Preparation method and application of cationic water-based siloxane oligomer

文档序号:61951 发布日期:2021-10-01 浏览:35次 中文

阅读说明:本技术 一种阳离子型水性硅氧烷低聚物的制备方法及应用 (Preparation method and application of cationic water-based siloxane oligomer ) 是由 王祥军 张会励 王飞 张齐桓 于 2021-07-15 设计创作,主要内容包括:本申请公开了一种阳离子型水性硅氧烷低聚物的制备方法及应用,采用一元酸为催化剂,加入氨丙基三乙氧基硅烷,再加入二元、三元硅氧烷进行先水解后缩合生成含胺基水性硅氧烷低聚物。本发明产物用在双组分硅氧烷木器清漆中形成交联结构,提高了膜的干性、光泽、硬度、耐性、手感,提供了水溶性。(The application discloses a preparation method and application of a cationic waterborne siloxane oligomer. The product of the invention is used in the double-component siloxane woodenware varnish to form a cross-linked structure, thereby improving the dryness, the gloss, the hardness, the tolerance and the hand feeling of the film and providing water solubility.)

1. A method for preparing a cationic aqueous siloxane oligomer, comprising the steps of:

the first step is as follows: adding 35-50 parts of binary siloxane and 10-15 parts of ternary siloxane into 30-35 parts of aminopropyltriethoxysilane by mass parts;

the second step is that: adding a mixture of 25-30 parts of water and a monoacid catalyst at the temperature of 20-60 ℃;

the third step: stirring and reacting for more than or equal to 4 hours at the temperature of 20-60 ℃ under the protection of nitrogen;

the fourth step: adding water for dilution, removing the alcohol solvent in vacuum or heating, filtering and packaging to obtain the cationic water-based siloxane oligomer.

2. A method of preparing a cationic aqueous siloxane oligomer according to claim 1, characterized in that: the binary siloxane and the ternary siloxane are one or a combination of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane and benzyltriethoxysilane.

3. A method of preparing a cationic aqueous siloxane oligomer according to claim 1, characterized in that: the monoacid catalyst is formic acid, acetic acid, hydrochloric acid or phosphoric acid.

4. A method of preparing a cationic aqueous siloxane oligomer according to claim 1, characterized in that: the monobasic acid catalyst accounts for 10-15% of the volume of the mixture of the water and the monobasic acid catalyst, and the water accounts for 85-90% of the volume of the mixture.

5. Use of the cationic aqueous siloxane oligomer prepared by the preparation method of any one of claims 1 to 4 in water-soluble wiping agents, metal surface decorative white baking paints and wood varnishes.

6. Use according to claim 5, characterized in that the cationic aqueous siloxane oligomer is used in a water-soluble wiping agent: adding 4 parts of formic acid and 5 parts of ethanol into 40 parts of cationic water-based siloxane oligomer according to the mass part ratio, uniformly stirring, adding 0240.1 parts of defoaming agent, stirring for 5 minutes, adding 4-7.5 parts of alcohol-soluble dye, uniformly stirring, finally adding 43.4-46.9 parts of deionized water, uniformly stirring, filtering and packaging by a 400-mesh filter screen to obtain the water-soluble color wiping agent; cleaning the surface of the wood, and continuously rubbing the surface of the wood by dipping a rag with a wiping agent until the color meets the requirement; wiping the coated surface with clean rag until the texture is clear and the color is uniform; standing for 2-3 hr for drying; the dried color-coated wood is continuously coated with finish varnish on the surface or directly used, and has the function of inhibiting the expansion of ribs.

7. Use according to claim 5, characterized in that the cationic aqueous siloxane oligomer is used in a white baking paint for the decoration of metal surfaces: adding 4 parts of formic acid, 0240.2 parts of defoaming agent, 20 parts of titanium dioxide and 1 part of dispersing agent into 24 parts of cationic waterborne siloxane oligomer according to the mass part ratio, mixing and dispersing to enable the particle size to be less than 2 microns, adding 8 parts of methyl etherified amino resin, 24 parts of cationic waterborne siloxane oligomer and 5 parts of ethanol, uniformly stirring, adding 13.8 parts of deionized water, and continuously uniformly stirring to obtain the metal surface decorative white baking paint; the coating is sprayed on a clean metal surface, the thickness of a wet film is 40-50 microns, and a white decorative coating with high gloss and high hardness can be obtained after baking for 30 minutes at 140 ℃.

8. The use according to claim 5, wherein the cationic aqueous siloxane oligomer is used in wood varnish: adding 3-5 parts of formic acid, 0.1-0.2 part of defoaming agent, 0.1-0.2 part of wetting agent, 2-5 parts of ethanol and 15-30 parts of deionized water into 20-30 parts of cationic water-based siloxane oligomer according to the mass part ratio, and uniformly mixing to obtain a component A; weighing 20-30 parts of water-soluble tertiary carboxylic acid glycidyl ester resin, 10-20 parts of modified silica sol solution, 5-10 parts of glycidyl ether and 3-5 parts of alcohol ether solvent according to the mass part ratio, and uniformly mixing to obtain a component B; and weighing 35-55% of the component A and 45-65% of the component B according to the mass percentage, adding the component B into the component A, stirring for 5-10 minutes to prepare working solution, filtering the working solution, and stirring and curing the filtered working solution for 30 minutes to obtain the wood varnish.

9. The use of claim 6, wherein the alcohol soluble dye is alcohol soluble dye-red essence, alcohol soluble dye-yellow essence, alcohol soluble dye-black essence, or alcohol soluble dye-blue essence.

Technical Field

The invention belongs to the technical field of water-based siloxane oligomers, and particularly relates to a preparation method and application of a cationic water-based siloxane oligomer.

Background

The water-based paint is an important means for reducing PM2.5 due to greenhouse effect, the consumption of the wood lacquer in 2019 all the year around is 170 ten thousand tons, wherein the proportion of the water-based wood lacquer is less than 10%, the average Volatile Organic Compounds (VOC) per ton of 90% solvent wood lacquer accounts for 50-60%, and 80 ten thousand tons of volatile organic compounds are discharged to the atmosphere in the year. Such serious pollution is highly appreciated by the countries, and regulations gradually limit the amount of VOC emissions, and politically encourages support for the progress of coating wateriness. The water-based work of the wood paint is vigorously developed by various domestic paint factories.

The traditional oily wood lacquer obtains long-term market recognition by the characteristics of high fullness, high hardness, quick drying and low cost, and the waterborne wood lacquer can be recognized by the market only by achieving the appearance effect of solvent type products, so that the waterborne wood lacquer can be truly replaced, and the waterborne wood lacquer is favored by wide consumers.

The water-borne wood varnish which is commercialized at present comprises water-borne two-component polyurethane varnish consisting of a polyurethane curing agent and a hydroxyl polymer, and single-component varnish consisting of acrylic emulsion and isocyanate dispersion. The water-based two-component polyurethane has the advantages that the comprehensive performance is more acceptable by the market, the appearance effect and the hardness are not inferior to those of a solvent type polyurethane, and the defects of low construction solid content, long curing time, limited organic matters and free isocyanic acid are overcome. The acrylic emulsion and the isocyanate dispersion can not be a substitute of high-grade wood varnish in the true sense on the whole, and have a certain distance in hardness, gloss and medium resistance. The product of the invention is added into a double-curing siloxane waterborne wood varnish, and has the effects of increasing curing property, improving construction solid content, wetting wood surface and blocking the rib expansion phenomenon caused by tannic acid in a system. The wood varnish is a dual-component water-based wood varnish, the organic volatile content of the product is low, the construction is carried out with high solid content, and the varnish film has high gloss, high hardness, good visualization and clearness; the harmful substance is zero, and the paint does not contain isocyanate component, formaldehyde, metal catalyst and free isocyanic acid radical; the product is quick to dry and short in curing period, and can be used after 48 hours. Is a waterborne product of woodenware varnish and home decoration materials.

The wood has wide application and various textures, so that the coating has high demand and high performance requirement. Wood aspects include softwood, hardwood; the wood materials have different strength, texture, grease and water absorption, and coating defects such as rib expansion, light loss, whitening, oil return, collapse, cracking and the like are often caused. Because water has extremely strong wettability to wood, the defects of the coating films are further amplified in the process of adopting the water-based wood paint, and the technical difficulty of water-based wood paint is increased. The water-based paint is usually realized by changing the state of the paint and changing the polarity of the paint. The state comprises a water-soluble type, an emulsion type, a suspension type or a mixture of the three types; the polarity includes anion, cation, and non-ion. These water-based methods are more or less limited for wood, and defects such as swelling, oil returning, and collapse occur more frequently.

Disclosure of Invention

The technical problem to be solved is as follows: the application mainly provides a preparation method and application of a cationic water-based siloxane oligomer, and solves the technical problems of low construction solid content, long curing time, limited organic matter content, free isocyanic acid and the like in the prior art. The technical scheme is as follows:

a method for preparing a cationic aqueous siloxane oligomer comprising the steps of:

the first step is as follows: adding 35-50 parts of binary siloxane and 10-15 parts of ternary siloxane into 30-35 parts of aminopropyltriethoxysilane by mass parts;

the second step is that: adding a mixture of 25-30 parts of water and a monoacid catalyst at the temperature of 20-60 ℃;

the third step: stirring and reacting for more than or equal to 4 hours at the temperature of 20-60 ℃ under the protection of nitrogen;

the fourth step: adding water for dilution, removing the alcohol solvent in vacuum or heating, filtering and packaging to obtain the cationic water-based siloxane oligomer.

As a preferred technical scheme of the invention: the binary siloxane and the ternary siloxane are one or a combination of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane and benzyltriethoxysilane.

As a preferred technical scheme of the invention: the monoacid catalyst is formic acid, acetic acid, hydrochloric acid or phosphoric acid.

As a preferred technical scheme of the invention: the monobasic acid catalyst accounts for 10-15% of the volume of the mixture of the water and the monobasic acid catalyst, and the water accounts for 85-90% of the volume of the mixture.

The invention also discloses application of the cationic water-based siloxane oligomer prepared by the preparation method in water-soluble wiping dyes, metal surface decoration white baking paint and wood varnish.

As a preferred technical scheme of the invention: the application of the cationic water-based siloxane oligomer in the water-soluble wiping agent is as follows: adding 4 parts of formic acid and 5 parts of ethanol into 40 parts of cationic water-based siloxane oligomer according to the mass part ratio, uniformly stirring, adding 0.1 part of defoaming agent, stirring for 5 minutes, adding 4-7.5 parts of alcohol-soluble dye, uniformly stirring, finally adding 43.4-46.9 parts of deionized water, uniformly stirring, filtering and packaging by a 400-mesh filter screen to obtain the water-soluble color wiping agent; cleaning the surface of the wood, and continuously rubbing the surface of the wood by dipping a rag with a wiping agent until the color meets the requirement; wiping the coated surface with clean rag until the texture is clear and the color is uniform; standing for 2-3 hr for drying; the dried color-coated wood is continuously coated with finish varnish on the surface or directly used, and has the function of inhibiting the expansion of ribs.

As a preferred technical scheme of the invention: the application of the cationic water-based siloxane oligomer in the metal surface decorative white baking paint is as follows: adding 4 parts of formic acid, 0.2 part of defoaming agent, 20 parts of titanium dioxide and 1 part of dispersing agent into 24 parts of cationic waterborne siloxane oligomer according to the mass part ratio, dispersing to enable the particle size to be less than 2 microns, adding 8 parts of methyl etherified amino resin, 24 parts of cationic waterborne siloxane oligomer and 5 parts of ethanol, uniformly stirring, adding 13.8 parts of deionized water, and continuously uniformly stirring to obtain metal surface decorative white baking paint; the coating is sprayed on a clean metal surface, the thickness of a wet film is 40-50 microns, and a white decorative coating with high gloss and high hardness can be obtained after baking for 30 minutes at 140 ℃.

As a preferred technical scheme of the invention: the application of the cationic water-based siloxane oligomer in the wood varnish is as follows: adding 3-5 parts of formic acid, 0.1-0.2 part of defoaming agent, 0.1-0.2 part of wetting agent, 2-5 parts of ethanol and 15-30 parts of deionized water into 20-30 parts of cationic water-based siloxane oligomer according to the mass part ratio, and uniformly mixing to obtain a component A; weighing 20-30 parts of water-soluble tertiary carboxylic acid glycidyl ester resin, 10-20 parts of modified silica sol solution, 5-10 parts of glycidyl ether and 3-5 parts of alcohol ether solvent according to the mass part ratio, and uniformly mixing to obtain a component B; and weighing 35-55% of the component A and 45-65% of the component B according to the mass percentage, adding the component B into the component A, stirring for 5-10 minutes to prepare working solution, filtering the working solution, and stirring and curing the filtered working solution for 30 minutes to obtain the wood varnish.

As a preferred technical scheme of the invention: the alcohol soluble dye is alcohol soluble dye-red essence, alcohol soluble dye-yellow essence, alcohol soluble dye-black essence or alcohol soluble dye-blue essence.

Has the advantages that: compared with the prior art, the preparation method of the cationic water-based siloxane oligomer has the following technical effects by adopting the technical scheme:

1. the double-curing siloxane waterborne wood varnish is added into a double-curing siloxane waterborne wood varnish, and has the effects of increasing the curing property, improving the construction solid content, wetting the surface of wood and preventing the rib expansion phenomenon caused by tannic acid in a system. The wood varnish is a dual-component water-based wood varnish, the organic volatile content of the product is low, the construction is carried out with high solid content, and the varnish film has high gloss, high hardness, good visualization and clearness; the harmful substance is zero, and the paint does not contain isocyanate component, formaldehyde, metal catalyst and free isocyanic acid radical; the product is quick to dry and short in curing period, and can be used after 48 hours. Is a waterborne product of woodenware varnish and home decoration materials.

2. The varnish is composed of a three-layer coating structure of wiping, back sealing and finishing, and can be singly used or matched according to the actual use condition.

3. The clarity and the light transmittance of the coating film can be improved by 2 percent, and the stereoscopic impression of wood textures is enhanced; the coating film has high hardness, and can reach 3H pencil hardness on hardwood; the coating film has low surface tension and self-cleaning function.

4. The coating overcomes the hidden environmental-friendly defects that the currently commonly adopted waterborne double-component polyurethane woodenware varnish contains free isocyanate, contains a metal catalyst and a ketone solvent.

5. The coating film overcomes the defect that the currently commonly adopted single-component Polyurethane (PUD) cannot form high definition. The coating overcomes the defects of easy stain, low hardness and low construction solid content of the woodware varnish prepared from the water-soluble acrylic resin or acrylic emulsion.

6. The product of the patent technology can be used as color spreading carrier resin of a color wiping agent, and is suitable for decoration requirements of wood, metal, glass, stone, fingernails and partial plastic surfaces. The product of the invention forms a three-dimensional film structure in the dual-component woodenware varnish through a cross-linking reaction with an epoxy group, and shows a series of characteristics of high gloss, high energy hardness, medium resistance, abrasion resistance and the like.

Detailed Description

A method for preparing a cationic aqueous siloxane oligomer comprising the steps of:

the first step is as follows: adding 35-50 parts of binary siloxane and 10-15 parts of ternary siloxane into 30-35 parts of aminopropyltriethoxysilane by mass parts;

the second step is that: adding a mixture of 25-30 parts of water and a monoacid catalyst at the temperature of 20-60 ℃;

the third step: stirring and reacting for more than or equal to 4 hours at the temperature of 20-60 ℃ under the protection of nitrogen;

the fourth step: adding water for dilution, removing the alcohol solvent in vacuum or heating, filtering and packaging to obtain the cationic water-based siloxane oligomer.

The binary siloxane and the ternary siloxane are one or a combination of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane and benzyltriethoxysilane.

The monoacid catalyst is formic acid, acetic acid, hydrochloric acid or phosphoric acid.

The monobasic acid catalyst accounts for 10-15% of the volume of the mixture of the water and the monobasic acid catalyst, and the water accounts for 85-90% of the volume of the mixture.

Example 1

The application of the cationic water-based siloxane oligomer in the water-soluble wiping agent is as follows: adding 4 parts of formic acid and 5 parts of ethanol into 40 parts of cationic water-based siloxane oligomer according to the mass part ratio, uniformly stirring, adding 0240.1 parts of defoaming agent, stirring for 5 minutes, adding 4-7.5 parts of alcohol-soluble dye, uniformly stirring, finally adding 43.4-46.9 parts of deionized water, uniformly stirring, filtering and packaging by a 400-mesh filter screen to obtain the water-soluble color wiping agent; cleaning the surface of the wood, and continuously rubbing the surface of the wood by dipping a rag with a wiping agent until the color meets the requirement; wiping the coated surface with clean rag until the texture is clear and the color is uniform; standing for 2-3 hr for drying; the dried color-coated wood is continuously coated with finish varnish on the surface or directly used, and has the function of inhibiting the expansion of ribs.

Example 2

The application of the cationic water-based siloxane oligomer in the metal surface decorative white baking paint is as follows: adding 4 parts of formic acid, 0240.2 parts of defoaming agent, 20 parts of titanium dioxide and 1 part of dispersing agent into 24 parts of cationic waterborne siloxane oligomer according to the mass part ratio, mixing and dispersing to enable the particle size to be less than 2 microns, adding 8 parts of methyl etherified amino resin, 24 parts of cationic waterborne siloxane oligomer and 5 parts of ethanol, uniformly stirring, adding 13.8 parts of deionized water, and continuously uniformly stirring to obtain the metal surface decorative white baking paint; the coating is sprayed on a clean metal surface, the thickness of a wet film is 40-50 microns, and a white decorative coating with high gloss and high hardness can be obtained after baking for 30 minutes at 140 ℃.

Example 3

The application of the cationic water-based siloxane oligomer in the wood varnish is as follows: adding 3-5 parts of formic acid, 0.1-0.2 part of defoaming agent, 0.1-0.2 part of wetting agent, 2-5 parts of ethanol and 15-30 parts of deionized water into 20-30 parts of cationic water-based siloxane oligomer according to the mass part ratio, and uniformly mixing to obtain the component A.

B, component B:

weighing 20-30 parts of water-soluble tertiary carboxylic acid glycidyl ester resin, 10-20 parts of modified silica sol solution, 5-10 parts of glycidyl ether and 3-5 parts of alcohol ether solvent according to the mass part ratio, and uniformly mixing to obtain a component B; and weighing 35-55% of the component A and 45-65% of the component B according to the mass percentage, adding the component B into the component A, stirring for 5-10 minutes to prepare working solution, filtering the working solution, and stirring and curing the filtered working solution for 30 minutes to obtain the wood varnish.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.

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