Antibacterial polyvinylpyrrolidone composite coating and preparation method thereof

Abstract

The invention discloses an antibacterial polyvinylpyrrolidone composite coating and a preparation method thereof, and belongs to the technical field of antibacterial coatings, the antibacterial polyvinylpyrrolidone composite coating comprises the following raw materials: isophorone diisocyanate, dibutyltin dilaurate, polyether triol, hydroxyethyl acrylate, a reactive diluent, antibacterial modified polyvinylpyrrolidone and a photoinitiator 1173; wherein the antibacterial modified polyvinylpyrrolidone is prepared by the following steps: adding functionalized polyvinylpyrrolidone into deionized water, uniformly stirring, then adding methacryloyloxyethyl trimethyl ammonium chloride and a benzisothiazolinone derivative, stirring and mixing, then adding 4, 4 '-azo (4-cyanevaleric acid), simultaneously introducing nitrogen to remove air, and stirring and mixing to obtain the antibacterial modified polyvinylpyrrolidone. Heating to 70 DEG C, reacting for 6-7 hours, dialyzing after the reaction is completed, and freeze-drying to obtain the antibacterial modified polyvinylpyrrolidone. The composite coating prepared by the invention has excellent antibacterial performance and long-acting antibacterial effect at the same time.

Description

Technical Field

[0001] The invention belongs to the technical field of antibacterial coatings, and in particular relates to an antibacterial polyvinyl pyrrolidone composite coating and a preparation method thereof. Background Art

[0002] Antimicrobial coatings can form an antimicrobial layer on the coating surface, effectively killing pathogens and microorganisms on the surface. In addition, antimicrobial coatings can also protect products from damage in some special environments, such as moisture, degradation, chemical or mechanical damage, etc., and are therefore widely used in toilets, hospitals, nursing homes, schools, public transportation, offices and other places.

[0003] Benzisothiazolinone compounds have become an important additive in antibacterial coatings due to their broad-spectrum antibacterial activity, influence on cell membranes, and destruction of biofilms. Benzisothiazolinone has a strong penetrating effect on microbial cell walls and cell membranes, and can enter the cells to act on proteins and other molecules containing S elements, so that the S atoms in the benzoisothiazolinone molecules are attacked by nucleophilic reagents, resulting in SN bond rupture, and forming SS bonds with receptors, thereby causing the normal physiological functions of microbial cells to be destroyed. Directly blending benzoisothiazolinone with polymer coatings, killing bacteria by releasing sterilization, cannot maintain a long-term antibacterial mechanism, and may also cause a series of problems such as environmental pollution. Therefore, how to use benzoisothiazolinone compounds as antibacterial agents to improve the antibacterial properties of antibacterial coatings is a technical problem that needs to be solved at present. Summary of the invention

[0004] The object of the present invention is to provide an antibacterial polyvinyl pyrrolidone composite coating and a preparation method thereof, so as to solve the problems in the background technology.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An antibacterial polyvinyl pyrrolidone composite coating comprises the following raw materials in parts by weight:

[0007] 12-13 parts of isophorone diisocyanate, 0.3-0.35 parts of dibutyltin dilaurate, 83-85 parts of polyether triol, 3.6-4 parts of hydroxyethyl acrylate, 100 parts of reactive diluent, 15-20 parts of antibacterial modified polyvinyl pyrrolidone and 0.08-1 parts of photoinitiator 1173;

[0008] The antibacterial modified polyvinyl pyrrolidone is prepared by the following steps:

[0009] Functionalized polyvinyl pyrrolidone is added to deionized water and stirred evenly, then methacryloyloxyethyl trimethyl ammonium chloride and benzisothiazolinone derivatives are added and stirred and mixed evenly, and then 4,4'-azo (4-cyanovaleric acid) is added, and nitrogen is filled to exclude air to protect the reaction, and then the temperature is raised to 70°C for reaction for 6-7 hours. After the reaction is completed, it is dialyzed with a 1000Da dialysis bag, and freeze-dried to obtain antibacterial modified polyvinyl pyrrolidone. The dithioester group contained in the functionalized polyvinyl pyrrolidone has the function of reversible addition-fragmentation chain transfer polymerization, so that methacryloyloxyethyl trimethyl ammonium chloride and benzisothiazolinone derivatives are blocked on the molecular chain of the functionalized polyvinyl pyrrolidone to obtain antibacterial modified polyvinyl pyrrolidone with excellent antibacterial properties.

[0010] Furthermore, the active diluent is a mixture of isobornyl methacrylate, 1,6-hexanediol diacrylate, and trimethylolpropane triacrylate in a mass ratio of 5:3:2.

[0011] Furthermore, the usage ratio of the functionalized polyvinyl pyrrolidone, deionized water, methacryloyloxyethyl trimethyl ammonium chloride, benzisothiazolinone derivative and 4,4'-azo (4-cyanovaleric acid) is 1 g: 20 mL: 1-1.5 g: 1.5-2 g: 40 mg.

[0012] Furthermore, the functionalized polyvinyl pyrrolidone is prepared by the following steps:

[0013] Step A1, adding potassium ethyl xanthate to anhydrous ethanol and stirring to dissolve, then slowly adding 1-bromoethylbenzene ethanol solution dropwise under ice-water bath conditions, heating to room temperature while stirring and reacting for 12 hours, filtering and rotary evaporation, and then performing column chromatography separation with a solution of petroleum ether: ethyl acetate = 20:1, and then rotary evaporation to remove the solvent to obtain a xanthate compound; potassium ethyl xanthate and 1-bromoethylbenzene are subjected to substitution reaction in anhydrous ethanol to obtain a xanthate compound containing a dithioester group;

[0014] Step A2, adding azobisisobutyronitrile and xanthate compound to N-vinyl pyrrolidone and stirring and mixing, while introducing nitrogen to remove oxygen, stirring and reacting at 70°C for 2h, then adding dichloromethane and stirring and mixing for 30min, then slowly pouring into sufficient anhydrous ether for precipitation to remove unreacted small molecules, washing with ether, filtering, and freeze-drying to obtain functionalized polyvinyl pyrrolidone. Under the initiation of azobisisobutyronitrile, the xanthate compound is used to polymerize N-vinyl pyrrolidone to obtain a functionalized polyvinyl pyrrolidone containing a dithioester group at the end.

[0015] Furthermore, the dosage ratio of the potassium ethyl xanthate, anhydrous ethanol and 1-bromoethylphenethanol solution is 4g:100mL:28-30mL; the volume ratio of 1-bromoethylbenzene to anhydrous ethanol in the 1-bromoethylphenethanol solution is 3:25.

[0016] Furthermore, the dosage ratio of the azobisisobutyronitrile, the xanthate compound, the N-vinyl pyrrolidone, the dichloromethane and the deionized water is 130 mg: 0.45-0.5 mL: 32-35 mL: 100-150 mL.

[0017] Furthermore, the benzisothiazolinone derivative is prepared by the following steps:

[0018] Step B1, adding benzisothiazolinone and potassium carbonate to N,N-dimethylformamide and stirring to mix, then slowly adding 1,3-dibromo-2-propanol, and heating to 70°C and stirring to react for 12 hours, cooling to room temperature and adding deionized water, then extracting with ethyl acetate, filtering and rotary evaporation to remove ethyl acetate, and purifying with a chromatographic column to obtain an intermediate; the imino group in the benzisothiazolinone and the bromine in the 1,3-dibromo-2-propanol undergo a nucleophilic substitution reaction to obtain an intermediate containing two symmetrical benzisothiazolinones;

[0019] Step B2, adding the intermediate and potassium carbonate to dry dichloromethane and stirring to mix, then adding acryloyl chloride at 0°C under nitrogen protection, stirring and reacting at room temperature for 24 hours, cooling to room temperature, adding deionized water, then extracting with ethyl acetate, filtering and rotary evaporation to remove ethyl acetate, purifying with a chromatographic column to obtain a benzisothiazolinone derivative. The hydroxyl group in the intermediate further undergoes a nucleophilic substitution reaction with acryloyl chloride, thereby obtaining a benzisothiazolinone derivative containing a carbon-carbon double bond.

[0020] Furthermore, the usage ratio of the benzisothiazolinone, potassium carbonate, N,N-dimethylformamide and 1,3-dibromo-2-propanol is 3g:2.7g:30mL:2.1-2.2g:30-50mL.

[0021] Furthermore, the usage ratio of the intermediate, potassium carbonate, dichloromethane, acryloyl chloride and deionized water is 3.6 g: 1.4 g: 30 mL: 1.8-2 g: 30-50 mL.

[0022] A method for preparing an antibacterial polyvinyl pyrrolidone composite coating comprises the following steps:

[0023] Add dibutyltin dilaurate to isophorone diisocyanate, then slowly add polyether triol, stir and react at 50°C for 2 hours, then add hydroxyethyl acrylate, continue to keep warm and react for 1.5 hours, cool to room temperature, add active diluent to obtain polyurethane acrylate prepolymer; add antibacterial modified polyvinyl pyrrolidone and photoinitiator to the polyurethane acrylate prepolymer, stir and mix to obtain antibacterial polyvinyl pyrrolidone composite coating.

[0024] Beneficial effects of the present invention:

[0025] The present invention firstly utilizes functionalized polyvinyl pyrrolidone containing a dithioester group to carry out a block polymerization reaction with methacryloyloxyethyl trimethyl ammonium chloride and a benzisothiazolinone derivative, and blocks two different antibacterial compounds onto the molecular chain of the functionalized polyvinyl pyrrolidone. The molecular chain end of the prepared antibacterial modified polyvinyl pyrrolidone is still a dithioester group, which can continue to participate in the polymerization of a polyurethane acrylate base material, thereby fixing the antibacterial modified polyvinyl pyrrolidone in the polyurethane acrylate base material by chemical bonding, effectively avoiding the loss of bactericidal components and improving the long-term effectiveness of the antibacterial coating.

[0026] On the one hand, the present invention uses a quaternary ammonium salt antibacterial compound, methacryloyloxyethyl trimethyl ammonium chloride, in combination with a benzisothiazolinone antibacterial compound, a benzisothiazolinone derivative, to block the quaternary ammonium salt antibacterial compound on the molecular chain of functionalized polyvinyl pyrrolidone. The quaternary ammonium salt antibacterial compound can attack the membrane structure of bacteria inside the bacterial body, thereby killing the bacteria. The benzisothiazolinone derivative contains two benzisothiazolinone functional units, so that the number of functional units in contact with bacteria within a fixed area is more, thereby having stronger broad-spectrum antibacterial performance. The two antibacterial compounds act synergistically, which can not only avoid bacterial drug resistance, but also exert more excellent antibacterial performance. On the other hand, the excellent biocompatibility of polyvinyl pyrrolidone is utilized to attach to the membrane surface of bacteria and even enter the interior of bacteria, so that the antibacterial modified polyvinyl pyrrolidone with excellent antibacterial performance is fully contacted with the bacterial body, thereby achieving a more efficient effect of killing bacteria. DETAILED DESCRIPTION

[0027] 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.

[0028] Example 1

[0029] This embodiment provides a functionalized polyvinyl pyrrolidone, which is prepared by the following steps:

[0030] Step A1, adding 4 g of potassium ethyl xanthate to 100 mL of anhydrous ethanol and stirring to dissolve, then slowly adding dropwise 28 mL of 1-bromoethylphenethanol solution in an ice-water bath, wherein the volume ratio of 1-bromoethylbenzene to anhydrous ethanol in the 1-bromoethylphenethanol solution is 3:25, warming to room temperature while reacting for 12 h, filtering and rotary evaporation, and then separating by column chromatography with a solution of petroleum ether: ethyl acetate = 20:1, and then rotary evaporation to remove the solvent to obtain a xanthate compound;

[0031] Step A2, add 130 mg of azobisisobutyronitrile and 0.45 mL of xanthate compound to 32 mL of N-vinylpyrrolidone and stir to mix, while introducing nitrogen to remove oxygen, stirring and reacting at 70 ° C for 2 hours, then adding 100 mL of dichloromethane and stirring to mix for 30 minutes, and then slowly pouring into a sufficient amount of anhydrous ether to precipitate, washing with ether, filtering, and freeze-drying to obtain functionalized polyvinylpyrrolidone.

[0032] Example 2

[0033] This embodiment provides a functionalized polyvinyl pyrrolidone, which is prepared by the following steps:

[0034] Step A1, adding 4 g of potassium ethyl xanthate to 100 mL of anhydrous ethanol and stirring to dissolve, then slowly adding dropwise 29 mL of 1-bromoethylphenethanol solution in an ice-water bath, wherein the volume ratio of 1-bromoethylbenzene to anhydrous ethanol in the 1-bromoethylphenethanol solution is 3:25, warming to room temperature while reacting for 12 h, filtering and rotary evaporation, and then separating by column chromatography with a solution of petroleum ether: ethyl acetate = 20:1, and then rotary evaporation to remove the solvent to obtain a xanthate compound;

[0035] Step A2, add 130 mg of azobisisobutyronitrile and 0.48 mL of xanthate compound to 34 mL of N-vinylpyrrolidone and stir to mix, while introducing nitrogen to remove oxygen, stirring and reacting at 70 ° C for 2 hours, then adding 130 mL of dichloromethane and stirring to mix for 30 minutes, and then slowly pouring into a sufficient amount of anhydrous ether to precipitate, washing with ether, filtering, and freeze-drying to obtain functionalized polyvinylpyrrolidone.

[0036] Example 3

[0037] This embodiment provides a functionalized polyvinyl pyrrolidone, which is prepared by the following steps:

[0038] Step A1, adding 4 g of potassium ethyl xanthate to 100 mL of anhydrous ethanol and stirring to dissolve, then slowly adding dropwise 30 mL of 1-bromoethylphenethanol solution in an ice-water bath, wherein the volume ratio of 1-bromoethylbenzene to anhydrous ethanol in the 1-bromoethylphenethanol solution is 3:25, warming to room temperature while reacting for 12 h, filtering and rotary evaporation, and then separating by column chromatography with a solution of petroleum ether: ethyl acetate = 20:1, and then rotary evaporation to remove the solvent to obtain a xanthate compound;

[0039] Step A2, add 130 mg of azobisisobutyronitrile and 0.5 mL of xanthate compound to 35 mL of N-vinylpyrrolidone and stir to mix, while introducing nitrogen to remove oxygen, stirring and reacting at 70 ° C for 2 hours, then adding 150 mL of dichloromethane and stirring to mix for 30 minutes, and then slowly pouring into a sufficient amount of anhydrous ether to precipitate, washing with ether, filtering, and freeze-drying to obtain functionalized polyvinylpyrrolidone.

[0040] Example 4

[0041] This embodiment provides a benzisothiazolinone derivative, which is prepared by the following steps:

[0042] Step B1, add 3 g of benzisothiazolinone and 2.7 g of potassium carbonate to 30 mL of N, N-dimethylformamide and stir to mix, then slowly add 2.1 g of 1,3-dibromo-2-propanol, and heat to 70 ° C. and stir to react for 12 h. After cooling to room temperature, add 30 mL of deionized water, and then extract with ethyl acetate. After filtering, remove ethyl acetate by rotary evaporation, and purify with a chromatographic column to obtain an intermediate;

[0043] Step B2, add 3.6 g of the intermediate and 1.4 g of potassium carbonate to 30 mL of dry dichloromethane and stir to mix, then add 1.8 g of acryloyl chloride at 0 ° C and nitrogen protection, and stir the reaction at room temperature for 24 hours. After cooling to room temperature, add 30 mL of deionized water, then extract with ethyl acetate, filter and evaporate to remove ethyl acetate, and purify with a chromatographic column to obtain a benzisothiazolinone derivative.

[0044] Example 5

[0045] This embodiment provides a benzisothiazolinone derivative, which is prepared by the following steps:

[0046] Step B1, add 3 g of benzisothiazolinone and 2.7 g of potassium carbonate to 30 mL of N, N-dimethylformamide and stir to mix, then slowly add 2.2 g of 1,3-dibromo-2-propanol, and heat to 70 ° C. and stir to react for 12 hours, cool to room temperature, add 40 mL of deionized water, and then extract with ethyl acetate, filter and evaporate to remove ethyl acetate, and purify with a chromatographic column to obtain an intermediate;

[0047] Step B2, add 3.6 g of the intermediate and 1.4 g of potassium carbonate to 30 mL of dry dichloromethane and stir to mix, then add 1.9 g of acryloyl chloride at 0 ° C and under nitrogen protection, and stir the reaction at room temperature for 24 hours. After cooling to room temperature, add 40 mL of deionized water, then extract with ethyl acetate, filter and evaporate to remove ethyl acetate, and purify with a chromatographic column to obtain a benzisothiazolinone derivative.

[0048] Example 6

[0049] This embodiment provides a benzisothiazolinone derivative, which is prepared by the following steps:

[0050] Step B1, add 3 g of benzisothiazolinone and 2.7 g of potassium carbonate to 30 mL of N, N-dimethylformamide and stir to mix, then slowly add 2.2 g of 1,3-dibromo-2-propanol, and heat to 70 ° C. and stir to react for 12 h. After cooling to room temperature, add 50 mL of deionized water, and then extract with ethyl acetate. After filtering, remove ethyl acetate by rotary evaporation, and purify with a chromatographic column to obtain an intermediate;

[0051] Step B2, add 3.6 g of the intermediate and 1.4 g of potassium carbonate to 30 mL of dry dichloromethane and stir to mix, then add 2 g of acryloyl chloride at 0 ° C and under nitrogen protection, and stir the reaction at room temperature for 24 hours. After cooling to room temperature, add 50 mL of deionized water, then extract with ethyl acetate, filter and evaporate to remove ethyl acetate, and purify with a chromatographic column to obtain a benzisothiazolinone derivative.

[0052] Example 7

[0053] This embodiment provides an antibacterial modified polyvinyl pyrrolidone, which is prepared by the following steps:

[0054] 1 g of the functionalized polyvinyl pyrrolidone prepared in Example 1 was added to 20 mL of deionized water and stirred evenly, then 1 g of methacryloyloxyethyl trimethyl ammonium chloride and 2 g of the benzisothiazolinone derivative prepared in Example 4 were added and stirred evenly, and then 40 mg of 4,4'-azo (4-cyanovaleric acid) was added, and nitrogen was introduced to exclude air. The temperature was raised to 70° C. and reacted for 6 h. After the reaction was completed, it was dialyzed with a 1000 Da dialysis bag and freeze-dried to obtain antibacterial modified polyvinyl pyrrolidone.

[0055] Example 8

[0056] This embodiment provides an antibacterial modified polyvinyl pyrrolidone, which is prepared by the following steps:

[0057] 1 g of the functionalized polyvinyl pyrrolidone prepared in Example 2 was added to 20 mL of deionized water and stirred evenly, and then 1.2 g of methacryloyloxyethyl trimethyl ammonium chloride and 1.8 g of the benzisothiazolinone derivative prepared in Example 5 were added and stirred evenly, and then 40 mg of 4,4'-azo (4-cyanovaleric acid) was added, and nitrogen was introduced to exclude air. The temperature was raised to 70°C and reacted for 7 hours. After the reaction was completed, it was dialyzed with a 1000Da dialysis bag and freeze-dried to obtain antibacterial modified polyvinyl pyrrolidone.

[0058] Example 9

[0059] This embodiment provides an antibacterial modified polyvinyl pyrrolidone, which is prepared by the following steps:

[0060] 1 g of the functionalized polyvinyl pyrrolidone prepared in Example 3 was added to 20 mL of deionized water and stirred evenly, and then 1.5 g of methacryloyloxyethyl trimethyl ammonium chloride and 1.5 g of the benzisothiazolinone derivative prepared in Example 6 were added and stirred and mixed evenly, and then 40 mg of 4,4'-azo (4-cyanovaleric acid) was added, and nitrogen was introduced to exclude air. The temperature was raised to 70° C. and reacted for 7 h. After the reaction was completed, it was dialyzed with a 1000 Da dialysis bag and freeze-dried to obtain antibacterial modified polyvinyl pyrrolidone.

[0061] Comparative Example 1

[0062] This comparative example is different from Example 9 in that 1.5 g of methacryloyloxyethyltrimethylammonium chloride and 1.5 g of the benzisothiazolinone derivative prepared in Example 6 are replaced by 3 g of methacryloyloxyethyltrimethylammonium chloride, and the remaining raw materials and steps are the same.

[0063] Comparative Example 2

[0064] This comparative example is different from Example 9 in that 1.5 g of methacryloyloxyethyltrimethylammonium chloride and 1.5 g of the benzisothiazolinone derivative prepared in Example 6 are replaced by 3 g of the benzisothiazolinone derivative prepared in Example 6, and the remaining raw materials and steps are the same.

[0065] Example 10

[0066] An antibacterial polyvinyl pyrrolidone composite coating comprises the following raw materials in parts by weight:

[0067] 12 parts of isophorone diisocyanate, 0.3 parts of dibutyltin dilaurate, 83 parts of polyether triol, 3.6 parts of hydroxyethyl acrylate, 100 parts of active diluent, 15 parts of antibacterial modified polyvinyl pyrrolidone prepared in Example 7 and 11730.08 parts of photoinitiator; wherein the active diluent is a mixture of isobornyl methacrylate, 1,6-hexanediol diacrylate and trimethylolpropane triacrylate in a mass ratio of 5:3:2;

[0068] The preparation method of the antibacterial polyvinyl pyrrolidone composite coating comprises the following steps:

[0069] Add dibutyltin dilaurate to isophorone diisocyanate, then slowly add polyether triol, stir and react at 50°C for 2 hours, then add hydroxyethyl acrylate, continue to keep warm and react for 1.5 hours, cool to room temperature, add active diluent to obtain polyurethane acrylate prepolymer; add antibacterial modified polyvinyl pyrrolidone and photoinitiator to the polyurethane acrylate prepolymer, stir and mix to obtain antibacterial polyvinyl pyrrolidone composite coating.

[0070] Embodiment 11

[0071] An antibacterial polyvinyl pyrrolidone composite coating comprises the following raw materials in parts by weight:

[0072] 12.5 parts of isophorone diisocyanate, 0.32 parts of dibutyltin dilaurate, 84 parts of polyether triol, 3.8 parts of hydroxyethyl acrylate, 100 parts of active diluent, 18 parts of antibacterial modified polyvinyl pyrrolidone prepared in Example 8 and 0.09 parts of photoinitiator 1173; wherein the active diluent is a mixture of isobornyl methacrylate, 1,6-hexanediol diacrylate and trimethylolpropane triacrylate in a mass ratio of 5:3:2;

[0073] The preparation method of the antibacterial polyvinyl pyrrolidone composite coating comprises the following steps:

[0074] Add dibutyltin dilaurate to isophorone diisocyanate, then slowly add polyether triol, stir and react at 50°C for 2 hours, then add hydroxyethyl acrylate, continue to keep warm and react for 1.5 hours, cool to room temperature, add active diluent to obtain polyurethane acrylate prepolymer; add antibacterial modified polyvinyl pyrrolidone and photoinitiator to the polyurethane acrylate prepolymer, stir and mix to obtain antibacterial polyvinyl pyrrolidone composite coating.

[0075] Example 12

[0076] An antibacterial polyvinyl pyrrolidone composite coating comprises the following raw materials in parts by weight:

[0077] 13 parts of isophorone diisocyanate, 0.35 parts of dibutyltin dilaurate, 85 parts of polyether triol, 4 parts of hydroxyethyl acrylate, 100 parts of active diluent, 20 parts of antibacterial modified polyvinyl pyrrolidone prepared in Example 9 and 1 part of photoinitiator 1173; wherein the active diluent is a mixture of isobornyl methacrylate, 1,6-hexanediol diacrylate and trimethylolpropane triacrylate in a mass ratio of 5:3:2;

[0078] The preparation method of the antibacterial polyvinyl pyrrolidone composite coating comprises the following steps:

[0079] Add dibutyltin dilaurate to isophorone diisocyanate, then slowly add polyether triol, stir and react at 50°C for 2 hours, then add hydroxyethyl acrylate, continue to keep warm and react for 1.5 hours, cool to room temperature, add active diluent to obtain polyurethane acrylate prepolymer; add antibacterial modified polyvinyl pyrrolidone and photoinitiator to the polyurethane acrylate prepolymer, stir and mix to obtain antibacterial polyvinyl pyrrolidone composite coating.

[0080] Comparative Example 3

[0081] Compared with Example 12, this comparative example directly replaces the antibacterial modified polyvinylpyrrolidone prepared in Example 9 with an equal amount of an antibacterial component composed of methacryloyloxyethyltrimethylammonium chloride and the benzisothiazolinone derivative prepared in Example 6 in a mass ratio of 1:1, and the remaining raw materials and steps are the same.

[0082] Comparative Example 4

[0083] Compared with Example 12, this comparative example uses an equal amount of the antibacterial modified polyvinyl pyrrolidone prepared in Comparative Example 1 to replace the antibacterial modified polyvinyl pyrrolidone prepared in Example 9, and the other raw materials and steps are the same.

[0084] Comparative Example 5

[0085] Compared with Example 12, this comparative example uses an equal amount of the antibacterial modified polyvinyl pyrrolidone prepared in Comparative Example 2 to replace the antibacterial modified polyvinyl pyrrolidone prepared in Example 9, and the other raw materials and steps are the same.

[0086] The coatings prepared in Examples 10 to 12 and Comparative Examples 3 to 5 were applied to the surface of the glass plate, and then -2 The antibacterial coating was obtained by light curing under a high-pressure mercury lamp. The performance of the coating sample was tested. According to GB / T 6739-2006 standard, the pencil hardness of the coating was tested using an electric pencil hardness tester; according to GB / T21866-2008 standard, Escherichia coli and golden coccus were used to test the antibacterial performance of the coating; the results are shown in Table 1:

[0087] Table 1

[0088]

[0089] It can be seen from the data in Table 1 that the composite coatings prepared in Examples 10 to 12 have more excellent antibacterial properties.

[0090] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0091] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An antibacterial polyvinyl pyrrolidone composite coating, characterized in that: It includes the following raw materials in parts by weight: 12-13 parts of isophorone diisocyanate, 0.3-0.35 parts of dibutyltin dilaurate, 83-85 parts of polyether triol, 3.6-4 parts of hydroxyethyl acrylate, 100 parts of reactive diluent, 15-20 parts of antibacterial modified polyvinyl pyrrolidone and 11730.08-1 part of photoinitiator; The antibacterial modified polyvinyl pyrrolidone is prepared by the following steps: Functionalized polyvinyl pyrrolidone is added into deionized water and stirred evenly, and then methacryloyloxyethyl trimethyl ammonium chloride and benzisothiazolinone derivative are added and stirred and mixed, and then 4,4'-azo (4-cyanovaleric acid) is added, and nitrogen is introduced to exclude air, and then the temperature is raised to 70°C to react for 6-7h. After the reaction is completed, dialyzation is performed and freeze-drying is performed to obtain antibacterial modified polyvinyl pyrrolidone.

2. The antibacterial polyvinyl pyrrolidone composite coating according to claim 1, characterized in that: The active diluent is a mixture of isobornyl methacrylate, 1,6-hexanediol diacrylate and trimethylolpropane triacrylate in a mass ratio of 5:3:

2.

3. The antibacterial polyvinyl pyrrolidone composite coating according to claim 1, characterized in that: The dosage ratio of the functionalized polyvinyl pyrrolidone, deionized water, methacryloyloxyethyl trimethyl ammonium chloride, benzisothiazolinone derivative and 4,4'-azo (4-cyanovaleric acid) is 1g: 20mL: 1-1.5g: 1.5-2g: 40mg.

4. The antibacterial polyvinyl pyrrolidone composite coating according to claim 1, characterized in that: The functionalized polyvinyl pyrrolidone comprises the following steps: Step A1, adding potassium ethyl xanthate to anhydrous ethanol and stirring to dissolve, then slowly adding 1-bromoethylphenethanol solution dropwise under ice-water bath conditions, warming to room temperature while stirring for 12 hours, filtering and rotary evaporation, and then separating by column chromatography, and then rotary evaporation to remove the solvent to obtain a xanthate compound; Step A2, add azobisisobutyronitrile and xanthate compound to N-vinyl pyrrolidone and stir and mix, while introducing nitrogen, stirring and reacting at 70°C for 2 hours, then adding dichloromethane and stirring and mixing for 30 minutes, then pouring into sufficient anhydrous ether for precipitation, washing with ether, filtering, and freeze-drying to obtain functionalized polyvinyl pyrrolidone.

5. The antibacterial polyvinyl pyrrolidone composite coating according to claim 4, characterized in that: The dosage ratio of the potassium ethyl xanthate, anhydrous ethanol and 1-bromoethylphenethanol solution is 4g:100mL:28-30mL; the volume ratio of 1-bromoethylbenzene to anhydrous ethanol in the 1-bromoethylphenethanol solution is 3:

25.

6. The antibacterial polyvinyl pyrrolidone composite coating according to claim 4, characterized in that: The dosage ratio of the azobisisobutyronitrile, the xanthate compound, the N-vinyl pyrrolidone, the dichloromethane and the deionized water is 130 mg: 0.45-0.5 mL: 32-35 mL: 100-150 mL.

7. The antibacterial polyvinyl pyrrolidone composite coating according to claim 1, characterized in that: The benzisothiazolinone derivative is prepared by the following steps: Step B1, adding benzisothiazolinone and potassium carbonate to N,N-dimethylformamide and stirring to mix, then slowly adding 1,3-dibromo-2-propanol, and heating to 70° C. and stirring to react for 12 hours, cooling to room temperature, adding deionized water, and then extracting with ethyl acetate, filtering and rotary evaporation, and purifying to obtain an intermediate; Step B2: Add the intermediate and potassium carbonate to dry dichloromethane and stir to mix, then add acryloyl chloride at 0°C under nitrogen protection, and stir to react at room temperature for 24 hours. After cooling to room temperature, add deionized water, then extract with ethyl acetate, filter and remove ethyl acetate by rotary evaporation, purify to obtain a benzisothiazolinone derivative.

8. The antibacterial polyvinyl pyrrolidone composite coating according to claim 7, characterized in that: The usage ratio of the benzisothiazolinone, potassium carbonate, N,N-dimethylformamide and 1,3-dibromo-2-propanol is 3g:2.7g:30mL:2.1-2.2g:30-50mL.

9. The antibacterial polyvinyl pyrrolidone composite coating according to claim 7, characterized in that: The usage ratio of the intermediate, potassium carbonate, dichloromethane, acryloyl chloride and deionized water is 3.6 g: 1.4 g: 30 mL: 1.8-2 g: 30-50 mL.

10. The method for preparing an antibacterial polyvinyl pyrrolidone composite coating according to claim 1, characterized in that: The following steps are involved: Add dibutyltin dilaurate to isophorone diisocyanate, then slowly add polyether triol, stir and react at 50°C for 2 hours, then add hydroxyethyl acrylate, continue to keep warm and react for 1.5 hours, cool to room temperature, add active diluent to obtain polyurethane acrylate prepolymer; add antibacterial modified polyvinyl pyrrolidone and photoinitiator to the polyurethane acrylate prepolymer, stir and mix to obtain antibacterial polyvinyl pyrrolidone composite coating.

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