阅读说明：本技术 一种疏水涂层材料及其制备方法和应用 (Hydrophobic coating material and preparation method and application thereof ) 是由 吴永玲 于 2021-02-26 设计创作，主要内容包括：本方法公开了一种疏水涂层材料的制备方法,包括：1)将与第一组份对应的氨基硅烷于水中水解,得到第一组份的水溶液；2)将与第二组份对应的氟碳硅烷于醇溶剂中水解,得到第二组份的醇溶液；3)将第一组份的水溶液与第二组份的醇溶液混合均匀,得到混合溶液,即得疏水涂层材料；其中,所述第一组分为至少含有一种伯胺基团的氨基硅醇；第二组份为氟碳链不超过6的氟硅醇。本发明还提供了疏水涂层材料及其应用。织物表面提供一步喷涂涂层,提供了即时的疏水和防水性能。(The method discloses a preparation method of a hydrophobic coating material, which comprises the following steps: 1) hydrolyzing aminosilane corresponding to the first component in water to obtain an aqueous solution of the first component; 2) hydrolyzing the fluorocarbon silane corresponding to the second component in an alcohol solvent to obtain an alcohol solution of the second component; 3) uniformly mixing the aqueous solution of the first component and the alcoholic solution of the second component to obtain a mixed solution, namely the hydrophobic coating material; wherein the first component is an aminosilicol containing at least one primary amine group; the second component is fluorine silanol with a fluorine carbon chain not more than 6. The invention also provides a hydrophobic coating material and application thereof. The fabric surface provides a one-step spray coating that provides instant hydrophobic and water-repellent properties.)

1. A method for preparing a hydrophobic coating material, comprising:

1) hydrolyzing aminosilane corresponding to the first component in water to obtain an aqueous solution of the first component;

2) hydrolyzing the fluorocarbon silane corresponding to the second component in an alcohol solvent to obtain an alcohol solution of the second component;

3) uniformly mixing the aqueous solution of the first component and the alcoholic solution of the second component to obtain a mixed solution, namely the hydrophobic coating material;

wherein the first component is an aminosilicol containing at least one primary amine group; the second component is fluorine silanol with a fluorine carbon chain not more than 6.

2. The method of claim 1, further comprising:

4) and distilling the mixed solution, and concentrating to obtain a concentrated solution with a volume of 20-52% of the original mixed solution.

3. The method of preparing the hydrophobic coating material of claim 1 wherein the first component has the formula i

Wherein the content of the first and second substances,

R₁selected from-OH, -Cl, -OCH₃or-OCH₂CH₃；

R₂Selected from-OH, -Cl, -OCH 3, or-OCH 2CH 3;

x is selected from-C₃H₆-, or-CnH₂n–NH–C₃H₆-, n is 1, 2 or 3.

4. The method of preparing a hydrophobic coating material of claim 1 wherein the second component has the formula II,

wherein:

R₃is-OH, -Cl, -OCH₃or-OCH₂CH₃；

R₄Selected from-OH, -Cl, -OCH₃or-OCH₂CH₃；

m is 0, 1 or 2;

x is 1, 2, 3, 4, 5 or 6;

y＝3-13。

5. the method of preparing a hydrophobic coating material according to claim 1 wherein the first component is present in the aqueous solution in an amount of from 2 wt% to 30 wt%.

6. The method of preparing a hydrophobic coating material according to claim 1 wherein the second component is present in an alcohol solution in an amount of 0.8 to 12% by weight.

7. The method of preparing a hydrophobic coating material according to claim 1, wherein the mass ratio of the aqueous solution of the first component to the alcoholic solution of the second component is 1: 0.18-2.5; preferably, the alcohol solvent is selected from ethanol, isopropanol, methanol or 1-methoxy-2-propanol, or a mixed solvent formed by mixing two or more of the alcohol solvents in any ratio.

8. The hydrophobic coating material is characterized by comprising 2-30 wt% of amino silanol, 0.8-12 wt% of fluorosilicone, 0-25 wt% of organic alcohol solvent, and the balance of water and additives; wherein the aminosilicol contains at least one primary amine functional group; the length of the fluorocarbon chain of the fluorosilicone alcohol is not more than 6; the additive is selected from an auxiliary agent or a bacteriostatic agent for increasing the softness of the fabric, and the content of the additive accounts for 2-30 wt% of the total weight of the solution;

preferably, the hydrophobic coating material is prepared according to the preparation method of any one of claims 1 to 7.

9. A method of preparing a hydrophobic coating on a substrate surface, comprising: the hydrophobic coating material of claim 8 is used for wetting the surface of a base material by spraying or soaking, and the hydrophobic coating material is obtained after drying and curing;

preferably, the substrate is a fabric; more preferably, the hydrophobic coating material is diluted 1-10 times with distilled water before use; further preferably, the curing time is 1 to 24 hours if the drying and curing are carried out at normal temperature, and the curing time is 3 to 30 minutes if the drying and curing are carried out at 60 to 150 ℃.

10. A material having a hydrophobic surface, prepared by the method of claim 9.

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to a composition for preparing an inorganic-organic composite water-based coating, and a preparation method and application thereof.

Background

Most of the existing hydrophobic fabric coating technologies are based on organic high molecular materials, such as: the alkyl or partial fluoroalkyl high molecular material is dissolved in organic solvent and coated or compounded with fabric to form hydrophobic fabric. Solvent-based coatings are limited in industrial application due to the problems of environmental pollution caused by volatile harmful gases present in the solvent-based coatings, and the control and regulatory limitations of solvent-based coatings in many countries and regions. On the contrary, the hydrophobic coating material has higher technical value in practical application due to the characteristics of relative environmental protection and non-flammability. Water-soluble hydrophobic fabric coatings can be divided into three categories according to the prior art: the first type is encapsulation and delivery of hydrophobic substances in aqueous phase by forming an oil emulsion in water; the second is by synthesizing a water-soluble polymer with hydrophobic sectors in each polymer chain; the third category is the preparation of hydrophobic coatings by preparing aqueous dispersion solutions of hydrophobic nanoparticles.

Based on the technique of forming an oil emulsion in water, an emulsifier (surfactant) is generally left on the surface of the coating after drying, which may have adverse effects on the environment and may reduce the effectiveness of reapplication of the coating due to accumulation on the substrate. The technology based on water-soluble hydrophobic polymers avoids environmental problems caused by the use of emulsifiers, but due to the softness of the polymers, the adhesion to the fabric surface is weak and the durability is low. For techniques relying on water to disperse hydrophobic nanoparticles, most cannot produce a clear coating. In addition, the adhesion between the nanoparticles and the fabric is low, so that the coating particles are easy to fall off from the surface of the fabric, and the nanoparticle pollution can be caused to a human body.

In particular, to enhance the adhesion between hydrophobic substances and the fabric, one or more base coatings are often introduced by providing a plurality of coatings. Or the fabric must be soaked in the coating solution for a sufficient time to ensure effective adhesion of the hydrophobic substance to the fabric surface. However, the two coating methods have the disadvantages of complex coating process, large material consumption and the like.

Water-soluble hydrophobic solutions require longer drying times due to the low solubility of hydrophobic additives in water, and it is more difficult to formulate stable water-based solutions than solvent-based solutions.

In addition, the toxic components of coating formulations, especially fluorochemicals commonly used in the prior art, such as long chain perfluoroalkyl groups (longer than C6), pose a wide environmental concern due to unfavorable bioaccumulation rates and decomposition to perfluoroacid, posing a toxic threat to humans. Therefore, in order to ensure the environmental safety, the formula must use a fluorine-free component or a short-chain fluorocarbon alkyl material, which is also a technical problem to be solved by the current sofa hydrophobic coating.

Disclosure of Invention

Aiming at the defects of the solvent-type hydrophobic coating in the prior art and meeting the requirements of hydrophobic coating materials, the invention develops the material for generating the coating on the surface of the fabric by a coating spraying or soaking method.

The technical problem of the invention can be solved by the following technical scheme:

a method of preparing a hydrophobic coating material, comprising:

1) hydrolyzing aminosilane corresponding to the first component in water to obtain an aqueous solution of the first component;

2) hydrolyzing the fluorocarbon silane corresponding to the second component in an alcohol solvent to obtain an alcohol solution of the second component;

3) uniformly mixing the aqueous solution of the first component and the alcoholic solution of the second component to obtain a mixed solution, namely the hydrophobic coating material;

wherein the first component is an aminosilicol containing at least one primary amine group; the second component is fluorine silanol with a fluorine carbon chain not more than 6.

In one embodiment according to the present invention, further comprising:

4) and distilling the mixed solution, and concentrating to obtain a concentrated solution with a volume of 20-52% of the original mixed solution.

In one embodiment according to the present invention, the first component has the formula I,

wherein the content of the first and second substances,

R₁selected from-OH, -Cl, -OCH₃or-OCH₂CH₃；

R₂Selected from-OH, -Cl, -OCH₃,or–OCH₂CH₃；

X is selected from-C₃H₆-, or-CnH₂n–NH–C₃H₆-, n is 1, 2 or 3.

In one embodiment according to the present invention, the second component has the formula II,

wherein:

R₃is-OH, -Cl, -OCH₃or-OCH₂CH₃；

R₄Selected from-OH, -Cl, -OCH₃or-OCH₂CH₃；

m is 0, 1 or 2;

x is 1, 2, 3, 4, 5 or 6;

y＝3-13。

in one embodiment according to the invention, the content of the first component in the aqueous solution is from 2 wt% to 30 wt%.

In one embodiment according to the invention, the content of the second component in the alcohol solution is 0.8 wt% to 12 wt%.

In one embodiment according to the present invention, the mass ratio of the aqueous solution of the first component to the alcoholic solution of the second component is 1: 0.18-2.5; preferably, the alcohol solvent is selected from ethanol, isopropanol, methanol or 1-methoxy-2-propanol, or a mixed solvent formed by mixing two or more of the alcohol solvents in any ratio.

The invention also discloses a hydrophobic coating material, which comprises 2 to 30 weight percent of amino-containing silanol, 0.8 to 12 weight percent of fluorosilicone, 0 to 25 weight percent of organic alcohol solvent, and the balance of water and additives; wherein the aminosilicol contains at least one primary amine functional group; the length of the fluorocarbon chain of the fluorosilicone alcohol is not more than 6; the additive is selected from an auxiliary agent or a bacteriostatic agent for increasing the softness of the fabric, and the content of the additive accounts for 2-30 wt% of the total weight of the solution; (1) the textile flexibility-increasing assistant can be organic silicone oil, hydroxyl silicone oil, polyurethane aqueous solution, etc. (2) organic compound (such as quaternary amine compound, polyimidazolium salt, etc.) with bactericidal function or inorganic nano-particles (compound solution containing silver ion, nano-zinc oxide solution, nano-titanium oxide solution, mesoporous nano-silica particle carrying slow-release organic bactericidal salt solution, and their mixed and hybridized material).

Preferably, the hydrophobic coating material is prepared according to the preparation method.

The invention further discloses a method for preparing the hydrophobic coating on the surface of the substrate, which comprises the following steps: soaking the surface of the base material by using the hydrophobic coating material through spraying or soaking, and drying and curing to obtain the coating material;

preferably, the substrate is a fabric; more preferably, prior to use, the hydrophobic coating material is diluted 1-10 times with distilled water; further preferably, the curing time is 1 to 24 hours if the drying and curing are carried out at normal temperature, and the curing time is 3 to 30 minutes if the drying and curing are carried out at 60 to 150 ℃.

The invention also provides a material with the hydrophobic surface, which is prepared by the method.

The invention has the beneficial effects that:

the hydrophobic coating material provided by the invention is nonflammable, high in safety and more convenient to use.

The coating solution provided by the invention can be diluted by water and applied to all fabrics by spraying or soaking, can be dried in air and provides remarkable hydrophobic and oil-proof properties. The hydrophobic coating material provided by the invention can provide a one-step spraying coating for all wearable fabric surfaces, and provides instant hydrophobic and waterproof performances. This simplifies the coating process, reduces material consumption, is a manufacturing process suitable for large scale applications and is cost effective.

On one hand, the hydrophobic coating formed by the hydrophobic coating material can be directly dried in the atmospheric environment, and can be used by consumers in daily life; on the other hand, hydrophobic coatings are also capable of rapid curing at high temperatures within minutes, which results in more efficient manufacturing cycles for industrial applications.

The hydrophobic coating materials disclosed herein will form a transparent hydrophobic coating on a textile substrate. Thus, the hydrophobic coating does not change the color appearance of the fabric. The coated fabric can withstand 5-10 washes and can be subsequently reapplied and the substrate fabric can be reused.

Drawings

FIG. 1: after the pure cotton cloth is coated, (a) the water contact angle is 142.5 degrees; (b) oil contact angle was 138.5 °;

FIG. 2: photographs after 2 minutes of water droplets (left) and oil droplets (right) on a pure cotton cloth coated with the hydrophobic coating of the present invention;

FIG. 3: photos of coffee droplets (left) and water droplets (right) after the wool blended fabric was coated, leaving no trace after tilting;

FIG. 4: photographs of ink (left) and water (right) drops after carpet application, no trace left after tilting;

FIG. 5: performance display of hydrophobic oleophobic easy-to-clean coating, left: respectively dripping black soy sauce, coffee, chili sauce and soy sauce onto the coated cloth and the uncoated cloth; and (3) right: after washing with clear water for 10 seconds, the pictures show that the coated cloth leaves no trace, and no obvious stain is left on the coated cloth.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

Example 1:

an aqueous solution of aminosilicone was prepared by hydrolyzing 3-aminopropyltriethoxysilane (APTES, Sigma Aldrich) in water overnight. The weight ratio of the 3-aminopropyltriethoxysilane to the water is 1: 3.6. subsequently, an isopropyl alcohol solution containing 5 wt% of fluorosilane was dropped into the aqueous solution of aminosilicone while continuously stirring the aqueous solution of aminosilicone. Controlling the volume ratio of the fluorosilane isopropanol solution to the amino silanol aqueous solution to be 1: 4. after stirring for 1 hour, the mixture was sprayed onto the cotton fabric until the fabric was completely wet. The coated cotton fabric was then dried in an atmospheric environment for 3 hours. The contact angle of a 0.5 mul water drop was measured to be 142.5 deg. and the contact angle of a 0.5 mul vegetable oil was measured to be 138.5 deg. on a dry coated cotton fabric. The contact angle measurement image is shown in fig. 1.

Example 2

An aqueous solution of aminosilicone was prepared by hydrolyzing 3-aminopropyltriethoxysilane (APTES, Sigma Aldrich) in water overnight. The weight ratio of the 3-aminopropyltriethoxysilane to the water is 1: 18. subsequently, while the aqueous aminosilicone solution was kept under stirring, 10ml of an isopropyl alcohol solution containing 5 wt% of fluorosilane was dropped into the prepared aqueous aminosilicone solution. After stirring for 1 hour, the mixture was distilled at 50 ℃/120mb for about 15 minutes, and the volume of the remaining solution was 25 ml. Then, one cotton fabric was soaked in the remaining solution for 3 minutes, and then the coated cotton fabric was dried in an oven at 100 degrees celsius for 3 minutes. The contact angle of 2 mul water drops was measured to be 144.5 deg. and the contact angle of 2 mul vegetable oil was measured to be 139.2 deg. on the dried coated cotton fabric. After the drop of water and oil remained on the cloth for 2 minutes, the contact angle did not change, as shown in fig. 2.

Example 3

An aqueous solution of aminosilicone was prepared by hydrolyzing 3-aminopropyltriethoxysilane (APTES, Sigma Aldrich) in water overnight. The weight ratio of the 3-aminopropyltriethoxysilane to the water is 1: 1.8. subsequently, 3g of water was added to 11 g of the prepared aqueous solution of aminosilicone while maintaining the stirring state of the aqueous solution. Then, 23g of an isopropanol solution of 5 wt% fluorosilane was added dropwise to the aqueous solution. After stirring for 1 hour, the mixture was distilled at 50 ℃/170mb for about 25 minutes, and the weight of the remaining solution was 9 g. Then 2 grams of the solution in the remaining solution was diluted with 18 grams of water. After uniform mixing, the diluted solution was sprayed onto the wool-nylon blend fabric until the fabric was completely wet, and then dried in an oven at 100 ℃ for 20 minutes. Contact angles of 2 μ L coffee and water droplets were measured on the dried coated denim fabric, 145 ° and 142.4 °, respectively, as shown in fig. 3.

Example 4

An aqueous solution of aminosilicone was prepared by hydrolyzing 3-aminopropyltriethoxysilane (APTES, Sigma Aldrich) in water overnight. The weight ratio of the 3-aminopropyltriethoxysilane to the water is 1: 3.6. adding a few drops of acetic acid/acetic acid into the solution, adjusting the pH value of the solution to 3-4, then adding 5% by weight of hydroxyl silicone oil (molecular weight is between 550 and 2000) into the solution, fully mixing the solution uniformly (stirring by magnetic force for 2-4 hours or more), then uniformly spraying the solution on a carpet, and drying in an oven at 100 ℃ for 20 minutes. The contact angles of 10 μ L of ink drop and water drop were measured as 165 ° and 160 °, respectively, as shown in fig. 4. These droplets roll down automatically as the carpet tilts, leaving no marks on the carpet surface.

Example 5

A diluted hydrophobic solution was prepared using the same formulation as described in example 3. The polyester/cotton blend fabric (65% polyester and 35% cotton) was soaked in the solution until the fabric was completely wet, and then the coated polyester/cotton blend fabric was dried in an atmospheric environment for 2 hours. The contact angle of a 2 mul drop of water was measured to be 151.1 deg. on the coated polyester/cotton blend fabric after being completely dried. The coated cloths were then tested for easy-to-clean performance with black soy sauce, coffee, chili paste, soy sauce, respectively. Fig. 5 shows photographs of the coated and uncoated cloths after dropping black soy sauce, coffee, chili paste, soy sauce, and after washing with clear water for 10 seconds, respectively, showing that the coated cloth left no mark, while the uncoated cloth left a significant stain.

Example 6:

the weight ratio of 3-aminopropyltriethoxysilane to water described in example 4 was 1: 3.6 adding silver nanoparticles (particle diameter is 10-20 nm), and 2-aminoethyl-3-aminopropyltrimethoxysilane (DAMO) is used as a capping agent to avoid silver ion precipitation. Silver nanoparticles were combined with a DAMO capping agent at a ratio of 1: 3, a stable silver-doped sol-gel solution can be obtained and can be stored for a long time without precipitating silver particles. The concentrations of silver nanoparticles were set at 5ppm,50ppm, and 250ppm, respectively. Then, the antibacterial property was measured using Escherichia coli and Staphylococcus aureus by JIS Z2801. Table 1 shows the antibacterial effect of the nanosilver containing coating: when the concentration of the silver nanoparticles in the coating reaches 50ppm, the killing rate of staphylococcus aureus and escherichia coli reaches 99.9%, and a sufficient sterilization effect is achieved. When the coating contains 250ppm of nano-silver, the killing rate of staphylococcus aureus reaches 99.999 percent, the killing rate of escherichia coli reaches 99.99 percent, and the coating has a very strong sterilization effect.

Table 1: antibacterial effect of coating containing nano silver

Example 7:

the weight ratio of 3-aminopropyltriethoxysilane to water described in example 4 was 1: 3.6 adding zinc oxide nano particles (with the particle diameter of 10-30 nanometers) into the solution, and measuring the antibacterial effect, wherein the content of zinc oxide is 2-10%. In another experiment, silver ions were doped into a zinc oxide solution while synthesizing zinc oxide nanoparticles, with a silver to zinc oxide weight ratio in the range of 2-5%, and then an antibacterial effect test was also performed. Due to the photocatalytic property of zinc oxide, the two types of samples were also subjected to ultraviolet irradiation sterilization, activation of the surface photosensitivity of ZnO, followed by sterilization property measurement. Table 2 shows the antimicrobial effect of coatings containing zinc oxide and silver doped zinc oxide: the sterilization rate measured after the alcohol sterilization is 98-99%, the sterilization performance is greatly improved after the ultraviolet sterilization, the sterilization rate of the coating containing 5% of ZnO reaches 99.95%, and the sterilization capability of the coating is improved by 1000 times and reaches 99.9999% by using silver as chemical doping of ZnO.

Table 2: antibacterial Effect of coating containing Nano Zinc oxide and silver-doped Nano Zinc oxide (tested with E.coli)

Example 8:

the weight ratio of 3-aminopropyltriethoxysilane to water described in example 4 was 1: 3.6, adding 2-5% of mesoporous silica nanoparticles (the particle diameter is 30-50 nanometers), wherein the mesoporous size is 2.5nm, 2-5% of polyimidazolium salt (PIM) is carried in the mesopores, the polyimidazolium salt is synthesized autonomously, and the molecular weight is 45. Table 3 shows the antibacterial effect of the coating containing nanosilica and polyimidazolium salts: the combination of the silicon dioxide and the PIM has the bactericidal rate reaching 99.997 percent.

Table 3: antibacterial Effect of coatings containing Nano-silica particles and polyimidazolium salt (PIM) (test with E.coli)

Silica particle content	PIM content	Rate of sterilization
			2％	2％	99.997％
3％	2％	99.997％
			2％	5％	99.997％

The above examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention; it should be noted that various changes and modifications can be made by those skilled in the art without departing from the scope of the inventive concept, which falls within the scope of the invention; therefore, all equivalent changes and modifications within the scope of the claims of the present invention should be covered by the claims of the present invention.