CN111944359B - Preparation method for constructing micro-nano-level super-hydrophobic coating by self-assembling core-shell type cellulose nanoparticles - Google Patents

Preparation method for constructing micro-nano-level super-hydrophobic coating by self-assembling core-shell type cellulose nanoparticles Download PDF

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CN111944359B
CN111944359B CN202010850099.XA CN202010850099A CN111944359B CN 111944359 B CN111944359 B CN 111944359B CN 202010850099 A CN202010850099 A CN 202010850099A CN 111944359 B CN111944359 B CN 111944359B
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CN111944359A (en
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王永贵
黄薇
汤相宇
谢延军
肖泽芳
王海刚
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Northeast Forestry University
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • B82—NANOTECHNOLOGY
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D2203/00—Other substrates
    • B05D2203/22—Paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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    • C—CHEMISTRY; METALLURGY
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    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/10—Esters of organic acids

Abstract

The invention discloses a preparation method of a micro-nano-level super-hydrophobic coating constructed by self-assembly of core-shell cellulose nano-particles, and relates to a preparation method of a super-hydrophobic coating. The invention aims to solve the problem that the heat stability of the super-hydrophobic coating prepared by the existing method by using the cellulose fatty acid ester is poor. The method comprises the following steps: firstly, synthesizing core-shell type hydrophobic cellulose fatty acid ester nano particles; and secondly, preparing a super-hydrophobic surface. The method is used for preparing the micro-nano-level super-hydrophobic coating constructed by self-assembly of the core-shell type cellulose nano-particles.

Description

Preparation method for constructing micro-nano-level super-hydrophobic coating by self-assembling core-shell type cellulose nanoparticles
Technical Field
The invention relates to a preparation method of a super-hydrophobic coating.
Background
With the increasing exhaustion of global resources, the utilization of renewable resources is more and more emphasized by people in order to meet the strategic demand of sustainable development. In nature, cellulose is a natural polymer material with the most abundant content, is mainly derived from wood, cotton, hemp, straw, bagasse and the like, has the characteristics of reproducibility, low cost, low density, high specific strength, good biocompatibility, degradability and the like, and is a precious natural renewable resource for human beings. The research of preparing various functional materials, especially cellulose-based superhydrophobic materials, by physically and chemically modifying cellulose attracts great interest of scientists. The cellulose is a linear polymer formed by connecting D-pyran glucose units through beta-1, 4-glycosidic bonds, contains a large number of hydroxyl groups, and provides conditions for preparing the super-hydrophobic material. The super-hydrophobization of the cellulose has important significance for widening the application of cellulose resources in the fields of environmental protection, papermaking, chemical industry, medicine, building, food and the like and solving the resource and environmental problems in the world at present.
The wettability of a solid surface is generally characterized by the contact angle of a liquid on the surface. The hydrophilic surface is a surface with a contact angle less than 90 degrees; surfaces with contact angles greater than 90 ° are referred to as hydrophobic surfaces; surfaces with contact angles greater than 150 ° and rolling angles less than 10 ° are referred to as superhydrophobic surfaces. Over two thousand years ago, people have used lotus flowers which are "silted but not stained", that is, the phenomenon that some plant leaves almost always keep self-cleaning is observed for a long time, wherein the lotus leaves are a typical example. There are two main surface microstructures in natural plant leaves with superhydrophobicity: one is a layered micro-and nano-structure and the other is a single micro-structure. Therefore, the construction of a special microstructure becomes a major method for preparing a superhydrophobic material.
The artificial super-hydrophobic surface is manufactured by adopting two methods on the basis of the inspiration of lotus leaves: hierarchical micro-and nano-structures (micro-and nano-structures) are formed on a hydrophobic substrate, or a hierarchically structured surface of a material with low surface free energy is chemically modified. Numerous studies have demonstrated that the combination of surface roughness with low surface free energy materials is key to the preparation of superhydrophobic materials. However, the existing methods for preparing the super-hydrophobic coating with good thermal stability by using the cellulose fatty acid ester are still few, and the excellent characteristics of the super-hydrophobic coating are worthy of being researched and utilized.
Disclosure of Invention
The invention provides a preparation method for constructing a micro-nano-level super-hydrophobic coating by self-assembly of core-shell cellulose nano-particles, aiming at solving the problem that the thermal stability of the super-hydrophobic coating prepared by using cellulose fatty acid ester in the existing method is poor.
A preparation method for constructing a micro-nano-level super-hydrophobic coating by self-assembly of core-shell cellulose nanoparticles is carried out according to the following steps:
firstly, synthesizing core-shell type hydrophobic cellulose fatty acid ester nano particles:
firstly, drying cellulose, then adding the dried cellulose into anhydrous N, N-dimethylacetamide, magnetically and uniformly stirring the cellulose at a stirring speed of 200 r/min-500 r/min to obtain a mixture, heating the mixture to 50-100 ℃, dropwise adding fatty acyl chloride into the mixture at a temperature of 50-100 ℃, and carrying out shading reaction for 2-10 hours to obtain a reaction system;
the molar ratio of the glucose unit to the fatty acyl chloride in the dried cellulose is 1 (1-2.5);
secondly, adding the reaction system into ethanol solution to separate out a product, then centrifugally separating for 5-10 min under the conditions that the rotating speed is 5000-10000 r/min and the temperature is 10-30 ℃, removing the upper layer liquid, separating and drying the lower layer product, and dispersing the dried lower layer product into tetrahydrofuran to obtain a dispersion liquid;
thirdly, repeating the dispersion liquid for 5 to 10 times according to the first step to obtain the dispersion liquid with the dissolved product;
centrifugally separating the dispersion liquid with the dissolved product for 30-60 min under the conditions of the rotating speed of 1000-2000 r/min and the temperature of 10-30 ℃, dispersing the centrifuged upper layer liquid into an ethanol solution after centrifugation, centrifugally separating for 5-10 min under the conditions of the rotating speed of 5000-10000 r/min and the temperature of 10-30 ℃, separating and drying the lower layer product after centrifugal separation, and dispersing the dried lower layer product into tetrahydrofuran to obtain a core-shell type hydrophobic cellulose fatty acid ester nano-particle suspension;
secondly, preparing a super-hydrophobic surface:
putting core-shell hydrophobic cellulose fatty acid ester nano-particle suspension into a centrifuge tube, then putting the suspension on a tubular oscillator, dropwise adding an ethanol solution into the centrifuge tube at a dropwise adding speed of 10-200 mu L/min to obtain cellulose fatty acid ester nano-particles which are self-assembled to construct nano-convex micro-particles;
the volume ratio of the tetrahydrofuran in the first step to the ethanol solution in the second step is 1 (1-10);
secondly, under the conditions that the rotating speed is 5000 r/min-10000 r/min and the temperature is 10-30 ℃, cellulose fatty acid ester nano-particles are self-assembled to construct nano-convex micro-particles, centrifugal separation is carried out for 10-30 min, upper-layer liquid containing tetrahydrofuran is removed, and lower-layer solid is reserved;
dispersing the lower layer solid into ethanol solution, centrifugally separating for 10-30 min at the rotation speed of 5000-10000 r/min and the temperature of 10-30 ℃, and separating and drying the lower layer product after centrifugal separation;
fourthly, repeating the second step and the third step for 10 times or more than 10 times to obtain cellulose micro-nano particle suspension;
and fifthly, spraying the cellulose micro-nano particle suspension on the surface of the substrate by using a spray gun at a position 5-20 cm away from the substrate by using a nozzle, and thus finishing the preparation method for constructing the micro-nano level super-hydrophobic coating by self-assembling the core-shell type cellulose nano particles.
The invention has the beneficial effects that: according to the invention, fatty acyl chloride and cellulose are subjected to esterification reaction, and hydrophobic cellulose fatty acid ester is prepared into nano particles with a core-shell structure, so that micro-nano-scale super-hydrophobic coating materials can be constructed by self-assembling nano-convex micro particles, and can be effectively applied to different substrates, and the contact angles of the prepared super-hydrophobic coatings exceed 150 degrees, and the rolling angles are less than 10 degrees. The core-shell structure imparts special properties to the coating in that the core structure provides its thermal stability, allowing it to survive in a high temperature environment (200 ℃) without changing its superhydrophobicity; the shell structure provides the adhesiveness between the particles during the self-assembly construction of the cellulose nano-particles, so that the particles are tightly connected when the solvent is volatilized, and a continuous rough surface with pores is constructed to provide super-hydrophobicity; the coating has the characteristic of endowing various substrates with super-hydrophobicity, and mainly comprises self-cleaning performance; the preparation method of the coating has rich expandability, and the super-hydrophobic surfaces with different characteristics can be prepared according to different requirements.
The invention relates to a preparation method for constructing a micro-nano-level super-hydrophobic coating by self-assembly of core-shell type cellulose nano-particles.
Drawings
FIG. 1 is a transmission electron micrograph of a core-shell type hydrophobic cellulose fatty acid ester nanoparticle prepared according to one step IV of the example, magnified 10000 times;
FIG. 2 is a transmission electron micrograph of a core-shell hydrophobic cellulose fatty acid ester nanoparticle prepared according to one step IV of the example, at magnification of 50000 times;
FIG. 3 is a schematic representation of an untreated glass substrate surface with an aqueous methylene blue solution applied dropwise thereto;
fig. 4 is a diagram of a methylene blue aqueous solution dripped on the surface of a micro-nano-scale super-hydrophobic coating constructed by self-assembly of core-shell type cellulose nanoparticles with glass as a substrate prepared in the first embodiment;
FIG. 5 is a pictorial representation of an untreated wood substrate surface with an aqueous methylene blue solution applied thereto;
fig. 6 is a diagram of a methylene blue aqueous solution dripped on the surface of a micro-nano-scale super-hydrophobic coating constructed by self-assembly of core-shell cellulose nanoparticles with wood as a substrate prepared in the first embodiment;
FIG. 7 is a pictorial representation of an untreated textile substrate having methylene water solution dripped onto the surface;
fig. 8 is a diagram of a methylene blue aqueous solution dripped on the surface of a micro-nano-level super-hydrophobic coating constructed by self-assembly of core-shell type cellulose nano-particles prepared in the first embodiment and using textiles as substrates;
FIG. 9 is a pictorial representation of an untreated paper substrate surface with an aqueous methylene blue solution dripped thereon;
fig. 10 is a diagram of a methylene blue aqueous solution dripped on the surface of a micro-nano-scale super-hydrophobic coating constructed by self-assembly of paper-based core-shell cellulose nanoparticles prepared in the first embodiment;
fig. 11 is a scanning electron microscope image of the micro-nano-scale superhydrophobic coating surface constructed by self-assembly of the core-shell cellulose nanoparticles with glass as the substrate prepared in the first embodiment, magnified by 500 times;
fig. 12 is a scanning electron microscope image of the micro-nano-scale superhydrophobic coating surface self-assembled by the core-shell type cellulose nanoparticle using glass as the substrate prepared in the first embodiment, magnified 5000 times;
fig. 13 is a contact angle diagram of the surface of the micro-nano-scale superhydrophobic coating constructed by self-assembly of the core-shell cellulose nanoparticles with glass as the substrate according to the first embodiment and water.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the embodiment is a preparation method for constructing a micro-nano-level super-hydrophobic coating by self-assembling core-shell type cellulose nano-particles, which is carried out according to the following steps:
firstly, synthesizing core-shell type hydrophobic cellulose fatty acid ester nano particles:
firstly, drying cellulose, then adding the dried cellulose into anhydrous N, N-dimethylacetamide, magnetically and uniformly stirring the cellulose at a stirring speed of 200 r/min-500 r/min to obtain a mixture, heating the mixture to 50-100 ℃, dropwise adding fatty acyl chloride into the mixture at a temperature of 50-100 ℃, and carrying out shading reaction for 2-10 hours to obtain a reaction system;
the molar ratio of the glucose unit to the fatty acyl chloride in the dried cellulose is 1 (1-2.5);
secondly, adding the reaction system into ethanol solution to separate out a product, then centrifugally separating for 5-10 min under the conditions that the rotating speed is 5000-10000 r/min and the temperature is 10-30 ℃, removing the upper layer liquid, separating and drying the lower layer product, and dispersing the dried lower layer product into tetrahydrofuran to obtain a dispersion liquid;
thirdly, repeating the dispersion liquid for 5 to 10 times according to the first step to obtain the dispersion liquid with the dissolved product;
centrifugally separating the dispersion liquid with the dissolved product for 30-60 min under the conditions of the rotating speed of 1000-2000 r/min and the temperature of 10-30 ℃, dispersing the centrifuged upper layer liquid into an ethanol solution after centrifugation, centrifugally separating for 5-10 min under the conditions of the rotating speed of 5000-10000 r/min and the temperature of 10-30 ℃, separating and drying the lower layer product after centrifugal separation, and dispersing the dried lower layer product into tetrahydrofuran to obtain a core-shell type hydrophobic cellulose fatty acid ester nano-particle suspension;
secondly, preparing a super-hydrophobic surface:
putting core-shell hydrophobic cellulose fatty acid ester nano-particle suspension into a centrifuge tube, then putting the suspension on a tubular oscillator, dropwise adding an ethanol solution into the centrifuge tube at a dropwise adding speed of 10-200 mu L/min to obtain cellulose fatty acid ester nano-particles which are self-assembled to construct nano-convex micro-particles;
the volume ratio of the tetrahydrofuran in the first step to the ethanol solution in the second step is 1 (1-10);
secondly, under the conditions that the rotating speed is 5000 r/min-10000 r/min and the temperature is 10-30 ℃, cellulose fatty acid ester nano-particles are self-assembled to construct nano-convex micro-particles, centrifugal separation is carried out for 10-30 min, upper-layer liquid containing tetrahydrofuran is removed, and lower-layer solid is reserved;
dispersing the lower layer solid into ethanol solution, centrifugally separating for 10-30 min at the rotation speed of 5000-10000 r/min and the temperature of 10-30 ℃, and separating and drying the lower layer product after centrifugal separation;
fourthly, repeating the second step and the third step for 10 times or more than 10 times to obtain cellulose micro-nano particle suspension;
and fifthly, spraying the cellulose micro-nano particle suspension on the surface of the substrate by using a spray gun at a position 5-20 cm away from the substrate by using a nozzle, and thus finishing the preparation method for constructing the micro-nano level super-hydrophobic coating by self-assembling the core-shell type cellulose nano particles.
And in the second step, spraying the cellulose micro-nano particle suspension on the surface of the substrate by using a spray gun, and performing next spraying after blowing the solvent in the suspension by using air flow after each spraying.
The beneficial effects of the embodiment are as follows: according to the embodiment, fatty acyl chloride and cellulose are subjected to esterification reaction, and hydrophobic cellulose fatty acid ester is prepared into nano particles with a core-shell structure, so that micro particles with nano protrusions can be constructed in a self-assembly manner to construct a micro-nano-level super-hydrophobic coating material, the micro-nano-level super-hydrophobic coating material can be effectively applied to different substrates, contact angles of the prepared super-hydrophobic coatings exceed 150 degrees, and rolling angles of the prepared super-hydrophobic coatings are smaller than 10 degrees. The core-shell structure imparts special properties to the coating in that the core structure provides its thermal stability, allowing it to survive in a high temperature environment (200 ℃) without changing its superhydrophobicity; the shell structure provides the adhesiveness between the particles during the self-assembly construction of the cellulose nano-particles, so that the particles are tightly connected when the solvent is volatilized, and a continuous rough surface with pores is constructed to provide super-hydrophobicity; the coating has the characteristic of endowing various substrates with super-hydrophobicity, and mainly comprises self-cleaning performance; the preparation method of the coating has rich expandability, and the super-hydrophobic surfaces with different characteristics can be prepared according to different requirements.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the fatty acyl chloride in the first step is saturated fatty acyl chloride with a fatty chain length of 6-16 or unsaturated fatty acyl chloride with a fatty chain length of 6-16. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the cellulose in the first step is microcrystalline cellulose, needle-leaf bleaching chemical pulp or broad-leaf bleaching chemical pulp. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the cellulose drying in the first step is vacuum drying in a vacuum drying oven at the temperature of 60-80 ℃, and the vacuum drying time is more than or equal to 24 hours. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the volume ratio of the mass of the dried cellulose to the volume of the anhydrous N, N-dimethylacetamide in the first step is 1g (10-60) mL. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the volume percentage of the ethanol solution in the first step is 70-100%; the volume ratio of the reaction system to the ethanol solution in the first step is 1 (5-15); the ratio of the mass of the dried lower-layer product to the volume of tetrahydrofuran in the first step is 1g (20-60) mL. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the volume percentage of the ethanol solution in the first step is 70-100%; the volume ratio of the centrifuged upper layer liquid to the ethanol solution in the first step (15) - (5) is 1; the ratio of the mass of the dried lower-layer product in the first step to the volume of the tetrahydrofuran is 1g (20-60) mL. The others are the same as the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the volume percentage of the ethanol solution in the second step is 70-90%. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the volume percentage of the ethanol solution in the second step is 70-90%. The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: spraying the cellulose micro-nano particle suspension on the surface of the substrate by using a spray gun in the second step (v), wherein the spraying amount is 0.03mg/mm2～0.1mg/mm2(ii) a The substrate in the second-fifth step is glass, wood, textile, paper, metal or plastic. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a preparation method for constructing a micro-nano-level super-hydrophobic coating by self-assembly of core-shell cellulose nanoparticles is carried out according to the following steps:
firstly, synthesizing core-shell type hydrophobic cellulose fatty acid ester nano particles:
drying cellulose, adding the dried cellulose into anhydrous N, N-dimethylacetamide, magnetically and uniformly stirring at the stirring speed of 300r/min to obtain a mixture, heating the mixture to 60 ℃, dropwise adding fatty acyl chloride into the mixture at the temperature of 60 ℃, and carrying out shading reaction for 7 hours to obtain a reaction system;
the molar ratio of the glucose unit to the fatty acyl chloride in the dried cellulose is 1: 2.5;
secondly, adding the reaction system into an ethanol solution to separate out a product, then, centrifugally separating for 5min under the conditions that the rotating speed is 8000r/min and the temperature is 15 ℃, removing an upper layer of liquid, separating and drying a lower layer of product, and dispersing the dried lower layer of product into tetrahydrofuran to obtain a dispersion liquid;
thirdly, repeating the dispersion liquid for 6 times according to the first step and the second step to obtain the dispersion liquid dissolved with the product;
centrifugally separating the dispersion liquid with the dissolved product for 30min under the conditions of the rotating speed of 2000r/min and the temperature of 15 ℃, dispersing the centrifuged upper layer liquid into an ethanol solution after centrifugation, centrifugally separating for 8min under the conditions of the rotating speed of 9000r/min and the temperature of 15 ℃, separating and drying the lower layer product after centrifugal separation, and dispersing the dried lower layer product into tetrahydrofuran to obtain a core-shell type hydrophobic cellulose fatty acid ester nanoparticle suspension;
secondly, preparing a super-hydrophobic surface:
putting core-shell hydrophobic cellulose fatty acid ester nanoparticle suspension in a centrifuge tube, then putting the centrifuge tube on a tubular oscillator, dropwise adding an ethanol solution into the centrifuge tube at a dropping speed of 100 mu L/min to obtain cellulose fatty acid ester nanoparticle self-assembled to construct nano-raised microparticles;
the volume ratio of the tetrahydrofuran in the first step to the ethanol solution in the second step is 1: 3;
under the conditions that the rotating speed is 10000r/min and the temperature is 15 ℃, cellulose fatty acid ester nano-particles are self-assembled to construct nano-convex micro-particles, centrifugal separation is carried out for 30min, upper-layer liquid containing tetrahydrofuran is removed, and lower-layer solid is reserved;
dispersing the lower layer solid into ethanol solution, centrifugally separating for 30min at the rotation speed of 10000r/min and the temperature of 15 ℃, and separating and drying the lower layer product after centrifugal separation;
fourthly, repeating the second step and the third step for 10 times to obtain cellulose micro-nano particle turbid liquid;
and fifthly, spraying the cellulose micro-nano particle suspension on the surface of the substrate by using a spray gun at a position 10cm away from the substrate by using a nozzle, and finishing the preparation method for constructing the micro-nano hierarchical super-hydrophobic coating by self-assembling the core-shell type cellulose nano particles.
The fatty acyl chloride in the first step is 10-undecenoyl chloride.
The cellulose in the first step is microcrystalline cellulose.
The cellulose drying in the first step is specifically vacuum drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours.
The volume ratio of the mass of the dried cellulose to the volume of the anhydrous N, N-dimethylacetamide in the first step is 1g:30 mL.
The volume percentage of the ethanol solution in the first step is 95 percent; the volume ratio of the reaction system to the ethanol solution in the first step is 1: 6; the ratio of the mass of the dried lower-layer product in the first step to the volume of the tetrahydrofuran is 1g:40 mL.
The volume percentage of the ethanol solution in the first step is 95 percent; the volume ratio of the centrifuged upper layer liquid to the ethanol solution in the first step (IV) is 1: 6; the ratio of the mass of the dried lower product to the volume of tetrahydrofuran in the step one to that in the step four is 1g:40 mL.
And the volume percentage of the ethanol solution in the second step is 90%.
The volume percentage of the ethanol solution in the second step is 90 percent.
Spraying the cellulose micro-nano particle suspension on the surface of the substrate by using a spray gun in the second step (v), wherein the spraying amount is 0.05mg/mm2(ii) a The substrate in the second-fifth step is glass, wood, textile (textile mixed by polyester fiber and cotton) and paper.
The reaction system in the first step is a tawny mixture.
In the first embodiment, the micro-nano-level super-hydrophobic coating surface constructed by self-assembling the core-shell type cellulose nano-particles with the glass as the substrate has a contact angle of 159 +/-3 degrees with water and a rolling angle of 7 +/-2 degrees.
In the first embodiment, the micro-nano-level super-hydrophobic coating prepared by self-assembling the glass-based core-shell cellulose nanoparticles can still maintain the super-hydrophobicity at a high temperature of 200 ℃, and after heating for 5 hours, the contact angle of the micro-nano-level super-hydrophobic coating with water is 156 +/-5 degrees, and the rolling angle of the micro-nano-level super-hydrophobic coating is 8 +/-3 degrees.
FIG. 1 is a transmission electron micrograph of a core-shell type hydrophobic cellulose fatty acid ester nanoparticle prepared by one step (iv) of the example at 10000 times magnification, and FIG. 2 is a transmission electron micrograph of a core-shell type hydrophobic cellulose fatty acid ester nanoparticle prepared by one step (iv) of the example at 50000 times magnification; as can be seen from the figure, the prepared hydrophobic cellulose esterification product is a spherical nanoparticle with a core-shell structure, and the structure is gradually formed in the cellulose esterification process: the acyl chloride reacts with hydroxyl exposed in the amorphous area of the outer layer on the cellulose chain to form a soft shell, and along with the reaction, the cellulose crystalline area which does not participate in the reaction is partially coated by the acyl substituted part of the outer layer to form an inner core and gradually form spherical nano particles.
FIG. 3 is a schematic representation of an untreated glass substrate surface with an aqueous methylene blue solution applied dropwise thereto; fig. 4 is a diagram of a methylene blue aqueous solution dripped on the surface of a micro-nano-scale super-hydrophobic coating constructed by self-assembly of core-shell type cellulose nanoparticles with glass as a substrate prepared in the first embodiment; as can be seen, the dyed water drops exhibit hydrophilicity on the untreated glass surface and excellent superhydrophobicity on the treated glass surface, indicating that the prepared coating can be applied to a glass substrate and exhibits excellent superhydrophobic performance.
FIG. 5 is a pictorial representation of an untreated wood substrate surface with an aqueous methylene blue solution applied thereto; fig. 6 is a diagram of a methylene blue aqueous solution dripped on the surface of a micro-nano-scale super-hydrophobic coating constructed by self-assembly of core-shell cellulose nanoparticles with wood as a substrate prepared in the first embodiment; as can be seen, the untreated wood surface was stained and saturated with the stained water droplets, while the treated wood surface was stained and saturated with the unstained water droplets, indicating that the prepared coating was applicable to wood substrates and exhibited excellent superhydrophobic properties.
FIG. 7 is a pictorial representation of an untreated textile substrate having methylene water solution dripped onto the surface; fig. 8 is a diagram of a methylene blue aqueous solution dripped on the surface of a micro-nano-level super-hydrophobic coating constructed by self-assembly of core-shell type cellulose nano-particles prepared in the first embodiment and using textiles as substrates; as can be seen, the untreated textile surface was saturated and dyed by the dyed water droplets, while the treated textile surface was dyed and saturated by the undyed water droplets, indicating that the prepared coating can be applied to textile substrates and exhibits excellent superhydrophobic properties.
FIG. 9 is a pictorial representation of an untreated paper substrate surface with an aqueous methylene blue solution dripped thereon; fig. 10 is a diagram of a methylene blue aqueous solution dripped on the surface of a micro-nano-scale super-hydrophobic coating constructed by self-assembly of paper-based core-shell cellulose nanoparticles prepared in the first embodiment; as can be seen, the untreated paper is saturated and dyed by the dyed water droplets, while the treated paper surface is dyed and saturated by the undyed water droplets, indicating that the prepared coating can be applied to paper substrates and exhibits excellent superhydrophobic performance.
Fig. 11 is a scanning electron microscope image of the micro-nano-scale superhydrophobic coating surface self-assembled and constructed by the glass-based core-shell type cellulose nanoparticles prepared in the first embodiment at a magnification of 500 times, and fig. 12 is a scanning electron microscope image of the micro-nano-scale superhydrophobic coating surface self-assembled and constructed by the glass-based core-shell type cellulose nanoparticles prepared in the first embodiment at a magnification of 5000 times; it can be seen from the figure that due to the adhesive effect of the shell structure, microparticles constructed by self-assembly of the core-shell hydrophobic cellulose fatty acid ester nanoparticles are gradually and tightly connected with the solvent volatilization to form a continuous rough surface with pores.
Fig. 13 is a contact angle diagram of the surface of the micro-nano-scale super-hydrophobic coating constructed by self-assembling the core-shell cellulose nano-particles with the glass as the substrate and water prepared in the first embodiment, and it can be known that the micro-nano-scale coating constructed by self-assembling the core-shell hydrophobic cellulose fatty acid ester nano-particles has excellent super-hydrophobic performance.
Example two: the difference between the present embodiment and the first embodiment is: dripping fatty acyl chloride into the mixture at the temperature of 50 ℃, and carrying out shading reaction for 5 hours; the fatty acyl chloride in the first step is caproyl chloride; the volume ratio of the tetrahydrofuran in the first step to the ethanol solution in the second step is 1: 5. The rest is the same as the first embodiment.
The contact angle of the micro-nano-level super-hydrophobic coating constructed by self-assembling the core-shell type cellulose nano-particles prepared in the second embodiment with the wood as the substrate is 154 +/-7 degrees, and the rolling angle is 8 +/-3 degrees.
The core-shell cellulose nanoparticles prepared in the second embodiment, which are based on wood, are self-assembled to form the micro-nano-level super-hydrophobic coating, the super-hydrophobicity of the micro-nano-level super-hydrophobic coating can be still maintained at a high temperature of 200 ℃, after the micro-nano-level super-hydrophobic coating is heated for 4 hours, the contact angle with water is 150 +/-6 degrees, and the rolling angle is 10 +/-2 degrees.
Example three: the difference between the present embodiment and the first embodiment is: dripping fatty acyl chloride into the mixture at the temperature of 70 ℃, and carrying out shading reaction for 6 hours; the fatty acyl chloride in the first step is heptanoyl chloride; the volume ratio of the tetrahydrofuran in the first step to the ethanol solution in the second step is 1: 1. The rest is the same as the first embodiment.
The micro-nano-level super-hydrophobic coating prepared by self-assembling the core-shell cellulose nanoparticles with the wood as the substrate in the third embodiment has a contact angle of 158 +/-2 degrees with water and a rolling angle of 6 +/-3 degrees.
The micro-nano-level super-hydrophobic coating prepared by self-assembling the core-shell cellulose nano-particles with the wood as the substrate in the third embodiment can still maintain the super-hydrophobicity at the high temperature of 200 ℃, and after the micro-nano-level super-hydrophobic coating is heated for 4 hours, the contact angle with water is 154 +/-7 degrees, and the rolling angle is 8 +/-4 degrees.
Example four: the difference between the present embodiment and the first embodiment is: dripping fatty acyl chloride into the mixture at the temperature of 80 ℃, and carrying out shading reaction for 8 hours; the fatty acyl chloride in the first step is pelargonyl chloride; the volume ratio of the tetrahydrofuran in the first step (r) to the ethanol solution in the second step (r) is 1:2. The rest is the same as the first embodiment.
In the fourth embodiment, the micro-nano-level super-hydrophobic coating prepared by self-assembling the core-shell cellulose nanoparticles with the wood as the substrate has a contact angle of 160 +/-4 degrees with water and a rolling angle of 5 +/-2 degrees.
The core-shell cellulose nanoparticles prepared in the fourth embodiment, which are based on wood, are self-assembled to form the micro-nano-level super-hydrophobic coating, the super-hydrophobicity of the micro-nano-level super-hydrophobic coating can be still maintained at a high temperature of 200 ℃, after the micro-nano-level super-hydrophobic coating is heated for 4 hours, the contact angle with water is 158 +/-6 degrees, and the rolling angle is 9 +/-3 degrees.
Example five: the difference between the present embodiment and the first embodiment is: dripping fatty acyl chloride into the mixture at the temperature of 100 ℃, and carrying out shading reaction for 8 hours; the fatty acyl chloride in the first step is undecanoyl chloride; the volume ratio of the tetrahydrofuran in the first step to the ethanol solution in the second step is 1: 4. The rest is the same as the first embodiment.
In the fifth embodiment, the micro-nano-level super-hydrophobic coating prepared by self-assembling the core-shell cellulose nanoparticles with the wood as the substrate has a contact angle of 162 +/-4 degrees with water and a rolling angle of 8 +/-1 degrees.
The micro-nano-level super-hydrophobic coating prepared by self-assembling the core-shell cellulose nano-particles with the wood as the substrate in the fifth embodiment can still maintain the super-hydrophobicity at the high temperature of 200 ℃, and after the micro-nano-level super-hydrophobic coating is heated for 4 hours, the contact angle with water is 159 +/-4 degrees, and the rolling angle is 10 +/-3 degrees.
Example six: the difference between the present embodiment and the first embodiment is: dripping fatty acyl chloride into the mixture at the temperature of 90 ℃, and carrying out shading reaction for 8 hours; the fatty acyl chloride in the first step is decanoyl chloride; the volume ratio of the tetrahydrofuran in the first step (IV) to the ethanol solution in the second step (IV) is 1: 6. The rest is the same as the first embodiment.
In the sixth embodiment, the micro-nano-level super-hydrophobic coating prepared by self-assembling the core-shell cellulose nanoparticles with the wood as the substrate has a contact angle of 164 +/-7 degrees with water and a rolling angle of 6 +/-2 degrees.
The core-shell cellulose nanoparticles prepared in the sixth embodiment, which are based on wood, are self-assembled to form the micro-nano-scale superhydrophobic coating, the superhydrophobic coating still can maintain the superhydrophobicity at a high temperature of 200 ℃, after the coating is heated for 4 hours, the contact angle with water is 157 +/-5 degrees, and the rolling angle is 7 +/-3 degrees.

Claims (10)

1. A preparation method for constructing a micro-nano-level super-hydrophobic coating by self-assembly of core-shell cellulose nanoparticles is characterized by comprising the following steps:
firstly, synthesizing core-shell type hydrophobic cellulose fatty acid ester nano particles:
firstly, drying cellulose, then adding the dried cellulose into anhydrous N, N-dimethylacetamide, magnetically and uniformly stirring the cellulose at a stirring speed of 200 r/min-500 r/min to obtain a mixture, heating the mixture to 50-100 ℃, dropwise adding fatty acyl chloride into the mixture at a temperature of 50-100 ℃, and carrying out shading reaction for 2-10 hours to obtain a reaction system;
the molar ratio of the glucose unit to the fatty acyl chloride in the dried cellulose is 1 (1-2.5);
secondly, adding the reaction system into ethanol solution to separate out a product, then centrifugally separating for 5-10 min under the conditions that the rotating speed is 5000-10000 r/min and the temperature is 10-30 ℃, removing the upper layer liquid, separating and drying the lower layer product, and dispersing the dried lower layer product into tetrahydrofuran to obtain a dispersion liquid;
thirdly, repeating the dispersion liquid for 5 to 10 times according to the first step to obtain the dispersion liquid with the dissolved product;
centrifugally separating the dispersion liquid with the dissolved product for 30-60 min under the conditions of the rotating speed of 1000-2000 r/min and the temperature of 10-30 ℃, dispersing the centrifuged upper layer liquid into an ethanol solution after centrifugation, centrifugally separating for 5-10 min under the conditions of the rotating speed of 5000-10000 r/min and the temperature of 10-30 ℃, separating and drying the lower layer product after centrifugal separation, and dispersing the dried lower layer product into tetrahydrofuran to obtain a core-shell type hydrophobic cellulose fatty acid ester nano-particle suspension;
secondly, preparing a super-hydrophobic surface:
putting core-shell hydrophobic cellulose fatty acid ester nano-particle suspension into a centrifuge tube, then putting the suspension on a tubular oscillator, dropwise adding an ethanol solution into the centrifuge tube at a dropwise adding speed of 10-200 mu L/min to obtain cellulose fatty acid ester nano-particles which are self-assembled to construct nano-convex micro-particles;
the volume ratio of the tetrahydrofuran in the first step to the ethanol solution in the second step is 1 (1-10);
secondly, under the conditions that the rotating speed is 5000 r/min-10000 r/min and the temperature is 10-30 ℃, cellulose fatty acid ester nano-particles are self-assembled to construct nano-convex micro-particles, centrifugal separation is carried out for 10-30 min, upper-layer liquid containing tetrahydrofuran is removed, and lower-layer solid is reserved;
dispersing the lower layer solid into ethanol solution, centrifugally separating for 10-30 min at the rotation speed of 5000-10000 r/min and the temperature of 10-30 ℃, and separating and drying the lower layer product after centrifugal separation;
fourthly, repeating the second step and the third step for 10 times or more than 10 times to obtain cellulose micro-nano particle suspension;
and fifthly, spraying the cellulose micro-nano particle suspension on the surface of the substrate by using a spray gun at a position 5-20 cm away from the substrate by using a nozzle, and thus finishing the preparation method for constructing the micro-nano level super-hydrophobic coating by self-assembling the core-shell type cellulose nano particles.
2. The preparation method of the core-shell cellulose nanoparticle self-assembled micro-nano-level super-hydrophobic coating according to claim 1, wherein the fatty acid chloride in the first step is a saturated fatty acid chloride with a fatty chain length of 6-16 or an unsaturated fatty acid chloride with a fatty chain length of 6-16.
3. The preparation method of the core-shell type cellulose nano-particle self-assembled micro-nano-level super-hydrophobic coating according to claim 1, wherein the cellulose in the first step is microcrystalline cellulose, needle-leaf bleaching chemical pulp or broad-leaf bleaching chemical pulp.
4. The preparation method of the micro-nano-level super-hydrophobic coating layer constructed by the self-assembly of the core-shell type cellulose nano-particles according to claim 1, wherein the cellulose drying in the first step is vacuum drying in a vacuum drying oven at a temperature of 60-80 ℃, and the vacuum drying time is not less than 24 hours.
5. The preparation method of the core-shell cellulose nanoparticle self-assembled micro-nano-level super-hydrophobic coating according to claim 1, wherein the volume ratio of the mass of the dried cellulose to the volume of anhydrous N, N-dimethylacetamide in the step one is 1g (10-60) mL.
6. The preparation method of the core-shell type cellulose nanoparticle self-assembled micro-nano-level super-hydrophobic coating according to claim 1, wherein the volume percentage of the ethanol solution in the first step is 70-100%; the volume ratio of the reaction system to the ethanol solution in the first step is 1 (5-15); the ratio of the mass of the dried lower-layer product to the volume of tetrahydrofuran in the first step is 1g (20-60) mL.
7. The preparation method of the core-shell type cellulose nanoparticle self-assembled micro-nano-level super-hydrophobic coating according to claim 1, wherein the volume percentage of the ethanol solution in the first step (r) is 70-100%; the volume ratio of the centrifuged upper layer liquid to the ethanol solution in the first step (15) - (5) is 1; the ratio of the mass of the dried lower-layer product in the first step to the volume of the tetrahydrofuran is 1g (20-60) mL.
8. The preparation method of the micro-nano-level super-hydrophobic coating constructed by self-assembling the core-shell type cellulose nano-particles according to claim 1, wherein the volume percentage of the ethanol solution in the second step is 70-90%.
9. The method for preparing the micro-nano-level super-hydrophobic coating by self-assembling the core-shell type cellulose nano-particles according to claim 1, wherein the volume percentage of the ethanol solution in the second step is 70-90%.
10. The method for preparing the micro-nano-level super-hydrophobic coating by the self-assembly of the core-shell type cellulose nano-particles according to claim 1, wherein the second step is to spray the cellulose micro-nano-particle suspension on the surface of the substrate by a spray gun, wherein the spraying amount is 0.03mg/mm2～0.1mg/mm2(ii) a The substrate in the second-fifth step is glass, wood, textile, paper, metal or plastic.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5059659A (en) * 1987-05-29 1991-10-22 Harry P. Gregor Surface treatments to impart hydrophilicity
CN101745352A (en) * 2009-12-15 2010-06-23 中国科学院化学研究所 Superhydrophobic surface material and special nano-particles thereof with core-shell structures
KR20170119837A (en) * 2016-04-20 2017-10-30 상명대학교산학협력단 Solid indicator and manufacturing method of the same
CN108137896A (en) * 2015-09-04 2018-06-08 凯米罗总公司 Core shell polymer beads as Cypres
CN108912939A (en) * 2017-04-10 2018-11-30 东北林业大学 A kind of transparency swelling type water flame-proof paint and its preparation method and application
CN110467849A (en) * 2019-08-16 2019-11-19 于素阁 A kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method
CN110499073A (en) * 2019-09-03 2019-11-26 东北林业大学 A method of using nano-cellulose and nano particle, as raw material, fluorine-free modified dose of modification prepares super hydrophobic coating in aqueous solution
CN111019482A (en) * 2019-12-24 2020-04-17 齐鲁工业大学 Preparation and application of super-hydrophobic/oleophobic coating with excellent performance
CN111234483A (en) * 2020-01-15 2020-06-05 东北林业大学 Surface fatty acylated cellulose nano-particle/polylactic acid composite membrane and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5059659A (en) * 1987-05-29 1991-10-22 Harry P. Gregor Surface treatments to impart hydrophilicity
CN101745352A (en) * 2009-12-15 2010-06-23 中国科学院化学研究所 Superhydrophobic surface material and special nano-particles thereof with core-shell structures
CN108137896A (en) * 2015-09-04 2018-06-08 凯米罗总公司 Core shell polymer beads as Cypres
KR20170119837A (en) * 2016-04-20 2017-10-30 상명대학교산학협력단 Solid indicator and manufacturing method of the same
CN108912939A (en) * 2017-04-10 2018-11-30 东北林业大学 A kind of transparency swelling type water flame-proof paint and its preparation method and application
CN110467849A (en) * 2019-08-16 2019-11-19 于素阁 A kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method
CN110499073A (en) * 2019-09-03 2019-11-26 东北林业大学 A method of using nano-cellulose and nano particle, as raw material, fluorine-free modified dose of modification prepares super hydrophobic coating in aqueous solution
CN111019482A (en) * 2019-12-24 2020-04-17 齐鲁工业大学 Preparation and application of super-hydrophobic/oleophobic coating with excellent performance
CN111234483A (en) * 2020-01-15 2020-06-05 东北林业大学 Surface fatty acylated cellulose nano-particle/polylactic acid composite membrane and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Cellulose-based Superhydrophobic Surface Decorated with Functional Groups Showing Distinct Wetting Abilities to Manipulate Water Harvesting;Wei Huang;《APPLIED MATERIALS & INTERFACES》;20200811;第12卷(第36期);第40968-40978页 *
Hydrophobic silane coating films for the inhibition of water ingress into the nanometer pore of calcium silicate hydrate gels;Yu Jiao;et al.;《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》;20190921;第21卷(第35期);第19026-19038页 *
WPC-LVL共挤出复合材料的抗弯性能;王海刚;《建筑材料学报》;20180831;第21卷(第4期);第695-700页 *
自清洁超疏水无胶纳米纤丝化复合材料的制备及其性能;杨玉山;《东北林业大学学报》;20200630;第48卷(第6期);第80-85页 *

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