CN112358809B - Anti-fog coating based on organic silicon and preparation method and application thereof - Google Patents
Anti-fog coating based on organic silicon and preparation method and application thereof Download PDFInfo
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- CN112358809B CN112358809B CN202011176851.3A CN202011176851A CN112358809B CN 112358809 B CN112358809 B CN 112358809B CN 202011176851 A CN202011176851 A CN 202011176851A CN 112358809 B CN112358809 B CN 112358809B
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Abstract
The invention belongs to the technical field of coatings, and discloses an antifogging coating based on organosilicon, a preparation method and application thereof, wherein tetraalkoxysilane is prehydrolyzed under an acidic condition to obtain a prehydrolysis product; then carrying out cohydrolysis condensation with trialkoxysilane with epoxy functional groups to obtain a uniform cohydrolysis condensation product; then reacting with polyamine to prepare epoxy-amine addition compound, and distilling out the residual amine substances in the system by reduced pressure to obtain the anti-fog coating based on the organic silicon. The anti-fog coating based on the organic silicon has the advantages of simple synthesis method, uniform system, low viscosity and the like, can be well adhered to a PC substrate, and has good wear resistance, scratch resistance, water resistance, chemical resistance and antifogging property.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an antifogging coating based on organic silicon, and a preparation method and application thereof.
Background
The transparent material has wide application in daily life and plays an important role. Unfortunately, these materials exhibit natural fogging under untreated use conditions, as water vapor inevitably condenses on the substrate surface. This phenomenon not only affects the optical properties of the material, but also causes a series of social problems of beauty, convenience, even hygiene and safety. Under the background, research on the technical field of anti-fog has attracted more and more attention and has great potential value.
The antifogging coating is a functional coating which can reduce and prevent the surface of a substrate from being atomized. The method is to coat a thin coating on the surface of a substrate, and modify or change the surface characteristics of the substrate so as to adjust the wettability between the surface of the substrate and water drops. Both hydrophilic and hydrophobic surfaces can achieve reduced fogging by altering the droplet morphology. The hydrophilic surface forms an almost continuous water film on the surface based on the affinity between the water droplets and the substrate, and the surface maintains high optical performance despite condensation, representing a distinct advantage. The antifogging coating can be divided into a plurality of types according to different preparation methods, and good antifogging coatings can be obtained by etching methods, plasma treatment methods or the like, but the methods have high cost and high requirements on equipment, and have great difficulty in application to actual life although the performances are good. Therefore, the research of changing the wettability of the substrate by coating the surface of the substrate with a film by wet chemical synthesis is very important. The main film forming species related to the synthesis method are various, the traditional antifogging spray takes surfactant substances as effective antifogging components, the preparation process is simple, but the timeliness is low due to easy abrasion and consumption, and the CN 109135673A patent prepares the lens antifogging spray by utilizing components such as buffering agents, soap water, surfactants, purified water and the like, the spray aims at improving the antifogging effect by being sprayed on the surfaces of other antifogging films, and the spray has great limitation. In addition, a hydrophilic antifogging coating with excellent performance can be obtained by using inorganic materials, but a heat treatment deposition process in the preparation process becomes a difficult challenge for practical application on polymer substrates (such as PET, PC and the like), and the patent CN 1224036A provides a titanium sol-gel coating added with nano inorganic compound particles, which presents high hydrophilicity under photoinduction and is a multifunctional coating with antifogging performance, but the coating has limited practical application due to the limitation of photoinduction or stimulation conditions. Patent US 4551484 utilizes the physical diffusion of polyurethane into the interior of the coating upon contact with a hydrophilic surfactant, but the antifogging properties of the coating are significantly reduced due to the precipitation of the surfactant. Organic and organic-inorganic composite systems are the main development trend of antifogging coatings, with obvious advantages. The resin for synthesizing the organic high molecular polymer has various types, easily obtained raw materials, and long antifogging life because the molecular structure of the resin contains a large amount of hydrophilic and water-absorbing groups. The film forming main body commonly used for the antifogging coating is unsaturated polyester, polyacrylate and polyacrylamide, amino resin, vinyl family and polyether family substances and the like. Patent CN 104212293a prepares an aqueous acrylic antifogging coating composed of a bottom layer and a surface layer, so as to ensure good mechanical properties and hydrophilicity at the same time. For organic-inorganic composite systems, the hydrophilicity of which is provided by both organic and inorganic components, and the mechanical properties of which are provided mainly by inorganic components, combining the advantages of both organic and inorganic materials, an important research point in the field of antifogging is that patent CN 108473811a, an important research point, prepares an antifogging coating composition comprising functionalized silica particles and multifunctional (meth) acrylate monomers, said articles exhibiting antifogging properties and often also mechanical durability.
In summary, there are several obvious disadvantages in the above patents, first, although the prepared antifogging coating has antifogging property after coating, it is limited by the preparation method, and the antifogging coating prepared by using inorganic material is difficult to be widely used; secondly, the antifogging property is only one of the functions, and the wear resistance, the scratch resistance, the solvent resistance and other properties of the coating film are poor; finally, antifog coatings are finally applied to transparent substrates, and many patents make little mention of the transparency of the coating, while the transparency of the cured coating itself has a direct impact on the observation of the fogging phenomenon.
Disclosure of Invention
In order to solve the defects, the invention provides an antifogging coating based on organic silicon. The antifogging coating based on the organic silicon has the advantages of good water solubility, low flammability, low Voc content and the like, and the formed antifogging coating has high transparency, good wear resistance and adhesive force, excellent chemical resistance and the like. The main raw materials are three-functionality and four-functionality alkoxy silane, a proper silane coupling agent is added into the alkoxy silane, the alkoxy silane and the silane coupling agent are hydrolyzed and subjected to two-phase condensation reaction under the acid or alkaline condition to form a network structure taking-Si-O-Si-as a framework, and a hydrophilic chain segment is introduced by utilizing the structural adjustability of a functional group part of the silane coupling agent to achieve better antifogging performance.
The invention also provides a preparation method of the antifogging coating and application of the coating in a mild environment condition in daily life.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an antifogging coating based on organosilicon comprises the steps of carrying out prehydrolysis on tetraalkoxysilane under an acidic condition to obtain a prehydrolysis product; then carrying out cohydrolysis condensation with trialkoxysilane with epoxy functional groups to obtain a uniform cohydrolysis condensation product; then reacting with polyamine to prepare epoxy-amine addition compound, and distilling out the residual amine substances in the system by reduced pressure to obtain the anti-fog coating based on the organic silicon.
Preferably, the method comprises the following steps:
(1) preparation of prehydrolyzate: uniformly mixing a solvent and water, adjusting the pH value of a system to be 1.5-2.5 by using an acid, slowly dropwise adding tetraalkoxysilane into an acidic medium, and reacting for 2-3h at 50 +/-10 ℃;
(2) preparation of cohydrolytic condensate: uniformly mixing trialkoxysilane with an epoxy functional group with water, slowly dropwise adding the trialkoxysilane into the prehydrolyzate obtained in the step (1), adjusting the pH to 1.5-2.5 by using acid, raising the temperature to 65 +/-10 ℃, and reacting for 5-6h to obtain a cohydrolysis condensate;
(3) preparation of epoxy-amine adduct: slowly dripping an amine compound into the product obtained in the step (2), and continuously reacting for 4-5h at the temperature of 65 +/-10 ℃ to obtain an epoxy-amine addition product; the molar ratio of the amine compound to the trialkoxysilane with the epoxy functional group added in the step (2) is more than 1;
(4) preparing the organic silicon antifogging coating: and (4) removing the residual amine substances in the epoxy-amine adduct obtained in the step (3) by reduced pressure distillation, and standing to obtain the organic silicon antifogging coating.
The purpose of removing the excessive amine substances by reduced pressure distillation in the step (4) is to keep the color of the system uniform and prevent the solution from yellowing.
Preferably, the tetraalkoxysilane in step (1) comprises one of ethyl orthosilicate and methyl orthosilicate.
Preferably, the mass ratio of the solvent to the water in the step (1) is (30-40): 1; the solvent is one or two of methanol, ethanol, isopropanol, diacetone alcohol and dipropylene glycol methyl ether; the acid in the step (1) and (2) is one of hydrochloric acid, phosphoric acid, acetic acid and formic acid.
Preferably, the molar ratio of water to tetraalkoxysilane in step (1) is (4-1): 1; the molar ratio of the water to the trialkoxysilane with an epoxy functional group in the step (2) is 3: 1.
Preferably, the trialkoxysilane with an epoxy functional group in the step (2) is one of gamma-glycidoxy trimethoxysilane, gamma-glycidoxy triethoxysilane, 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane and 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane.
Preferably, the amine compound in step (3) is diethanolamine or polyetheramine.
Preferably, the molar ratio of the tetraalkoxysilane added in step (1) to the trialkoxysilane with an epoxy functional group added in step (2) is 1 (2-6).
Preferably, the molar ratio of the amine compound added in the step (3) to the trialkoxysilane with an epoxy functional group added in the step (2) is (1.05-1.1): 1.
the application of the anti-fog coating based on the organic silicon prepared by the method comprises the following steps: coating the obtained organic silicon antifogging coating on a PC substrate, precuring for 30 +/-10 min in a baking oven at 50 +/-10 ℃, and then adjusting the temperature to 110 +/-10 ℃ for curing for 3 +/-1 h to obtain the organic silicon antifogging coating.
Part of the raw materials in the invention are described as follows:
the theoretical formula of the tetraalkoxysilane is:
The theoretical structural formula of the gamma-glycidoxy trimethoxy silane is as follows:
the principle of the invention is that the tetraalkoxysilane and the trialkoxysilane with epoxy functional groups are subjected to cohydrolysis condensation under an acidic condition to form a network structure with-Si-O-Si-as a framework, and meanwhile, a hydrophilic substance is introduced by utilizing the reactivity of the epoxy groups to improve the hydrophilicity of a coating. The thermal curing film forming can further increase the crosslinking degree of the system, thereby increasing the water resistance of the coating, and the structure taking Si-O bonds as main components can improve the wear resistance, heat resistance, chemical resistance and the like of the coating.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) the method adopts the cohydrolysis condensation reaction of the tetraalkoxysilane and the trialkoxysilane with the epoxy group under the acidic condition, avoids the phenomenon of easy occurrence of gel under the alkaline condition, and greatly shortens the time of hydrolysis condensation.
(2) The invention adopts the method that the tetraalkoxysilane is slowly dripped into the prepared reaction medium, the tetraalkoxysilane is kept in a small amount state, the reactants are diluted until the polymerization rate is reduced at the stage, and the higher water content can promote the hydrolysis and prevent the polycondensation.
(3) The trialkoxysilane with the epoxy group has good compatibility with a system, and the epoxy group has good reactivity, and the introduction of the hydrophilic chain segment by using the epoxy group has better adjustability on the structure of a product, and meanwhile, the epoxy group does not change in the cohydrolysis condensation process under the acidic condition, namely the structure of the final product is not influenced.
(4) According to the invention, a small molecular substance diethanolamine and trialkoxysilane with epoxy groups are subjected to epoxy ring-opening addition reaction, hydrophilic groups (chain segments) are introduced into the reaction, and hydroxyl is used as a main hydrophilic group; under the condition that the surface rich in hydroxyl hydrophilic groups is easily polluted by the outside so as to destroy the hydrophilicity, the invention uses the action of polyetheramine substances to replace diethanol amine, and under the same epoxy ring-opening addition reaction, the hydrophilicity provided by the polyetheramine is realized by a polyoxyethylene structure.
(5) The invention utilizes the ring-opening addition reaction of amine substances and epoxy groups as reactants, and simultaneously neutralizes the acid environment, avoids the step of neutralizing by adding other alkaline substances, and reduces the complexity of the system and the complexity of operation.
(6) The invention carries out reduced pressure distillation treatment on the final product to remove redundant amine substances in the system, avoids the phenomenon that the system is yellow under the action of the amine substances after the product is placed for a long time, and ensures the stability of the appearance of the product.
(7) The anti-fog coating based on the organic silicon, which is prepared by the invention, has the advantages of simple synthesis method, uniform system and the like, can be well adhered to a PC substrate, can be used on different transparent substrates such as glass, plastic and the like, and the main chain structure taking Si-O bonds as repeating units endows the coating with good wear resistance, water resistance, chemical resistance and good adhesion with the substrate, and simultaneously, the introduction of the hydrophilic structure ensures the good anti-fog performance of the coating under the mild condition.
Drawings
FIG. 1 is a schematic diagram of the synthesis of TEOS-KH560/(DEA or PEA) based on the anti-fog coating of silicone.
Fig. 2 is a test chart of antifogging property, and a to f correspond to the test results of example 8, example 2, example 4, example 1, example 6 and comparative example 1, respectively.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) 0.29g (0.016mol) of deionized water and 8.57g of diacetone alcohol are uniformly mixed and added into a three-neck flask provided with a stirrer and a condenser, the mixture is heated to 50 ℃, the pH value of the system is adjusted to 2 by using a small amount of 0.12mol/L hydrochloric acid, then 0.83g (0.004mol) of ethyl orthosilicate is slowly added into the three-neck flask, and the mixture is reacted for 2 hours to obtain a prehydrolysis product of the ethyl orthosilicate.
(2) Uniformly mixing 1.89g (0.008mol) of gamma-glycidoxy trimethoxy silane and 0.43g (0.024mol) of deionized water, slowly adding the mixture into the prehydrolyzate obtained in the step (1), adjusting the pH to 2 by using hydrochloric acid obtained in the step (1), raising the temperature to 65 ℃, and reacting for 6 hours to obtain a hydrolysis condensation product.
(3) Slowly adding 0.88g (0.0084mol) of Diethanolamine (DEA) into the hydrolysis condensation product obtained in the step (2), and continuously reacting at 65 ℃ for 4 hours to obtain the epoxy-amine adduct.
(4) And (4) distilling off redundant amine substances in the system under reduced pressure, and standing to obtain the antifogging coating based on the organic silicon.
(5) And (3) coating the organic silicon antifogging coating obtained in the step (4) on a PC substrate, precuring for 30min in a 50 ℃ oven, and then adjusting the temperature to 110 ℃ for curing for 3h to obtain the organic silicon antifogging coating.
Example 2
In comparison with example 1, a silicone-based antifogging coating of this example was prepared, except that deionized water was added in an amount of 0.22g (0.012mol) in step (1), and the rest was identical.
Example 3
In comparison with example 1, a preparation based on a silicone antifogging coating of this example is different in that 2.84g (0.012mol) of gamma-glycidoxypropyltrimethoxysilane is added in step (2), and the rest is identical.
Example 4
In comparison with example 1, a preparation based on a silicone antifogging coating of this example was carried out with the difference that 3.78g (0.016mol) of gamma-glycidoxypropyltrimethoxysilane was added in step (2), and the rest was identical.
Example 5
In comparison with example 1, a preparation based on a silicone antifogging coating of this example was carried out with the exception that 4.73g (0.02mol) of gamma-glycidoxypropyltrimethoxysilane was added in step (2), and the rest was identical.
Example 6
Compared with example 1, the preparation of an anti-fog coating based on organosilicon in this experimental example is different in that the solvent added in step (1) is changed from diacetone alcohol to dipropylene glycol methyl ether, and the rest is identical.
Example 7
In comparison with example 1, a silicone-based antifogging coating of this example was prepared, except that the solvent added in step (1) was changed from diacetone alcohol to isopropyl alcohol, and the rest was identical.
Example 8
In comparison with example 1, a silicone-based antifogging coating of this example was prepared, except that DEA in step (3) was replaced with PEA, and the rest was identical.
Comparative example 1
(1) 0.29g (0.016mol) of deionized water and 8.57g of diacetone alcohol are uniformly mixed and added into a three-neck flask provided with a stirrer and a condenser, the mixture is heated to 50 ℃, the pH value of the system is adjusted to 2 by using a small amount of 0.12mol/L hydrochloric acid, then 0.83g (0.004mol) of ethyl orthosilicate is slowly added into the three-neck flask, and the mixture is reacted for 2 hours to obtain a prehydrolysis product of the ethyl orthosilicate.
(2) Uniformly mixing 1.89g (0.008mol) of gamma-glycidoxy trimethoxy silane and 0.43g (0.024mol) of deionized water, slowly adding into the prehydrolyzate obtained in the step (1), raising the temperature to 65 ℃, and reacting for 6h to obtain a hydrolysis condensation product.
(3) Standing for 24h, coating the product obtained in the step (2) on a PC substrate, pre-curing in a 50 ℃ oven for 30min, and then adjusting the temperature to 110 ℃ for curing for 3h to obtain the organic silicon coating.
Comparative example 2
(1) 0.29g (0.016mol) of deionized water and 8.57g of diacetone alcohol are uniformly mixed and added into a three-neck flask provided with a stirrer and a condenser, the mixture is heated to 50 ℃, the pH value of the system is adjusted to 2 by using a small amount of 0.12mol/L hydrochloric acid, then 0.83g (0.004mol) of ethyl orthosilicate is slowly added into the three-neck flask, and the mixture is reacted for 2 hours to obtain a prehydrolysis product of the ethyl orthosilicate.
(2) Uniformly mixing 1.89g (0.008mol) of gamma-glycidoxy trimethoxy silane and 0.43g (0.024mol) of deionized water, slowly adding the mixture into the prehydrolyzate obtained in the step (1), adjusting the pH to 2 by using hydrochloric acid obtained in the step (1), raising the temperature to 65 ℃, and reacting for 6 hours to obtain a hydrolysis condensation product.
(3) Slowly adding 0.88g (0.0084mol) of Diethanolamine (DEA) into the hydrolysis condensation product obtained in the step (2), and continuously reacting at 65 ℃ for 4 hours to obtain the epoxy-amine adduct.
(4) And (4) distilling off redundant amine substances in the system under reduced pressure, and standing to obtain the antifogging coating based on the organic silicon.
(5) Adding into
BL XP 2706 curing agent (purchased from Bayer company) is evenly mixed and coated with a film, and then is pre-cured at 50 ℃ and thermally cured at 135 ℃ for 1h to obtain the coating.
The silicone-based coatings obtained in examples 1 to 8 and comparative examples 1 to 2 above were subjected to a performance test, and the corresponding analytical test methods were as follows:
pencil hardness: the coated substrate is tested with a pencil of known pencil hardness at which the coating reaches that pencil hardness if no scratches are apparent, and if not, the pencil hardness is determined by replacing the pencil with the lesser pencil hardness.
Adhesion force: the adhesion of the coating was determined by the cross-cut method using a 10mm x 10mm coated substrate, cross-cut into 100 1mm x 1mm squares, tape applied to the top, and the tape pulled from the coating 3-5 times, if the coating fell off during the repeated application and pulling, the coating failed the adhesion test (here indicated as 1) and, conversely, passed the test (here indicated as 0).
Water resistance: the coated substrate is immersed in distilled water for 12h, and if the coating does not generate foaming, falling off and the like, the coating is proved to have higher water resistance, namely the test is passed, and conversely, the coating has poorer water resistance, namely the test is not passed.
Solvent resistance: the coated substrate was wiped with cotton cloth soaked with ethanol and acetone, and the number of wiping was recorded, and if the coating did not blister or damage, it indicated that the coating had good solvent resistance, i.e., the test was passed, whereas if the coating had poor solvent resistance, i.e., the test was not passed.
Transparency: transparency of the cured semi-coated coating was tested by line-of-sight imaging comparing the line-of-sight clarity of the coated versus uncoated substrate and demonstrating high transparency if no change in the color or shape of the image was observed, whereas poor transparency. To better quantify the transparency of the coating, the transmittance of the coating was tested using an ultraviolet-visible (UV-vis) spectrometer.
Breath antifogging test: the coated base material is placed at a position 1-2cm close to a human mouth, an experimenter exhales, if the surface of the base material is not fogged, the coated base material has good expiratory antifogging property, and if the surface of the base material is obviously fogged, the surface antifogging property is poor.
Steam antifogging test: the semi-coated substrate is placed in a 250mL beaker or disposable plastic cup containing hot water at 50 ℃ or directly on a hot water bath and the time required for the coated and uncoated substrate surface to be completely covered with mist is observed, if the coated substrate has a phenomenon of significantly delayed fogging, indicating that the coating has antifogging properties and the antifogging time is recorded.
The test results are given in table 1 below:
table 1: results of Performance test of each example and comparative example
As can be seen from the comparison results in Table 1, the main chain structure with Si-O bonds as repeating units is adopted, and the color and the shape of the image are not changed, namely the image has high transparency, by comparing the coated and uncoated observed images after the coating is cured; in addition, the transparency of the coating is further illustrated by a UV-vis photometer versus a coating transmittance test, which is confirmed by the test data. On one hand, the high transparency of the coating enables the antifogging performance test of the base material to have stronger reliability, namely the antifogging performance test cannot be influenced by the transparency of the coating; on the other hand, high transparency makes visual observation clearer during application. In addition, the obtained coating has good hardness, water resistance and solvent resistance, and a hydrophilic chain segment is introduced into the coating by utilizing the silane substance containing the epoxy group, so that the coating is endowed with good expiration antifogging property and steam antifogging property. As can be seen from FIG. 2, the side of the uncoated layer has no antifogging property, and the surface is obviously atomized, so that the transparency of the base material is reduced, the sight is blurred, and the presentation effect of the original pattern is influenced; one side of the coating has good antifogging property, the surface of the coating has no fogging phenomenon, the presentation effect of the original pattern is basically not influenced, and the influence on the transparency of the base material is very small. In addition, as can be seen from the test effect graph f presented in comparative example 1, under the condition without antifogging property, the surfaces of the coated and uncoated substrates are obviously fogged, the sight is blurred, and the transparency is greatly reduced.
The above embodiments are merely exemplary embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The preparation method of the antifogging coating based on the organic silicon is characterized by comprising the following steps:
(1) preparation of prehydrolyzate: uniformly mixing a solvent and water, adjusting the pH of the system to be 1.5-2.5 by using an acid, slowly dropwise adding tetraalkoxysilane into an acidic medium, and reacting for 2-3h at 50 +/-10 ℃; the solvent is one or two of diacetone alcohol and dipropylene glycol methyl ether;
(2) preparation of cohydrolytic condensate: uniformly mixing trialkoxysilane with an epoxy functional group with water, slowly dropwise adding the trialkoxysilane into the prehydrolysis product obtained in the step (1), adjusting the pH to be 1.5-2.5 by using acid, raising the temperature to 65 +/-10 ℃, and reacting for 5-6h to obtain a cohydrolysis condensation product;
(3) preparation of epoxy-amine adduct: slowly dripping an amine compound into the product obtained in the step (2), and continuously reacting for 4-5h at the temperature of 65 +/-10 ℃ to obtain an epoxy-amine addition product; the molar ratio of the amine compound to the trialkoxysilane with the epoxy functional group added in the step (2) is more than 1; the amine compound is polyether amine;
(4) preparing the organic silicon antifogging coating: removing residual amine substances in the epoxy-amine adduct obtained in the step (3) by adopting reduced pressure distillation, and standing to obtain the organic silicon antifogging coating;
the mass ratio of the solvent to the water in the step (1) is (30-40) to 1; the molar ratio of the water to the tetraalkoxysilane in the step (1) is (4-1) to 1; the molar ratio of the water to the trialkoxysilane with the epoxy functional group in the step (2) is 3: 1; the molar ratio of the tetraalkoxysilane added in the step (1) to the trialkoxysilane with an epoxy functional group added in the step (2) is 1 (2-6).
2. The method according to claim 1, wherein the tetraalkoxysilane in step (1) comprises one of ethyl orthosilicate and methyl orthosilicate.
3. The method according to claim 2, wherein the acid in step (1) (2) is one of hydrochloric acid, phosphoric acid, acetic acid and formic acid.
4. The method according to claim 3, wherein the trialkoxysilane having an epoxy functional group in the step (2) is one of gamma-glycidoxytrimethoxysilane, gamma-glycidoxytriethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, and 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane.
5. The method according to claim 4, wherein the molar ratio of the amine compound added in step (3) to the trialkoxysilane having an epoxy functional group added in step (2) is (1.05 to 1.1): 1.
6. the silicone-based anti-fog coating prepared by the method for preparing the silicone-based anti-fog coating of any one of claims 1 to 5.
7. The application of the organosilicon-based antifogging coating of claim 6, wherein the organosilicon antifogging coating is coated on a PC substrate, pre-cured in an oven at 50 +/-10 ℃ for 30 +/-10 min, and then cured for 3 +/-1 h at 110 +/-10 ℃ to obtain the organosilicon antifogging coating.
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| CN115073748A (en) * | 2022-06-29 | 2022-09-20 | 安庆中拓新材料科技有限公司 | Non-ionic water-based organic silicon resin and preparation method thereof |
| CN115322645A (en) * | 2022-09-15 | 2022-11-11 | 广东晟毅新材料科技有限公司 | Preparation method of antifogging coating |
| CN115322379A (en) * | 2022-09-19 | 2022-11-11 | 开封夸克新材料有限公司 | Epoxy modified organic silicon resin and preparation method and application thereof |
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