Antibacterial and anti-adhesion ceramic coating and preparation method thereof

Abstract

The present invention relates to the technical field of coatings, and discloses an antibacterial and anti-adhesion ceramic coating and a preparation method thereof. The present invention is provided by adding nano-ceramic particles, phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, a fluorine-containing flame retardant, an acrylic resin, a leveling agent BYK-306, and a diluent butyl acetate into a stirrer, stirring, and obtaining an antibacterial and anti-adhesion ceramic coating after completion. The phosphorus element and the guanidine group in the phosphorus-containing quaternary ammonium salt-modified sulfaguanidine and the fluorine-containing flame retardant have good flame retardant effects, and the quaternary ammonium salt therein has good antibacterial effects. The quaternary ammonium salt group also has good anti-adhesion effects, and the introduction of fluorine elements therein can form a smooth and non-adhesion fluorinated carbonized layer on its surface, so it also has good anti-adhesion effects.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to an antibacterial and anti-adhesion ceramic coating and a preparation method thereof. Background Art

[0002] Paint is a commonly used chemical material, the main components of which are resin and various additives. It can form a protective film on the surface of objects and is widely used in mechanical equipment, building materials, furniture and other fields. However, its antibacterial and anti-adhesion effect is poor, so how to avoid this phenomenon is the key to solving the problem. For example, patent CN118496733A discloses an antibacterial and anti-mildew nano-ceramic composite coating and its preparation method. The nano-ceramic composite coating provided by the invention is obtained by chemical modification to obtain a resin component with antibacterial and anti-mildew properties, and also has the advantages of high impact resistance, good waterproof performance and good flame retardant performance, but the anti-adhesion effect is poor. Summary of the invention

[0003] 1. Technical issues to be solved

[0004] In order to solve the problems in the background technology, the present invention provides an antibacterial and anti-adhesion ceramic coating and a preparation method thereof, which has good flame retardant, antibacterial and anti-adhesion effects.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical solution: an antibacterial and anti-adhesion ceramic coating, comprising the following components by weight: 15-30 parts by weight of nano-ceramic particles, 4-7 parts by weight of phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, 5-8 parts by weight of fluorine-containing flame retardant, 10-12 parts by weight of acrylic resin, 0.1-0.25 parts by weight of leveling agent BYK-306, and 0.2-0.4 parts by weight of diluent butyl acetate;

[0007] The preparation method of the phosphorus-containing quaternary ammonium salt modified sulfaguanidine is:

[0008] (1) adding phosphorus pentoxide to triethyl thiophosphate, stirring and reacting at 45-60° C. for 2-4 hours, adding anhydrous ethanol, heating to 95-110° C., reacting for 10-14 hours, washing with deionized water, and drying to obtain diethyl thiophosphate;

[0009] (2) adding diethyl thiophosphate and 2,2-bis(bromomethyl)-1,3-propylene glycol to an acetone solvent, stirring to dissolve, and then adding a sodium hydroxide aqueous solution with a molar concentration of 5-7 mol / L, reacting at 60-80° C. for 4-7 hours, and then dropping dilute hydrochloric acid to neutralize, concentrating to remove the solvent, filtering, washing and drying to obtain an intermediate 1;

[0010] (3) adding sulfaguanidine to anhydrous ethanol solvent, stirring and mixing, heating to 70-95° C. to completely dissolve it, then continuing to add p-dimethylaminobenzaldehyde, stirring and reacting for 10-16 hours, then adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stirring and reacting at 75-85° C. for 6-10 hours, and then washing with anhydrous ethanol and deionized water 2-3 times each after completion, and drying to obtain modified sulfaguanidine;

[0011] (4) adding modified sulfaguanidine and 2-chloroethanol to N,N-dimethylformamide solvent, stirring and dissolving, and carrying out quaternization reaction at 60-80° C. for 7-15 hours. After the reaction, distilling under reduced pressure, washing and drying are performed to obtain hydroxylated quaternary ammonium salt modified sulfaguanidine;

[0012] (5) Adding hydroxylated quaternary ammonium salt-modified sulfaguanidine, intermediate 1, succinyl chloride and pyridine catalyst to a reactor filled with acetone solvent, reacting at 75-95° C. for 8-10 hours, adding water to the solution after the reaction, precipitating, filtering and washing to obtain phosphorus-containing quaternary ammonium salt-modified sulfaguanidine.

[0013] In the above reaction process, triethyl thiophosphate is reacted with phosphorus pentoxide and anhydrous ethanol to introduce a hydroxyl group to obtain diethyl thiophosphate, which is then further reacted with 2,2-di(bromomethyl)-1,3-propanediol to increase the degree of substitution of phosphorus and introduce a dihydroxyl group to obtain intermediate 1; the amino group in sulfaguanidine and the aldehyde group in p-dimethylaminobenzaldehyde are condensed, and then 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added thereto for an addition reaction to introduce a tertiary amine group, thereby obtaining modified sulfaguanidine; the tertiary amine group in the modified sulfaguanidine and the chlorine in 2-chloroethanol are reacted to introduce a quaternary ammonium salt group and a hydroxyl group, thereby obtaining hydroxylated quaternary ammonium salt-modified sulfaguanidine; the hydroxylated quaternary ammonium salt-modified sulfaguanidine and the hydroxyl group in intermediate 1 and the acyl chloride group in succinyl chloride are reacted to obtain phosphorus-containing quaternary ammonium salt-modified sulfaguanidine.

[0014] Furthermore, the mass ratio of triethyl thiophosphate, phosphorus pentoxide and anhydrous ethanol in (1) is 1:0.3-0.6:1.1-1.4.

[0015] Furthermore, the mass ratio of diethyl thiophosphate to 2,2-bis(bromomethyl)-1,3-propylene glycol in (2) is 1.2-1.6:1.

[0016] Furthermore, in (3), the mass ratio of sulfaguanidine, p-dimethylaminobenzaldehyde, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:0.8-1.5:2.2-2.6.

[0017] Furthermore, the mass ratio of the modified sulfaguanidine to 2-chloroethanol in (4) is 1:2.3-2.8.

[0018] Furthermore, in the (5), the mass ratio of the hydroxylated quaternary ammonium salt-modified sulfaguanidine, the intermediate 1, succinyl chloride, and the pyridine catalyst is 1.1-1.35:1:2.1-2.5:0.01-0.03.

[0019] Furthermore, the preparation method of the fluorine-containing flame retardant is: adding perfluorooctanoyl chloride and hydroxylated quaternary ammonium salt-modified sulfaguanidine to tetrahydrofuran solvent, and then continuing to add triethylamine catalyst thereto, reacting at 75-100° C. for 4-6 hours, and after the reaction is completed, removing the solvent by reduced pressure distillation, washing, and recrystallization to obtain the fluorine-containing flame retardant.

[0020] In the above reaction process, the acyl chloride group in perfluorooctanoyl chloride reacts with the hydroxyl group in hydroxylated quaternary ammonium salt-modified sulfaguanidine to obtain a fluorine-containing flame retardant.

[0021] Furthermore, the mass ratio of the perfluorooctanoyl chloride, the hydroxylated quaternary ammonium salt-modified sulfaguanidine, and the triethylamine catalyst is 1.4-1.6:1:0.02-0.03.

[0022] Furthermore, the preparation method of the antibacterial and anti-adhesion ceramic coating is as follows: nano-ceramic particles, phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, fluorine-containing flame retardant, acrylic resin, leveling agent BYK-306, and diluent butyl acetate are added into a stirrer, stirred for 8-14 minutes, and then the antibacterial and anti-adhesion ceramic coating is obtained.

[0023] (III) Beneficial effects:

[0024] In the technical solution of the present invention, nano ceramic particles, phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, fluorine-containing flame retardant, acrylic resin, leveling agent BYK-306, and diluent butyl acetate are added into a stirrer and stirred to obtain an antibacterial and anti-adhesion ceramic coating.

[0025] Phosphorus and guanidine groups in phosphorus-containing quaternary ammonium salt-modified sulfaguanidine and fluorine-containing flame retardants have good flame retardant effects, and the quaternary ammonium salts have good antibacterial effects. When phosphorus is heated, it will decompose to generate phosphoric acid, and further polymerize into polymetaphosphoric acid. The generated polymetaphosphoric acid is a strong dehydrating agent that can dehydrate the polymer surface to form a carbon film. This carbon film not only isolates oxygen in the air, but also has a flame retardant effect; guanidine groups can decompose to produce non-flammable gases such as ammonia and nitrogen during combustion, which has a flame retardant effect. Quaternary ammonium salt groups also have good anti-adhesion effects. The introduction of fluorine elements can form a smooth fluorocarbon layer on the surface that is not easy to adhere to objects, so it also has a good anti-adhesion effect. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Example 1

[0028] (1) Add 0.3 g of phosphorus pentoxide to 1 g of triethyl thiophosphate, stir and react at 45° C. for 2 h. After the reaction is completed, add 1.1 g of anhydrous ethanol, heat to 95° C., and react for 10 h. After the reaction is completed, wash with deionized water and dry to obtain diethyl thiophosphate;

[0029] (2) Add 1.2 g of diethyl thiophosphate and 1 g of 2,2-bis(bromomethyl)-1,3-propanediol to 65 mL of acetone solvent, stir to dissolve, then continue to add 4 ml of 5 mol / L sodium hydroxide aqueous solution, react at 60° C. for 4 h, and then dropwise add dilute hydrochloric acid to neutralize to pH 7, concentrate to remove the solvent, filter, wash and dry to obtain intermediate 1;

[0030] (3) adding 1 g of sulfaguanidine to 70 mL of anhydrous ethanol solvent, stirring and mixing, heating to 70° C. to completely dissolve it, then adding 0.8 g of p-dimethylaminobenzaldehyde, stirring and reacting for 10 h, then adding 2.2 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stirring and reacting at 75° C. for 6 h, and then washing with anhydrous ethanol and deionized water twice each, and drying to obtain modified sulfaguanidine;

[0031] (4) adding 1 g of modified sulfaguanidine and 2.3 g of 2-chloroethanol to 75 mL of N,N-dimethylformamide solvent, stirring and dissolving, and carrying out quaternization reaction at 60° C. for 7 h. After the reaction, distilling under reduced pressure, washing and drying are performed to obtain hydroxylated quaternary ammonium salt modified sulfaguanidine;

[0032] (5) Add 1.1 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine, 1 g of intermediate 1, 2.1 g of succinyl chloride and 0.01 g of pyridine catalyst to a reactor filled with 60 mL of acetone solvent, react at 75° C. for 8 h, add water to the solution after the reaction, precipitate, filter and wash to obtain phosphorus-containing quaternary ammonium salt-modified sulfaguanidine;

[0033] (6) 1.4 g of perfluorooctanoyl chloride and 1 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine were added to 76 mL of tetrahydrofuran solvent, and then 0.02 g of triethylamine catalyst was added thereto, and the mixture was reacted at 75° C. for 4 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the mixture was washed and recrystallized to obtain a fluorinated flame retardant;

[0034] (7) 15 g of nano-ceramic particles, 4 g of phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, 5 g of fluorine-containing flame retardant, 10 g of acrylic resin, 0.1 g of leveling agent BYK-306, and 0.2 g of diluent butyl acetate were added into a stirrer and stirred for 8 min. After stirring, an antibacterial and anti-adhesion ceramic coating was obtained.

[0035] Example 2

[0036] (1) Add 0.6 g of phosphorus pentoxide to 1 g of triethyl thiophosphate, stir and react at 60° C. for 4 h. After the reaction, add 1.4 g of anhydrous ethanol, heat to 110° C., react for 14 h. After the reaction, wash with deionized water and dry to obtain diethyl thiophosphate;

[0037] (2) Add 3.2 g of diethyl thiophosphate and 2 g of 2,2-bis(bromomethyl)-1,3-propanediol to 80 mL of acetone solvent, stir to dissolve, then continue to add 7 ml of 7 mol / L sodium hydroxide aqueous solution, react at 80° C. for 7 h, and then dropwise add dilute hydrochloric acid to neutralize to pH 7, concentrate to remove the solvent, filter, wash and dry to obtain intermediate 1;

[0038] (3) adding 1 g of sulfaguanidine to 90 mL of anhydrous ethanol solvent, stirring and mixing, heating to 95° C. to completely dissolve it, then adding 1.5 g of p-dimethylaminobenzaldehyde, stirring and reacting for 16 h, then adding 2.2-2.6 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stirring and reacting at 85° C. for 10 h, and then washing with anhydrous ethanol and deionized water 3 times each, and drying to obtain modified sulfaguanidine;

[0039] (4) adding 3 g of modified sulfaguanidine and 8.4 g of 2-chloroethanol to 95 mL of N,N-dimethylformamide solvent, stirring and dissolving, and carrying out quaternization reaction at 80° C. for 15 h. After completion, distilling under reduced pressure, washing and drying to obtain hydroxylated quaternary ammonium salt modified sulfaguanidine;

[0040] (5) Add 1.35 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine, 1 g of intermediate 1, 2.5 g of succinyl chloride and 0.03 g of pyridine catalyst to a reactor filled with 85 mL of acetone solvent, and react at 95° C. for 10 h. After the reaction, add water to the solution to precipitate, filter and wash to obtain phosphorus-containing quaternary ammonium salt-modified sulfaguanidine;

[0041] (6) 1.6 g of perfluorooctanoyl chloride and 1 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine were added to 95 mL of tetrahydrofuran solvent, and then 0.03 g of triethylamine catalyst was added thereto, and the mixture was reacted at 100° C. for 6 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the mixture was washed and recrystallized to obtain a fluorinated flame retardant;

[0042] (7) 30 g of nano-ceramic particles, 7 g of phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, 8 g of fluorine-containing flame retardant, 12 g of acrylic resin, 0.25 g of leveling agent BYK-306, and 0.4 g of diluent butyl acetate were added into a stirrer and stirred for 14 min to obtain an antibacterial and anti-adhesion ceramic coating.

[0043] Example 3

[0044] (1) Add 0.5 g of phosphorus pentoxide to 1 g of triethyl thiophosphate, stir and react at 55° C. for 3 h. After the reaction, add 1.3 g of anhydrous ethanol, heat to 100° C., react for 12 h. After the reaction, wash with deionized water, and dry to obtain diethyl thiophosphate;

[0045] (2) Add 1.8 g of diethyl thiophosphate and 1.5 g of 2,2-bis(bromomethyl)-1,3-propanediol to 75 mL of acetone solvent, stir to dissolve, then continue to add 5 ml of 6 mol / L sodium hydroxide aqueous solution, react at 70° C. for 6 h, and then dropwise add dilute hydrochloric acid to neutralize to pH 7, concentrate to remove the solvent, filter, wash and dry to obtain intermediate 1;

[0046] (3) 1 g of sulfaguanidine was added to 80 mL of anhydrous ethanol solvent, stirred and mixed, heated to 85° C. to completely dissolve it, and then 1.2 g of p-dimethylaminobenzaldehyde was added, stirred and reacted for 13 h, and then 2.4 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added thereto, stirred and reacted at 80° C. for 8 h, and after completion, the mixture was washed twice with anhydrous ethanol and deionized water, respectively, and dried to obtain modified sulfaguanidine;

[0047] (4) adding 2 g of modified sulfaguanidine and 6.2 g of 2-chloroethanol to 85 mL of N,N-dimethylformamide solvent, stirring and dissolving, and carrying out quaternization reaction at 70° C. for 12 h. After the reaction, distilling under reduced pressure, washing and drying are performed to obtain hydroxylated quaternary ammonium salt modified sulfaguanidine;

[0048] (5) Add 1.2 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine, 1 g of intermediate 1, 2.3 g of succinyl chloride and 0.02 g of pyridine catalyst to a reactor filled with 75 mL of acetone solvent, and react at 80° C. for 9 h. After the reaction, add water to the solution to precipitate, filter and wash to obtain phosphorus-containing quaternary ammonium salt-modified sulfaguanidine;

[0049] (6) 1.5 g of perfluorooctanoyl chloride and 1 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine were added to 82 mL of tetrahydrofuran solvent, and then 0.025 g of triethylamine catalyst was added thereto, and the mixture was reacted at 85° C. for 5 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the mixture was washed and recrystallized to obtain a fluorinated flame retardant;

[0050] (7) 25 g of nano-ceramic particles, 6 g of phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, 7 g of fluorine-containing flame retardant, 11 g of acrylic resin, 0.15 g of leveling agent BYK-306, and 0.3 g of diluent butyl acetate were added into a stirrer and stirred for 12 min. After stirring, an antibacterial and anti-adhesion ceramic coating was obtained.

[0051] Example 4

[0052] (1) Add 0.3 g of phosphorus pentoxide to 1 g of triethyl thiophosphate, stir and react at 45° C. for 2 h. After the reaction is completed, add 1.1 g of anhydrous ethanol, heat to 95° C., and react for 10 h. After the reaction is completed, wash with deionized water and dry to obtain diethyl thiophosphate;

[0053] (2) Add 1.2 g of diethyl thiophosphate and 1 g of 2,2-bis(bromomethyl)-1,3-propanediol to 65 mL of acetone solvent, stir to dissolve, then continue to add 7 ml of 5 mol / L sodium hydroxide aqueous solution, react at 60° C. for 4 h, and then dropwise add dilute hydrochloric acid to neutralize to pH 7, concentrate to remove the solvent, filter, wash and dry to obtain intermediate 1;

[0054] (3) adding 1 g of sulfaguanidine to 90 mL of anhydrous ethanol solvent, stirring and mixing, heating to 95° C. to completely dissolve it, then adding 1.5 g of p-dimethylaminobenzaldehyde, stirring and reacting for 16 h, then adding 2.2-2.6 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stirring and reacting at 85° C. for 10 h, and then washing with anhydrous ethanol and deionized water 3 times each, and drying to obtain modified sulfaguanidine;

[0055] (4) adding 3 g of modified sulfaguanidine and 8.4 g of 2-chloroethanol to 95 mL of N,N-dimethylformamide solvent, stirring and dissolving, and carrying out quaternization reaction at 80° C. for 15 h. After completion, distilling under reduced pressure, washing and drying to obtain hydroxylated quaternary ammonium salt modified sulfaguanidine;

[0056] (5) Add 1.2 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine, 1 g of intermediate 1, 2.3 g of succinyl chloride and 0.02 g of pyridine catalyst to a reactor filled with 75 mL of acetone solvent, and react at 80° C. for 9 h. After the reaction, add water to the solution to precipitate, filter and wash to obtain phosphorus-containing quaternary ammonium salt-modified sulfaguanidine;

[0057] (6) 1.5 g of perfluorooctanoyl chloride and 1 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine were added to 82 mL of tetrahydrofuran solvent, and then 0.025 g of triethylamine catalyst was added thereto, and the mixture was reacted at 75° C. for 4 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the mixture was washed and recrystallized to obtain a fluorinated flame retardant;

[0058] (7) 25 g of nano-ceramic particles, 6 g of phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, 7 g of fluorine-containing flame retardant, 11 g of acrylic resin, 0.15 g of leveling agent BYK-306, and 0.3 g of diluent butyl acetate were added into a stirrer and stirred for 12 min. After stirring, an antibacterial and anti-adhesion ceramic coating was obtained.

[0059] Example 5

[0060] (1) Add 0.6 g of phosphorus pentoxide to 1 g of triethyl thiophosphate, stir and react at 60° C. for 4 h. After the reaction, add 1.4 g of anhydrous ethanol, heat to 110° C., react for 14 h. After the reaction, wash with deionized water and dry to obtain diethyl thiophosphate;

[0061] (2) Add 3.2 g of diethyl thiophosphate and 2 g of 2,2-bis(bromomethyl)-1,3-propanediol to 80 mL of acetone solvent, stir to dissolve, then continue to add 4 ml of 7 mol / L sodium hydroxide aqueous solution, react at 80° C. for 7 h, and then dropwise add dilute hydrochloric acid to neutralize to pH 7, concentrate to remove the solvent, filter, wash and dry to obtain intermediate 1;

[0062] (3) 1 g of sulfaguanidine was added to 80 mL of anhydrous ethanol solvent, stirred and mixed, heated to 85° C. to completely dissolve it, and then 1.2 g of p-dimethylaminobenzaldehyde was added, stirred and reacted for 13 h, and then 2.4 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added thereto, stirred and reacted at 80° C. for 8 h, and after completion, the mixture was washed twice with anhydrous ethanol and deionized water, respectively, and dried to obtain modified sulfaguanidine;

[0063] (4) adding 2 g of modified sulfaguanidine and 6.2 g of 2-chloroethanol to 85 mL of N,N-dimethylformamide solvent, stirring and dissolving, and carrying out quaternization reaction at 70° C. for 12 h. After the reaction, distilling under reduced pressure, washing and drying are performed to obtain hydroxylated quaternary ammonium salt modified sulfaguanidine;

[0064] (5) Add 1.2 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine, 1 g of intermediate 1, 2.3 g of succinyl chloride and 0.02 g of pyridine catalyst to a reactor filled with 75 mL of acetone solvent, and react at 80° C. for 9 h. After the reaction, add water to the solution to precipitate, filter and wash to obtain phosphorus-containing quaternary ammonium salt-modified sulfaguanidine;

[0065] (6) 1.5 g of perfluorooctanoyl chloride and 1 g of hydroxylated quaternary ammonium salt-modified sulfaguanidine were added to 82 mL of tetrahydrofuran solvent, and then 0.025 g of triethylamine catalyst was added thereto, and the mixture was reacted at 100° C. for 4 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the mixture was washed and recrystallized to obtain a fluorinated flame retardant;

[0066] (7) 25 g of nano-ceramic particles, 6 g of phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, 7 g of fluorine-containing flame retardant, 11 g of acrylic resin, 0.15 g of leveling agent BYK-306, and 0.3 g of diluent butyl acetate were added into a stirrer and stirred for 12 min. After stirring, an antibacterial and anti-adhesion ceramic coating was obtained.

[0067] Comparative Example 1

[0068] The difference between this comparative example and Example 5 is that sulfaguanidine is used instead of phosphorus-containing quaternary ammonium salt to modify sulfaguanidine.

[0069] Comparative Example 2

[0070] The difference between this comparative example and Example 5 is that perfluorooctanoyl chloride is used instead of the fluorinated flame retardant.

[0071] Comparative Example 3

[0072] The difference between this comparative example and Example 5 is that sulfaguanidine is used instead of sulfaguanidine modified by phosphorus-containing quaternary ammonium salt, and perfluorooctanoyl chloride is used instead of fluorine-containing flame retardant.

[0073] The oxygen index meter was used to test the limiting oxygen index of the coating, and the horizontal and vertical combustion instrument was used to test the combustion grade of the coating. The test results are shown in Table 1.

[0074] Table 1: Flame retardancy tests.

[0075]

[0076]

[0077] It can be seen from Table 1 that Examples 1-5 of the present invention have better flame retardant effects than Comparative Examples 1-3.

[0078] Pipette 1 mL of a 10 8 CFU / mL of Staphylococcus aureus was added to PBS buffer, and then diluted 10-fold to 10 5 CFU / mL, then add the coating sample (1cm×1cm×0.2cm), and then culture it in a constant temperature incubator at 37℃ with shaking for 24h. After culture, add PBS buffer to dilute the bacterial solution 10 times in sequence, and then transfer 0.5mL of the bacterial solution to the agar medium, and continue to culture it at 37℃ with shaking for 24h. After culture, count the colonies and count the antibacterial rate.

[0079] Table 2: Antibacterial performance test.

[0080] Group Antibacterial rate (%) Example 1 98.4 Example 2 99.6 Example 3 98.7 Example 4 98.3 Example 5 98.7 Comparative Example 1 84.1 Comparative Example 2 81.3 Comparative Example 3 78.2

[0081] It can be seen from Table 2 that Examples 1-5 of the present invention have better antibacterial effects than Comparative Examples 1-3.

[0082] The anti-adhesion performance of bacteria is measured by the contact angle test method. The contact angle refers to the angle from the solid-liquid interface through the liquid interior to the gas-liquid interface at the junction of solid, liquid and gas phases. It is called the contact angle, also known as the wetting angle. The larger the contact angle, the less the liquid wets the surface and the better the anti-adhesion performance.

[0083] Table 3: Anti-adhesion performance test.

[0084] Group Contact angle (°) Example 1 126.9 Example 2 132.5 Example 3 128.7 Example 4 128.6 Example 5 129.5 Comparative Example 1 101.2 Comparative Example 2 98.5 Comparative Example 3 83.2

[0085] It can be seen from Table 3 that Examples 1-5 of the present invention have better anti-adhesion effects than Comparative Examples 1-3.

[0086] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0087] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. An antibacterial and anti-adhesion ceramic coating, characterized in that: The invention comprises the following components by weight: 15-30 parts by weight of nano ceramic particles, 4-7 parts by weight of phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, 5-8 parts by weight of fluorine-containing flame retardant, 10-12 parts by weight of acrylic resin, 0.1-0.25 parts by weight of leveling agent BYK-306, and 0.2-0.4 parts by weight of diluent butyl acetate; The preparation method of the phosphorus-containing quaternary ammonium salt modified sulfaguanidine is: (1) adding phosphorus pentoxide to triethyl thiophosphate, stirring and reacting at 45-60° C. for 2-4 hours, adding anhydrous ethanol, heating to 95-110° C., reacting for 10-14 hours, washing with deionized water, and drying to obtain diethyl thiophosphate; (2) adding diethyl thiophosphate and 2,2-bis(bromomethyl)-1,3-propylene glycol to an acetone solvent, stirring to dissolve, and then adding a sodium hydroxide aqueous solution with a molar concentration of 5-7 mol / L, reacting at 60-80° C. for 4-7 hours, and then dropping dilute hydrochloric acid to neutralize, concentrating to remove the solvent, filtering, washing and drying to obtain an intermediate 1; (3) adding sulfaguanidine to anhydrous ethanol solvent, stirring and mixing, heating to 70-95° C. to completely dissolve it, then continuing to add p-dimethylaminobenzaldehyde, stirring and reacting for 10-16 hours, then adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stirring and reacting at 75-85° C. for 6-10 hours, and then washing with anhydrous ethanol and deionized water 2-3 times each after completion, and drying to obtain modified sulfaguanidine; (4) adding modified sulfaguanidine and 2-chloroethanol to N,N-dimethylformamide solvent, stirring and dissolving, and carrying out quaternization reaction at 60-80° C. for 7-15 hours. After the reaction, distilling under reduced pressure, washing and drying are performed to obtain hydroxylated quaternary ammonium salt modified sulfaguanidine; (5) adding hydroxylated quaternary ammonium salt-modified sulfaguanidine, intermediate 1, succinyl chloride and pyridine catalyst to a reactor filled with acetone solvent, reacting at 75-95° C. for 8-10 hours, adding water to the solution after the reaction, precipitating, filtering and washing to obtain phosphorus-containing quaternary ammonium salt-modified sulfaguanidine; The mass ratio of the hydroxylated quaternary ammonium salt-modified sulfaguanidine, the intermediate 1, succinyl chloride, and the pyridine catalyst in (5) is 1.1-1.35:1:2.1-2.5:0.01-0.03; The preparation method of the fluorine-containing flame retardant is as follows: perfluorooctanoyl chloride and hydroxylated quaternary ammonium salt-modified sulfaguanidine are added to a tetrahydrofuran solvent, and then a triethylamine catalyst is added thereto, and the reaction is carried out at 75-100° C. for 4-6 hours. After the reaction is completed, the solvent is removed by reduced pressure distillation, and the fluorine-containing flame retardant is washed and recrystallized to obtain the fluorine-containing flame retardant.

2. The antibacterial and anti-adhesion ceramic coating according to claim 1, characterized in that: The mass ratio of triethyl thiophosphate, phosphorus pentoxide and anhydrous ethanol in (1) is 1:0.3-0.6:1.1-1.

4.

3. The antibacterial and anti-adhesion ceramic coating according to claim 1, characterized in that: The mass ratio of diethyl thiophosphate to 2,2-bis(bromomethyl)-1,3-propylene glycol in (2) is 1.2-1.6:

1.

4. The antibacterial and anti-adhesion ceramic coating according to claim 1, characterized in that: The mass ratio of sulfaguanidine, p-dimethylaminobenzaldehyde and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in (3) is 1:0.8-1.5:2.2-2.

6.

5. The antibacterial and anti-adhesion ceramic coating according to claim 1, characterized in that: The mass ratio of modified sulfaguanidine to 2-chloroethanol in (4) is 1:2.3-2.

8.

6. The antibacterial and anti-adhesion ceramic coating according to claim 1, characterized in that: The mass ratio of the perfluorooctanoyl chloride, hydroxylated quaternary ammonium salt modified sulfaguanidine and triethylamine catalyst is 1.4-1.6:1:0.02-0.

03.

7. A method for preparing the antibacterial and anti-adhesion ceramic coating according to any one of claims 1 to 6, characterized in that: The preparation method of the antibacterial and anti-adhesion ceramic coating comprises the following steps: adding nano ceramic particles, phosphorus-containing quaternary ammonium salt-modified sulfaguanidine, fluorine-containing flame retardant, acrylic resin, leveling agent BYK-306, and diluent butyl acetate into a stirrer, stirring for 8-14 minutes, and obtaining the antibacterial and anti-adhesion ceramic coating.

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