CN113249970A - Preparation method of environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface - Google Patents
Preparation method of environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 54
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 46
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 41
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 33
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 29
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- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims abstract description 27
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a preparation method of an environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface, which is implemented according to the following steps: preparing an environment-responsive microcapsule by a miniemulsion polymerization method by using diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as reaction monomers, azodiisobutyronitrile as a thermal initiator, divinylbenzene as a crosslinking agent and hexadecane as a stabilizer; and step two, ultrasonically dispersing the environment-responsive microcapsules prepared in the step one in deionized water to obtain a microcapsule solution, then treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and then drying the material in a drying oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material. The surface of the material prepared by the invention can realize reversible conversion between super-hydrophobicity and hydrophilicity, and has better hydrophobicity and environmental response performance.
Description
Technical Field
The invention belongs to the technical field of material surface modification, and relates to a preparation method of an environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface.
Background
The super-hydrophobic material is a material with a contact angle between the surface of the material and water of more than 150 degrees and a rolling angle of less than 10 degrees, and the surface of the super-hydrophobic material has strong water resistance, so that the super-hydrophobic material has good self-cleaning property, moisture resistance and the like. The excellent non-wettability of the super-hydrophobic surface has a very large application prospect in industrial production and daily life. Common traditional materials such as cotton cloth, wood plastic, paper, concrete and the like are widely applied in production and life, but the materials have obvious moisture absorption phenomena, if the materials are placed in an environment with higher humidity for a long time, the phenomena of mildew, corrosion and the like can occur, meanwhile, the dimensional stability of the materials can not be guaranteed, the service life of the materials is greatly shortened, and the application range is limited.
The microcapsule is a spherical particle with the diameter ranging from nanometer to micrometer, utilizes artificial or natural high molecular materials as wall materials, and encapsulates solid or liquid, inorganic or organic, hydrophobic or hydrophilic materials as core materials in the microcapsule to achieve the desired purpose. The responsive microcapsule is made of wall material with environmental response type, so that the microcapsule has environmental response, and when the environment is changed, the microcapsule generates a series of changes. Patent No. 202010834945.9 discloses a preparation method of a super-hydrophobic microcapsule polymer cement-based anticorrosive paint, and a microcapsule paint for cement corrosion prevention is prepared.
At present, the preparation of the super-hydrophobic surface of the microcapsule is relatively little researched.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface, and the prepared material surface can realize reversible conversion between super-hydrophobic and hydrophilic and has better hydrophobic performance and environment-responsive performance.
The technical scheme adopted by the invention is that the preparation method of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface is implemented according to the following steps:
preparing an environment-responsive microcapsule by a miniemulsion polymerization method by using diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as reaction monomers, azodiisobutyronitrile as a thermal initiator, divinylbenzene as a crosslinking agent and hexadecane as a stabilizer;
and step two, ultrasonically dispersing the environment-responsive microcapsules prepared in the step one in deionized water to obtain a microcapsule solution, then treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and then drying the material in a drying oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material.
In the first step, the molar ratio of the diethylaminoethyl methacrylate, the styrene, the nonafluorohexyl methacrylate and the glycidyl methacrylate is 0.5-2.0: 0.5-2.0: 0.5-2.0: 0.5 to 2.0.
In the first step, the dosage of the azodiisobutyronitrile and the divinylbenzene is respectively 3 percent and 5 percent of the mass of the monomer, and the dosage of the hexadecane is 50 percent of the mass of the monomer.
The miniemulsion polymerization method in the first step specifically comprises the following steps:
fully and uniformly mixing diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate, glycidyl methacrylate, azobisisobutyronitrile, divinylbenzene and hexadecane, dropwise adding the mixture into a water phase, emulsifying for 20-30 min, transferring the mixture into a three-neck flask, and performing emulsion at 400-800 r min-1Reacting for 8-10 hours under mechanical stirring, controlling the temperature at 60-80 ℃, then centrifuging, cleaning, drying in a vacuum drying oven at 60-80 ℃ for 20-24 hours, and then preserving in vacuum to obtain the environment-responsive microcapsule.
The water phase is deionized water with sodium dodecyl benzene sulfonate as surfactant.
When the oil phase is dripped into the water phase in the step one, a homogenizer is adopted for stirring, and the speed is 10000r min-1～20000r min-1。
In the second step, the material in the surface of the material treated by the microcapsule solution is any one of cotton cloth, wood plastic, paper, ceramic, cement and concrete.
2, the method for treating the surface of the material by the microcapsule solution has four methods: one method is a dipping and rolling method, wherein a microcapsule solution is used for soaking a material for 10-30 min, an aluminum sheet which is smooth and larger than the area of the material is used for extrusion, and the material is dried in an oven; the second is a coating method, namely microcapsule solution is sprayed, spin-coated and roll-coated on the surface of the material for 1 to 5 times; the third is a printing method, namely, the microcapsule solution is printed on the surface of the material by a screen printing mode; the fourth is the impregnation method, i.e. the material is directly soaked into a relatively dilute microcapsule solution.
The invention has the advantages that
(1) The environment-responsive super-hydrophobic-hydrophilic reversible conversion paper prepared by the invention has pH response characteristics, and simultaneously can be subjected to hydrophobic and hydrophilic reversible conversion: soaking or coating a hydrophilic surface of paper (cotton cloth, wood plastic, paper, ceramic, cement, concrete and the like) with the obtained environment-responsive microcapsule dispersion liquid, drying to obtain a hydrophobic surface, dripping neutral liquid on the hydrophobic surface, and keeping the contact angle between the liquid drop and the hydrophobic surface to be about 145 degrees, wherein the liquid drop has super-hydrophobicity; dropping a liquid drop with pH value of 13 on a hydrophobic surface, wherein the contact angle between the liquid drop and the hydrophobic surface is kept about 150 degrees overall, and the liquid drop has super-hydrophobicity; dropping a liquid drop with pH of 1 on a hydrophobic surface, completely absorbing the liquid drop by 120s, and keeping the contact angle between the liquid drop and the hydrophobic surface at about 148 degrees after the surface is rinsed and dried, and continuing to drop the liquid drop with pH of 13 on the hydrophobic surface. So that the surface of the material has environmental responsiveness to different pH values, super hydrophobicity for neutral and alkaline liquids, hydrophilicity for acidic solutions and reversible conversion property.
(2) The environment-responsive microcapsule prepared by the invention can be applied to various fields. The pH response microcapsule prepared by the research has the characteristics of a tiny size structure, excellent dispersion stability, compatibility of each component and the like, has intelligent responsiveness, and can be applied to the aspects of biosensing, drug delivery and the like.
(3) The environment-responsive microcapsule prepared by the invention can be stored for a long time, is prepared into dispersion liquid when in use, is time-saving and labor-saving, and has low cost. The large-scale production of the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material can be realized through coating, printing and other equipment, the research investment of new equipment is avoided, and the economic benefit is great;
(4) the invention enlarges the application range of the super-hydrophobic material, and the environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface prepared by the invention ensures that the hydrophilic surface of the common material can obtain a hydrophobic surface under neutral and alkaline conditions and a hydrophilic surface under acidic conditions. This property is of great use value in particular industrial applications. The super-hydrophobic-hydrophilic reversible transformation can be more than dozens of times, the application range of the super-hydrophobic material is expanded, and the super-hydrophobic material has very wide application prospect in the future
Drawings
Fig. 1 is a photograph of a contact angle of a superhydrophobic surface of an environment-responsive superhydrophobic-hydrophilic reversible conversion material prepared in example 2 of the present invention with water after the surface is treated with a liquid drop having a pH of 13;
fig. 2 is a photograph of a contact angle of a superhydrophobic surface treated with a liquid droplet having a pH of 7 on an environment-responsive superhydrophobic-hydrophilic reversible conversion surface prepared in example 2 of the present invention with water;
fig. 3 is a photograph of the contact angle of the hydrophilic surface with water after the environment-responsive superhydrophobic-hydrophilic reversible conversion surface prepared in example 2 of the present invention is treated with a droplet of pH 1;
FIG. 4 is a photograph of the contact angle of the surface of untreated paper with water;
fig. 5 is a graph showing the variation of particle size of the environmentally responsive microcapsule prepared in example 4 of the present invention after being treated with pH1 and pH7 solutions;
fig. 6 is a graph showing the change of water contact angle of the environment-responsive superhydrophobic-hydrophilic reversible transformation material prepared in example 4 of the present invention after being treated with a solution having a pH of 1 or 7;
FIG. 7 is a scanning electron micrograph of the surface of untreated paper;
FIG. 8 is a surface scanning electron micrograph of the environmentally responsive superhydrophobic-hydrophilic paper prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The preparation method of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface is implemented according to the following steps:
firstly, mixing and uniformly mixing diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate serving as reaction monomers, azodiisobutyronitrile serving as a thermal initiator, divinylbenzene serving as a crosslinking agent and hexadecane serving as a stabilizerAfter the mixture is homogenized, the mixture is dripped into the water phase drop by drop, emulsified for 20-30 min, and then transferred into a three-neck flask at 400-800 r min-1Reacting for 8-10 hours under mechanical stirring, controlling the temperature at 60-80 ℃, then centrifuging, cleaning, drying in a vacuum drying oven at 60-80 ℃ for 20-24 hours, and then preserving in vacuum to obtain the environment-responsive microcapsule; wherein the molar ratio of the diethylaminoethyl methacrylate, the styrene, the nonafluorohexyl methacrylate and the glycidyl methacrylate is 0.5-2.0: 0.5-2.0: 0.5-2.0: 0.5-2.0, wherein the dosage of the azodiisobutyronitrile and the divinylbenzene is respectively 3% and 5% of the mass of the monomer, and the dosage of the hexadecane is 50% of the mass of the monomer. The water phase is deionized water containing Sodium Dodecyl Benzene Sulfonate (SDBS) as surfactant, and the oil phase is dropped into the water phase and stirred by homogenizer at 10000r min-1～20000r min-1。
Step two, ultrasonically dispersing the environment-responsive microcapsules prepared in the step one in deionized water to obtain a microcapsule solution, then treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and drying the material in a drying oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material; wherein the material is any one of cotton cloth, wood plastic, paper, ceramic, cement and concrete; there are four methods of treating the surface of the material with the microcapsule solution: one method is a dipping and rolling method, wherein a microcapsule solution is used for soaking a material for 10-30 min, an aluminum sheet which is smooth and larger than the area of the material is used for extrusion, and the material is dried in an oven; the second is a coating method, namely microcapsule solution is sprayed, spin-coated and roll-coated on the surface of the material for 1 to 5 times; the third is a printing method, namely, the microcapsule solution is printed on the surface of the material by a screen printing mode; the fourth is the impregnation method, i.e. the material is directly soaked into a relatively dilute microcapsule solution.
The realization process of the responsiveness of the microcapsule mainly depends on ionization and deionization, and is realized along with H in the environment of the microcapsule+At an increased concentration, the tertiary amine group is rapidly protonated, thus leaving the N atom with a positive charge; the positive charge on the polymer skeleton is increased, and the molecular chain has a large amount of charges with the same signStronger coulomb repulsion occurs, resulting in increased hydrophilicity of the hydrophobic microcapsules with concomitant swelling of the size. Conversely, as the ambient pH increases, the microcapsule polymer backbone follows H+The concentration is reduced, the protonation degree is reduced, and coulomb repulsion between molecular chains is gradually disappeared, so that the microcapsule is restored to the original compact and hydrophobic state.
Example 1
Taking diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as monomers, azodiisobutyronitrile as a thermal initiator, divinylbenzene as a cross-linking agent, hexadecane as a stabilizer, taking the above materials as an oil phase, and selecting Sodium Dodecyl Benzene Sulfonate (SDBS) as a surfactant to be dissolved in deionized water to serve as a continuous phase (water phase). And (3) after fully and uniformly mixing the oil phase, dropwise adding the oil phase into the water phase to emulsify for 20min under the high-speed stirring of a homogenizer. Standing for 30min to form white emulsion, transferring into three-neck flask, and standing for 400r min-1Reacting for 8 hours under mechanical stirring, controlling the temperature at 80 ℃, centrifuging, cleaning, drying in a vacuum drying oven at 80 ℃ for 24 hours, and then preserving in vacuum to obtain the environment-responsive microcapsule;
in the first step, the monomer molar ratio of diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate is 1:1:0.8:1, the dosage of azobisisobutyronitrile is 0.209g, the dosage of divinylbenzene is 0.348g and the dosage of hexadecane is 3.483 g.
And step two, ultrasonically dispersing the environment-responsive microcapsule in deionized water, treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and drying the immersed surface of the material in an oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material.
The concentration of the microcapsules in the aqueous polymer solution in the second step is 10mg/100 mL.
Example 2
Step one, taking diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as monomers and azo-bis-isobutyronitrile as a heat initiatorThe hair agent is prepared by taking divinyl benzene as a cross-linking agent, taking hexadecane as a stabilizing agent, taking the materials as an oil phase, and selecting Sodium Dodecyl Benzene Sulfonate (SDBS) as a surfactant to be dissolved in deionized water to serve as a continuous phase (water phase). And (3) after fully and uniformly mixing the oil phase, dropwise adding the oil phase into the water phase to emulsify for 30min under the high-speed stirring of a homogenizer. Standing for 30min to form white emulsion, transferring into three-neck flask at 800r min-1Reacting for 10h under mechanical stirring, controlling the temperature at 80 ℃, centrifuging, cleaning, drying in a vacuum drying oven at 80 ℃ for 24h, and then storing in vacuum to obtain the environment-responsive microcapsule;
in the first step, the monomer ratio of diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate is 1:1:0.6:1, the dosage of azobisisobutyronitrile is 0.189g, the dosage of divinylbenzene is 0.315g and the dosage of hexadecane is 3.151 g.
And step two, ultrasonically dispersing the environment-responsive microcapsule in deionized water, treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and drying the immersed surface of the material in an oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material.
The concentration of the microcapsules in the aqueous polymer solution in the second step was 50mg/100 mL.
Example 3
Taking diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as monomers, azodiisobutyronitrile as a thermal initiator, divinylbenzene as a cross-linking agent, hexadecane as a stabilizer, taking the above materials as an oil phase, and selecting Sodium Dodecyl Benzene Sulfonate (SDBS) as a surfactant to be dissolved in deionized water to serve as a continuous phase (water phase). And (3) after fully and uniformly mixing the oil phase, dropwise adding the oil phase into the water phase to emulsify for 25min under the high-speed stirring of a homogenizer. Standing for 30min to form white emulsion, transferring into three-neck flask, and standing for 600r min-1Reacting for 9h under mechanical stirring, controlling the temperature at 70 ℃, centrifuging, cleaning, drying in a vacuum drying oven at 60 ℃ for 24h, and then preserving in vacuum to obtain the environment-responsive microcapsule;
in the first step, the monomer ratio of diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate is 1:1:0.7:1, the dosage of azobisisobutyronitrile is 0.199g, the dosage of divinylbenzene is 0.331g and the dosage of hexadecane is 3.317 g.
And step two, ultrasonically dispersing the environment-responsive microcapsule in deionized water, treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and drying the immersed surface of the material in an oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material.
The concentration of the microcapsules in the aqueous polymer solution in step two was 70mg/100 mL.
Example 4
Taking diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as monomers, azodiisobutyronitrile as a thermal initiator, divinylbenzene as a cross-linking agent, hexadecane as a stabilizer, taking the above materials as an oil phase, and selecting Sodium Dodecyl Benzene Sulfonate (SDBS) as a surfactant to be dissolved in deionized water to serve as a continuous phase (water phase). And (3) after fully and uniformly mixing the oil phase, dropwise adding the oil phase into the water phase to emulsify for 20min under the high-speed stirring of a homogenizer. Standing for 30min to form white emulsion, transferring into three-neck flask, and standing for 400r min-1Reacting for 8 hours under mechanical stirring, controlling the temperature at 80 ℃, centrifuging, cleaning, drying in a vacuum drying oven at 80 ℃ for 24 hours, and then preserving in vacuum to obtain the environment-responsive microcapsule;
in the first step, the monomer ratio of diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate is 1:1:0.4:1, the dosage of azobisisobutyronitrile is 0.169g, the dosage of divinylbenzene is 0.282g and the dosage of hexadecane is 2.819 g.
And step two, ultrasonically dispersing the environment-responsive microcapsule in deionized water, treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and drying the immersed surface of the material in an oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material.
The concentration of the microcapsules in the aqueous polymer solution in the second step was 20mg/100 mL.
Example 5
The preparation method of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface is implemented according to the following steps:
step one, taking diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as reaction monomers, azodiisobutyronitrile as a thermal initiator, divinylbenzene as a cross-linking agent and hexadecane as a stabilizing agent, uniformly mixing the components, dropwise adding the mixture into a water phase, emulsifying for 30min, transferring the mixture into a three-neck flask, and carrying out emulsification at 800r min-1Reacting for 10 hours under mechanical stirring, controlling the temperature at 60 ℃, then centrifuging, cleaning, drying in a vacuum drying oven at 60 ℃ for 20 hours, and then preserving in vacuum to obtain the environment-responsive microcapsule; wherein the molar ratio of the diethylaminoethyl methacrylate, the styrene, the nonafluorohexyl methacrylate and the glycidyl methacrylate is 0.5: 0.5: 0.5: 0.5, 3% and 5% of azobisisobutyronitrile and divinylbenzene, respectively, and 50% of hexadecane, based on the mass of the monomers. The water phase is deionized water containing Sodium Dodecyl Benzene Sulfonate (SDBS) as surfactant, and the oil phase is dropped into the water phase and stirred by homogenizer at 10000r min-1。
Step two, ultrasonically dispersing the environment-responsive microcapsules prepared in the step one in deionized water to obtain a microcapsule solution, then treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and drying the material in a drying oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material; wherein the material is any one of cotton cloth, wood plastic, paper, ceramic, cement and concrete; there are four methods of treating the surface of the material with the microcapsule solution: one is a dipping method, wherein a microcapsule solution is used for soaking a material for 10min, an aluminum sheet which is smooth and larger than the area of the material is used for extrusion, and the material is dried in an oven; the second method is a coating method, namely microcapsule solution is sprayed, spin-coated and roll-coated on the surface of the material for 5 times; the third is a printing method, namely, the microcapsule solution is printed on the surface of the material by a screen printing mode; the fourth is the impregnation method, i.e. the material is directly soaked into a relatively dilute microcapsule solution.
Example 6
The preparation method of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface is implemented according to the following steps:
step one, taking diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as reaction monomers, azodiisobutyronitrile as a thermal initiator, divinylbenzene as a cross-linking agent and hexadecane as a stabilizing agent, uniformly mixing the components, dropwise adding the mixture into a water phase, emulsifying for 25min, transferring the mixture into a three-neck flask, and carrying out 600r min-1Reacting for 9 hours under mechanical stirring, controlling the temperature at 70 ℃, then centrifuging, cleaning, drying in a vacuum drying oven at 70 ℃ for 20 hours, and then preserving in vacuum to obtain the environment-responsive microcapsule; wherein the molar ratio of the diethylaminoethyl methacrylate, the styrene, the nonafluorohexyl methacrylate and the glycidyl methacrylate is 1:1: 1:1, the azodiisobutyronitrile and the divinylbenzene are respectively used in an amount of 3% and 5% by mass of the monomer, and the hexadecane is used in an amount of 50% by mass of the monomer.
The water phase is deionized water containing Sodium Dodecyl Benzene Sulfonate (SDBS) as surfactant, and the oil phase is dropped into the water phase, and stirred by homogenizer at 15000r min-1。
Step two, ultrasonically dispersing the environment-responsive microcapsules prepared in the step one in deionized water to obtain a microcapsule solution, then treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and drying the material in a drying oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material; wherein the material is any one of cotton cloth, wood plastic, paper, ceramic, cement and concrete; there are four methods of treating the surface of the material with the microcapsule solution: one is a dipping method, wherein a microcapsule solution is used for soaking a material for 20min, an aluminum sheet which is smooth and larger than the area of the material is used for extrusion, and the material is dried in an oven; the second method is a coating method, namely microcapsule solution is sprayed, spin-coated and roll-coated on the surface of the material for 3 times; the third is a printing method, namely, the microcapsule solution is printed on the surface of the material by a screen printing mode; the fourth is the impregnation method, i.e. the material is directly soaked into a relatively dilute microcapsule solution.
Example 7
The preparation method of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface is implemented according to the following steps:
step one, taking diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as reaction monomers, azodiisobutyronitrile as a thermal initiator, divinylbenzene as a cross-linking agent and hexadecane as a stabilizing agent, uniformly mixing the components, dropwise adding the mixture into a water phase, emulsifying for 20min, transferring the mixture into a three-neck flask, and carrying out 400r min-1Reacting for 10h under mechanical stirring, controlling the temperature at 60 ℃, then centrifuging, cleaning, drying in a vacuum drying oven at 60 ℃ for 22h, and then preserving in vacuum to obtain the environment-responsive microcapsule; wherein the molar ratio of the diethylaminoethyl methacrylate, the styrene, the nonafluorohexyl methacrylate and the glycidyl methacrylate is 2.0: 2.0: 2.0: 2.0, azobisisobutyronitrile and divinylbenzene were used in amounts of 3% and 5% respectively, and hexadecane in an amount of 50% by mass of the monomers.
The water phase is deionized water containing Sodium Dodecyl Benzene Sulfonate (SDBS) as surfactant, and the oil phase is dropped into the water phase and stirred by homogenizer at 20000r min-1。
Step two, ultrasonically dispersing the environment-responsive microcapsules prepared in the step one in deionized water to obtain a microcapsule solution, then treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and drying the material in a drying oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material; wherein the material is any one of cotton cloth, wood plastic, paper, ceramic, cement and concrete; there are four methods of treating the surface of the material with the microcapsule solution: one is a dipping method, wherein a microcapsule solution is used for soaking a material for 30min, an aluminum sheet which is smooth and larger than the area of the material is used for extrusion, and the material is dried in an oven; the second method is a coating method, namely microcapsule solution is sprayed, spin-coated and roll-coated on the surface of the material for 1 time; the third is a printing method, namely, the microcapsule solution is printed on the surface of the material by a screen printing mode; the fourth is the impregnation method, i.e. the material is directly soaked into a relatively dilute microcapsule solution.
The contact angle between the surface of the environment-responsive superhydrophobic-hydrophilic reversible conversion material obtained in example 2 of the present invention and water is about 150 ° after being treated with a droplet of pH 13, as shown in fig. 1; the contact angle of the superhydrophobic surface treated with the droplet of pH7 with water was about 145 °, as shown in fig. 2; the environment-responsive super-hydrophobic-hydrophilic reversible conversion surface is changed into a hydrophilic surface after being treated by liquid drops with the pH value of 1, and the contact angle between the surface and water is reduced to about 0 ℃ within 120s, as shown in figure 3;
fig. 4 is a photograph of the contact angle of the surface of untreated paper with water, from which it can be seen that water rapidly penetrates and wets the paper, and the contact angle is 0 degrees, indicating that the surface of untreated paper has good affinity with water and does not have the ability to be hydrophobic.
Fig. 5 is a graph showing the particle size change of the environmentally responsive microcapsules prepared in example 4 after being treated with solutions of pH1 and pH7, wherein the microcapsules show significant size differences under different pH conditions, and acid solution is gradually added from pH7 to pH1, so that the average particle size of the microcapsules is increased from 40nm to about 70 nm; then, alkali liquor is dripped to adjust the pH value to 7, and the particle size is recovered to about 40 nm; then acid liquor is dripped to the pH value 1, the particle size is increased to about 70nm, 10 times of cycle treatment is carried out between the pH value 7 and the pH value 1, the average particle size of the microcapsule is always cycled between about 40nm and 70nm, and the pH response swelling-shrinking transformation is reversible and has better fatigue resistance.
Fig. 6 shows a substrate modified with microcapsules prepared in example 4, treated 10 times with a solution of pH1 and pH 7. When the pH of the solution is adjusted to be neutral every time, the contact angle between the surface of the substrate and water is about 150 degrees, and the substrate has super-hydrophobic property; every time the acid solution is dripped to reach the pH value of 1, the contact angle between the substrate surface and water is reduced to 0 ℃ within 120s, and the hydrophilic property is realized. These behaviors indicate that the wettability of the substrate surface is changed greatly after the substrate surface is treated by the environment-responsive material, and the material surface can be subjected to adjustability conversion between super-hydrophobic and hydrophilic properties under the treatment of different solvents.
FIG. 7 is a scanning electron micrograph of the surface of the untreated paper showing that the fibers on the surface of the paper are very smooth and free of any materials and coarse structures.
As can be seen from fig. 8, the fiber surface of the paper treated by the environmental-responsive microcapsule dispersion prepared in example 3 has a thin micro-nano rough protruding structure, and the outer contour of the fiber is clear without being adhered to other fibers, which indicates that the apparent fiber performance of the paper treated by the environmental-responsive microcapsule is not affected.
The following experiments are adopted to verify the effect of the invention:
1. influence of different monomer proportions on contact
Only the monomer proportions of diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate adopted in the first step are different, other reaction parameters are the same as those in example 1, the material is paper, and the contact angle with water is shown in Table 1:
TABLE 1 Effect of different monomer ratios on contact Angle
| nDEAEMA:nPBMA:nst:nGMA | 1:0.125:1:1 | 1:0.25:1:1 | 1:0.5:1:1 | 1:0.75:1:1 | 1:1:1:1 |
| Contact angle with water (pH 1) | 10±1° | 10±1° | 130±5° | 130±5° | 130±2° |
| Contact angle with water (pH 7) | 20±1° | 150±5° | 150±5° | 150±5° | 150±5° |
| Contact angle with water (pH 13) | 30±1° | 150±5° | 145±5° | 145±5° | 150±5° |
As can be seen from table 1, when the monomer ratio of diethylaminoethyl methacrylate, nonafluorohexyl methacrylate, styrene, and glycidyl methacrylate is 1:0.25:1:1, the environment-responsive superhydrophobic-hydrophilic reversible conversion paper prepared from the responsive microcapsule has better hydrophobic property and environment-responsive property.
2. Influence of different monomers on contact angle
Only in step one, the fluoromonomer is different, and the nonafluorohexyl methacrylate is exchanged for hexafluorobutyl methacrylate (HFBMA).
TABLE 2 Effect of different monomers on contact Angle
| nDEAEMA:nHFBMA:nst:nGMA | 1:0.125:1:1 | 1:0.25:1:1 | 1:0.5:1:1 | 1:0.75:1:1 | 1:1:1:1 |
| Contact angle with water (pH 1) | 10±1° | 10±1° | 10±1° | 10±1° | 110±5° |
| Contact angle with water (pH 7) | 10±1° | 10±1° | 20±1° | 150±5° | 150±5° |
| Contact angle with water (pH 13) | 10±1° | 10±1° | 30±1° | 150±5° | 150±5° |
As can be seen from table 2, when the monomer ratio of diethylaminoethyl methacrylate, hexafluorobutyl methacrylate, styrene, and glycidyl methacrylate is 1:0.75:1:1, the environment-responsive superhydrophobic-hydrophilic reversible transition paper prepared from the responsive microcapsule has better hydrophobic property and environment-responsive property. The optimum ratio is different from the use of nonafluorohexyl methacrylate.
3. Effect of different microcapsule Dispersion concentrations on contact Angle
Microcapsules using nonafluorohexyl methacrylate monomer are exemplified. Only in the case of different microcapsule solution concentrations, diethylaminoethyl methacrylate, nonafluorohexyl methacrylate, styrene, glycidyl methacrylate were used as monomers in a molar ratio of 1:0.25:1:1, the material was cotton, the other reaction conditions and parameters were the same as in example 4, and the results are shown in Table 3:
TABLE 3 Effect of different microcapsule concentrations on contact Angle
As shown in Table 3, 20mg of the environment-responsive microcapsules are dissolved in 100mL of deionized water, the obtained solution is used for soaking cotton cloth, the contact angle between the surface of the cotton cloth and water reaches 162 +/-2 degrees, and the contact angle is reduced as the content of the microcapsules is continuously increased.
Claims (8)
1. The preparation method of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material surface is characterized by comprising the following steps:
preparing an environment-responsive microcapsule by a miniemulsion polymerization method by using diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate as reaction monomers, azodiisobutyronitrile as a thermal initiator, divinylbenzene as a crosslinking agent and hexadecane as a stabilizer;
and step two, ultrasonically dispersing the environment-responsive microcapsules prepared in the step one in deionized water to obtain a microcapsule solution, then treating the surface of the material by using the microcapsule solution, immersing the treated surface of the material by using an aluminum sheet, and then drying the material in a drying oven to obtain the surface of the environment-responsive super-hydrophobic-hydrophilic reversible conversion material.
2. The method for preparing the surface of the environment-responsive superhydrophobic-hydrophilic reversible conversion material according to claim 1, wherein in the first step, the molar ratio of the substances of diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate and glycidyl methacrylate is 0.5-2.0: 0.5-2.0: 0.5-2.0: 0.5 to 2.0.
3. The method for preparing the surface of the environmentally-responsive superhydrophobic-hydrophilic reversible conversion material according to claim 1, wherein the amounts of azobisisobutyronitrile and divinylbenzene used in the first step are respectively 3% and 5% of the mass of the monomers, and the amount of hexadecane used in the first step is 50% of the mass of the monomers.
4. The method for preparing the surface of the environment-responsive superhydrophobic-hydrophilic reversible transformation material according to claim 1, wherein the miniemulsion polymerization method in the first step is specifically:
fully and uniformly mixing diethylaminoethyl methacrylate, styrene, nonafluorohexyl methacrylate, glycidyl methacrylate, azobisisobutyronitrile, divinylbenzene and hexadecane, dropwise adding the mixture into a water phase, emulsifying for 20-30 min, transferring the mixture into a three-neck flask, and performing emulsion at 400-800 r min-1Reacting for 8-10 hours under mechanical stirring, controlling the temperature at 60-80 ℃, then centrifuging, cleaning, drying in a vacuum drying oven at 60-80 ℃ for 20-24 hours, and then preserving in vacuum to obtain the environment-responsive microcapsule.
5. The method for preparing the surface of the environment-responsive superhydrophobic-hydrophilic reversible conversion material according to claim 4, wherein the aqueous phase is deionized water with sodium dodecyl benzene sulfonate as a surfactant.
6. The method for preparing the surface of the environment-responsive superhydrophobic-hydrophilic reversible transformation material according to claim 4, wherein the oil phase is dropped into the water phase in the first step, and the mixture is stirred by a homogenizer at a speed of 10000r min-1～20000r min-1。
7. The method for preparing the surface of the environment-responsive superhydrophobic-hydrophilic reversible conversion material according to claim 1, wherein the material in the surface of the material treated with the microcapsule solution in the second step is any one of cotton cloth, wood plastic, paper, ceramic, cement and concrete.
8. The method for preparing the surface of the environment-responsive superhydrophobic-hydrophilic reversible transformation material according to claim 1, wherein there are four methods for treating the surface of the material with the microcapsule solution in 2: one method is a dipping and rolling method, wherein a microcapsule solution is used for soaking a material for 10-30 min, an aluminum sheet which is smooth and larger than the area of the material is used for extrusion, and the material is dried in an oven; the second is a coating method, namely microcapsule solution is sprayed, spin-coated and roll-coated on the surface of the material for 1 to 5 times; the third is a printing method, namely, the microcapsule solution is printed on the surface of the material by a screen printing mode; the fourth is the impregnation method, i.e. the material is directly soaked into a relatively dilute microcapsule solution.
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