阅读说明：本技术 一种水溶性叔碳酸缩水甘油酯树脂的制备方法及应用 (Preparation method and application of water-soluble glycidyl versatate resin ) 是由 张齐恒 张会励 王飞 王祥军 于 2021-07-15 设计创作，主要内容包括：本申请公开了一种水溶性叔碳酸缩水甘油酯树脂的制备方法及应用,使用二元有机酸、三元有机酸、叔碳酸缩水甘油酯、γ―(2,3-环氧丙氧)丙基三甲氧基硅烷、2-咪唑烷酮或N-羟乙基-2-咪唑烷酮、丙二醇甲醚或二丙二醇二甲醚、乙醇或异丙醇、丁醇、丙二醇甲醚、去离子水,反应生成分子量在1000～2000的留有活性羧基基团、活性缩水甘油醚基团的水溶型聚合物,即水溶性叔碳酸缩水甘油酯树脂。该水溶性叔碳酸缩水甘油酯树脂对颜料有润湿效果,对木质中的单宁酸有抑制作用,在双组分硅氧烷木器清漆中有提高施工固体成分,参加交联反应功能。(The application discloses a preparation method and application of water-soluble glycidyl versatate resin, which comprises the steps of using binary organic acid, ternary organic acid, glycidyl versatate, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 2-imidazolidinone or N-hydroxyethyl-2-imidazolidinone, propylene glycol methyl ether or dipropylene glycol dimethyl ether, ethanol or isopropanol, butanol, propylene glycol methyl ether and deionized water to react to generate a water-soluble polymer which has a molecular weight of 1000-2000 and is provided with an active carboxyl group and an active glycidyl ether group, namely the water-soluble glycidyl versatate resin. The water-soluble tert-carbonic acid glycidyl ester resin has a wetting effect on pigments, has an inhibiting effect on tannic acid in wood, and has a function of improving construction solid components and participating in a crosslinking reaction in the double-component siloxane wood varnish.)

1. A preparation method of water-soluble glycidyl versatate resin is characterized by comprising the following steps:

the first step is as follows: adding propylene glycol methyl ether or dipropylene glycol dimethyl ether into one or two of phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride and citric acid, and adding tert-carbonic acid glycidyl ester and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane at the temperature of 20-80 ℃;

the second step is that: heating to 120-200 ℃, and reacting for 1-4 hours;

the third step: cooling to 60-90 ℃, adding 2-imidazolidinone or N-hydroxyethyl-2-imidazolidinone, and reacting at 60-90 ℃ for 1-3 hours;

the fourth step: adding ethanol, isopropanol, butanol, propylene glycol monomethyl ether or deionized water, and filtering to obtain the water-soluble tert-carbonic acid glycidyl ester resin.

2. The method for producing a water-soluble glycidyl versatate resin according to claim 1, characterized in that: under the condition that the total molar number of one or two of the phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride and citric acid is 1, the addition ratio of the tertiary carbonic acid glycidyl ester to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 1-3 g, and the addition amount of the propylene glycol methyl ether or the dipropylene glycol dimethyl ether is 10-15% of the weight of one or two of the phthalic anhydride, the tetrahydrophthalic anhydride, the trimellitic anhydride and the citric acid.

3. The method for producing a water-soluble glycidyl versatate resin according to claim 1, characterized in that: and under the condition that the total molar number of one or two of the phthalic anhydride, the tetrahydrophthalic anhydride, the trimellitic anhydride and the citric acid is 1, the adding amount of the 2-imidazolidinone or the N-hydroxyethyl-2-imidazolidinone is 0.2 to 1.5 gram molecule.

4. The method for producing a water-soluble glycidyl versatate resin according to claim 1, characterized in that: the addition amount of the ethanol, the isopropanol, the butanol, the propylene glycol methyl ether or the deionized water is five to fifteen percent of the weight of the material.

5. The method for producing a water-soluble glycidyl versatate resin according to claim 1, characterized in that: the reaction conditions in the second step are specifically that stirring is kept for 10 to 15 minutes at 120 ℃ under the protection of nitrogen, and the temperature is increased to 165 to 185 ℃, and stirring reaction is carried out for 1 to 2 hours.

6. The method for producing a water-soluble glycidyl versatate resin according to claim 1, characterized in that: the reaction conditions in the third step are specifically that the temperature is reduced to 60-90 ℃, 2-imidazolidinone or N-hydroxyethyl-2-imidazolidinone is dropwise added within 0.5-1.5 hours, and then the mixture is stirred and reacted for 1-3 hours within the range of 60-90 ℃.

7. The method for producing a water-soluble glycidyl versatate resin according to claim 1, characterized in that: the reaction conditions in the fourth step are specifically that the temperature is reduced to 50-60 ℃, and ethanol, isopropanol, butanol, propylene glycol monomethyl ether or deionized water is added.

8. The application of the water-soluble tertiary carboxylic acid glycidyl ester resin prepared by the preparation method of any one of claims 1 to 7 in woodware wiping agent, metal surface coating, anti-doodling wall paint and woodware varnish.

9. The application of the water-soluble glycidyl versatate resin in the woodware wiping agent is characterized in that: adding 80 parts of water-soluble tertiary carbonic acid glycidyl ester resin into a container with a stirrer according to the mass part ratio, adding 1.6-3.8 parts of propylene glycol methyl ether into the material, gradually rotating the stirring speed from slow to fast, taking the speed as good as splashing, adding 0.2 part of defoaming agent, stirring for 5 minutes, adding 8-15 parts of alcohol-soluble dye, stirring uniformly, adding 3.2-8 parts of ethanol, stirring uniformly, filtering and packaging by a 400-mesh filter screen;

the application of the water-soluble glycidyl versatate resin in the metal surface coating is as follows: adding 4.3 parts of dimethylethanolamine, 0.2 part of defoaming agent, 3.2 parts of propylene glycol methyl ether and 6.6 parts of ethanol into 50 parts of water-soluble glycidyl versatate resin according to the mass part ratio, mixing in a container with stirring, adding 25.7 parts of deionized water after uniform mixing, continuously mixing until the mixture is transparent, packaging for later use, adding 10 parts of isocyanate curing agent when in use, mixing the two, stirring for 30 minutes to obtain a metal surface coating, cleaning the metal surface, coating the metal surface coating, keeping the thickness of a wet film at 50-70 micrometers, and drying after standing for 12 hours;

the application of the water-soluble glycidyl versatate resin in the anti-graffiti wall paint is as follows: adding 30 parts of dimethyldiethoxysilane and 4 parts of propylene glycol monomethyl ether into 50 parts of water-soluble glycidyl versatate resin according to the mass part ratio, dropwise adding 16 parts of deionized water, controlling the temperature to be below 50 ℃, stirring for 12 hours, filtering, packaging, and then spraying, roll coating and brush coating on the building wall; the application of the water-soluble glycidyl versatate resin in the wood varnish is as follows: adding 10-20 parts of modified silica sol, 5-10 parts of glycidyl ether and 3-5 parts of propylene glycol methyl ether into 20-30 parts of water-soluble tert-carbonic acid glycidyl ester resin according to the mass part ratio, and uniformly mixing.

10. The use of claim 9, wherein the alcohol soluble dye is alcohol soluble dye-red essence 10 parts, or alcohol soluble dye-yellow essence 15 parts, or alcohol soluble dye-black essence 8 parts, or alcohol soluble dye-blue essence 10 parts.

Technical Field

The invention belongs to the technical field of functionalized water-based resin, and particularly relates to a preparation method and application of water-soluble glycidyl versatate resin.

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 (see another patent of the invention of the application) is a dual-component water-based wood varnish, the organic volatile content of the product is low, the construction is carried out at high solid content, 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 protection and decoration of the wood surface are mainly realized by adopting a film coating mode, the wood has wide application, and the coating has large demand and high performance requirement due to diverse textures. 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 water-soluble tert-carbonic acid glycidyl ester resin, and solves the technical problems that the prior art has hidden environmental protection defects, cannot form high definition, is easy to stain, has low hardness, low construction solid content and the like.

The technical scheme is as follows:

a preparation method of water-soluble glycidyl versatate resin comprises the following steps:

the first step is as follows: adding propylene glycol methyl ether or dipropylene glycol dimethyl ether into one or two of phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride and citric acid, and adding tert-carbonic acid glycidyl ester and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane at the temperature of 20-80 ℃;

the second step is that: heating to 120-200 ℃, and reacting for 1-4 hours;

the third step: cooling to 60-90 ℃, adding 2-imidazolidinone or N-hydroxyethyl-2-imidazolidinone, and reacting at 60-90 ℃ for 1-3 hours;

the fourth step: adding ethanol, isopropanol, butanol, propylene glycol monomethyl ether or deionized water, and filtering to obtain the water-soluble tert-carbonic acid glycidyl ester resin.

As a preferred technical scheme of the invention: under the condition that the total molar number of one or two of the phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride and citric acid is 1, the addition ratio of the tertiary carbonic acid glycidyl ester to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 1-3 g, and the addition amount of the propylene glycol methyl ether or the dipropylene glycol dimethyl ether is 10-15% of the weight of one or two of the phthalic anhydride, the tetrahydrophthalic anhydride, the trimellitic anhydride and the citric acid.

As a preferred technical scheme of the invention: and under the condition that the total molar number of one or two of the phthalic anhydride, the tetrahydrophthalic anhydride, the trimellitic anhydride and the citric acid is 1, the adding amount of the 2-imidazolidinone or the N-hydroxyethyl-2-imidazolidinone is 0.2 to 1.5 gram molecule.

As a preferred technical scheme of the invention: the addition amount of the ethanol, the isopropanol, the butanol, the propylene glycol methyl ether or the deionized water is five to fifteen percent of the weight of the material.

As a preferred technical scheme of the invention: the reaction conditions in the second step are specifically that stirring is kept for 10 to 15 minutes at 120 ℃ under the protection of nitrogen, and the temperature is increased to 165 to 185 ℃, and stirring reaction is carried out for 1 to 2 hours.

As a preferred technical scheme of the invention: the reaction conditions in the third step are specifically that the temperature is reduced to 60-90 ℃, 2-imidazolidinone or N-hydroxyethyl-2-imidazolidinone is dropwise added within 0.5-1.5 hours, and then the mixture is stirred and reacted for 1-3 hours within the range of 60-90 ℃.

As a preferred technical scheme of the invention: the reaction conditions in the fourth step are specifically that the temperature is reduced to 50-60 ℃, and ethanol, isopropanol, butanol, propylene glycol monomethyl ether or deionized water is added.

The invention also discloses application of the water-soluble tert-carbonic acid glycidyl ester resin prepared by the preparation method in woodware wiping color agents, metal surface coatings, anti-doodling wall paints and woodware varnishes.

As a preferred technical scheme of the invention: the application of the water-soluble glycidyl versatate resin in the woodware wiping agent is as follows:

adding 80 parts of water-soluble tert-carbonic acid glycidyl ester resin into a container with a stirrer according to the mass part ratio, adding 1.6-3.8 parts of propylene glycol methyl ether into the material, gradually rotating the stirring speed from slow to fast, taking the speed as good as splashing, adding 0240.2 parts of defoaming agent, stirring for 5 minutes, adding 8-15 parts of alcohol-soluble dye, stirring uniformly, finally adding 3.2-8 parts of ethanol, stirring uniformly, filtering and packaging by a 400-mesh filter screen;

the application of the water-soluble glycidyl versatate resin in the metal surface coating is as follows: adding 4.3 parts of dimethylethanolamine, 0.2 part of defoaming agent, 3.2 parts of propylene glycol methyl ether and 6.6 parts of ethanol into 50 parts of water-soluble glycidyl versatate resin according to the mass part ratio, mixing in a container with stirring, adding 25.7 parts of deionized water after uniform mixing, continuously mixing until the mixture is transparent, packaging for later use, adding 10 parts of isocyanate curing agent when in use, mixing the two, stirring for 30 minutes to obtain a metal surface coating, cleaning the metal surface, coating the metal surface coating, keeping the thickness of a wet film at 50-70 micrometers, and drying after standing for 12 hours;

the application of the water-soluble glycidyl versatate resin in the anti-graffiti wall paint is as follows: adding 30 parts of dimethyldiethoxysilane and 4 parts of propylene glycol monomethyl ether into 50 parts of water-soluble glycidyl versatate resin according to the mass part ratio, dropwise adding 16 parts of deionized water, controlling the temperature to be below 50 ℃, stirring for 12 hours, filtering, packaging, and then spraying, roll coating and brush coating on the building wall;

the application of the water-soluble glycidyl versatate resin in the wood varnish is as follows: adding 10-20 parts of modified silica sol, 5-10 parts of glycidyl ether and 3-5 parts of propylene glycol methyl ether into 20-30 parts of water-soluble tert-carbonic acid glycidyl ester resin according to the mass part ratio, and uniformly mixing.

As a preferred technical scheme of the invention: the alcohol soluble dye is alcohol soluble dye-red essence 10 parts, or alcohol soluble dye-yellow essence 15 parts, or alcohol soluble dye-black essence 8 parts, or alcohol soluble dye-blue essence 10 parts.

Has the advantages that: compared with the prior art, the preparation method of the water-soluble tert-carbonic acid glycidyl ester resin has the following technical effects:

1. the technology of the patent is added into the double-component waterborne wood varnish of a double-layer curing siloxane system, and plays roles of increasing curing property, improving construction solid content, wetting wood surface and blocking the rib expansion phenomenon caused by tannic acid in the system. The varnish is composed of a three-layer coating structure of color wiping, back sealing and finishing, and can be independently used or matched with any one according to the actual use condition. 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.

2. 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. 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.

3. 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.

Detailed Description

A preparation method of water-soluble glycidyl versatate resin comprises the following steps:

the first step is as follows: adding propylene glycol methyl ether or dipropylene glycol dimethyl ether into one or two of phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride and citric acid, and adding tert-carbonic acid glycidyl ester and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane at the temperature of 20-80 ℃;

the second step is that: heating to 120-200 ℃, and reacting for 1-4 hours;

the third step: cooling to 60-90 ℃, adding 2-imidazolidinone or N-hydroxyethyl-2-imidazolidinone, and reacting at 60-90 ℃ for 1-3 hours;

the fourth step: adding ethanol, isopropanol, butanol, propylene glycol monomethyl ether or deionized water, and filtering to obtain the water-soluble tert-carbonic acid glycidyl ester resin.

Under the condition that the total molar number of one or two of the phthalic anhydride, the tetrahydrophthalic anhydride, the trimellitic anhydride and the citric acid is 1, the addition ratio of the tertiary carbonic acid glycidyl ester to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 1-3 gram-molecule ratio. The addition amount of propylene glycol methyl ether or dipropylene glycol dimethyl ether is 10-15% of the weight of one or two of phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride and citric acid; and under the condition that the total molar number of one or two of the phthalic anhydride, the tetrahydrophthalic anhydride, the trimellitic anhydride and the citric acid is 1, the adding amount of the 2-imidazolidinone or the N-hydroxyethyl-2-imidazolidinone is 0.2 to 1.5 gram molecule. The addition amount of the ethanol, the isopropanol, the butanol, the propylene glycol methyl ether or the deionized water is five to fifteen percent of the weight of the material. The reaction conditions in the second step are specifically that stirring is kept for 10 to 15 minutes at 120 ℃ under the protection of nitrogen, and the temperature is increased to 165 to 185 ℃, and stirring reaction is carried out for 1 to 2 hours. The reaction conditions in the third step are specifically that the temperature is reduced to 60-90 ℃, 2-imidazolidinone or N-hydroxyethyl-2-imidazolidinone is dropwise added within 0.5-1.5 hours, and then the mixture is stirred and reacted for 1-3 hours within the range of 60-90 ℃. The reaction conditions in the fourth step are specifically that the temperature is reduced to 50-60 ℃, and ethanol, isopropanol, butanol, propylene glycol monomethyl ether or deionized water is added.

Example 1

The application of the water-soluble glycidyl versatate resin in the woodware wiping agent comprises the following steps:

adding 80 parts of water-soluble tert-carbonic acid glycidyl ester resin into a container with a stirrer according to the mass part ratio, adding 1.6-3.8 parts of propylene glycol methyl ether into the material, gradually rotating the stirring speed from slow to fast, taking the speed as good as splashing, adding 0240.2 parts of defoaming agent, stirring for 5 minutes, adding 8-15 parts of alcohol-soluble dye, stirring uniformly, finally adding 3.2-8 parts of ethanol, stirring uniformly, filtering and packaging by a 400-mesh filter screen;

a method of use;

s1: 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.

S2: and wiping the coated surface by using a clean rag until the texture is clear and the color is uniform.

S3: the mixture can be dried after being placed for 2 to 3 hours.

S4: the dried color-coated wood can be coated with finish varnish on the surface continuously or can be used directly.

Example 2

The application of the water-soluble glycidyl versatate resin in the metal surface coating comprises the following steps:

wherein the dosage of the dimethylethanolamine is calculated as follows: the product of the patent has solid content of neutralization degree (60)/milliequivalent of potassium hydroxide and equivalent of dimethylethanolamine.

Adding 4.3 parts of dimethylethanolamine, 0240.2 parts of defoaming agent, 3.2 parts of propylene glycol methyl ether and 6.6 parts of ethanol into 50 parts of water-soluble glycidyl versatate resin according to the mass part ratio, mixing in a container with a stirrer, adding 25.7 parts of deionized water after the mixture is uniform, continuously mixing until the mixture is transparent, packaging for later use, adding 10 parts of isocyanate curing agent when the mixture is used, mixing the two, stirring for 30 minutes to obtain a metal surface coating, cleaning the metal surface, coating the metal surface coating, keeping the thickness of a wet film at 50-70 micrometers, and drying after the mixture is placed for 12 hours.

Example 3

The application of the water-soluble glycidyl versatate resin in the anti-graffiti wall paint comprises the following steps:

adding 30 parts of dimethyl diethoxysilane and 4 parts of propylene glycol monomethyl ether into 50 parts of water-soluble glycidyl versatate resin according to the mass part ratio, dropwise adding 16 parts of deionized water, controlling the temperature to be below 50 ℃, stirring for 12 hours, filtering, packaging, and then spraying, roll coating and brush coating on the building wall.

Example 4

The application of the water-soluble glycidyl versatate resin in the wood varnish is as follows:

the first component of the double-component wood varnish is as follows:

name of Material	Specification of	Compounding amount
			Cationic aqueous siloxane oligomers	45-55％	20-30
Formic acid	20-40％	3-5
			Defoaming agent	80％	0.1-0.2
Wetting agent	100％	0.1-0.2
			Ethanol	Industrial grade	2-5
Deionized water	Industrial grade	15-30
			Total up to		35-55％

Weighing 20-30 parts of cationic water-based siloxane oligomer, 3-5 parts of acid catalyst formic acid, 0.1-0.2 part of defoaming agent, 0.1-0.2 part of wetting agent, 2-5 parts of alcohol ether solvent ethanol and 15-30 parts of deionized water according to the mass part ratio, and uniformly mixing.

Component B of double-component woodenware varnish

Adding 10-20 parts of modified silica sol, 5-10 parts of glycidyl ether and 3-5 parts of propylene glycol methyl ether into 20-30 parts of water-soluble tert-carbonic acid glycidyl ester resin according to the mass part ratio, and uniformly mixing. And 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 bi-component 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.