite microspheres having a multi-layer composite inorganic shell, the polymer composite spheres having a surface-bound inorganic shell layer or the polymer composite fibers having a surface-bound inorganic shell layer. The inorganic shell precursor refers to tetraethyl orthosilicate, butyl titanate, ferric chloride, ferrous chloride or aluminum trichloride.

The polymer in the polymer composite sphere or the polymer composite fiber surface-bonded with the inorganic shell layer may be selected from one or more of the following polymers: polyethylene terephthalate Glycol ester, nylon-6, nylon-66, acrylic, spandex, polyacrylic acid, polymethacrylic acid, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, cellulose acetate, polyethylene oxide fiber, hydroxypropyl Cellulose, hydroxypropyl methylcellulose, polyacrylamide, polymethacrylate, sulfonated polystyrene, polysulfone, polyvinyl chloride, hydroxyl-containing polypropylene, hydroxyl-containing polyethylene, polyethylene, Polypropylene, polybutadiene, ethylene-butadiene copolymer, methacrylic acid copolymer, polystyrene, styrene copolymer, polymethylstyrene, methylstyrene copolymer, polybenzyl chlorostyrene , benzyl chlorostyrene copolymer.

According to some embodiments, the method of preparing a sheet composite of the present invention comprises the following specific steps:

(1) Inorganic hollow microspheres, polymer composite spheres bonded to the inorganic shell layer or polymer composite fiber materials bonded to the inorganic shell layer and oxidizing substances (eg perchloric acid, potassium dichromate, Contact with potassium permanganate solution or concentrated sulfuric acid), wash, dry; and then with excess (ie, the hydrophobic group-containing silicon germanium coupling agent used exceeds inorganic hollow microspheres, surface-bound inorganic shell Reaction of a polymer composite sphere or a polymer composite fiber material having a surface combined with an inorganic shell layer The required molar amount, that is, the number of silicon germanium coupling agent molecules required per square nanometer of microspheres is at least 5) contact with a solution of a hydrophobic group-containing silicon germanium coupling agent; or inorganic hollow microspheres The polymer composite ball with the surface combined with the inorganic shell layer or the polymer composite fiber material with the surface combined with the inorganic shell layer directly and excessively (the hydrophobic group-containing silicon germanium coupling agent used exceeds the inorganic hollow microsphere, Contacting a polymer composite sphere having a surface-bound inorganic shell or a polymer composite fiber material having a surface-bound inorganic shell layer in contact with a silicon-germanium coupling agent containing a hydrophobic group, wherein The contact temperature of the solution of the crosslinking agent may include: the concentration range of the hydrophobic group-containing silicon germanium coupling agent is preferably 0.5 to 50% by weight, the contact temperature is higher than the freezing point of the solution and lower than the boiling point of the solution, and the contact The time is preferably from 30 minutes to 96 hours, and the inorganic hollow microspheres whose outer surface of the inorganic outer shell is modified by the hydrophobic group-containing silicon germanium coupling agent, and the polymer composite spheres or the surface bonded with the inorganic shell layer are obtained. Binding inorganic polymer composite fiber shell; and

(2) The outer surface obtained in the step (1) is broken by the inorganic hollow microspheres, the polymer composite spheres or the polymer composite fibers modified by the hydrophobic group-containing silicon germanium coupling agent, and the inorganic fragments are collected to obtain one side. Inorganic fragments of hydrophobic organic chemical groups; the excess of the obtained inorganic fragments and the excess (the hydrophilic group-containing silicon germanium coupling agent used exceeds the molar amount required to react with the inorganic particles containing one hydrophobic organic group on one side) The contact of the silicon germanium coupling agent solution containing a hydrophilic group, wherein the contact with the solution of the silicon germanium coupling agent may include: the concentration of the silicon germanium coupling agent containing the hydrophilic group is preferably 0.5 -50% by weight, the contact time is preferably from 30 minutes to 96 hours, the contact temperature is higher than the freezing point of the solution and lower than the boiling point of the solution, and a sheet having a hydrophobic organic chemical group on one side and a hydrophilic organic chemical group on the other side is obtained. Composite material.

Alternatively, in accordance with certain embodiments, the method of making a sheet composite of the present invention comprises the following specific steps:

( 1 ' ) an inorganic composite microsphere, a polymer composite sphere whose surface is bonded to an inorganic shell layer, or a polymer composite fiber material whose surface is bonded to an inorganic shell layer, and an oxidizing substance (such as perchloric acid, potassium dichromate, Contact with potassium permanganate or concentrated sulfuric acid), and then with excess (the fat-containing sulfhydryl-containing silicon germanium coupling agent exceeds the polymer composite sphere or surface with inorganic hollow microspheres, surface-bound inorganic shell layer The polymer composite fiber material combined with the inorganic shell layer is subjected to contact with a solution of a fat sulfhydryl group-containing silicon germanium coupling agent required for the reaction; or, the inorganic hollow microspheres are bonded to the surface of the inorganic shell Polymer composite spheres or polymer composite fiber materials with surface-bound inorganic shells directly and in excess (polymerization of fat-containing sulfhydryl-containing silicon germanium coupling agents exceeds polymerization with inorganic hollow microspheres, surface-bound inorganic shells) Contacting a solution of a fat-containing sulfhydryl group-containing silicon germanium coupling agent, which is required for the reaction of the composite composite ball or the polymer composite fiber material having a surface combined with the inorganic shell layer, The strip in contact with the solution of the silicon germanium coupling agent may include: the concentration of the fat-containing germanium-containing silicon germanium coupling agent is preferably in the range of 0.5 to 50% by weight, the contact temperature is higher than the freezing point of the solution and lower than the solution The boiling point, the contact time is preferably from 30 minutes to 96 hours, the inorganic hollow microspheres whose outer surface of the inorganic outer shell is hydrophobically modified by the fat sulfhydryl group, the polymer composite spheres whose surface is combined with the inorganic shell layer or the surface-bound inorganic shell layer Polymer composite fiber; and

(2') crushing the inorganic hollow microspheres, polymer composite spheres or polymer composite fibers hydrophobically modified by the fatty sulfhydryl group obtained in the step (Γ) to collect inorganic fragments; and the above surface contains a fat sulfhydryl hydrophobic group The inorganic shards of the sulphide and the excess (the molar amount required for the sulfhydryl group-containing silicon germanium coupling agent to be used in excess of the inorganic sheet containing a fatty sulfhydryl hydrophobic group on the surface) The solution is contacted, wherein the contact with the solution of the silicon germanium coupling agent may include: the concentration of the germanium-containing silicon germanium coupling agent is preferably in the range of 0.5 to 50% by weight, and the contact time is preferably 30 minutes to 96 hours. , the contact temperature is higher than the freezing point of the solution and lower than the boiling point of the solution; an inorganic sheet having a fat sulfhydryl group on one side and a sulfhydryl group on the other side is obtained; and then the inorganic sheet is further oxidized in excess (the oxidizing substance-containing solution used) The amount of the substance exceeds the molar amount required for the reaction with the sulfhydryl group on the surface of the inorganic sheet. The solution containing the oxidizing substance is in contact with the oxidizing substance. Conditions may include: contacting temperature is preferably 0 ° C-90 ° C, the contact time is at least 10 minutes, to obtain a sheet-like composite material having on one surface a hydrophobic group and the other surface of the embankment having a hydrophilic sulfonic acid group.

(1") coupling of inorganic hollow microspheres, polymer composite spheres with surface-bound inorganic shells or polymer composite fiber materials with surface-bound inorganic shells and excess (of fat-containing sulfhydryl-containing silicon germanium) The amount of the agent exceeds the molar amount required for the reaction of the inorganic composite microspheres, the polymer composite spheres bonded to the surface of the inorganic shell layer or the polymer composite fiber material of the surface-bound inorganic shell layer. The solution is contacted, wherein the contact with the solution of the silicon germanium coupling agent may include: the concentration of the fat-containing cerium-containing silicon germanium coupling agent solution is preferably in the range of 0.5 to 50% by weight, and the contact temperature is higher than the freezing point of the solution And below the boiling point of the solution, the contact time is preferably from 30 minutes to 96 hours, and the inorganic hollow microspheres whose outer surface of the inorganic outer shell is hydrophobically modified by the fat sulfhydryl group, the polymer composite spheres whose surface is bonded with the inorganic shell layer or the surface combination are obtained. a polymer composite fiber of an inorganic shell layer; and (2") a composite of inorganic hollow microspheres, polymer composite spheres or polymers which are hydrophobically modified by a fatty sulfhydryl group obtained in the step (1") The fiber is broken, and the inorganic chips are collected; the inorganic particles and the excess (the amount of the silicon ruthenium coupling agent containing the amino hydrophilic group used exceeds the molar amount required for the reaction with the inorganic sulfhydryl group-containing inorganic sheet) contain the amino group. Contacting a silicon germanium coupling agent solution of a water group, wherein The condition of contacting with the solution of the silicon germanium coupling agent may include: the concentration of the amino group-containing silicon germanium coupling agent solution is preferably in the range of 0.5 to 50% by weight, the contact temperature is higher than the freezing point of the solution and lower than the boiling point of the solution, and the contact time Preferably, it is 30 minutes to 96 hours; and then contacted with 2-bromoisobutyl bromide, wherein the conditions of contact with 2-bromoisobutyl bromide may include: the temperature of the contact may be -60 ° C to 20 ° C, The contact time may be from 10 minutes to 30 hours, and an inorganic sheet-like composite material having a hydrophilic/lipophilic dual property having a fat-based hydrophobic group on the surface and an organic group containing bromine on the other surface is obtained.

(1"') Inorganic hollow microspheres, polymer composite spheres with surface-bound inorganic shells or polymer composite fiber materials with surface-bound inorganic shells and excess (of fat-containing sulfhydryl-based silicon germanium) The amount of the coupling agent exceeds the molar amount required for the reaction of the inorganic composite microspheres, the polymer composite spheres bonded to the surface of the inorganic shell layer or the polymer composite fiber material of the surface-bound inorganic shell layer. The contact solution is contacted, wherein the condition of contacting the solution of the silicon germanium coupling agent may include: the concentration of the silicon germanium coupling agent solution containing the fat sulfhydryl group is preferably in the range of 0.5-50% by weight, and the contact temperature is higher than the solution The freezing point is lower than the boiling point of the solution, and the contact time is preferably from 30 minutes to 96 hours, and the inorganic hollow microspheres whose outer surface of the inorganic outer shell is hydrophobically modified by the fat sulfhydryl group or the polymer composite spheres or surfaces whose surface is combined with the inorganic shell layer are obtained. a polymer composite fiber bonded to an inorganic shell layer; and

(2"') The inorganic hollow microspheres, polymer composite spheres or polymer composite fibers obtained in the step (1"') are crushed to collect inorganic fragments; the inorganic fragments are excessively used (the phenyl group is used) The silicon germanium coupling agent exceeds a molar amount of a silicon germanium coupling agent solution required to react with an inorganic sheet having a fatty mercapto hydrophobic group on the surface, wherein the silicon germanium coupling agent is contacted with The contact condition of the solution may include: the concentration of the phenyl group-containing silicon germanium coupling agent solution is preferably 0.5-50% by weight, the contact temperature is higher than the freezing point of the solution and lower than the boiling point of the solution, and the contact time is preferably 30 minutes to 96 hours; and then the deuteration reaction is carried out by contacting with an excess of more than 50% by weight (the weight of concentrated sulfuric acid used exceeds the weight of the phenyl-containing inorganic sheet product) concentrated sulfuric acid, wherein the conditions of the sulfonation reaction may include: The reaction temperature may be from 0 ° C to 100 ° C, and the reaction time may be from 10 minutes to 1 week, and one surface having a fat sulfhydryl group and the other surface containing a benzenesulfonic acid group is obtained. Water / inorganic composite sheet-shaped double lipophilic properties.

( 1"") Inorganic hollow microspheres, polymer composite spheres with surface-bound inorganic shells or polymer composite fiber materials with surface-bound inorganic shells and excess (of fat-containing sulfhydryl-based silicon used) The ruthenium coupling agent exceeds the molar amount required for the reaction of the inorganic composite microspheres, the polymer composite spheres bonded to the surface of the inorganic shell layer or the polymer composite fiber material of the surface-bound inorganic shell layer) fat-containing sulfhydryl-based silicon The cerium coupling agent solution is contacted, wherein the condition of contacting the solution of the silicon germanium coupling agent may include: the concentration of the fat sulfhydryl group-containing silicon germanium coupling agent solution is preferably in the range of 0.5 to 50% by weight, and the contact temperature is high. At the freezing point of the solution and below the boiling point of the solution, the contact time is preferably from 30 minutes to 96 hours, and the inorganic hollow microspheres whose outer surface of the inorganic outer shell is hydrophobically modified by the aliphatic sulfhydryl group and the polymer composite surface-bound with the inorganic shell layer are obtained. a polymer composite fiber having a sphere or a surface bonded to an inorganic shell layer;

(2"") The inorganic hollow microspheres, polymer composite spheres or polymer composite fibers which are hydrophobically modified by the fatty sulfhydryl group obtained by the step (1"") are crushed to collect inorganic fragments; Contacting a silicon germanium coupling agent solution containing a phenyl group in excess of the amount of the silicon germanium coupling agent required to react with the inorganic germanium containing the aliphatic sulfonium group, wherein, with silicon The contact condition of the solution of the ruthenium coupling agent may include: the concentration of the phenyl group-containing silicon germanium coupling agent solution is preferably 0.5-50% by weight, the contact temperature is higher than the freezing point of the solution and lower than the boiling point of the solution, and the contact time is preferably Between 30 minutes and 96 hours; and then sulfonating with a concentration of more than 50% by weight (the weight of concentrated sulfuric acid used exceeds the weight of the phenyl-containing inorganic sheet product) concentrated sulfuric acid, wherein the conditions of the sulfonation reaction The reaction temperature may be from 0 ° C to 100 ° C, and the reaction time may be from 10 minutes to one week, and one surface has a fat sulfhydryl group and the other surface contains a benzene sulfonate group. Water / inorganic composite dual nature of the sheet oleophilic; and

(3"") The inorganic sheet-like composite material obtained in the step (2"") and the excess (the weight of the dichlorosulfoxide solution used exceeds the hydrophilic/lipophilic property of the benzenesulfonate group) The weight of the inorganic tablet is contacted with a solution of the thionyl chloride, wherein the conditions of contact with the thionyl chloride solution may include: the contact temperature may be 0 ° C or less, preferably -20 ° C to -60 ° C, contact The time is preferably from 30 minutes to 96 hours, and an inorganic sheet-like composite material having a hydrophilic/lipophilic dual property containing a fat sulfhydryl group on the other surface and benzenesulfonyl chloride on the other surface is obtained.

According to some embodiments, the method for preparing the sheet composite of the present invention may further comprise the following specific steps:

Mixing the sheet composite obtained in the step (2), the step (2,), the step (2"), the step (2"') or the step (3"") with the nanoparticle dispersion, wherein the amount of the nanoparticles Preferably, it is 0.1-100% by weight of the sheet-like composite material, the mixing temperature is lower than the boiling point of the solvent of the dispersion liquid and larger than the freezing point of the solvent of the dispersion liquid (the mixing temperature is generally preferably 0 ° C to 60 ° C), and the mixing time is generally more than 10 minutes ( Preferably, the mixing time is from 30 minutes to 96 hours); then solid-liquid separation is performed and the unadsorbed nanoparticles are removed to obtain one side containing nanoparticles, and the other side is step (2), step (2'), step (2") , Step (2"') or step (3"") of the organic chemical group of the sheet composite material A; or step (2), step (2'), step (2"), step (2 The sheet composite obtained by "') or step (3"") is first mixed with a solution of the nanoparticle precursor, wherein the amount of the nanoparticle precursor is preferably from 0.1 to 100% by weight of the sheet composite, and the mixing time is generally More than 10 minutes (preferably, the reaction time is 30 minutes to 96 hours), the mixing temperature is lower than the boiling point of the solvent of the dispersion and larger than the freezing point of the solvent of the dispersion (the mixing temperature is generally preferably 0 ° C to 60 ° C); Dispersing a solid product (ie, a sheet-like composite material adsorbed with a nanoparticle precursor) in a solvent used in the nanoparticle precursor solution, and adding an initiator (the amount of addition is 10% by weight or less, preferably 0.1-% of the solid product) 10% by weight) to carry out the reaction, the reaction temperature may be any temperature greater than the freezing point of the solvent and less than the boiling point of the solvent, for example, 0-80 ° C, the reaction time may be 2 seconds or more, and the nano-particles are formed on the surface of the sheet-like composite material. Grain, get one side containing nanoparticles, the other side is the step

(2), step (2,), step (2"), step (2"') or step (3"") of the hydrophobic organic chemical group of the sheet composite material B; or

Adding a sheet-like composite material containing bromine or a benzenesulfonyl chloride organic chemical group on the surface obtained in the step (2") or the step (3"") to a solution of a vinyl monomer, wherein the sheet composite product is The concentration in the vinyl monomer solution is 0.01-0.2% by weight; further, a polymerization initiator and a ligand are added, wherein the molar ratio of the polymerization initiator to the ligand is 1:1 to 1:3, and the polymerization initiator is a vinyl single 0.1-5 wt% of the body, reacting at 80 ° C - 100 ° C for 2-48 hours to obtain a side grafted polymer, and the other side is the hydrophobic organic chemistry in step (2') or step (3"") a sheet-like composite sheet material C; or

The sheet-like composite material obtained in the step (2), the step (2) step (2"), the step (2"') or the step (3"") has an opposite charge to the hydrophilic group on the surface of the sheet-like composite material. The aqueous solution of the polyelectrolyte A is mixed, wherein the concentration of the polyelectrolyte aqueous solution is 0-50% by weight, and the concentration of the composite material in the mixed liquid may be 0.1-50% by weight, preferably 1-10% by weight, and the mixing temperature may not be It is higher than 100 ° C, preferably 10-80 ° C, and the mixing time may be 10 minutes or more, preferably 30 minutes to 96 hours, and one layer of polyelectrolyte is adsorbed on one side, and step (2) is on the other side. step

(2'), Step (2"), Step (2"') or Step (3"") of the hydrophobic organic chemical group of the sheet-like composite sheet material D.

The sheet-like composite sheet material C or the sheet-like composite sheet material D is mixed with the nanoparticle aqueous dispersion, wherein the concentration of the sheet-like composite material in the mixed solution is 0.1 to 10% by weight, and the mixing temperature is preferably 0 ° C. -60 ° C, the mixing time is generally greater than 10 minutes (preferably 30 minutes to 96 hours), then into The solid-liquid separation and removal of the unadsorbed nano-particles are carried out to obtain a double-layer composite layer containing an organic group/polymer A/nanoparticle on one side, and step (2), step (2'), and step (2) on the other side. ), the inorganic sheet-like composite sheet material E of the hydrophobic organic chemical group in the step (2"') or the step (3""); or

Mixing the sheet-like composite material D with an aqueous solution (concentration of more than 0% by weight and 50% by weight or less) having a polyelectrolyte B opposite to the surface polyelectrolyte A of the sheet-like composite material D, wherein the sheet in the mixed solution The concentration of the composite D may be 0.1-50% by weight, preferably 1-10% by weight, the mixing temperature may be not higher than 100 ° C, preferably 10-80 ° C, and the mixing time may be 10 minutes or more. Preferably, from 30 minutes to 96 hours, an inorganic composite sheet F having an organic group/polymer A/polymer B on one side and a hydrophobic group on the surface is obtained.

The sheet-like composite material F is mixed with an aqueous solution of a polyelectrolyte C having an opposite charge to the surface polyelectrolyte B of the inorganic sheet-like composite material F, wherein the concentration of the polyelectrolyte C aqueous solution is more than 0% by weight and less than or equal to 50% by weight. The concentration of the sheet composite F in the mixed liquid may be 0.1-50% by weight, preferably 1-10% by weight, and the mixing temperature may be not higher than 100 ° C, preferably 10-80 ° C, and the mixing time may be 10 minutes or more, preferably 30 minutes to 96 hours, to obtain an inorganic composite sheet material adsorbed with three layers of polyelectrolyte; repeating the above steps of adsorbing the polyelectrolyte, each adsorbed polyelectrolyte and last adsorption The polyelectrolyte has opposite charges; the final product is washed with water, separated, dried to obtain a layer of polyelectrolyte adsorbed on one side, and the other side is step (2), step (2'), step (2"), step (2"' Or the inorganic sheet-like composite material G of the hydrophobic organic chemical group in the step (3"").

Among them, in each of the above steps, after each contact or mixing, solid-liquid separation may be performed, and the solid product may be washed and dried. The solid-liquid separation can be carried out by a conventional method such as filtration or centrifugal separation. It may be washed with water or an inorganic solvent to remove the reaction medium or unreacted raw materials.

The silicon germanium coupling agent described in the method for preparing a sheet-like composite material of the present invention may be a silicon germanium coupling agent represented by formula 2 or formula 3:

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

Equation 2

In Formula 2, X may be an integer of 1-4;

RC _n H _2n -Si(Ri) _m (R2)3 _-m

Equation 3

In Formula 3, n may be an integer from 0 to 24; m can be 0-3;

And independently of Cl, CH ₃ , OCH ₃ , OCH ₂ CH ₃ or OC ₂ OCH _{3 ;}

R may be -H, -NH ₂ , HS -, -SCN, -NHCONH ₂ , Cl-, NH ₂ (CH ₂ ) ₂ NH -, (CH ₃ ) ₂ -C(Br)-C(0)-NH -, -S0 ₃ , -Ph-SOCl ₂ , -Ph-S0 ₃ , 2,3-epoxypropoxy, methacryloxy, (CH ₂ ) ₃ -S _x -, -CH ₃ , CH ₂ =CH- or Ph, where x is an integer from 1 to 4.

Wherein Ph represents a phenyl group.

The chemical group as shown in Formula 1 includes two types of hydrophilic organic chemical groups and hydrophobic organic chemical groups: when R is -NH ₂ , HS-, -SCN, -NHCONH ₂ , CI-, NH ₂ (CH ₂ ₂ NH-, (CH ₃ ) ₂ -C(Br)-C(0)-NH -, -S0 ₃ , -Ph-SOCl ₂ , -Ph-S0 ₃ , 2,3-epoxypropoxy or In the case of a methacryloyloxy group, the chemical group as shown in Formula 1 is a hydrophilic organic chemical group; when R is (C3⁄4:> ₃ -S _x -,

When -C3⁄4, CH ₂ =CH- or Ph, the chemical group as shown in Formula 1 is a hydrophobic chemical group. Divided into different silicon germanium coupling agents according to the difference of the group R, respectively, as follows:

The fat sulfhydryl group-containing silicon germanium coupling agent refers to a silicon germanium coupling agent in which R in the formula 3 is hydrogen or 3⁄4; the silicon germanium coupling agent containing a phenyl group refers to R in the formula 3. a silicon germanium coupling agent which is a phenyl group; the hydrophilic group-containing silicon germanium coupling agent means that R in the formula 3 is: amino group (NH ₂ ), SCN,

a silicon germanium coupling agent of NHCONH ₂ , Cl, NH ₂ (CH ₂ ) ₂ NH, 2, 3_glycidoxy or methacryloyloxy;

The ruthenium-containing silicon germanium coupling agent refers to a silicon germanium coupling agent in which R is a mercapto group (HS); the amino group-containing silicon germanium coupling agent means that R in the formula 3 is NH ₂ , NH ₂ (CH ₂ ) ₂ NH, NHCONH ₂ silicon germanium coupling agent.

In the above method, the solvent used for the solution of the silicon germanium coupling agent is a nonaqueous solvent, generally: a fatty anthracene hydrocarbon having 6 to 10 carbon atoms, an aromatic hydrocarbon having 6 to 10 carbon atoms or anhydrous ethanol. Preferred is anhydrous ethanol or a fatty anthracene having 6 to 10 carbon atoms.

In the step (2'), the organic solvent may be used for washing, and the organic solvent may be hexane, helium, toluene or acetone.

The oxidizing substance in the step (2') is potassium permanganate aqueous solution, perchloric acid solution, potassium dichromate solution or any mixture thereof.

The solvent for dissolving thionyl chloride in the step (3"") is: hydrazine, hydrazine-dimethylformamide, benzene, chloroform or carbon tetrachloride.

The chemical composition of the nanoparticles is selected from one or more of the following:

Si0 ₂ , Ti0 ₂ , GeO, Au, Ag, Fe, Pd, Pt, FeO, Fe ₃ 0 ₄ , Fe ₂ 0 ₃ , A1 ₂ 0 ₃ , Sn0 ₂ , Cu(OH) ₂ , MnFe ₂ 0 ₄ , CaC0 ₃ , CdS, CoO, NiO, ZnO, Ce0 ₂ , polyphenylene Amine, sulfonated polystyrene, styrene polymer copolymer, acrylic or acrylate polymer, chitin, glucose, and the like.

The precursor of the nanoparticle refers to a chemical substance capable of generating nanoparticles, such as tetraethyl orthosilicate, butyl titanate, aniline, ferric chloride, silver nitrate or chloroauric acid.

The solvent of the solution of the nanoparticle dispersion or the nanoparticle precursor is a solvent which is incapable of dissolving the nanoparticles, and is generally preferably water, ethanol, acetone or any mixture thereof.

The initiator for preparing nanoparticles in situ by the precursor of the nanoparticle comprises: sodium persulfate, potassium persulfate, benzoyl peroxide, acid (hydrochloric acid, sulfuric acid, nitric acid:) or alkali (ammonia, sodium hydroxide) , potassium hydroxide, etc. :).

The polyelectrolyte is sodium polyacrylate, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, polyacrylamide, polyaniline, polyvinyl alcohol, polyethylene glycol, sulfonated polystyrene, Sodium polystyrene sulfonate, polydiallyldimethylammonium chloride, sodium carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, polypyridone, sodium alginate, Hydroxymethyl starch, polydimethyldiallylammonium chloride or polyethylene terephthalate.

The vinyl monomers are acrylates, styrene and derivatives thereof, or acrylonitrile.

The polymerization initiator is cuprous chloride or cuprous bromide.

The ligand is 2,2,-bipyridyl or hydrazine, hydrazine, hydrazine, hydrazine, hydrazine-pentamethyldiethyltriamine or the like.

The reaction medium used for the polymerization may be acetone, toluene, anthracene (having a carbon number of 5 to 18) or ethanol.

The sheet-like composite material having the dual properties of the surface of the present invention can be used as an emulsifier or in the fields of coatings, polymer materials and the like. Due to the different chemicals on the front and back sides of the sheet-like composite material, the sheet-like composite material can exhibit different properties in different materials, such as: when one surface of the sheet-like composite material sheet contains conductive material polyaniline, and the other When a surface is a non-conductive long-chain hydrocarbon ( ), the inorganic sheet composite can be used to prepare a single-sided conductive polymer film; when the sheet composite has oppositely charged chemical groups on both sides, the sheet composite The material itself can be self-assembled to prepare a layer-by-layer assembled material; when one surface of the sheet composite has a polar group and the other surface is a fluorenyl chain, then the sheet composite can be used. Self-assembly of the polymer electrolyte on one side to obtain a self-assembled film. DRAWINGS

Figure 1. Emulsifying properties of a sheet composite having dual properties prepared in Example 6 of the present invention in hexane/water. Figure 2. The surface of the front and back sides of the sheet composite having the dual properties of the table prepared in Example 9 of the present invention;

(a) the outer surface of the sheet-like composite (containing fat sulfhydryl groups), (b) the inner surface of the sheet-like composite (adsorbing polyaniline nanoparticles by a benzenesulfonic acid group). detailed description

The following is further illustrated by the specific examples, but the scope of the invention should not be limited to the following examples.

Example 1

10 g of polystyrene microspheres having a diameter of 300 nm was placed in a 500 mL three-necked flask, 100 mL of concentrated sulfuric acid was added, and the mixture was stirred at 40 ° C for 2 hours, thoroughly washed with distilled water, and then washed twice with ethanol (100 mL each time), and dried under vacuum. The product was added to a 250 mL three-necked flask, and 100 mL of absolute ethanol and 2 g of tetraethyl orthosilicate were added, soaked at room temperature for 6 hours, centrifuged, then washed once with 100 mL of ethanol, and added with 50 mL of ethanol and 5 mL of distilled water, soaked for 2 hours. Adding to a 250 mL three-necked flask, adding 100 mL of anhydrous ethanol and 2 g of butyl titanate, soaking at room temperature for 6 hours, centrifuging, then washing once with 100 mL of ethanol, adding 50 mL of ethanol and 5 mL of distilled water, soaking for 2 hours, and filtering; Add to a 250 mL three-necked flask, add 100 mL of absolute ethanol and 2 g of tetraethyl orthosilicate, soak for 6 hours at room temperature, centrifuge, then wash once with 100 mL of ethanol, add 50 mL of ethanol and 5 mL of distilled water, soak for 2 hours, and filter. Drying was carried out to obtain a polystyrene composite microsphere having a sandwich structure of a surface inorganic layer of Si0 ₂ /Ti0 ₂ /SiO ₂ .

2 g of the above microspheres were added to a 250 mL three-necked flask, and 50 g of dried hexamidine and 0.5 g of octadecyltriethoxysilane were added, refluxed for 30 minutes, and centrifuged; then washed thoroughly with absolute ethanol, dried. The product was dissolved in N,N-dimethylformamide, centrifuged, thoroughly washed with N,N-dimethylformamide and water, centrifuged, dried, and ground with a mortar to obtain a partial surface modified. Multi-layer inorganic sheet; then the dried inorganic sheet was added to a 100 mL three-necked flask, 50 mL of anhydrous toluene and 0.5 g of γ-aminopropyltrimethoxysilane were added, reacted at 60 ° C for 48 hours, centrifuged, and toluene was used. It is sufficiently washed and dried to obtain a sheet-like composite material having an octadecyl group on one side and an aminopropyl group on the other side and having a Si0 ₂ /Ti0 ₂ /SiO ₂ multilayer composite inorganic substrate. Example 2

Hollow glass microspheres (3010, Zibo Glass Beads Research Institute) 4 g was added to a lOOmL Erlenmeyer flask; 50 mL of absolute ethanol and 1 g of phenyltriethoxysilane were added; After refluxing for 10 hours, it was filtered, washed well with absolute ethanol, filtered and dried. The product is then crushed with a crucible or a ball mill to obtain a sheet-like composite material having a phenyl hydrophobic group on one side and an inorganic hydrophilic group on the other side. Example 3

2 g of the inorganic sheet obtained in Example 2 was placed in a lOOmL Erlenmeyer flask; 50 mL of anhydrous toluene and 1 ml of T-aminopropyltriethoxysilane were added, and reacted at 60 ° C for 6 hours under nitrogen atmosphere, and filtered. The mixture was washed well with anhydrous toluene, filtered, and dried to obtain a sheet-like composite material having a phenyl hydrophobic group on one side and an amino hydrophilic group on the other side. Example 4

0.5 g of floating beads (a ceramic ball produced by Shanghai Huijing Nano New Material Co., Ltd.) was added to a 250 mL three-necked round flask, and 20 mL of hydrogen peroxide and 5011^98% by weight of concentrated sulfuric acid were added and activated at 80 ° C for 24 hours; Wash and dry. Then, it was placed in a lOOmL Erlenmeyer flask, and 50 mL of toluene and 0.1 g of dodecylethoxysilane were added, and reacted at 60 ° C for 48 hours, filtered, washed thoroughly with toluene, and dried. After crushing, it was added to a 100 mL Erlenmeyer flask, and 50 mL of anhydrous toluene and 0.1 g of γ-mercaptopropyltrimethoxysilane were added, and reacted at 0 ° C for 72 hours, filtered, washed thoroughly with toluene, filtered, and dried to obtain a side. A sheet-like composite material containing a long-chain fluorenyl group and a fluorenyl group on the other side.

The obtained inorganic tablet containing a long-chain fluorenyl group and having a fluorenyl group on the other side is added to a 10% by weight potassium permanganate solution, and heated to 80 ° C for 6 hours to obtain a sulfonic acid group on one side and a long side on the other side. Chain-based composite material. Example 5

Hollow glass microspheres (3010, Zibo Glass Beads Research Institute) 4 g was added to a lOOmL Erlenmeyer flask; 50 mL of anhydrous toluene and 1 g of dodecylmethyldimethoxysilane were added; After refluxing for 4 hours under water, it was filtered, washed thoroughly with absolute ethanol and water, filtered and dried. Then the product was crushed with a crucible or a ball mill, the chips were placed in a 100 mL round bottom flask, 50 mL of absolute ethanol, 0.5 g of Y-aminopropyltriethoxysilane, and reacted at 60 ° C for 12 hours. Wash thoroughly with absolute ethanol, filter and dry.

The prepared dried sample was added to a 100 mL round bottom flask, 40 mL of toluene and 0.5 g of 2-bromoisobutyl bromo bromide were added, and the mixture was reacted at 0 ° C for 2 hours to distill off the solvent and the unreacted material; a group of sheet-like composite materials containing a fat sulfhydryl group on the other side. Example 6

2 g of hollow glass microspheres was added to a 100 mL three-necked flask containing 50 mL of anhydrous toluene; 0.2 g of octadecyltriethoxysilane was added; after refluxing for 48 hours in anhydrous state, it was filtered, and anhydrous toluene was used. The water ethanol is washed thoroughly, filtered and dried. Then grinding and crushing, vacuum drying; the product was added to a 100 mL three-necked flask containing 50 mL of helium, adding 1 gram of phenyltrimethoxysilane, reacting at 60 ° C for 24 hours; centrifuging, using heptane, absolute ethanol Washing, filtering, drying;

The product was added to a 100 mL two-necked flask containing 4011^98% by weight of concentrated sulfuric acid solution, stirred at 40 ° C for 4 hours, and centrifuged; washed thoroughly with water, centrifuged, and dried to obtain a side of benzenesulfonic acid group and the other side. It is a fat-based flaky composite material (as shown in Figure 1, it has a good emulsification effect in oil-water systems). Example 7

The product of Example 6 was added to 10 mL of a -30 ° C solution of thionyl chloride in hydrazine-dimethylformamide. After 12 hours of reaction, the product was separated into an ice water bath and washed thoroughly with water to obtain A sheet-like composite material containing a benzenesulfonyl chloride group and a surface of a fat sulfhydryl group. Example 8

0.1 g of the product of Example 1 was placed in a 10 mL test tube, and 5 mL of an aqueous dispersion of 0.5% by weight of sulfonated polystyrene nanoparticles was added, and the mixture was adsorbed at room temperature for 6 hours, centrifuged, and thoroughly washed with distilled water. A sheet composite having an inorganic nanoparticle adsorbed on its surface and a octadecyl hydrophobic group on one side was obtained. Example 9

0.1 g of the product of Example 6 was placed in a 10 mL test tube, 5 mL of 0.5% by weight aqueous aniline solution was added, and the reaction was carried out for 6 hours at room temperature, centrifuged, washed three times with 10 mL of distilled water, and 5 mL of water and potassium persulfate were added for 30 minutes. Separate by centrifugation, wash thoroughly with water, separate and dry. As shown in Fig. 2, a sheet-like composite material having a surface adsorbed with polyaniline nanoparticles and a fatty thiol group on one side was obtained (see Fig. 2 for different forms of the surface). Example 10

5克。 The product prepared in Example 5 was added to a 50 mL round bottom flask, adding 20 mg of cuprous bromide and styrene 0.5 g, and Ν, Ν, Ν, Ν, Ν-pentamethyldiethyltriamine 20mg; 0°C Atom Transfer Radical Polymerization (ATRP Reaction) For 24 hours, a surface silicon germanium coupling agent was obtained which was grafted with polystyrene on the basis of modification, and the other surface contained a sheet-like composite material of 18 fluorene. Example 11

0.5 g of the product of Example 7 was placed in a 50 mL single-mouth bottle, 20 mL of anhydrous, oxygen-free toluene was added, 20 mg of cuprous bromide and 20 mg of bipyridine were added, 1 g of methyl methacrylate was added, and the reaction was carried out at 80 ° C for 4 hours. Separated by centrifugation, thoroughly washed with toluene, acetone, water, and dried to obtain a sheet-like composite material whose surface was grafted with polymethyl methacrylate (PMMA) and the other surface was a fatty sulfhydryl hydrophobic group. Example 12

0.2 g of the product of Example 6 was placed in a 50 mL single-mouth bottle, and 10 mL of a 5 wt% aqueous solution of polydiallyldimethylammonium chloride was added thereto, stirred at room temperature for 6 hours, centrifuged, and washed 5 times with water (10 ml each time). Vacuum drying gave a sheet-like composite material in which a layer of polydiallyldimethylammonium chloride was assembled on one side and the surface was a fatty mercapto group. Example 13

0.1 g of the product of Example 12 was added to a 10 mL test tube, 10 g of a 5% by weight aqueous dispersion of sulfonated polystyrene nanospheres was added and adsorbed for 6 hours; centrifuged, washed with water, and dried to obtain a surface of benzenesulfonate. Acidic group/polyelectrolyte/sulfonated polystyrene nanospheres double layer structure, and the surface is a fat sulfhydryl group-like sheet composite. Example 14

Adding 10 mL of a mixed solution of FeCl ₃ and FeCl _{2 in a} molar ratio of 2:1 (the total concentration of divalent iron ions and ferric ions is ?mol/L) directly to 50 mL of a 5 wt% aqueous sodium hydroxide solution, iron The salt is hydrolyzed and crystallized instantaneously to form Fe ₃ 0 ₄ nanoparticles; it is sufficiently washed with acetone and water, and dried to obtain Fe ₃ 0 ₄ nanoparticles.

After the product was 0.1 g Example 12 was added to 5mL of anhydrous ethanol and 0.1 g Fe ₃ 0 ₄ nanoparticles dispersion at room temperature for 2 hours adsorption centrifuged, twice washed with ethanol, centrifuged and dried, to obtain a surface of an organic group The double layer structure of the group/polymer electrolyte/Fe ₃ 0 ₄ magnetic nanoparticles, and the other surface is a sheet-like composite material of a fat sulfhydryl hydrophobic group. Example 15 0.1 g of the product of Example 12 was added to a 10 mL test tube, 10 mL of a 5 wt% aqueous solution of sodium polystyrene sulfonate was added, stirred at room temperature for 6 hours, centrifuged, washed 5 times with water, and dried under vacuum to give a benzenesulfonic acid group on one side. A two-layer polyelectrolyte composite structure of agglomerate/polydiallyldimethylammonium chloride/sodium polystyrene sulfonate, and a sheet-like composite material having a surface of a fat sulfhydryl group. Example 16

0.2 g of the product of Example 15 was placed in a 50 mL single-mouth bottle, and 20 g of a 5% by weight aqueous solution of polydiallyldimethylammonium chloride was added, and the product was repeatedly separated, washed, and the product was added to 20 g. The aqueous solution of sodium polystyrene sulfonate in a weight % is centrifuged; then the polydiallyldimethylammonium chloride is repeatedly adsorbed again, finally centrifuged, washed, and vacuum dried to obtain a multilayer which is combined with a multilayer polyelectrolyte. The composite structure, and the other side is a sheet-like composite material of a fat-based hydrophobic group. Example 17

2 克mL three-necked bottle was added with 2 g of aluminum sulfate and 50 mL of water, and a 5 wt% aqueous solution of sodium hydroxide was added dropwise to pH = 5, and 2 g of nylon fiber was taken out of the solution and immediately taken out and dried. It was added to a 100 mL three-necked flask containing 50 mL of anhydrous toluene; 0.2 g of Y-chloropropylmethyldiethoxysilane was added; after reacting at 60 ° C for 8 hours, it was filtered, washed thoroughly with absolute ethanol, and dried. Then, the mixture was ground and crushed, the product was added to water, the upper suspension was decanted, the lower inorganic precipitate was taken, washed with water, and dried under vacuum; the product was added to 50 mL of anhydrous helium, and 1 g of γ-mercaptopropyltrimethoxysilane was added. The reaction was carried out at 60 ° C for 24 hours; the mixture was centrifuged, washed thoroughly with heptane and absolute ethanol, filtered, and dried to obtain a sheet-like composite material having one side being a chloropropyl group and the other side being a fluorenyl group. Example 18

10 g of polystyrene microspheres having a diameter of 5 mm was placed in a 500 mL three-necked flask, and 100 mL of concentrated sulfuric acid was added thereto, stirred at 40 ° C for 2 hours, thoroughly washed with distilled water, then washed twice with ethanol, and dried under vacuum. Add the product to a 250 mL three-necked flask, add 100 mL of absolute ethanol and 2 g of butyl titanate, soak for 6 hours at room temperature, centrifuge, then wash once with ethanol, add 50 mL of ethanol and 5 mL of distilled water, soak for 2 hours, filter; The immersion was repeated in a 250 mL three-necked flask until the thickness of the surface Ti0 ₂ adsorption layer was ΙΟΟμηι, and polystyrene microspheres in which the Ti0 ₂ inorganic layer was bonded were obtained.

2 g of the above dried microspheres were added to a 250 mL three-necked flask, and 50 mL of anhydrous hexane and 0.5 g of Y-diethylenetriaminopropylmethyldimethoxysilane were added, refluxed for 30 minutes, centrifuged, and then anhydrous. Ethanol Wash thoroughly, dry, crush the product in liquid nitrogen, dissolve with N, N-dimethylformamide, centrifuge, ultrasonically wash with N, N-dimethylformamide and water, and dry to obtain partial surface modification. Ti0 ₂ granules, then added to a 100 mL three-necked flask, adding 50 mL of anhydrous toluene and 0.5 g of γ-(2,3-epoxypropoxy oxy) propyltrimethoxysilane, reacted at 0 ° C for 48 hours, centrifuged The mixture was separated, washed thoroughly with toluene, and dried to obtain a Ti0 ₂ inorganic sheet containing a vinyl group on one side and a (2, 3-epoxypropoxy oxy:) propyl group on the other side. Example 19

20 g of styrene monomer (St), 1.6 g of polyvinylpyrrolidone (PVP, molecular weight: 30,000), 95 g of ethanol, and 5 g of water were mixed, and the reaction was stirred at 73 ° C, 100 rpm for 2 hours. After that, it was washed by centrifugation and dried to obtain a polystyrene sphere of about 3 μm.

The gram of tetraethyl orthosilicate (TE0S) is added dropwise to the above reaction system, and 2 g of 0. 2 M hydrochloric acid is added, and 0.2 g of tetraethyl orthosilicate (TE0S) is added dropwise to the above reaction system. The reaction was carried out at room temperature for 4 hours with stirring. Then, it was spray-dried at 80 ° C, and the powder was collected to obtain a silica-based polystyrene composite microsphere.

0.2 g of the polystyrene composite microspheres prepared above was added to 100 mL of anhydrous hydrazine, 0.1 g of octadecyltrichlorosilane was added, and the reaction was stirred at 40 ° C for 18 hours; centrifuged and washed thoroughly with hydrazine , dried, to obtain a modified inorganic composite sphere; the modified inorganic composite sphere was dispersed in N, N-dimethylformamide (DMF), ultrasonically dispersed for 3 hours, centrifuged, and then washed four times with DMF, After centrifugation, the product was ground in a mortar; the chips were then dispersed in toluene, phenyltriethoxysilane was added, refluxed for 6 hours, centrifuged, washed with toluene, and dried; the product was added to a mass concentration of 98 g. The mixture was reacted at 40 ° C for 6 hours in concentrated sulfuric acid, centrifuged, washed thoroughly with water, and dried to obtain a hydrophilic, hydrophobic nanoparticle on the other surface.

Claims

Claim

An inorganic sheet-like composite material having a dual property on a surface, the sheet-like composite material comprising an inorganic sheet-like substrate and a single-layer, double-layer composite or multi-layer composite chemical substance on both surfaces of the substrate And the chemical substances on the two surfaces of the substrate are different; the chemical substances of the single layer are composed of organic chemical groups, nanoparticles bonded by organic chemical groups, or polymers bonded by organic chemical groups. The double-layer composite chemical is a two-layer composite structure formed by complexing a nano-particle or a polymer on a single-layer structure of a polymer bonded by an organic chemical group; A chemical substance is a multilayer composite structure formed by repeatedly adsorbing a polymer on a single layer structure of a polymer bonded by an organic chemical group;

(b) in the two-layer composite structure, the organic chemical group has an opposite charge property to the polymer of the first layer, and the nanoparticle has an opposite charge property to the polymer of the first layer, or The polymer of the first layer has an opposite charge property to the polymer of the second layer;

(c) In the multilayer composite structure, the polymers in the adjacent two layers are different and have opposite charge properties.

The sheet composite according to claim 1, wherein the organic chemical group is a chemical group as shown in Formula 1:

RC _n H _2n - (Formula 1)

In Equation 1, n is an integer from 0 to 24;

R is -NH ₂ , HS- , -SCN , -NHCONH ₂ , CI- , NH ₂ (CH ₂ ) ₂ NH- , (CH ₃ ) ₂ -C(Br)-C(0)-NH -, -S0 ₃ , -Ph-SOCl ₂ , -Ph-S0 ₃ , 2,3-epoxypropoxy, methacryloxy, (CH ₂ ) ₃ -S _x -, -CH ₃ , CH ₂ =CH- Or Ph, where _x is 1-4; when n=0, R is not -H, -NH ₂ , CI- or -S0 ₃ .

The sheet-like composite material according to claim 1, wherein the substrate is an inorganic substrate composed of the same inorganic substance, or a multilayer composite inorganic substrate composed of different inorganic substances; One or more selected from the group consisting of oxides or hydroxides of silicon, aluminum, titanium, magnesium, zirconium, iron, zinc, tin, and calcium.

The sheet-like composite material according to claim 1, wherein the nanoparticles are one or more selected from the group consisting of metal nanoparticles, inorganic nanoparticles, and organic nanoparticles; One or more of nanoparticles from Au, Ag, Fe, Pd, and Pt; the inorganic nanoparticles are selected from the group consisting of SiO ₂ , Ti _{2 2} , GeO, FeO, Fe ₃ 0 ₄ , Fe ₂ 0 ₃ One or more of nanoparticles of A1 ₂ 0 ₃ , Sn0 ₂ , Cu(OH) ₂ , Eu ₂ 0 ₃ , MnFe ₂ 0 ₄ , CaC0 ₃ , CdS, CoO, NiO, ZnO, and Ce0 ₂ ; The organic nanoparticles are one or more selected from the group consisting of polyaniline, sulfonated polystyrene, polystyrene, styrene copolymer, polyacrylic acid, polyacrylate, chitin, and glucose nanoparticles.

The sheet composite according to claim 1, wherein the polymer is a polyelectrolyte, polymethyl methacrylate, polystyrene and a derivative thereof, or polyacrylonitrile; and the polyelectrolyte is polyacrylic acid Sodium, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, polyacrylamide, polyaniline, polyvinyl alcohol, polyethylene glycol, sulfonated polystyrene, sodium polystyrene sulfonate, poly Diallyldimethylammonium chloride, sodium carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, polypyridone, sodium alginate, hydroxymethyl starch, polydimethylene Diallyl ammonium chloride, or polyethylene terephthalate.

6. A method of preparing a sheet-like composite material, the method comprising the steps of:

a. Inorganic hollow microspheres, polymer composite spheres having an inorganic shell layer bonded thereto, or polymer composite fibers having an inorganic shell layer bonded thereto are contacted with chemical substance A to obtain an inorganic shell-modified inorganic a hollow polymer composite hollow fiber, an inorganic shell modified polymer composite sphere or an inorganic shell modified polymer composite fiber;

b. The outer shell of the inorganic hollow microsphere modified by the inorganic shell obtained in step a is crushed, or the polymer composite sphere modified by the inorganic shell obtained in step a or the polymer composite fiber modified by the inorganic shell is modified. The inorganic shell is separated from the polymer component and the inorganic shell is broken, and then the inorganic fragments are collected;

c. contacting the inorganic fragments obtained in step b with the chemical substance B to obtain the sheet composite material,

Wherein the chemical substance A and the chemical substance B are different, and the chemical substances A and B each independently comprise a silicon germanium coupling agent, and optionally include perchloric acid, dichromate, permanganate, sulfuric acid, One or more of a nanoparticle, a polymer, and a mixture of nanoparticles and a polymer.

7. Method ³ according to claim 6, wherein the method comprises the steps of:

(1) contacting the inorganic hollow microspheres, the polymer composite spheres whose surface is combined with the inorganic shell layer or the polymer composite fiber material of the surface-bound inorganic shell layer with an aqueous solution of an oxidizing substance, and then with an excess of hydrophobic groups Contacting the solution of the silicon germanium coupling agent; or the inorganic hollow microspheres, the polymer composite spheres whose surface is combined with the inorganic shell layer or the polymer composite fiber material of the surface combined with the inorganic shell layer directly and excessively containing hydrophobic groups Contacting a solution of a silicon germanium coupling agent to obtain an inorganic hollow microsphere modified with a hydrophobic group-containing silicon germanium coupling agent on the outer surface of the inorganic outer shell, or a polymer composite sphere having a surface combined with an inorganic shell layer or a polymer composite fiber having a surface-bonded inorganic shell layer, wherein a temperature of contact with the solution of the silicon germanium coupling agent is higher than a freezing point of the solution and lower than a boiling point of the solution;

(2) the outer surface obtained in the step (1) is broken by inorganic hollow microspheres, polymer composite spheres or polymer composite fibers modified with a hydrophobic group-containing silicon germanium coupling agent to collect inorganic fragments; The chips are contacted with a solution of an excess of a hydrophilic group-containing silicon germanium coupling agent to obtain a sheet-like composite material having different organic chemical groups on both sides.

8. The method of claim 6 wherein the method comprises the steps of:

(1') contacting the inorganic hollow microspheres, the polymer composite spheres whose surface is combined with the inorganic shell layer or the polymer composite fiber material of the surface-bound inorganic shell layer with an aqueous solution of an oxidizing substance, and then with excess fat Contacting a solution of a ruthenium-based silicon germanium coupling agent; or directly mixing the inorganic hollow microspheres, the polymer composite spheres whose surface is combined with the inorganic shell layer, or the polymer composite fiber material of the surface-bound inorganic shell layer with excess fat Contacting a solution of a ruthenium-based silicon germanium coupling agent to obtain an inorganic hollow microsphere whose outer surface of the inorganic shell is hydrophobically modified by a fat sulfhydryl group, a polymer composite sphere having a surface-bound inorganic shell layer or a surface-bound inorganic shell layer a polymer composite fiber, wherein a temperature of contact with a solution of a silicon germanium coupling agent is higher than a freezing point of the solution and lower than a boiling point of the solution; and (2') a fat sulfhydryl group obtained by the step (Γ) The modified inorganic hollow microspheres, polymer composite spheres or polymer composite fibers are broken, and inorganic fragments are collected; the inorganic fragments are coupled with silicon germanium containing an excess of sulfhydryl groups. The solution is contacted, and then contacted with a solution containing an excess of the oxidizing substance at 0 ° C - 90 ° C for at least 10 minutes to obtain a sheet having a fat sulfhydryl hydrophobic group on the surface and a sulfonic acid group on the other surface. Composite material.

9. The method of claim 6 wherein the method comprises the steps of:

(1") polymer composite spheres or surfaces with inorganic hollow microspheres and surface bonded inorganic shells The polymer composite fiber material combined with the inorganic shell layer is contacted with the excess fat sulfhydryl-containing silicon germanium coupling agent solution to obtain inorganic hollow microspheres whose surface is inorganically modified by the aliphatic sulfhydryl group, and the surface-bound inorganic substance a polymer composite sphere of a shell layer or a polymer composite fiber having a surface combined with an inorganic shell layer, wherein a temperature of contact with the solution of the silicon germanium coupling agent is higher than a freezing point of the solution and lower than a boiling point of the solution;

(2") The inorganic hollow microspheres, polymer composite spheres or polymer composite fibers which are hydrophobically modified by the fatty sulfhydryl group obtained by the step (1") are crushed to collect inorganic fragments; the inorganic fragments are excessively contained with an amino group. The water-based silicon germanium coupling agent solution is contacted, and then contacted with 2-bromoisobutyl bromide to obtain a hydrophilic group having a hydrophobic group on the surface and a bromo group on the other surface. / oleophilic dual-like sheet composite.

10. The method of claim 6 wherein the method comprises the steps of:

(1"') the inorganic hollow microspheres, the polymer composite spheres bonded to the inorganic shell layer or the polymer composite fiber materials bonded to the inorganic shell layer and the excess thiol-containing silicon germanium coupling agent solution Contacting, obtaining an inorganic hollow microsphere whose outer surface of the inorganic shell is hydrophobically modified by a fat sulfhydryl group, a polymer composite sphere having a surface-bound inorganic shell layer or a polymer composite fiber having a surface-bound inorganic shell layer, wherein, with silicon germanium The temperature at which the solution of the coupling agent is contacted is higher than the freezing point of the solution and lower than the boiling point of the solution;

(2"') The inorganic hollow microspheres, polymer composite spheres or polymer composite fibers which are hydrophobically modified by the fatty sulfhydryl group obtained by the step (Γ") are crushed to collect inorganic fragments; the inorganic fragments and the excess benzene are contained. The solution of the silicon germanium coupling agent is contacted, and then the deuteration reaction is carried out with excess concentrated sulfuric acid at a temperature of more than 0 ° C to less than 100 ° C to obtain a surface containing a fat sulfhydryl group and the other surface containing benzenesulfonate. An acid-based inorganic sheet-like composite material having hydrophilic/lipophilic dual properties.

11. The method of claim 6 wherein the method comprises the steps of:

( 1"") a solution of an inorganic hollow microsphere, a polymer composite sphere whose surface is bonded to an inorganic shell layer, or a polymer composite fiber material whose surface is bonded to an inorganic shell layer, and an excess of a fat-containing sulfhydryl group-containing silicon germanium coupling agent. Contacting, obtaining inorganic hollow microspheres whose outer surface of the inorganic shell is hydrophobically modified by a fatty sulfhydryl group, polymer composite spheres having a surface-bound inorganic shell layer or polymer composite fibers having a surface-bound inorganic shell layer, wherein The temperature at which the solution of the ruthenium coupling agent is contacted is higher than the freezing point of the solution and lower than the boiling point of the solution;

(2"") The inorganic hollow microspheres which are hydrophobically modified by the fatty sulfhydryl group obtained in the step (1""), The polymer composite sphere or the polymer composite fiber is broken, and the inorganic fragments are collected; the inorganic fragments are contacted with a solution of the excess phenyl group-containing silicon germanium coupling agent, and then the excess concentrated sulfuric acid is greater than o ° c to less than 100 ° The oximation reaction is carried out at a temperature of C to obtain a sheet-like composite material having a hydrophilic/lipophilic dual property having a fat sulfhydryl group on the surface and a benzenesulfonic acid group on the other surface;

(3"") The sheet-like composite material having a hydrophilic/lipophilic property containing a benzenesulfonic acid group obtained in the step (2"") is added to an excess of the thionyl chloride solution at -20 ° C to -60 Contacting at a temperature of ° C gave an inorganic sheet-like composite material having a hydrophilic/lipophilic dual property on one surface containing a fat sulfhydryl group and the other surface containing benzenesulfonyl chloride.

The method of any of claims 7-11, wherein the method further comprises the steps of:

Mixing the sheet composite obtained in the step (2), the step (2,), the step (2"), the step (2"') or the step (3"") with the nanoparticle dispersion, wherein the amount of the nanoparticles It is 0.1-100% by weight of the sheet composite, the mixing temperature is lower than the boiling point of the solvent of the dispersion and larger than the freezing point of the solvent of the dispersion, and then solid-liquid separation is performed to remove the unadsorbed nanoparticles in the solid product to obtain a nanometer containing one side. a flaky composite sheet material A having a hydrophobic organic chemical group in the step (2), the step (2'), the step (2"), the step (2"') or the step (3""); Or

The sheet composite obtained by the step (2), the step (2,), the step (2"), the step (2"') or the step (3"") is first mixed with a solution of the nanoparticle precursor, wherein, the nano The particle precursor is used in an amount of 0.1 to 100% by weight of the sheet composite, and then subjected to solid-liquid separation; thereafter, the solid product is dispersed in a solvent used for the nanoparticle precursor solution, an initiator is added, and the nanoparticle precursor is passed through The nanoparticle is directly formed on the surface of the inorganic sheet-like composite material, and solid-liquid separation is performed to obtain one side containing nanoparticles, and the other side is step (2), step (2'), step (2"), step (2"' Or the sheet-like composite material B of the hydrophobic organic chemical group in the step (3""); or

Adding a sheet-like composite material containing bromine or a benzenesulfonyl chloride organic chemical group on the surface obtained by the step (2") or the step (3"") to a solution of a vinyl monomer, wherein the sheet composite material is The concentration by weight of the vinyl monomer solution is 0.01%-0.2%; the polymerization initiator is further added and the ligand is reacted at 80 ° C - 100 ° C for 2 to 48 hours, wherein the molar ratio of the polymerization initiator to the ligand is 1:1 to 1:3, the polymerization initiator is 0.1 to 5% by weight of the vinyl monomer, and one side is grafted polymer, and the other side is hydrophobic organic in step (2') or step (3"") a sheet-like composite material C of a chemical group; or a sheet-like composite material obtained by the step (2), the step (2,), the step (2"), the step (2"') or the step (3"") Polyelectrolysis with opposite charge to the hydrophilic group on the surface of the sheet composite The aqueous solution of the mass A is mixed, wherein the concentration of the aqueous solution of the polyelectrolyte A is more than 0% by weight and 50% by weight or less, and the amount of the sheet-like composite material is such that the concentration of the sheet-like composite material in the mixed liquid is 0.1 to 50% by weight. %, the mixing temperature is less than 100 ° C, and one side is adsorbed with a layer of polyelectrolyte A, and the other side is step (2), step (2'), step (2"), step (2"') or step (3" The sheet-like composite material D of the hydrophobic organic chemical group in ").

The method according to claim 12, wherein the method further comprises the step of: affixing the sheet composite material C or the inorganic sheet composite material D with the nanoparticle aqueous dispersion

Mixing at 0 ° C to 60 ° C, wherein the concentration of the sheet-like composite sheet material in the mixed solution is 0.1 to 10% by weight, and a double layer composite layer containing an organic group/polymer/nanoparticle layer is obtained on one side, and the other side is a step. a sheet-like composite material E of a hydrophobic organic chemical group in (2), step (2'), step (2"), step (2"') or step (3""); or

The inorganic sheet-like composite material D is mixed with an aqueous solution of a polyelectrolyte B having a charge opposite to that of the polyelectrolyte A on the surface of the inorganic sheet-like composite material D, wherein the concentration of the aqueous solution of the polyelectrolyte B is more than 0% by weight and less than 50% by weight, the concentration of the sheet composite D in the mixed liquid is 0.1-50% by weight, the mixing temperature is less than 100 ° C, and a double layer composite layer having an organic group/polyelectrolyte A/polyelectrolyte B on one side is obtained, An inorganic composite sheet F having a hydrophobic group on one side.

The method according to claim 13, wherein the method further comprises the step of: mixing the sheet-like composite material F with an aqueous solution of a polyelectrolyte C having an opposite charge to the polyelectrolyte B of the surface of the sheet-like composite material F, Wherein, the concentration of the polyelectrolyte C aqueous solution is more than 0% by weight and less than or equal to 50% by weight, the concentration of the sheet-like composite material F in the mixed liquid is 0.1-50% by weight, and the mixing temperature is less than 100 ° C, and three layers are adsorbed. Polyelectrolyte inorganic composite sheet material; repeating the operation step of adsorbing the polyelectrolyte multiple times, each adsorbed polyelectrolyte has opposite charge to the last adsorbed polyelectrolyte, and one side adsorbs a plurality of polyelectrolytes, and the other side is The sheet-like composite material G of the hydrophobic organic chemical group in the step (2), the step (2'), the step (2"), the step (2"') or the step (3"").

The method according to any one of claims 7-11, wherein:

The silicon germanium coupling agent is a silicon germanium coupling agent represented by formula 2 or formula 3:

Equation 2

In Formula 2, X is an integer of 1-4; RC _n H _2n - Si(Ri ) _m (R ₂ ) _3-m

Equation 3

In Equation 3, n is an integer from 0 to 24;

m can be 0-3;

And each independently is Cl, CH ₃ , OCH ₃ , OCH ₂ CH ₃ or OC ₂ OCH _3;

R is -H, -NH ₂ , HS -, -SCN, -NHCONH ₂ , CI-, NH ₂ (CH ₂ ) ₂ NH -, (CH ₃ ) ₂ -C(Br)-C(0)-NH - , -S0 ₃ , -Ph-SOCl ₂ , -Ph-S0 ₃ , 2,3-epoxypropoxy, methacryloxy, (CH ₂ ) ₃ -S _x -, -CH ₃ , CH ₂ =CH- or Ph, where x is an integer from 1 to 4.