CN111205735A

CN111205735A - Waterproof antibacterial coating and preparation method thereof

Info

Publication number: CN111205735A
Application number: CN202010136388.3A
Authority: CN
Inventors: 张孟杰
Original assignee: 张孟杰
Current assignee: Miao Zhenlu
Priority date: 2020-03-02
Filing date: 2020-03-02
Publication date: 2020-05-29
Anticipated expiration: 2040-03-02
Also published as: CN111205735B

Abstract

The invention discloses a waterproof antibacterial coating which comprises the following components in parts by weight: 56-62 parts of perfluorinated silanized epoxy resin, 13-15 parts of branched antibacterial curing agent, 1.1-1.3 parts of flatting agent, 21-32 parts of pigment and filler, 0.8-1.1 parts of degassing agent and 1.2-1.4 parts of benzoin. According to the invention, two antibacterial units, namely isothiazolinone is directly introduced into two ends of the curing agent to form the bis-isothiazolinone antibacterial curing agent, the bis-isothiazolinone antibacterial curing agent and epoxy resin are subjected to hyperbranched crosslinking modification to form a hyperbranched compact structure, and a large number of antibacterial groups are uniformly dispersed on a branched structure chain, so that the whole coating is uniform from inside to outside and has high antibacterial performance, and the antibacterial performance is uniform and stable, so that the antibacterial performance of the whole coating is high.

Description

Waterproof antibacterial coating and preparation method thereof

Technical Field

The invention belongs to the field of paint preparation, and relates to a waterproof antibacterial paint and a preparation method thereof.

Background

The surface of household appliances such as refrigerators is usually coated with a waterproof coating, which not only can realize high-efficiency corrosion resistance, but also can effectively prevent water from permeating, thereby influencing the service life of the appliances, meanwhile, the appliances are frequently used and are easy to deform under the impact of external force, therefore, the impact resistance can be realized by using the impact resistance paint, as the epoxy resin chain contains flexible groups, the impact resistance paint has certain impact resistance and can be widely applied, but the impact resistance still can not meet the requirement, meanwhile, for the sanitation and safety of the household appliances, the antibacterial auxiliary agent is usually added into the paint and is directly and uniformly mixed through physical action, but the physical mixing easily causes non-uniform mixing, thereby influencing the integral antibacterial performance of the coating.

Disclosure of Invention

The invention aims to provide a waterproof antibacterial coating and a preparation method thereof, wherein the prepared epoxy resin contains long-chain alkyl ether, so that the flexibility of the epoxy resin is improved, and further the impact resistance of the epoxy resin is improved.

The purpose of the invention can be realized by the following technical scheme:

the waterproof antibacterial coating comprises the following components in parts by weight:

56-62 parts of perfluorinated silanized epoxy resin, 13-15 parts of branched antibacterial curing agent, 1.1-1.3 parts of flatting agent, 21-32 parts of pigment and filler, 0.8-1.1 parts of degassing agent and 1.2-1.4 parts of benzoin;

the specific preparation process of the perfluorinated silanized epoxy resin is as follows:

step 1: weighing a certain amount of 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane and deionized water, simultaneously adding into a reaction vessel, stirring and mixing uniformly, heating to 80-90 ℃, then dropwise adding tetramethyldisiloxane into the mixture, controlling the dropping speed to be 2-2.5mL/min, then adding tetramethyl ammonium hydroxide into the reaction vessel, then carrying out reflux reaction for 1-1.5h, then heating to 120-125 ℃ for reflux reaction for 5-6h, carrying out reduced pressure distillation on the obtained product to obtain clear and transparent perfluorosilicone oil FPS, wherein 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane and tetramethyldisiloxane are mixed according to the mass ratio of 1:2, simultaneously, 32-34g of tetramethylammonium hydroxide is added into 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane per mole; because the 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane contains two siloxane bonds, the 1H,1H, 2H-perfluorooctylmethyldimethoxysilane can be hydrolyzed to generate two silicon hydroxyl groups, and simultaneously, the siloxane bond in the middle of the tetramethyldisiloxane is broken to generate hydroxyl-terminated silane, and simultaneously, because the steric hindrance of the 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane is larger, the two 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilanes cannot be subjected to dehydration polymerization, and the steric hindrance of the tetramethyldisiloxane is smaller, the dehydration condensation reaction can be carried out under the action of tetramethylammonium hydroxide, so that the tetramethyldisiloxane is introduced into the two ends of the 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane, and the reaction structural formula is as follows:

step 2: continuously introducing nitrogen into a reaction kettle for 30min, adding the FPS prepared in the step 1, allyl glycidyl ether and 3-chloro-2-methylpropene, then adding isopropanol into the reaction kettle, heating to 80-85 ℃, adding a catalyst platinum, carrying out constant-temperature reflux reaction for 4-5h, and then carrying out reduced pressure distillation to obtain an epoxy cross-linking agent, wherein the FPS, the allyl glycidyl ether and the 3-chloro-2-methylpropene are added according to the mass ratio of 1:1:1, and simultaneously, 425g of isopropanol and 2.31-2.36g of the catalyst platinum are added into each kilogram of FPS; under the catalytic action of a platinum catalyst, the silicon-hydrogen bonds at two ends of FPS molecules have higher activity and can perform addition reaction with olefin groups in allyl glycidyl ether and 3-chloro-2-methyl propylene, so that epoxy groups and alkyl chloride are respectively introduced into two ends of the prepared epoxy cross-linking agent, meanwhile, because the epoxy cross-linking agent contains a large amount of fluorine elements and silicon-oxygen bonds, the higher hydrophobic and oleophobic performance of the cross-linking agent is realized, and because of the introduction of a glycerol ether group, the flexibility of the compound is improved, the length of an alkyl chain is improved, and the hydrophobic performance of the product is further improved,

and step 3: weighing a certain amount of bisphenol A, adding the bisphenol A into an ethanol solution, adding an epoxy cross-linking agent, heating to 80-85 ℃, adding a 40% sodium hydroxide aqueous solution into a reaction container, carrying out constant-temperature reflux reaction for 6-7h to generate a solid, washing the solid with ethanol, and drying to obtain the perfluorinated silanized epoxy resin, wherein the reaction structural formula is shown in figure 1, 2.5-2.6kg of the epoxy cross-linking agent is added into each kg of bisphenol A, 10L of ethanol is added, 830-840mL of the 40% sodium hydroxide solution is added, since two ends of the epoxy cross-linking agent respectively contain epoxy groups and alkyl chlorides, the epoxy cross-linking agent can respectively react with phenolic hydroxyl groups at two ends of the bisphenol A to generate linear epoxy resin, and simultaneously since the epoxy cross-linking agent contains a large amount of fluorine elements and siloxane bonds, a large amount of fluorine elements and siloxane bonds are uniformly contained on a linear epoxy resin chain formed after polymerization, the prepared epoxy resin has high water-proof and oil-proof performance, the flexibility and the shock resistance of the epoxy resin are improved due to the long length of the main chain of the epoxy cross-linking agent and the bisphenol A, and the prepared product has high flexible groups due to the introduction of long ether chains in the epoxy cross-linking agent, so that the compatibility of the epoxy resin and other organic matters is improved, and the hydrophobic performance of the polymer is further improved due to the introduction of long alkyl chains in the epoxy cross-linking agent;

the branched antibacterial curing agent is prepared by the following specific steps:

① weighing a certain amount of ethylene glycol diglycidyl ether and acetone, adding into a reaction kettle, stirring for dissolving, adding 1, 2-benzisothiazolin-3-one, heating to 60-70 ℃, performing reflux reaction for 3-4h, and then performing reduced pressure distillation to obtain a product A, wherein the ethylene glycol diglycidyl ether and the 1, 2-benzisothiazolin-3-one are mixed according to the mass ratio of 1:2.06-2.08, and the reaction structural formula is shown as follows;

② adding boric acid into water, heating to 90-100 ℃, stirring for dissolving, refluxing, adding ethanolamine into the mixture after the boric acid is completely dissolved, refluxing for 18h, cooling to room temperature, filtering, washing and drying to obtain aminated boric acid ester, wherein the boric acid and ethanolamine are mixed according to a mass ratio of 1:2, the boric acid contains three boric acid groups, two acid groups react with ethanolamine, and the other boric acid group does not participate in the reaction;

③, adding the product A and acetone into a reaction kettle simultaneously, stirring and dissolving, adding 0.68-0.71g of aminated borate prepared in the step ②, stirring and reacting for 10-11h, reducing to room temperature, and distilling under reduced pressure to obtain a branched antibacterial curing agent, wherein each gram of the product A is added with 0.68-0.71g of aminated borate, the reaction structural formula is shown as follows, the aminated borate contains a boric acid group and can perform dehydration reaction with hydroxyl in the product A at high temperature, because two ends of the product A contain two hydroxyl groups, the product A can react with the aminated borate, and further the aminated borate is introduced into two ends of the obtained curing agent chain, because the aminated borate contains two amino groups in different directions at two ends, the curing of the epoxy resin can be realized in different directions, a crossed tree-like structure is formed when the epoxy resin is cured, the curing efficiency is improved, the epoxy resin can be rapidly cured, and simultaneously because the antibacterial group in the antibacterial curing agent contains 1, 2-benzisothiazolin-3-one, the cured resin contains a large amount of uniform ether bonds, the antibacterial curing agent is improved, the compatibility of the antibacterial agent and the antibacterial agent is improved, and the compatibility of the antibacterial agent and the product after the antibacterial agent is improved;

a preparation method of a waterproof antibacterial coating comprises the following specific preparation processes:

adding perfluorinated silanized epoxy resin, a branched antibacterial curing agent, a flatting agent, a pigment filler, a degassing agent and benzoin into a stirring kettle according to a certain proportion, uniformly mixing and stirring, adding the mixed materials into a melt extruder for extrusion, and screening the extruded sheets to obtain the waterproof antibacterial coating.

The invention has the beneficial effects that:

1. the epoxy resin prepared by the invention contains long-chain alkyl ether, so that the flexibility of the epoxy resin is improved, and the impact resistance of the epoxy resin is further improved, six amino groups contained in the used branched antibacterial curing agent react in different directions and are cured with the epoxy resin in different directions to generate a compact hyperbranched structure, so that the impact resistance of the coating is improved, meanwhile, long-chain ether bonds contained in the curing agent have high flexibility, and after the epoxy resin is subjected to crosslinking polymerization with the flexible epoxy resin, the prepared coating uniformly contains a large number of flexible groups, so that the impact resistance of the coating is improved, and the problem that the impact resistance of the existing epoxy resin coating still cannot meet the requirements is effectively solved.

2. The main chain of the epoxy resin prepared by the invention contains a large amount of siloxane bonds, has certain waterproof performance, and simultaneously, a large amount of fluorine elements are introduced to the branched chain to extend out, so that the outer layer and the inner layer of the epoxy resin chain have higher waterproof performance, and simultaneously, long-chain hydrophobic alkyl is introduced to the chain, so that the high hydrophobic performance of the epoxy resin is realized, when moisture contacts the surface, a large amount of fluorine elements on the branched chain extending out from the surface realize higher waterproof performance, and simultaneously, when the moisture penetrates inwards, the siloxane bonds and the long-chain alkyl on the main chain inside simultaneously act to realize higher hydrophobicity, so that the prepared epoxy resin has the waterproof performance from inside to outside, and simultaneously, a compact tree-shaped structure is formed after the branched antibacterial curing agent is subjected to hyperbranched crosslinking, so that the outer layer of the tree-shaped structure is hydrophobic fluorine elements, and the inner layer is waterproof silane oxygen bonds, so that the crosslinked coating has high waterproof performance.

3. According to the invention, two antibacterial units, namely isothiazolinone is directly introduced into two ends of the curing agent to form the bis-isothiazolinone antibacterial curing agent, the bis-isothiazolinone antibacterial curing agent and epoxy resin are subjected to hyperbranched crosslinking modification to form a hyperbranched compact structure, and a large number of antibacterial groups are uniformly dispersed on a branched structure chain, so that the whole coating is uniform from inside to outside and has high antibacterial performance, and the antibacterial performance is uniform and stable, so that the antibacterial performance of the whole coating is high.

Drawings

In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.

FIG. 1 is a reaction formula in the process of preparing perfluorosilanized epoxy resin in example 1 of the present invention.

Detailed Description

Referring to fig. 1, the following embodiments are described in detail:

example 1:

step 1: weighing 452g of 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane and deionized water, simultaneously adding the weighed materials into a reaction vessel, stirring and mixing the materials uniformly, heating the mixture to 80-90 ℃, then dropwise adding 268g of tetramethyldisiloxane into the mixture, controlling the dropwise adding speed to be 2-2.5mL/min, ensuring that the 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane and the tetramethyldisiloxane are mixed according to the mass ratio of 1:2, then adding 32g of tetramethylammonium hydroxide into the reaction vessel, carrying out reflux reaction for 1-1.5H, heating the mixture to 120-:

step 2: introducing nitrogen into a reaction kettle for 30min continuously, adding 556g of FPS prepared in the step 1, 114g of allyl glycidyl ether and 90g of 3-chloro-2-methylpropene into the reaction kettle, adding 223g of isopropanol into the reaction kettle, heating to 80-85 ℃, adding 1.28g of catalyst platinum, carrying out constant-temperature reflux reaction for 4-5h, and carrying out reduced pressure distillation to obtain an epoxy cross-linking agent, wherein the FPS, the allyl glycidyl ether and the 3-chloro-2-methylpropene are added according to the mass ratio of 1:1:1, and the reaction structural formula is shown as follows;

and step 3: weighing 1kg of bisphenol A, adding the bisphenol A into 10L of ethanol solution, adding 2.5kg of epoxy cross-linking agent, heating to 80-85 ℃, adding 830mL of 40% sodium hydroxide aqueous solution into a reaction container, carrying out constant-temperature reflux reaction for 6-7h to generate solid, washing the solid with ethanol, and drying to obtain the perfluorinated silanized epoxy resin, wherein the reaction structural formula is shown in figure 1.

Comparative example 1:

the specific procedure for preparing the perfluoroalkylsilylated epoxy resin was the same as in example 1 except that 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane in example 1 was replaced with trifluoropropyltrimethoxysilane.

Comparative example 2:

the specific preparation process of the silanized epoxy resin is as follows:

step 1: introducing nitrogen into a reaction kettle for 30min continuously, adding 134 g of tetramethyldisiloxane, 114g of allyl glycidyl ether and 90g of 3-chloro-2-methylpropene, adding 223g of isopropanol, heating to 80-85 ℃, adding 1.28g of catalyst platinum, carrying out constant-temperature reflux reaction for 4-5h, and carrying out reduced pressure distillation to obtain an epoxy cross-linking agent, wherein the weight ratio of the FPS, the allyl glycidyl ether and the 3-chloro-2-methylpropene is 1:1:1, and the reaction structural formula is shown as follows:

step 2: weighing 1kg of bisphenol A, adding the bisphenol A into 10L of ethanol solution, adding 1.8kg of epoxy cross-linking agent, heating to 80-85 ℃, adding 830mL of sodium hydroxide aqueous solution with the mass concentration of 40% into a reaction container, carrying out constant-temperature reflux reaction for 6-7h to generate solid, washing the solid with ethanol, and drying to obtain the silanized epoxy resin.

Comparative example 3:

weighing 1kg of hexafluorobisphenol A, adding the hexafluorobisphenol A into 10L of ethanol solution, then adding 0.36kg of epoxy chloropropane, heating to 80-85 ℃, adding 830mL of sodium hydroxide aqueous solution with the mass concentration of 40% into a reaction container, carrying out constant-temperature reflux reaction for 6-7h to generate solid, washing the solid with ethanol, and drying to obtain the fluorinated epoxy resin.

Example 2:

①, weighing 174g of ethylene glycol diglycidyl ether and 2L of acetone, simultaneously adding the ethylene glycol diglycidyl ether and 2L of acetone into a reaction kettle, stirring for dissolving, then adding 311g of 1, 2-benzisothiazolin-3-one into the reaction kettle, heating to 60-70 ℃, performing reflux reaction for 3-4h, and then performing reduced pressure distillation to obtain a product A, wherein the reaction structural formula is shown as follows, because both ends of the ethylene glycol diglycidyl ether contain epoxy groups, and simultaneously the amino group in the 1, 2-benzisothiazolin-3-one contains active amino hydrogen, the ethylene glycol diglycidyl ether can perform ring-opening reaction with the epoxy groups, the 1, 2-benzisothiazolin-3-one is introduced into both ends of the product, and two hydroxyl groups are generated, and because the 1, 2-benzisothiazolin-3-one has higher antibacterial performance, the prepared product A has higher antibacterial performance;

② adding boric acid into water, heating to 90-100 deg.C, stirring for dissolving, refluxing, adding ethanolamine after boric acid is completely dissolved, refluxing for 18h, cooling to room temperature, filtering, washing, and drying to obtain aminated borate, wherein boric acid and ethanolamine are mixed according to a ratio of 1: 2;

③, adding 1kg of product A and 10L of acetone into a reaction kettle simultaneously, stirring and dissolving, adding 680g of aminated borate prepared in the step ②, stirring and reacting for 10-11h, then reducing to room temperature, and carrying out reduced pressure distillation to obtain a branched antibacterial curing agent, wherein the reaction structural formula is shown in the specification, the aminated borate contains a boric acid group and can carry out dehydration reaction with hydroxyl in the product A at high temperature, because two ends of the product A contain two hydroxyl groups, the aminated borate can react with the aminated borate, and further the aminated borate is introduced into two ends of the obtained curing agent chain, because the aminated borate contains two amino groups in two ends in different directions, four amino groups at two ends of the curing agent product are in different directions, the epoxy resin can be cured in different directions, a crossed tree-like structure is formed, the curing efficiency is improved, the epoxy resin can be rapidly cured at low temperature, and simultaneously because the antibacterial group in the curing agent contains 1, 2-benzisothiazolin-3-one, a large amount of antibacterial agent is uniformly contained, the long-chain ether bond in the curing agent, and the compatibility of the product and the product is improved;

comparative example 4:

the specific preparation process of the antibacterial curing agent is the same as that of the embodiment 2, the ethylene glycol diglycidyl ether used in the embodiment 2 is replaced by 1, 2-epoxypropane, the obtained antibacterial curing agent has the following structural formula, amino groups in the curing agent form a chain structure with epoxy resin after curing, meanwhile, the curing agent does not have long-chain ether bonds, so that the flexibility and the impact resistance of a coating are reduced after the epoxy resin is cured, and meanwhile, the curing agent contains one 1, 2-benzisothiazolin-3-one, compared with the embodiment 2, the content of the 1, 2-benzisothiazolin-3-one in the coating after crosslinking and curing is less, so that the integral antibacterial performance of the coating is reduced;

example 3:

adding the components of the resin, the curing agent, the leveling agent, the pigment filler, the degassing agent and the benzoin into a stirring kettle according to the proportion shown in the following table 1, uniformly mixing and stirring, adding the mixed materials into a melt extruder for extrusion, and screening the extruded sheets to obtain the waterproof antibacterial coating of different samples;

respectively spraying the powder coatings prepared in the samples 1,2, 3, 4, 5 and 6 on the processed Q235 steel plate by an electrostatic spraying method, spraying the powder coatings in a single layer, baking the powder coatings at 180 ℃ for 5 minutes to obtain dry films with different thicknesses, and specifically determining the performance of the coating film, wherein the specific determination process and the determination result are as follows:

1. impact resistance test of the coating: according to the national standard GB/T1732-1993 'paint film impact resistance determination method', a heavy-duty impactor is adopted to carry out an impact resistance test on a coating, the paint film thickness of a sample 1, a sample 2, a sample 3, a sample 4, a sample 5 and a sample 6 is controlled to be 2.5mm, then each sample is subjected to an impact test for 4 times respectively, and the average value of the impact height of four times is determined, wherein the specific determination results are as follows:

the impact height of the coating prepared for sample 1 was 124cm, the impact height of the coating prepared for sample 2 was 108cm, the impact height of the coating prepared for sample 3 was 123cm, the impact height of the coating prepared for sample 4 was 121cm, the impact height of the coating prepared for sample 5 was 105cm, and the impact height of the coating prepared for sample 6 was 94 cm.

In conclusion, the coatings prepared in the samples 1, 3 and 4 have higher impact resistance, and the epoxy resins prepared in the examples 1, 1 and 2 all contain long-chain alkyl ether, so that the flexibility of the epoxy resins is improved, and further the impact resistance of the epoxy resins is improved, six amino groups contained in the branched antibacterial curing agent used at the same time react in different directions and are cured with the epoxy resins in different directions to generate a compact hyperbranched structure, so that the impact resistance of the coatings is improved, meanwhile, long-chain ether bonds contained in the curing agent have higher flexibility, and after the branched antibacterial curing agent is subjected to crosslinking polymerization with the flexible epoxy resins, the prepared coatings uniformly contain a large number of flexible groups, so that the impact resistance of the coatings is improved; in the embodiment 2, the curing agent is in a chain structure, so that the compactness of the coating prepared by crosslinking with the epoxy resin is reduced, the impact resistance of the coating is further influenced, and meanwhile, the curing agent does not contain long-chain ether bonds, so that the flexibility of the polymer coating generated after crosslinking polymerization is reduced, and the impact resistance of the polymer coating is further reduced; in the sample 5, the epoxy resin prepared in the comparative example 3 is directly reacted with hexafluorobisphenol A, so that the content of long-chain ether bonds in the crosslinked resin is reduced, and the impact resistance of the crosslinked resin is reduced; in example 6, the amount of long-chain ether bonds in the epoxy resin used in comparative example 3 is reduced, and the curing agent does not contain long-chain ether bonds, and simultaneously, the compactness of the polymer after curing and crosslinking is reduced, so that the impact resistance of the prepared coating is reduced.

2. And (3) testing the waterproof performance of the coating surface: an JGW-360A contact angle measuring instrument is selected, 5 mu L of water drops are tested on 5 different areas of the coating with the thickness of 0.5mm of the same sample, and the average value of the obtained final results is calculated, wherein the results are shown as follows;

the surface water contact angle of the coating prepared for sample 1 was 158.2 °, the surface water contact angle of the coating prepared for sample 2 was 156.7 ° cm, the surface water contact angle of the coating prepared for sample 3 was 154.1 ° cm, the surface water contact angle of the coating prepared for sample 4 was 133.8 ° cm, the surface water contact angle of the coating prepared for sample 5 was 144.2 ° cm, and the surface water contact angle of the coating prepared for sample 6 was 142.1 ° cm.

In conclusion, the coating prepared in the sample 1 has high waterproof performance, because the main chain of the epoxy resin prepared in the coating contains a large amount of siloxane bonds and has certain waterproof performance, and a large amount of fluorine elements are introduced to extend out of the branched chain, the outer layer and the inner layer of the epoxy resin chain both have high waterproof performance, and meanwhile, long-chain hydrophobic alkyl is introduced to the chain, so that high hydrophobic performance of the epoxy resin is realized, when moisture contacts the surface, a large amount of fluorine elements on the branched chain extending out of the surface realize high waterproof performance, and meanwhile, when the moisture penetrates inwards, the siloxane bonds and the long-chain alkyl on the main chain inside simultaneously act to realize high hydrophobic performance, so that the prepared epoxy resin has waterproof performance from inside to outside, and simultaneously, a compact tree-shaped structure is formed after the branched antibacterial curing agent is subjected to hyperbranched crosslinking, so that the outer layer of the tree-shaped structure is hydrophobic fluorine elements, the inner layer is waterproof silane oxygen bond and long-chain alkyl, so that the crosslinked coating has high waterproof performance; the waterproof property of the coating in sample 2 is slightly reduced, because the curing agent used in the coating is of a branched chain structure, the compactness of the coating is reduced, the fluorine element content of the outer layer of the epoxy resin used in sample 3 is reduced, the waterproof property of the outer layer of the epoxy resin is reduced, the whole waterproof property is reduced, meanwhile, the epoxy resin used in sample 4 does not contain a fluorine branched chain, only a main chain hydrophobic structure is adopted, further, the double-layer waterproof structure of the outer layer and the inner layer of the coating is damaged, the waterproof property of the coating is reduced, only the fluorine element is introduced into the main chain in sample 5 and sample 6, only the main chain has the hydrophobic structure, further, the double-layer waterproof structure of the outer layer and the inner layer of the coating is damaged.

3. And (3) testing the antibacterial performance of the coating: adding 0.2mL of Escherichia coli and Staphylococcus aureus into beef soup, culturing at 37 deg.C for 24 hr to obtain mother liquor, and diluting to 10 times^-5Or 10^-6Taking the obtained bacterial liquid as inoculated bacterial liquid; then according to GB/T4789.2-2003, 0.4mL of the bacterial liquid to be inoculated is sucked and uniformly dripped on the film coating surface of the blank control group and the film coating surface prepared in the samples 1-6, then the culture dish is placed in an aseptic environment for culturing for 3h, then the film coating surface is washed by sterilized water, the washed liquid is collected and shaken uniformly, then 0.2mL of the washing liquid is uniformly coated on a solid agar culture medium and cultured for 24h at 37 ℃, then bacterial colonies on the agar culture medium are counted, and the antibacterial rate P ═ (i) (bacterial strain) is calculatedR-R₁) R is 100%, R is the colony number of the blank control group, R₁The number of colonies of the coating films prepared in samples 1 to 6 was counted in triplicate for each sample coating film, and the average value of the triplicate was calculated, the calculation results being shown in Table 2;

TABLE 2 measurement results of antibacterial property of coating

As can be seen from Table 2, the antibacterial performance of the coatings prepared in samples 1, 3, 4 and 5 reaches more than 99%, because the coatings directly introduce two antibacterial units 1, 2-benzisothiazolin-3-one at the two ends of the curing agent to form a bis-isothiazolinone antibacterial curing agent, after the coatings are hyperbranched and modified with epoxy resin, a hyperbranched compact structure is formed, and a large number of antibacterial groups are uniformly dispersed on a branched structure chain, the whole coating has high antibacterial performance from inside to outside, and the antibacterial performance is uniform and stable, and because one antibacterial unit 1, 2-benzisothiazolin-3-one is directly introduced into the curing agent in sample 2, a mono-isothiazolinone antibacterial curing agent is formed, so that the isothiazolinone groups on the coating are reduced, and the antibacterial performance is reduced, in sample 6, the 1, 2-benzisothiazolin-3-one is directly added into the coating and is directly mixed under the physical action, but the mixing is not uniform easily, so that the antibacterial performance is influenced.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. The waterproof antibacterial coating is characterized by comprising the following components in parts by weight:

① weighing a certain amount of ethylene glycol diglycidyl ether and acetone, adding into a reaction kettle, stirring for dissolving, adding 1, 2-benzisothiazolin-3-one, heating to 60-70 deg.C, reflux reacting for 3-4h, and distilling under reduced pressure to obtain product A;

② adding boric acid into water, heating to 90-100 ℃, stirring for dissolving, refluxing, adding ethanolamine after boric acid is completely dissolved, refluxing for 18h, cooling to room temperature, filtering, washing and drying to obtain aminated boric acid ester;

③, adding the product A and acetone into the reaction kettle at the same time, stirring and dissolving, adding the aminated boric acid ester prepared in the step ②, stirring and reacting for 10-11h, then reducing the temperature to room temperature, and carrying out reduced pressure distillation to obtain the branched antibacterial curing agent.

2. The waterproof and antibacterial paint as claimed in claim 1, wherein in step ①, ethylene glycol diglycidyl ether and 1, 2-benzisothiazolin-3-one are mixed in a ratio of 1: 2.06-2.08.

3. The waterproof antibacterial paint as claimed in claim 1, wherein the boric acid and ethanolamine are prepared in a ratio of 1:2 in terms of the amount of the substance in step ②.

4. The waterproof and antibacterial paint as claimed in claim 1, wherein 0.68-0.71g of aminated borate ester is added per gram of product A in step ③.

5. The waterproof antibacterial coating material of claim 1, wherein the perfluorinated silanized epoxy resin is prepared by the following specific steps:

step 1: weighing a certain amount of 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane and deionized water, simultaneously adding the weighed materials into a reaction vessel, stirring and mixing the materials uniformly, heating the mixture to 80-90 ℃, dropwise adding tetramethyldisiloxane into the mixture at a speed of 2-2.5mL/min, adding tetramethylammonium hydroxide into the reaction vessel, carrying out reflux reaction for 1-1.5H, heating the mixture to 120-125 ℃, carrying out reflux reaction for 5-6H, and carrying out reduced pressure distillation on the obtained product to obtain clear and transparent perfluorosilicone oil FPS;

step 2: continuously introducing nitrogen into the reaction kettle for 30min, then adding the FPS prepared in the step 1, allyl glycidyl ether and 3-chloro-2-methylpropene, then adding isopropanol, heating to 80-85 ℃, adding a catalyst platinum, carrying out constant-temperature reflux reaction for 4-5h, and then carrying out reduced pressure distillation to obtain an epoxy cross-linking agent;

and step 3: weighing a certain amount of bisphenol A, adding the bisphenol A into an ethanol solution, adding an epoxy cross-linking agent, heating to 80-85 ℃, adding a 40% sodium hydroxide aqueous solution into a reaction container, carrying out constant-temperature reflux reaction for 6-7h to generate a solid, washing the solid with ethanol, and drying to obtain the perfluorinated silanized epoxy resin.

6. The waterproof and antibacterial paint as claimed in claim 5, wherein 1H,1H,2H, 2H-perfluorooctylmethyldimethoxysilane and tetramethyldisiloxane are mixed in the ratio of 1:2 in step 1.

7. The waterproof and antibacterial paint as claimed in claim 5, wherein the FPS, allyl glycidyl ether and 3-chloro-2-methyl propylene are added in the step 2 according to the ratio of 1:1:1, and simultaneously, 420-425g of isopropanol and 2.31-2.36g of platinum catalyst are added per kilogram of FPS.

8. The waterproof and antibacterial paint as claimed in claim 5, wherein in step 3, 2.5-2.6kg of epoxy cross-linking agent, 10L of ethanol and 830-840mL of 40% sodium hydroxide solution are added per kg of bisphenol A.

9. The preparation method of the waterproof antibacterial coating according to claim 1 is characterized by comprising the following specific preparation processes: