CN109679022A - A kind of preparation method of the floride-free super-hydrophobic coating with pH response - Google Patents

A kind of preparation method of the floride-free super-hydrophobic coating with pH response Download PDF

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CN109679022A
CN109679022A CN201811541747.2A CN201811541747A CN109679022A CN 109679022 A CN109679022 A CN 109679022A CN 201811541747 A CN201811541747 A CN 201811541747A CN 109679022 A CN109679022 A CN 109679022A
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floride
hydrophobic coating
preparation
free super
solvent
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杜斌
陈枫
罗如柏
周世生
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Xian University of Technology
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Xian University of Technology
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
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    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
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    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Abstract

The invention discloses it is a kind of with pH response floride-free super-hydrophobic coating preparation method, specifically: firstly, by DPAEMA, SMA, initiator and solvent be added to sealing reaction kettle in, it is stirred to react, products therefrom n-hexane is precipitated twice, vacuum drying obtains copolymer；Secondly, ammonium hydroxide, TMES and TEOS are dissolved in dehydrated alcohol, it is centrifuged, is dried in vacuo after being stirred to react, grinds granulating, as modified Nano SiO2Particle；Later by copolymer, modified Nano SiO2Particle and PDMS are dissolved in solvent, ultrasonic disperse, form uniform and stable solution, finally, substrate is impregnated in the solution, it is dry, floride-free super-hydrophobic coating can be formed.This approach enhance the degree of adhesions between coating and substrate, while improving the mechanical endurance and ultraviolet-resistent property of coating；When preparing super-hydrophobic coat, material therefor is not fluorine-containing, meets environmentally protective requirement.

Description

A kind of preparation method of the floride-free super-hydrophobic coating with pH response
Technical field
The invention belongs to hydrophobic material preparation technical fields, and in particular to a kind of floride-free super-hydrophobic coating with pH response Preparation method.
Background technique
Super hydrophobic material adheres to water droplet free-falling with lotus surface in nature, and mud is discussed without contaminating for research out According in automatically cleaning, water-oil separating, antibacterial damp-prrof packing aspect is widely used and is concerned.And at present it is many prepare it is super-hydrophobic Fluoropolymer-containing use is directed in the method for coating, this quasi polymer to problem brought by human health and environment not Hold and ignore, therefore for the demand to environmental protection and sustainable strategy, realizes similar function gesture without fluorine coating using environmental protection It must go.
A trend of Materials exactly combines functional material with structural material at present, it is made to meet material It can also assign material certain special functions while proper property, to widen the application range of material.In intellectual material field In, pH responsiveness material becomes most active and most development potentiality a branch due to easy to operate, without additionally modifying, It can be applied to daily life field, pharmaceutical sanitary field, industrial and agricultural production field and Defence business field, involve a wide range of knowledge general.
Using the floride-free super-hydrophobic coating that free-radical polymerized method processing machinery durability is strong and ultraviolet-resistent property is strong, and will It is applied in different substrates, can produce different functionalization products, enhance the surcharge of product, has wide Application prospect.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of floride-free super-hydrophobic coating with pH response, enhance coating Degree of adhesion between substrate, while improving the mechanical endurance and ultraviolet-resistent property of coating.
The technical scheme adopted by the invention is that a kind of preparation method of the floride-free super-hydrophobic coating with pH response, tool Body follows the steps below to implement:
Step 1, by DPAEMA, SMA, initiator and solvent be added reaction kettle in, backward reaction kettle in be passed through nitrogen arrange Except air therein, reaction kettle is sealed, is stirred to react 6h~10h under 60 DEG C~70 DEG C of constant temperature oil bath, then by products therefrom Twice with n-hexane precipitating, finally, being dried in vacuo 12h~for 24 hours under the conditions of 40 DEG C~70 DEG C, copolymer is obtained；
Step 2, ammonium hydroxide, TMES and TEOS that mass fraction is 25% are dissolved in dehydrated alcohol, at 60 DEG C~70 DEG C Constant temperature oil bath under be stirred to react 4h~6h, later use centrifugal treating, make to be separated by solid-liquid separation, by obtained solid matter spend from Sub- water washing 2 times is dried in vacuo 12h~for 24 hours under the conditions of 90 DEG C~120 DEG C, finally, being ground into partial size is 70~100nm's Particle, as modified Nano SiO2Particle；
Step 3, the modified Nano SiO that will be obtained after the copolymer obtained after step 1, step 22Particle and PDMS are being stirred It is dissolved in solvent in the state of mixing, ultrasonic disperse 30min forms uniform and stable solution；
Step 4, acetone, dehydrated alcohol and deionized water substrate is successively used to wash 2 times, later by substrate be immersed in through In the solution obtained after step 3, finally, substrate is dried 2h~4h under the conditions of 100 DEG C~130 DEG C, it can be formed floride-free super Hydrophobic coating.
The features of the present invention also characterized in that
In step 1, the time for being passed through nitrogen is 30min~60min；The mass ratio of DPAEMA, SMA, initiator and solvent For 6.28~12.56:3.38~13.52:0.08~0.24:65.
In step 1, initiator is azodiisobutyronitrile or dibenzoyl peroxide.
In step 1, solvent is ethyl acetate, toluene, any one or two kinds in acetonitrile.
In step 2, the mass ratio of ammonium hydroxide, TMES, TEOS and dehydrated alcohol is 2:1~3:2:50.
In step 3, modified Nano SiO2Particle, copolymer, PDMS and solvent mass ratio be 1~3:1~3:0.5:60.
In step 3, solvent is ethyl acetate, toluene, any one or two kinds in acetonitrile.
In step 4, soaking time is 20min~60min.
The beneficial effects of the present invention are:
The super-hydrophobic coat can combine from different substrates, convenient for manufacturing a variety of super-hydrophobic products, application range Extensively；And the degree of adhesion between coating and substrate is enhanced, while improving the mechanical endurance and ultraviolet-resistent property of coating；It is making Material therefor is not fluorine-containing when standby super-hydrophobic coat, meets environmentally protective requirement；In addition, preparation process is simple, valuableness is not needed Equipment, it is low in cost, be easy to industrialization.
Specific embodiment
The present invention is described in detail With reference to embodiment.
A kind of preparation method of the floride-free super-hydrophobic coating with pH response of the present invention, is specifically implemented according to the following steps:
Step 1, by [2- (isopropylamino) ethyl methacrylate] (DPAEMA), methacrylic acid octadecane ester (SMA), initiator and solvent are added in reaction kettle, backward reaction kettle in be passed through nitrogen and exclude air therein, sealing is reacted Kettle is stirred to react 6h~10h under 60 DEG C~70 DEG C of constant temperature oil bath, then products therefrom n-hexane is precipitated twice, finally, It is dried in vacuo 12h~for 24 hours under the conditions of 40 DEG C~70 DEG C, obtains copolymer；
The mass ratio of DPAEMA, SMA, initiator and solvent are 6.28~12.56:3.38~13.52:0.08~0.24: 65；
The time for being passed through nitrogen is 30min~60min；
Initiator is azodiisobutyronitrile (AIBN) or dibenzoyl peroxide (BPO)；
Solvent is ethyl acetate, toluene, any one or two kinds in acetonitrile；
Step 2, ammonium hydroxide, trimethylethoxysilane (TMES) and the ethyl orthosilicate (TEOS) for being 25% by mass fraction It is dissolved in dehydrated alcohol, is stirred to react 4h~6h under 60 DEG C~70 DEG C of constant temperature oil bath, use centrifugal treating later, make solid Liquid separation, obtained solid matter is washed with deionized 2 times, and 12h~for 24 hours is dried in vacuo under the conditions of 90 DEG C~120 DEG C, Finally, being ground into the particle that partial size is 70~100nm, as modified Nano SiO2Particle；
The mass ratio of ammonium hydroxide, TMES, TEOS and dehydrated alcohol is 2:1~3:2:50；
Step 3, the modified Nano SiO that will be obtained after the copolymer obtained after step 1, step 22Particle and poly dimethyl Siloxanes (PDMS) is dissolved in solvent while stirring, and ultrasonic disperse 30min forms uniform and stable solution；
Modified Nano SiO2Particle, copolymer, PDMS and solvent mass ratio be 1~3:1~3:0.5:60；
Solvent is ethyl acetate, toluene, any one or two kinds in acetonitrile；
Step 4, acetone, dehydrated alcohol and deionized water substrate is successively used to wash 2 times, later by substrate be immersed in through In the solution obtained after step 3, soaking time is 20min~60min, finally, substrate is done under the conditions of 100 DEG C~130 DEG C Dry 2h~4h can form floride-free super-hydrophobic coating；
Substrate is cotton fabric, paper, sponge or foam.
Embodiment 1
A kind of preparation method of the floride-free super-hydrophobic coating with pH response, is specifically implemented according to the following steps:
Step 1, by 6.28g [2- (isopropylamino) ethyl methacrylate] (DPAEMA), 3.38g methacrylic acid ten Eight alkyl esters (SMA), 0.08g AIBN are dissolved in 65g ethyl acetate, backward reaction kettle in be passed through 30min nitrogen exclude wherein Air, seal reaction kettle, be stirred to react 6h under 60 DEG C of constant temperature oil bath, then products therefrom n-hexane is precipitated twice, Finally, being dried in vacuo 12h under the conditions of 40 DEG C, copolymer is obtained；
Step 2, ammonium hydroxide, trimethylethoxysilane (TMES) and the ethyl orthosilicate (TEOS) for being 25% by mass fraction It is dissolved in dehydrated alcohol, 4h is stirred to react under 60 DEG C of constant temperature oil bath, use centrifugal treating later, make to be separated by solid-liquid separation, it will Obtained solid matter is washed with deionized 2 times, is dried in vacuo 12h under the conditions of 90 DEG C, finally, being ground into partial size is 70nm Particle, as modified Nano SiO2Particle；
The mass ratio of ammonium hydroxide, TMES, TEOS and dehydrated alcohol is 2:1:2:50；
Step 3, the modified Nano SiO that will be obtained after the copolymer obtained after step 1, step 22Particle and poly dimethyl Siloxanes (PDMS) is dissolved in ethyl acetate while stirring, and ultrasonic disperse 30min forms uniform and stable solution；
Modified Nano SiO2Particle, copolymer, PDMS and solvent mass ratio be 1:1:0.5:60；
Step 4, substrate (cotton fabric, paper, sponge and foam) is successively washed using acetone, dehydrated alcohol and deionization It washs 2 times, substrate is immersed in the solution obtained after step 3 later, soaking time 20min, finally, by substrate 100 Dry 2h, can form floride-free super-hydrophobic coating under the conditions of DEG C.
Embodiment 2
A kind of preparation method of the floride-free super-hydrophobic coating with pH response of the present invention, is specifically implemented according to the following steps:
Step 1, by 6.28g [2- (isopropylamino) ethyl methacrylate] (DPAEMA), 3.38g methacrylic acid ten Eight alkyl esters (SMA), 0.16g BPO are dissolved in 65g toluene, backward reaction kettle in be passed through 35min nitrogen and exclude sky therein Gas seals reaction kettle, 7h is stirred to react under 60 DEG C of constant temperature oil bath, then products therefrom n-hexane is precipitated twice, finally, It is dried in vacuo 16h under the conditions of 50 DEG C, obtains copolymer；
Step 2, ammonium hydroxide, trimethylethoxysilane (TMES) and the ethyl orthosilicate (TEOS) for being 25% by mass fraction It is dissolved in dehydrated alcohol, 4.5h is stirred to react under 60 DEG C of constant temperature oil bath, use centrifugal treating later, make to be separated by solid-liquid separation, Obtained solid matter is washed with deionized 2 times, is dried in vacuo 16h under the conditions of 100 DEG C, finally, being ground into partial size and being The particle of 80nm, as modified Nano SiO2Particle；
The mass ratio of ammonium hydroxide, TMES, TEOS and dehydrated alcohol is 2:1.5:2:50；
Step 3, the modified Nano SiO that will be obtained after the copolymer obtained after step 1, step 22Particle and poly dimethyl Siloxanes (PDMS) is dissolved in toluene while stirring, and ultrasonic disperse 30min forms uniform and stable solution；
Modified Nano SiO2Particle, copolymer, PDMS and solvent mass ratio be 1:2:0.5:60；
Step 4, substrate (cotton fabric, paper, sponge, foam) is successively washed using acetone, dehydrated alcohol and deionization It washs 2 times, substrate is immersed in the solution obtained after step 3 later, soaking time 30min, finally, by substrate 110 Dry 2h, can form floride-free super-hydrophobic coating under the conditions of DEG C.
Embodiment 3
A kind of preparation method of the floride-free super-hydrophobic coating with pH response of the present invention, is specifically implemented according to the following steps:
Step 1, by 9.42g [2- (isopropylamino) ethyl methacrylate] (DPAEMA), 6.76g methacrylic acid ten Eight alkyl esters (SMA) and 0.13g AIBN are dissolved in 65g ethylacetate/acetonitrile mixed liquor；Backward reaction kettle in be passed through 40min Nitrogen excludes air therein, seals reaction kettle, is stirred to react 8h under 65 DEG C of constant temperature oil bath, then by products therefrom use just oneself Alkane precipitates twice, finally, being dried in vacuo 18h under the conditions of 55 DEG C, obtains copolymer；
Step 2, ammonium hydroxide, trimethylethoxysilane (TMES) and the ethyl orthosilicate (TEOS) for being 25% by mass fraction It is dissolved in dehydrated alcohol, 5h is stirred to react under 65 DEG C of constant temperature oil bath, use centrifugal treating later, make to be separated by solid-liquid separation, it will Obtained solid matter is washed with deionized 2 times, is dried in vacuo 18h under the conditions of 110 DEG C, finally, being ground into partial size and being The particle of 90nm, as modified Nano SiO2Particle；
The mass ratio of ammonium hydroxide, TMES, TEOS and dehydrated alcohol is 2:2:2:50；
Step 3, the modified Nano SiO that will be obtained after the copolymer obtained after step 1, step 22Particle and poly dimethyl Siloxanes (PDMS) is dissolved in while stirring in ethylacetate/acetonitrile mixed liquor, ultrasonic disperse 30min, is formed uniform Stable solution；
Modified Nano SiO2Particle, copolymer, PDMS and solvent mass ratio be 2:1:0.5:60；
Step 4, substrate (cotton fabric, paper, sponge, foam) is successively washed using acetone, dehydrated alcohol and deionization It washs 2 times, substrate is immersed in the solution obtained after step 3 later, soaking time 40min, finally, by substrate 120 Dry 3h, can form floride-free super-hydrophobic coating under the conditions of DEG C.
Embodiment 4
A kind of preparation method of the floride-free super-hydrophobic coating with pH response of the present invention, is specifically implemented according to the following steps:
Step 1, by 9.42g [2- (isopropylamino) ethyl methacrylate] (DPAEMA), 10.14g methacrylic acid Octadecane ester (SMA) and 0.21g BPO are dissolved in 65g ethyl acetate/toluene mixture liquid；Backward reaction kettle in be passed through 50min nitrogen excludes air therein, seals reaction kettle, is stirred to react 9h under 65 DEG C of constant temperature oil bath, then by products therefrom Twice with n-hexane precipitating, finally, being dried in vacuo 20h under the conditions of 60 DEG C, copolymer is obtained；
Step 2, ammonium hydroxide, trimethylethoxysilane (TMES) and the ethyl orthosilicate (TEOS) for being 25% by mass fraction It is dissolved in dehydrated alcohol, 5h is stirred to react under 65 DEG C of constant temperature oil bath, use centrifugal treating later, make to be separated by solid-liquid separation, it will Obtained solid matter is washed with deionized 2 times, is dried in vacuo 12h under the conditions of 120 DEG C, finally, being ground into partial size and being The particle of 90nm, as modified Nano SiO2Particle；
The mass ratio of ammonium hydroxide, TMES, TEOS and dehydrated alcohol is 2:1:2:50；
Step 3, the modified Nano SiO that will be obtained after the copolymer obtained after step 1, step 22Particle and poly dimethyl Siloxanes (PDMS) is dissolved in while stirring in ethyl acetate/toluene mixture liquid, ultrasonic disperse 30min, is formed uniform Stable solution；
Modified Nano SiO2Particle, copolymer, PDMS and solvent mass ratio be 3:2:0.5:60；
Step 4, substrate (cotton fabric, paper, sponge, foam) is successively washed using acetone, dehydrated alcohol and deionization It washs 2 times, substrate is immersed in the solution obtained after step 3 later, soaking time 50min, finally, by substrate 120 Dry 3h, can form floride-free super-hydrophobic coating under the conditions of DEG C.
Embodiment 5
A kind of preparation method of the floride-free super-hydrophobic coating with pH response of the present invention, is specifically implemented according to the following steps:
Step 1, by 12.56g [2- (isopropylamino) ethyl methacrylate] (DPAEMA), 13.52g methacrylic acid Octadecane ester (SMA) and 0.16g AIBN are dissolved in 65g toluene/acetonitrile mixture；Backward reaction kettle in be passed through 60min nitrogen Gas excludes air therein, seals reaction kettle, is stirred to react 10h under 70 DEG C of constant temperature oil bath, then by products therefrom use just oneself Alkane precipitates twice, finally, being dried in vacuo for 24 hours under the conditions of 70 DEG C, obtains copolymer；
Step 2, ammonium hydroxide, trimethylethoxysilane (TMES) and the ethyl orthosilicate (TEOS) for being 25% by mass fraction It is dissolved in dehydrated alcohol, 6h is stirred to react under 70 DEG C of constant temperature oil bath, use centrifugal treating later, make to be separated by solid-liquid separation, it will Obtained solid matter is washed with deionized 2 times, is dried in vacuo for 24 hours under the conditions of 120 DEG C, finally, being ground into partial size and being The particle of 100nm, as modified Nano SiO2Particle；
The mass ratio of ammonium hydroxide, TMES, TEOS and dehydrated alcohol is 2:3:2:50；
Step 3, the modified Nano SiO that will be obtained after the copolymer obtained after step 1, step 22Particle and poly dimethyl Siloxanes (PDMS) is dissolved in solvent while stirring, and ultrasonic disperse 30min forms uniform and stable solution；
Modified Nano SiO2Particle, copolymer, PDMS and solvent mass ratio be 3:3:0.5:60；
Solvent is ethyl acetate, toluene, any one or two kinds in acetonitrile；
Step 4, substrate (cotton fabric, paper, sponge, foam) is successively washed using acetone, dehydrated alcohol and deionization It washs 2 times, substrate is immersed in the solution obtained after step 3 later, soaking time 60min, finally, by substrate 130 Dry 4h, can form floride-free super-hydrophobic coating under the conditions of DEG C.
The free-floride that substrate (cotton fabric, paper, the sponge and foam) surface in the embodiment of the present invention is formed respectively is super thin Water coating is immersed in 0.5h in the solution of pH>=7 and pH<7, later dry 4-6h under the conditions of 90 DEG C -120 DEG C, later to its property It can be carried out detection, result is as follows:
Water-oil separating Efficiency testing: using self-control oily-water seperating equipment, two bottomless bottles are staggered relatively, and centre is put It sets by pH response coating solution processing and alkaline solution (pH >=7) processed cotton fabric, paper, sponge and foam, is used in combination Fixture folder is fixed, and a large beaker is placed below package unit to collect permeation liquid.Three chloromethanes that oil red O is coloured The mixture of the deionized water of alkane and methylene blue staining pours into the vial of device top half, since cotton fabric is in alkalinity Under the conditions of super-hydrophobic/super-oleophilic, chloroform permeates rapidly smart fabric and water is retained in the vial of top, will permeate Chloroform collect measure its volume.Same method, cotton fabric, paper, sponge and foam respond coating by pH Solution processing and acid solution (pH < 7) processing, due to super hydrophilic/superoleophobic property of cotton fabric in acid condition, deionization Water permeates rapidly smart fabric and chloroform is retained in the vial of top, and the deionized water of infiltration is collected and measures it Volume.The oil of modified cotton fabric, paper, sponge and foam under alkalinity and acidic environment is calculated according to the oil phase or water phase of collection Water separative efficiency, as shown in table 1.
1 water-oil separating Efficiency testing result of table
As seen from the above table, copolymer/SiO2Cotton fabric, paper, sponge and the foam that/PDMS is modified all have good Water-oil separating efficiency, and the pH response coating prepared using this method is available to a variety of substrates.

Claims (8)

1. a kind of preparation method of the floride-free super-hydrophobic coating with pH response, which is characterized in that specifically real according to the following steps It applies:
Step 1, DPAEMA, SMA, initiator and solvent are added in reaction kettle, backward reaction kettle in be passed through nitrogen and exclude it In air, seal reaction kettle, be stirred to react 6h~10h under 60 DEG C~70 DEG C of constant temperature oil bath, then by products therefrom with just Hexane precipitation twice, finally, being dried in vacuo 12h~for 24 hours under the conditions of 40 DEG C~70 DEG C, obtains copolymer；
Step 2, ammonium hydroxide, TMES and TEOS that mass fraction is 25% are dissolved in dehydrated alcohol, in 60 DEG C~70 DEG C of perseverance It is stirred to react 4h~6h under warm oil bath, uses centrifugal treating later, makes to be separated by solid-liquid separation, the solid matter deionized water that will be obtained Washing 2 times is dried in vacuo 12h~for 24 hours under the conditions of 90 DEG C~120 DEG C, finally, it is ground into the particle that partial size is 70~100nm, As modified Nano SiO2Particle；
Step 3, the modified Nano SiO that will be obtained after the copolymer obtained after step 1, step 22Particle and PDMS are in stirring It is dissolved in solvent under state, ultrasonic disperse 30min forms uniform and stable solution；
Step 4, substrate is successively used acetone, dehydrated alcohol and deionized water to wash 2 times, substrate is immersed in through step later In the solution obtained after 3, finally, substrate is dried 2h~4h under the conditions of 100 DEG C~130 DEG C, floride-free super-hydrophobic can be formed Coating.
2. a kind of preparation method of floride-free super-hydrophobic coating with pH response according to claim 1, which is characterized in that In the step 1, the time for being passed through nitrogen is 30min~60min；The mass ratio of DPAEMA, SMA, initiator and solvent is 6.28~12.56:3.38~13.52:0.08~0.24:65.
3. a kind of preparation method of floride-free super-hydrophobic coating with pH response according to claim 1, which is characterized in that In the step 1, initiator is azodiisobutyronitrile or dibenzoyl peroxide.
4. a kind of preparation method of floride-free super-hydrophobic coating with pH response according to claim 1, which is characterized in that In the step 1, solvent is ethyl acetate, toluene, any one or two kinds in acetonitrile.
5. a kind of preparation method of floride-free super-hydrophobic coating with pH response according to claim 1, which is characterized in that In the step 2, the mass ratio of ammonium hydroxide, TMES, TEOS and dehydrated alcohol is 2:1~3:2:50.
6. a kind of preparation method of floride-free super-hydrophobic coating with pH response according to claim 1, which is characterized in that In the step 3, modified Nano SiO2Particle, copolymer, PDMS and solvent mass ratio be 1~3:1~3:0.5:60.
7. a kind of preparation method of floride-free super-hydrophobic coating with pH response according to claim 1, which is characterized in that In the step 3, solvent is ethyl acetate, toluene, any one or two kinds in acetonitrile.
8. a kind of preparation method of floride-free super-hydrophobic coating with pH response according to claim 1, which is characterized in that In the step 4, soaking time is 20min~60min.
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Application publication date: 20190426