CN114657789B - Organic silicon super-hydrophobic coating, super-hydrophobic coating based on organic silicon super-hydrophobic coating and application of organic silicon super-hydrophobic coating - Google Patents

Organic silicon super-hydrophobic coating, super-hydrophobic coating based on organic silicon super-hydrophobic coating and application of organic silicon super-hydrophobic coating Download PDF

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CN114657789B
CN114657789B CN202210443160.8A CN202210443160A CN114657789B CN 114657789 B CN114657789 B CN 114657789B CN 202210443160 A CN202210443160 A CN 202210443160A CN 114657789 B CN114657789 B CN 114657789B
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hydrophobic coating
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CN114657789A (en
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鲁路
刘红生
宗晟
李立华
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Jinan University
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Abstract

The invention belongs to the technical field of functional materials, and discloses an organic silicon super-hydrophobic coating, a super-hydrophobic coating based on the organic silicon super-hydrophobic coating and application of the organic silicon super-hydrophobic coating. The coating disclosed by the invention comprises the following raw materials in parts by weight: 2.0 to 5.0 portions of tetraethyl orthosilicate, 2.0 to 6.0 portions of hydroxyl-terminated blocking agent, 0.05 to 0.5 portions of silicon dioxide particles and a proper amount of catalyst. The tetraethyl orthosilicate, the hydroxyl-terminated blocking agent and the hydroxyl on the surface of the silicon dioxide in the coating undergo hydrolysis condensation reaction, a nano composite coarse structure with low surface energy and a rigid structure is constructed on the surface of the substrate in situ, so that the surface tension of the interface of the substrate is effectively reduced, the interface roughness is increased, the obtained coating has excellent light transmittance, wear resistance and corrosion resistance, a durable superhydrophobic effect can be realized, the water contact angle can reach 164 degrees, good superhydrophobic performance can be maintained after 100 times of washing, and the hydrophobicity and durability of the substrate are greatly improved.

Description

Organic silicon super-hydrophobic coating, super-hydrophobic coating based on organic silicon super-hydrophobic coating and application of organic silicon super-hydrophobic coating
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to an organic silicon super-hydrophobic coating, a super-hydrophobic coating based on the organic silicon super-hydrophobic coating and application of the organic silicon super-hydrophobic coating.
Background
The superhydrophobic surface refers to a surface with a contact angle with water of more than 150 degrees and a rolling angle of less than 10 degrees. The special surface wettability of the super-hydrophobic surface enables the super-hydrophobic surface to be widely applied to various fields such as electronic information, biological medicine, aerospace, new materials and the like, and has wide prospect, but the super-hydrophobic surface is still limited in industrial production and practical life application. One of the main reasons is that the durability of the coating is generally poor, and the micro-nano structure of the superhydrophobic surface is easily damaged by abrasion in use; secondly, the preparation process is complex, the preparation period is long, and a plurality of methods adopt a relatively complex process when constructing the surface microstructure, so that the time and the labor are consumed, and the cost investment is increased; thirdly, organic fluorides such as perfluorosilane are mostly adopted when the low surface energy treatment is carried out, and solvents are usually toxic and harmful organic reagents, so that the use range of finished products is greatly limited due to the problems of safety, environmental protection and the like, and the waste liquid treatment is time-consuming, labor-consuming and expensive, and is not suitable for large-scale industrial production.
The organosilicon has low surface energy and high thermal stability, is used as a flame retardant for fireproof and heat insulation of polymers, is widely used for preparing super-hydrophobic coatings, is more environment-friendly and economical than fluorine-containing materials, and is popular among the masses. Therefore, it is important to develop a simple, convenient, safe and environment-friendly method for preparing the super-hydrophobic coating with excellent performance.
Disclosure of Invention
In order to overcome the defects of poor durability and unsafe and environment-friendly preparation method of the prior art super-hydrophobic coating, the primary aim of the invention is to provide the organosilicon super-hydrophobic coating.
The invention further aims to provide a super-hydrophobic coating based on the organic silicon super-hydrophobic coating.
The invention further aims at providing a preparation method of the super-hydrophobic coating.
It is still another object of the present invention to provide the use of the above-described silicone superhydrophobic coating. The organosilicon superhydrophobic coating disclosed by the invention is applied to surface hydrophobicity modification, especially fabric surface modification, and the obtained superhydrophobic coating has good hydrophobicity and is durable.
The aim of the invention is achieved by the following scheme:
the organic silicon super-hydrophobic coating comprises the following raw materials in parts by weight: 2.0 to 5.0 portions of tetraethyl orthosilicate, 2.0 to 6.0 portions of hydroxyl-terminated blocking agent, 0.05 to 0.5 portions of silicon dioxide particles and a proper amount of catalyst.
The hydroxyl-terminated blocking agent comprises at least one of hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated polybutadiene polyurethane, hydroxyl-terminated polyether and the like.
The silica particles include, but are not limited to, siO 2 Nanoparticle, mesoporous SiO 2 Nanoparticles and hydrophobically modified SiO 2 At least one of the nanoparticles.
Further, the particle diameter of the silica particles is preferably 50 to 100nm, and the dispersibility is good.
The catalyst may be a conventional catalyst for dehydration condensation reaction, such as a base, including at least one of ammonia water, sodium hydroxide, sodium bicarbonate, sodium carbonate, and the like, without being limited thereto.
The organic silicon super-hydrophobic coating component also contains a solvent; the solvent includes, but is not limited to, at least one of organic solvents such as methanol, ethanol, acetone, and the like. The amount of the solvent to be used is adjusted according to the actual use.
The organosilicon superhydrophobic coating can be applied to surface hydrophobicity modification, in particular to fabric surface modification; the organic silicon super-hydrophobic coating can form a super-hydrophobic coating on the surface of a substrate by coating modes such as soaking or spraying, and has excellent corrosion resistance, durability and super-hydrophobicity.
The invention also provides a super-hydrophobic coating based on the organic silicon super-hydrophobic coating.
The invention also provides a preparation method of the super-hydrophobic coating, which comprises the following steps:
(1) Dispersing silica particles in a solvent to obtain a silica dispersion A; adding tetraethyl orthosilicate, a hydroxyl-terminated blocking agent and a catalyst into a solvent, and uniformly stirring to obtain a solution B;
(2) Soaking the substrate in the silicon dioxide dispersion liquid A in the step (1) and taking out; and coating the solution B on the surface of the substrate to react, and obtaining the super-hydrophobic coating after the reaction is finished.
In the step (1), the concentration of silica particles in the silica dispersion A is preferably 0.05 to 0.5% (m/V), kg/L.
The substrate can be glass material, metal material, ceramic material, wood, polymer material, artificial polymer fabric, natural polymer fabric, etc.
In the solution B, the concentration of tetraethyl orthosilicate is preferably 2.0-5.0% (m/V), kg/L.
The amount of catalyst is such that the pH of the solution B is adjusted to 8.5-9.5.
In step (2), the soaking time in the silica dispersion A may be 30min to 4h.
After removal, the substrate may be rinsed with solvent and dried before use in a subsequent reaction. The drying treatment can be carried out at 60-80deg.C; the drying treatment time may be 3 to 5 hours.
The reaction time may be 30min to 4h.
The reaction can be carried out at room temperature, preferably at 20-30 ℃.
After the reaction is finished, the mixture can be washed by a solvent and dried. Preferably in an oven at 60-80 deg.c for 3-5h.
The coating method can comprise dipping, spraying, curtain coating, wiping and other coating processing modes suitable for liquid.
In the above preparation method, the solvents may be the same or different and may be at least one of organic solvents such as methanol, ethanol, acetone, etc. Such as absolute ethanol.
The components, siO, of the coating according to the invention 2 The particles are firstly deposited on the surface of the fabric through hydrogen bond and electrostatic action, so that the surface roughness of the fabric is increased, then the added tetraethyl orthosilicate, hydroxyl-terminated blocking agent and hydroxyl on the surface of silicon dioxide are subjected to hydrolytic condensation reaction, a nano composite coarse structure with low surface energy and rigid structure is constructed on the surface of the substrate in situ, the surface tension of the interface of the substrate is effectively reduced, the interface roughness is increased, the obtained coating has excellent light transmittance, wear resistance and corrosion resistance, a durable superhydrophobic effect can be realized, the water contact angle can reach 164 degrees, and good superhydrophobic performance can be maintained after 100 times of washing, so that the hydrophobicity and durability of the substrate are greatly improved.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, nanoparticles with different sizes are effectively attached to a substrate through condensation reaction of hydroxyl groups, and a nano composite structure with certain structural rigidity is constructed, so that the surface energy is reduced, the roughness is improved, and the durable superhydrophobic function is realized.
(2) The solvent and the reagent in the coating are green and environment-friendly, the waste liquid treatment is simple and low in consumption in the use process, the defects of large amount of organic toxic reagents, complex manufacturing process, high cost, poor hydrophobic performance and the like in the traditional hydrophobic coating preparation process are overcome, and compared with the existing preparation method of most hydrophobic coatings, the method has obvious advantages and good industrialization prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a SiO produced in example 1 2 TEM image of nanoparticles.
FIG. 2 is a SiO produced in example 1 2 SEM image of nanoparticles.
Fig. 3 is a graph of static versus water contact angle measurements for the superhydrophobic polyester fabric prepared in example 1.
FIG. 4 is a mesoporous SiO prepared in example 2 2 TEM image of nanoparticles.
FIG. 5 is a mesoporous SiO prepared in example 2 2 SEM image of nanoparticles.
Fig. 6 is a graph of static versus water contact angle measurements for the superhydrophobic nylon fabric prepared in example 2.
Fig. 7 is a graph of static versus water contact angle measurements for the superhydrophobic cotton fabric prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. The materials referred to in the examples below are available commercially unless otherwise specified. The method is conventional unless otherwise specified. The dosage of each component is in parts by mass, parts by volume, g and mL.
Example 1
The organic silicon super-hydrophobic coating comprises the following raw materials in parts by weight: 2 parts of tetraethyl orthosilicate, 6 parts of hydroxyl-terminated sealing agent, 0.05 part of silicon dioxide particles, a proper amount of ammonia water and a proper amount of absolute ethyl alcohol.
A super-hydrophobic coating based on the organic silicon super-hydrophobic coating is prepared by a method comprising the following steps:
(1) The silica particles are prepared by a Stober method according to a conventional method, and ammonia water is used as a catalyst, and tetraethyl orthosilicate is used as a raw material to prepare SiO 2 And (3) nanoparticles. From TEM (FIG. 1) and SEM (FIG. 2), siO can be obtained 2 The average size of the nanoparticles was 80nm.
(2) SiO prepared in the step (1) is reacted with 2 Adding 0.05 parts by mass of particles into 100 parts by volume of absolute ethyl alcohol, uniformly dispersing, then placing the polyester fabric into the absolute ethyl alcohol, soaking for 2 hours, taking out, washing the fabric with the absolute ethyl alcohol for 3 times, and drying the fabric in an oven at 60 ℃ for 3 hours;
(3) Mixing 2 parts by mass of tetraethoxysilane, 6 parts by mass of hydroxyl-terminated polydimethylsiloxane and 100 parts by volume of absolute ethyl alcohol, adding ammonia water to adjust the pH to 9, uniformly stirring, soaking the fabric dried in the step (2), reacting for 2 hours, taking out, washing 3 times by absolute ethyl alcohol, and drying for 3 hours at the temperature of 60 ℃ in an oven to obtain the fabric with the super-hydrophobic coating on the surface.
(4) The contact angle test result for the obtained polyester fabric was 162 °, as shown in fig. 3. The prepared super-hydrophobic fabric is soaked in an ammonia water solution with the pH value of 9 for 12 hours, washed by absolute ethyl alcohol for 3 times, and the contact angle test result after drying is 161 degrees, so that the hydrophobic performance of the fabric is not obviously changed before and after alkaline corrosion. And placing the prepared superhydrophobic fabric in a pulsator washing machine for standard washing (15 min is one cycle), and washing for 100 times, wherein the contact angle test result is 143 degrees. The superhydrophobic fabric prepared in this example is illustrated to have excellent alkali corrosion resistance and durability.
Example 2
The organic silicon super-hydrophobic coating comprises the following raw materials in parts by weight: 3 parts of tetraethyl orthosilicate, 3 parts of hydroxyl-terminated blocking agent, 0.1 part of silicon dioxide particles, a proper amount of sodium hydroxide solution and a proper amount of anhydrous methanol.
A super-hydrophobic coating based on the organic silicon super-hydrophobic coating is prepared by a method comprising the following steps:
(1) The silica particles are prepared by a conventional method through a template method, cetyl trimethyl ammonium p-toluenesulfonate is taken as a template agent and triethanolamine is dissolved in deionized water, stirring is carried out for 1h at 80 ℃, tetraethyl orthosilicate is added after full dissolution, the reaction is continued for 2h, the obtained nano particles are subjected to centrifugation, washing, freeze drying, calcination and grinding for standby, and the prepared mesoporous SiO is known from TEM (figure 4) and SEM (figure 5) 2 The average size of the nanoparticles was 80nm.
(2) Mesoporous SiO prepared in the step (1) is prepared 2 Adding 0.1 part by mass of particles into 100 parts by volume of absolute methanol, uniformly dispersing, then placing nylon fabric into the mixture, soaking the mixture for 2 hours, taking out the mixture, washing the fabric with absolute ethanol for 3 times, and drying the fabric in an oven at 60 ℃ for 3 hours;
(3) Mixing 3 parts by mass of tetraethoxysilane, 3 parts by mass of hydroxyl-terminated polybutadiene polyurethane and 100 parts by volume of absolute methanol, adding a sodium hydroxide solution to adjust the pH to 9, uniformly stirring, soaking the fabric dried in the step (2), reacting for 2 hours, taking out, washing 3 times by absolute ethanol, and drying in an oven at 60 ℃ for 3 hours to obtain the fabric with the super-hydrophobic coating on the surface.
(4) The contact angle test result for the obtained nylon fabric was 164 °, as shown in fig. 6. The prepared super-hydrophobic fabric is soaked in hydrochloric acid solution with pH of 5 for 12 hours, washed by absolute ethyl alcohol for 3 times, and the contact angle test result after drying is 162 degrees, so that the hydrophobic performance of the fabric is not obviously changed before and after acid corrosion. And placing the prepared superhydrophobic fabric in a pulsator washing machine for standard washing (15 min is one cycle), and washing for 100 times, wherein the contact angle test result is 146 degrees. The superhydrophobic fabric prepared in this example is illustrated to have excellent acid corrosion resistance and durability.
Example 3
The organic silicon super-hydrophobic coating comprises the following raw materials in parts by weight: 5 parts of tetraethyl orthosilicate, 2 parts of hydroxyl-terminated sealing agent, 0.5 part of silicon dioxide particles, a proper amount of sodium carbonate solution and a proper amount of absolute ethyl alcohol.
A super-hydrophobic coating based on the organic silicon super-hydrophobic coating is prepared by a method comprising the following steps:
(1)SiO 2 the particle preparation was as in example 1.
(2) SiO prepared in the step (1) is reacted with 2 Adding 0.5 parts by mass of particles into 100 parts by volume of absolute ethyl alcohol, uniformly dispersing, putting cotton fabric into the absolute ethyl alcohol, soaking for 2 hours, taking out, washing the fabric with the absolute ethyl alcohol for 3 times, and drying the fabric in an oven at 60 ℃ for 3 hours;
(3) Mixing 5 parts by mass of tetraethoxysilane, 2 parts by mass of double-end hydroxyl polyether and 100 parts by volume of absolute ethyl alcohol, adding a sodium carbonate solution to adjust the pH to 9, uniformly stirring, soaking the fabric dried in the step (2), reacting for 2 hours, taking out, washing 3 times by absolute ethyl alcohol, and drying for 3 hours at the temperature of 60 ℃ in an oven to obtain a fabric with the super-hydrophobic coating on the surface, wherein the contact angle test result is 160 DEG, as shown in figure 7; corrosion resistance and durability are similar to those of the above embodiments, and will not be described in detail.
Comparative example 1
(1)SiO 2 The particle preparation was as in example 1.
(2) SiO prepared in the step (1) is reacted with 2 Adding 0.05 parts by mass of particles into 100 parts by volume of absolute ethyl alcohol, uniformly dispersing, then placing the polyester fabric into the absolute ethyl alcohol, soaking for 2 hours, taking out, washing the fabric with the absolute ethyl alcohol for 3 times, and drying the fabric in an oven at 60 ℃ for 3 hours; the polyester fabric contact angle test result obtained was 134 °. The prepared hydrophobic polyester fabric was washed 20 times in a pulsator washing machine, and the contact angle test result was 105 °.
It can be seen from this that SiO is used 2 Although the surface modification of the nano particles can obtain the effect of hydrophobic modification, the effect of super-hydrophobic can not be achieved, the obtained coating is unstable in structure and easy to damage, the hydrophobic performance is obviously reduced, and the service life of the product is greatly shortened.
Comparative example 2
Mixing 2 parts by mass of tetraethoxysilane, 6 parts by mass of hydroxyl-terminated blocking agent and 100 parts by volume of absolute ethyl alcohol, adding ammonia water to adjust the pH to 9, uniformly stirring, soaking the polyester fabric therein, taking out the polyester fabric after reacting for 2 hours, washing the polyester fabric with the absolute ethyl alcohol for 3 times, and drying the polyester fabric in an oven at 60 ℃ for 3 hours, wherein the contact angle test result of the obtained polyester fabric is 141 degrees. The prepared hydrophobic polyester fabric was washed 20 times in a pulsator washing machine, and the contact angle test result was 120 °.
Therefore, the effect of hydrophobic modification can be obtained by modifying the surface of the fabric by using tetraethyl orthosilicate and a hydroxyl-terminated blocking agent, but the effect of superhydrophobicity cannot be achieved, the obtained coating is unstable in structure and easy to damage, the hydrophobic performance is obviously reduced, and the service life of the product is greatly shortened.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (6)

1. The super-hydrophobic coating is characterized by comprising the following steps:
(1) Dispersing silica particles in a solvent to obtain a silica dispersion A; adding tetraethyl orthosilicate, a hydroxyl-terminated blocking agent and a catalyst into a solvent, and uniformly stirring to obtain a solution B;
(2) Soaking the substrate in the silicon dioxide dispersion liquid A in the step (1) and taking out; then soaking in the solution B, or spraying the solution B on the surface of the substrate to react, and obtaining the super-hydrophobic coating after the reaction is finished;
the hydroxyl-terminated blocking agent comprises at least one of hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated polybutadiene polyurethane and hydroxyl-terminated polyether end blocking agent.
2. The superhydrophobic coating of claim 1, wherein: in step (1), the concentration of silica particles in the silica dispersion A is 0.05 to 0.5% m/V; in the solution B, the concentration of tetraethyl orthosilicate is 2.0-5.0% m/V.
3. The superhydrophobic coating of claim 1, wherein: the amount of catalyst is such that the pH of the solution B is adjusted to 8.5-9.5.
4. The superhydrophobic coating of claim 1, wherein: in the step (2), the soaking time in the silicon dioxide dispersion liquid A is 30min-4h; the reaction time is 30min-4h.
5. The superhydrophobic coating of claim 1, wherein: the solvent is at least one of methanol, ethanol and acetone, which are the same or different.
6. The superhydrophobic coating of claim 1, wherein: the silica particles comprise SiO 2 Nanoparticle, mesoporous SiO 2 Nanoparticles and hydrophobically modified SiO 2 At least one of the nanoparticles.
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