CN113088120A - Preparation method of antibacterial coating for surface of plastic product - Google Patents
Preparation method of antibacterial coating for surface of plastic product Download PDFInfo
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- CN113088120A CN113088120A CN202110401517.1A CN202110401517A CN113088120A CN 113088120 A CN113088120 A CN 113088120A CN 202110401517 A CN202110401517 A CN 202110401517A CN 113088120 A CN113088120 A CN 113088120A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/388—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a preparation method of an antibacterial coating for the surface of a plastic product, which comprises the following steps: adding the antibacterial polyurethane acrylate oligomer, the reactive monomer diluent, the modified antibacterial agent, the photoinitiator and the auxiliary agent into a cleaning container, stirring at normal temperature, and uniformly mixing to obtain the antibacterial coating for the surface of the plastic product, wherein the weight parts of the raw materials are 40-80 parts of the antibacterial polyurethane acrylate oligomer, 10-55 parts of the reactive monomer diluent, 3-10 parts of the modified antibacterial agent, 0.3-3 parts of the photoinitiator and 3-10 parts of the auxiliary agent. In the invention, polyurethane acrylate is used as a film forming substrate, and a hexaquaternary phosphonium chain is embedded in the molecular structure of the film forming substrate, so that the film forming substrate has strong antibacterial performance; in addition, the synthesized N-monohalamine compound is added into the formula of the coating, and the N-monohalamine compound and the quaternary phosphonium salt structure are utilized to perform synergistic action, so that the migration and overflow of the N-monohalamine compound are avoided, and the antibacterial property of the coating is improved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a preparation method of an antibacterial coating for the surface of a plastic product.
Background
With the increasing development degree of plastic industrialization, plastic products are also increasingly penetrated into the lives, study and work of people. In order to improve the appearance, feel or some function of the plastic product, a layer of paint is often sprayed on the surface of the plastic product to achieve the purpose of beauty, durability or other functionality.
However, microorganisms, by forming in the form of plaque, can attack the coating, causing the coating to lose adhesion and thus the protective and functional effect on the substrate. And after a large amount of microorganisms grow, people can be exposed to a multi-bacterium environment, and harm is caused to human health. The problem is solved by adding an antibacterial agent into the coating base material to inhibit and kill fungi, so as to avoid the situation. However, various actions can occur between the antibacterial agent and the coating, which can affect the performance or antibacterial property of the coating, for example, the addition of metals such as silver, copper, zinc and the like and corresponding metal ions in the inorganic antibacterial agent can affect the mechanical property of the film-forming base material, so that the strength of the film-forming base material is reduced; the organic antibacterial agent has the problems of poor heat resistance, easy migration and the like in a film forming substrate, and finally causes antibacterial failure. Therefore, the chemical means of embedding antimicrobial agents into film-forming substrates has been a hot focus of the research community.
However, the antibacterial paint on the current market has the problems that the antibacterial performance is not enough, and the attachment of initial bacteria cannot be killed by 100 percent; the antibacterial efficiency is low, and the quick sterilization effect cannot be achieved in a short time; the partial antibacterial agent has short antibacterial aging, is unstable and has limited application range, and bacterial infection substances have drug resistance (such as quaternary ammonium, guanidine and imidazole antibacterial agents) on partial antibacterial coating, so that the antibacterial performance of the coating is reduced.
Therefore, the invention provides a preparation method of an antibacterial coating for the surface of a plastic product, which aims to solve the problems.
Disclosure of Invention
The invention aims to provide a preparation method of an antibacterial coating for the surface of a plastic product, provides an antibacterial coating with low cost, good stability and good bactericidal performance, and solves the problems of the existing antibacterial agent.
Based on the background material, the inventor takes urethane acrylate as a film forming substrate, and embeds an antibacterial connecting segment on the molecular chain of the urethane acrylate to increase the antibacterial property of the substrate; thirdly, the selection aspect of the antibacterial continuous segment avoids the antibacterial continuous segment (such as quaternary ammonium antibacterial agent) which is easy to generate drug resistance, such as quaternary phosphonium salt, chitosan, zinc oxide, titanium dioxide and the like; and finally, the generation of bacterial drug resistance is avoided, and the added antibacterial agent is modified by utilizing the compounding technical principle, so that the acting force between the added antibacterial agent and the base material is increased, the migration and overflow of the antibacterial agent are avoided, and the antibacterial failure is reduced.
Based on the above thought, the purpose of the invention can be realized by the following technical scheme:
a preparation method of antibacterial paint for the surface of a plastic product comprises the following steps:
adding the antibacterial polyurethane acrylate oligomer, the reactive monomer diluent, the modified antibacterial agent, the photoinitiator and the auxiliary agent into a cleaning container, stirring at normal temperature, and uniformly mixing to obtain the antibacterial coating for the surface of the plastic product, wherein the weight parts of the raw materials are 40-80 parts of the antibacterial polyurethane acrylate oligomer, 10-55 parts of the reactive monomer diluent, 3-10 parts of the modified antibacterial agent, 0.3-3 parts of the photoinitiator and 3-10 parts of the auxiliary agent.
Further, the antibacterial urethane acrylate oligomer is prepared by the following steps:
step S1, sequentially adding 1, 8-bis (diphenylphosphino) octane, 8-bromo-1-octanol and anhydrous acetonitrile into a three-neck round-bottom flask, uniformly mixing, carrying out reflux reaction at 100 ℃ for 20-30h, carrying out rotary evaporation to remove a solvent after the reaction is finished, adding tetrahydrofuran, stirring, washing, carrying out suction filtration, placing a filter cake in a vacuum drying oven, and drying at 40-60 ℃ for 20-30h to obtain a white solid compound I, wherein the reaction formula is shown as follows;
step S2, adding the compound I obtained in the step S1 and anhydrous dichloromethane into a three-neck round-bottom flask, stirring for 8-15min at the temperature of ice bath O ℃ by introducing nitrogen, and then slowly injecting PBr3Keeping the temperature of the ice bath O unchanged, removing the ice bath after reacting for 5-7 hours, changing to room temperature, continuing to react for 20-30 hours, removing the solvent by rotary evaporation after the reaction is finished, adding the obtained product into a tetrahydrofuran and ether mixed solution, and stirring to separate out a white solid compound II, wherein the reaction formula is shown as follows;
step S3, adding the reaction product II obtained in the step S2 and anhydrous acetonitrile into a three-neck round-bottom flask, carrying out reflux stirring at the temperature of 100 ℃, adding 1, 8-bis (diphenyl) octane for reacting for 20-30h, removing the solvent by rotary evaporation after the reaction is finished, adding anhydrous tetrahydrofuran, stirring, washing, carrying out suction filtration, and placing the obtained filter cake in a vacuum drying oven for 20-30h to obtain a compound III, wherein the reaction formula is shown as follows;
step S4, sequentially adding the compound III, 8-bromo-1-octanol and anhydrous acetonitrile obtained in the step S3 into a three-neck round-bottom flask, heating to 100 ℃ under the condition of nitrogen, stirring and reacting at constant temperature for 24 hours, removing the solvent after the reaction is completely performed by rotary evaporation, adding anhydrous tetrahydrofuran, stirring, washing and performing suction filtration, and placing the obtained filter cake in a vacuum drying oven for 20-30 hours to obtain a compound IV, wherein the reaction formula is shown as follows;
and S5, adding the compound IV obtained in the step S4 and isophorone diisocyanate into a three-neck round-bottom flask, stirring and heating to 50-60 ℃, reacting at a constant temperature for 1 hour, slowly dripping a catalyst dibutyltin dilaurate, heating to 65-70 ℃ after finishing the dripping, slowly adding polyether polyol into a constant-pressure dropping funnel, finishing the dripping within 30 minutes, stirring and reacting at the constant temperature for 3 hours, stopping heating, adjusting the temperature to 40-45 ℃, dripping acrylic acid-2-hydroxyethyl into the reaction system when the reaction temperature is reduced to 40-45 ℃, continuing to react at the constant temperature for 3 hours to ensure that NCO in the reaction system completely reacts, and obtaining the antibacterial polyurethane acrylate oligomer after the reaction is completely finished.
Further, in step S1, the use amount ratio of 1, 8-bis (diphenylphosphino) octane, 8-bromo-1-octanol and anhydrous acetonitrile is 0.04mol:0.08-0.1mol:250-300 ml.
Further, compound one, anhydrous dichloromethane, PBr in step S23The dosage ratio of the components is 1mmol:10-20ml:1-3 ml.
Further, the use amount ratio of the reaction product II, anhydrous acetonitrile and 1, 8-bis (diphenyl) octane in the step S3 is 1mmol:10-20ml:3-6 mmol.
Further, the using amount ratio of the compound of tris, 8-bromo-1-octanol and anhydrous acetonitrile in step S4 is 1mmol:2-3mmol:10-20 ml.
Further, in the step S5, the mass ratio of the compound IV to the isophorone diisocyanate to the dibutyltin dilaurate to the polyether polyol to the 2-hydroxyethyl acrylate is 4-6:12-18:0.03-0.1:80-85: 2.5-3.
Further, the reactive monomer diluent is one or a mixture of any several of trimethylolpropane triacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate and triethylene glycol diacrylate in any ratio.
Further, the modified antibacterial agent is a modified halamine antibacterial agent, and the preparation method comprises the following steps:
step A, placing cyanuric chloride and a solvent into a three-neck flask containing a stirrer and a thermometer, stirring to obtain a uniform solution, transferring the three-neck round-bottom flask into an ice bath, keeping the temperature of the ice bath between 0 and 5 ℃, stirring for 10 to 20min at the speed of 300r/min for 150-;
and step B, raising the temperature of the reaction system in the step A to 38-41 ℃, slowly adding sodium sulfanilate aqueous solution, stirring for 1.5-3h at the speed of 150-300r/min under the condition, adjusting the pH of the reaction system to 5-6 by using sodium carbonate solution, after the reaction is finished, carrying out suction filtration on the reaction liquid, washing the filter cake for 1-2 times by using absolute ethyl alcohol, and then placing the filter cake in a constant-temperature drying box at the temperature of 45-50 ℃ for 20-30h to obtain the modified antibacterial agent.
Further, the solvent in the step A is a mixture of methanol and dichloromethane according to a volume ratio of 1: 6.
Further, the dosage ratio of the cyanuric chloride, the solvent and the aqueous solution of 2,2,6, 6-tetramethylpiperidinol in the step A is 0.02mol: 100-.
Further, the mass concentration of the aqueous solution of 2,2,6, 6-tetramethylpiperidinol in step A was 0.4 mol/L.
Further, the amount of the sodium sulfanilate aqueous solution in step B is equal to the amount of the 2,2,6, 6-tetramethylpiperidinol aqueous solution in step A.
Furthermore, the sodium sulfanilate in the step B is prepared from sulfanilic acid, sodium carbonate and deionized water, and the mass ratio of the sulfanilic acid to the sodium carbonate is 2: 1.
Further, the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, alpha' -dimethyl benzil ketal, 2, 4, 6-trimethyl benzoyl-diphenyl phosphine oxide, 2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate, 2, 4, 6-trimethyl benzoyl, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone Mixture of any ratio of the seed.
Furthermore, the auxiliary agent is a mixture of a leveling agent, an adhesion promoter and a wetting agent in any ratio.
Further, the leveling agent is an acrylate leveling agent.
Further, the adhesion promoter is a titanate coupling agent.
Further, the wetting agent is polyoxyethylene fatty alcohol ether.
Has the advantages that:
according to the invention, polyurethane acrylate is used as a film forming substrate, and a hexaquaternary phosphonium chain end is embedded in the molecular structure of the film forming substrate, so that the film forming substrate has antibacterial performance, and the strong antibacterial performance and spectrum antibacterial performance of hexaquaternary phosphonium are utilized; in addition, the generation of bacterial drug resistance is avoided, the synthetic N-halamine compound is added into the formula of the coating by utilizing the compound technical principle, and the N-halamine compound and the quaternary phosphonium salt structure are utilized to carry out synergistic action, so that the migration and overflow of the N-halamine compound are avoided, and the antibacterial property of the coating is improved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the antibacterial urethane acrylate oligomer is prepared by the following steps:
step S1, sequentially adding 1, 8-bis (diphenylphosphino) octane, 8-bromo-1-octanol and anhydrous acetonitrile into a three-neck round-bottom flask, uniformly mixing, carrying out reflux reaction at 100 ℃ for 20 hours, carrying out rotary evaporation to remove a solvent after the reaction is finished, adding tetrahydrofuran, stirring, washing, carrying out suction filtration, and placing a filter cake into a vacuum drying oven to dry at 40 ℃ for 20 hours to obtain a white solid compound I, wherein the dosage ratio of the 1, 8-bis (diphenylphosphino) octane to the 8-bromo-1-octanol to the anhydrous acetonitrile is 0.04mol:0.08mol:250 ml;
step S2, adding the compound I obtained in the step S1 and anhydrous dichloromethane into a three-neck round-bottom flask, stirring for 10min by introducing nitrogen at the temperature of ice bath O ℃, and then slowly injecting PBr3Keeping the temperature of the ice bath O unchanged, removing the ice bath after 5 hours of reaction, changing to room temperature, continuing the reaction for 20 hours, removing the solvent by rotary evaporation after the reaction is finished, adding the obtained product into a tetrahydrofuran and diethyl ether mixed solution, stirring and separating out a white solid compound II, wherein the compound I, anhydrous dichloromethane and PBr3The dosage ratio of (1 mmol to 10: 1);
step S3, adding the reaction product II and anhydrous acetonitrile obtained in the step S2 into a three-neck round-bottom flask, carrying out reflux stirring at the temperature of 100 ℃, adding 1, 8-bis (diphenyl) octane for reacting for 20 hours, carrying out rotary evaporation to remove a solvent after the reaction is finished, adding anhydrous tetrahydrofuran, stirring, washing and carrying out suction filtration, and placing the obtained filter cake into a vacuum drying oven for 20 hours to obtain a compound III, wherein the dosage ratio of the reaction product II, the anhydrous acetonitrile to the 1, 8-bis (diphenyl) octane is 1mmol:10ml:3 mmol;
step S4, sequentially adding the compound III, 8-bromo-1-octanol and anhydrous acetonitrile obtained in the step S3 into a three-neck round-bottom flask, heating to 100 ℃ under the condition of nitrogen, stirring and reacting for 24 hours at constant temperature, removing the solvent after the reaction is completely performed by rotary evaporation, adding anhydrous tetrahydrofuran, stirring, washing and performing suction filtration, and placing the obtained filter cake into a vacuum drying oven for 20 hours to obtain a compound IV, wherein the dosage ratio of the compound III, 8-bromo-1-octanol and anhydrous acetonitrile is 1mmol:2mmol:10 ml;
and S5, adding the compound IV obtained in the step S4 and isophorone diisocyanate into a three-neck round-bottom flask, stirring and heating to 50 ℃, reacting at a constant temperature for 1h, slowly dropwise adding a catalyst dibutyltin dilaurate, heating to 65 ℃, slowly adding polyether polyol by using a constant-pressure dropping funnel, dropwise adding within 30min, stirring and reacting at a constant temperature for 3h, stopping heating, and adjusting the temperature to 40 ℃. And when the reaction temperature is reduced to 40 ℃, dropwise adding acrylic acid-2-hydroxyethyl into the reaction system, continuing to perform heat preservation reaction for 3 hours to ensure that NCO in the reaction system is reacted completely, and obtaining the antibacterial polyurethane acrylate oligomer after the reaction is completed, wherein the mass ratio of the compound IV, isophorone diisocyanate, dibutyltin dilaurate, polyether glycol and acrylic acid-2-hydroxyethyl is 4:12:0.03:80: 2.5.
Example 2:
the antibacterial urethane acrylate oligomer is prepared by the following steps:
step S1, sequentially adding 1, 8-bis (diphenylphosphino) octane, 8-bromo-1-octanol and anhydrous acetonitrile into a three-neck round-bottom flask, uniformly mixing, carrying out reflux reaction at 100 ℃ for 20 hours, carrying out rotary evaporation to remove a solvent after the reaction is finished, adding tetrahydrofuran, stirring, washing, carrying out suction filtration, and placing a filter cake into a vacuum drying oven to dry at 40 ℃ for 20 hours to obtain a white solid compound I, wherein the dosage ratio of the 1, 8-bis (diphenylphosphino) octane to the 8-bromo-1-octanol to the anhydrous acetonitrile is 0.04mol:0.09mol:280 ml;
step S2, adding the compound I obtained in the step S1 and anhydrous dichloromethane into a three-neck round-bottom flask, stirring for 10min by introducing nitrogen at the temperature of ice bath O ℃, and then slowly injecting PBr3Keeping the temperature of the ice bath O unchanged, removing the ice bath after 5 hours of reaction, changing to room temperature, continuing the reaction for 20 hours, removing the solvent by rotary evaporation after the reaction is finished, adding the obtained product into a tetrahydrofuran and diethyl ether mixed solution, stirring and separating out a white solid compound II, wherein the compound I, anhydrous dichloromethane and PBr3The dosage ratio of the (A) to the (B) is 1mmol to 15ml to 2 ml;
step S3, adding the reaction product II and anhydrous acetonitrile obtained in the step S2 into a three-neck round-bottom flask, carrying out reflux stirring at the temperature of 100 ℃, adding 1, 8-bis (diphenyl) octane for reacting for 20 hours, carrying out rotary evaporation to remove a solvent after the reaction is finished, adding anhydrous tetrahydrofuran, stirring, washing and carrying out suction filtration, and placing the obtained filter cake into a vacuum drying oven for 20 hours to obtain a compound III, wherein the dosage ratio of the reaction product II, the anhydrous acetonitrile to the 1, 8-bis (diphenyl) octane is 1mmol:15ml:5 mmol;
step S4, sequentially adding the compound III, 8-bromo-1-octanol and anhydrous acetonitrile obtained in the step S3 into a three-neck round-bottom flask, heating to 100 ℃ under the condition of nitrogen, stirring and reacting for 24 hours at constant temperature, removing the solvent after the reaction is completely performed by rotary evaporation, adding anhydrous tetrahydrofuran, stirring, washing and performing suction filtration, and placing the obtained filter cake into a vacuum drying oven for 20 hours to obtain a compound IV, wherein the dosage ratio of the compound III, 8-bromo-1-octanol and anhydrous acetonitrile is 1mmol:2.5mmol:15 ml;
and S5, adding the compound IV obtained in the step S4 and isophorone diisocyanate into a three-neck round-bottom flask, stirring and heating to 50 ℃, reacting at a constant temperature for 1h, slowly dropwise adding a catalyst dibutyltin dilaurate, heating to 65 ℃, slowly adding polyether polyol by using a constant-pressure dropping funnel, dropwise adding within 30min, stirring and reacting at a constant temperature for 3h, stopping heating, and adjusting the temperature to 40 ℃. And when the reaction temperature is reduced to 40 ℃, dropwise adding acrylic acid-2-hydroxyethyl into the reaction system, continuing to perform heat preservation reaction for 3 hours to ensure that NCO in the reaction system is reacted completely, and obtaining the antibacterial polyurethane acrylate oligomer after the reaction is completed, wherein the mass ratio of the compound IV, isophorone diisocyanate, dibutyltin dilaurate, polyether glycol and acrylic acid-2-hydroxyethyl is 5:16:0.06:82: 2.8.
Example 3:
the antibacterial urethane acrylate oligomer is prepared by the following steps:
step S1, sequentially adding 1, 8-bis (diphenylphosphino) octane, 8-bromo-1-octanol and anhydrous acetonitrile into a three-neck round-bottom flask, uniformly mixing, carrying out reflux reaction at 100 ℃ for 20 hours, carrying out rotary evaporation to remove a solvent after the reaction is finished, adding tetrahydrofuran, stirring, washing, carrying out suction filtration, and placing a filter cake into a vacuum drying oven to dry at 40 ℃ for 20 hours to obtain a white solid compound I, wherein the dosage ratio of the 1, 8-bis (diphenylphosphino) octane to the 8-bromo-1-octanol to the anhydrous acetonitrile is 0.04mol:0.1mol:300 ml;
step S2, adding the compound I obtained in the step S1 and anhydrous dichloromethane into a three-neck round-bottom flask, stirring for 10min by introducing nitrogen at the temperature of ice bath O ℃, and then slowly injecting PBr3Keeping the temperature of the ice bath O unchanged, removing the ice bath after 5 hours of reaction, changing to room temperature, continuing the reaction for 20 hours, removing the solvent by rotary evaporation after the reaction is finished, adding the obtained product into a tetrahydrofuran and diethyl ether mixed solution, stirring and separating out a white solid compound II, wherein the compound I, anhydrous dichloromethane and PBr3The dosage ratio of the (A) to the (B) is 1mmol to 20ml to 3 ml;
step S3, adding the reaction product II and anhydrous acetonitrile obtained in the step S2 into a three-neck round-bottom flask, carrying out reflux stirring at the temperature of 100 ℃, adding 1, 8-bis (diphenyl) octane for reacting for 20 hours, carrying out rotary evaporation to remove a solvent after the reaction is finished, adding anhydrous tetrahydrofuran, stirring, washing and carrying out suction filtration, and placing the obtained filter cake into a vacuum drying oven for 20 hours to obtain a compound III, wherein the dosage ratio of the reaction product II, the anhydrous acetonitrile to the 1, 8-bis (diphenyl) octane is 1mmol:20ml:6 mmol;
step S4, sequentially adding the compound III, 8-bromo-1-octanol and anhydrous acetonitrile obtained in the step S3 into a three-neck round-bottom flask, heating to 100 ℃ under the condition of nitrogen, stirring and reacting for 24 hours at constant temperature, removing the solvent after the reaction is completely performed by rotary evaporation, adding anhydrous tetrahydrofuran, stirring, washing and performing suction filtration, and placing the obtained filter cake into a vacuum drying oven for 20 hours to obtain a compound IV, wherein the dosage ratio of the compound III, 8-bromo-1-octanol and anhydrous acetonitrile is 1mmol:3mmol:20 ml;
and S5, adding the compound IV obtained in the step S4 and isophorone diisocyanate into a three-neck round-bottom flask, stirring and heating to 50 ℃, reacting at a constant temperature for 1h, slowly dropwise adding a catalyst dibutyltin dilaurate, heating to 65 ℃, slowly adding polyether polyol by using a constant-pressure dropping funnel, dropwise adding within 30min, stirring and reacting at a constant temperature for 3h, stopping heating, and adjusting the temperature to 40 ℃. And when the reaction temperature is reduced to 40 ℃, dropwise adding acrylic acid-2-hydroxyethyl into the reaction system, continuing to perform heat preservation reaction for 3 hours to ensure that NCO in the reaction system is reacted completely, and obtaining the antibacterial polyurethane acrylate oligomer after the reaction is completed, wherein the mass ratio of the compound IV, isophorone diisocyanate, dibutyltin dilaurate, polyether glycol and acrylic acid-2-hydroxyethyl is 6:18:0.1:85: 3.
Example 4:
the modified antibacterial agent is a modified halamine antibacterial agent, and the preparation method comprises the following steps:
step A, placing cyanuric chloride and a solvent into a three-neck flask containing a stirrer and a thermometer, stirring to obtain a uniform solution, transferring the three-neck round-bottom flask into an ice bath, keeping the temperature of the ice bath at 0 ℃, stirring for 15min at the speed of 200r/min, then slowly dropwise adding an aqueous solution of 2,2,6, 6-tetramethylpiperidinol into the three-neck flask, adjusting the pH value of a reaction system to 7 by using a sodium carbonate solution, and when the dropwise adding of the aqueous solution of 2,2,6, 6-tetramethylpiperidinol is finished, continuously stirring at the speed of 200r/min at a constant temperature for reaction for 1.5h, wherein the solvent is a mixture of methanol and dichloromethane in a volume ratio of 1: 6; the dosage ratio of the cyanuric chloride to the solvent to the aqueous solution of the 2,2,6, 6-tetramethyl piperidinol is 0.02mol:100ml:50 ml; the mass concentration of the aqueous solution of the 2,2,6, 6-tetramethyl piperidinol is 0.4 mol/L;
step B, raising the temperature of the reaction system in the step A to 38 ℃, slowly adding sodium sulfanilate aqueous solution, stirring for 1.5 hours at the speed of 200r/min under the condition, adjusting the pH of the reaction system to 5 by using sodium carbonate solution, after the reaction is finished, carrying out suction filtration on the reaction solution, washing a filter cake for 2 times by using absolute ethyl alcohol, and then placing the filter cake in a constant-temperature drying box at the temperature of 45 ℃ for 20 hours to obtain the modified antibacterial agent, wherein the adding amount of the sodium sulfanilate aqueous solution is equal to that of the aqueous solution of 2,2,6, 6-tetramethyl piperidinol in the step A; the sodium sulfanilate is prepared from sulfanilic acid, sodium carbonate and deionized water, and the mass ratio of the sulfanilic acid to the sodium carbonate is 2: 1.
Example 5:
the modified antibacterial agent is a modified halamine antibacterial agent, and the preparation method comprises the following steps:
step A, placing cyanuric chloride and a solvent into a three-neck flask containing a stirrer and a thermometer, stirring to obtain a uniform solution, transferring the three-neck round-bottom flask into an ice bath, keeping the temperature of the ice bath at 0 ℃, stirring for 15min at the speed of 200r/min, then slowly dropwise adding an aqueous solution of 2,2,6, 6-tetramethylpiperidinol into the three-neck flask, adjusting the pH value of a reaction system to 7 by using a sodium carbonate solution, and when the dropwise adding of the aqueous solution of 2,2,6, 6-tetramethylpiperidinol is finished, continuously stirring at the speed of 200r/min at a constant temperature for reaction for 1.5h, wherein the solvent is a mixture of methanol and dichloromethane in a volume ratio of 1: 6; the dosage ratio of the cyanuric chloride to the solvent to the aqueous solution of the 2,2,6, 6-tetramethyl piperidinol is 0.02mol:150ml:50-70 ml; the mass concentration of the aqueous solution of the 2,2,6, 6-tetramethyl piperidinol is 0.4 mol/L;
step B, raising the temperature of the reaction system in the step A to 38 ℃, slowly adding sodium sulfanilate aqueous solution, stirring for 1.5 hours at the speed of 200r/min under the condition, adjusting the pH of the reaction system to 5 by using sodium carbonate solution, after the reaction is finished, carrying out suction filtration on the reaction solution, washing a filter cake for 2 times by using absolute ethyl alcohol, and then placing the filter cake in a constant-temperature drying box at the temperature of 45 ℃ for 20-30 hours to obtain the modified antibacterial agent, wherein the adding amount of the sodium sulfanilate aqueous solution is equal to that of the aqueous solution of 2,2,6, 6-tetramethyl piperidinol in the step A; the sodium sulfanilate is prepared from sulfanilic acid, sodium carbonate and deionized water, and the mass ratio of the sulfanilic acid to the sodium carbonate is 2: 1.
Example 6:
the modified antibacterial agent is a modified halamine antibacterial agent, and the preparation method comprises the following steps:
step A, placing cyanuric chloride and a solvent into a three-neck flask containing a stirrer and a thermometer, stirring to obtain a uniform solution, transferring the three-neck round-bottom flask into an ice bath, keeping the temperature of the ice bath at 0 ℃, stirring for 15min at the speed of 200r/min, then slowly dropwise adding an aqueous solution of 2,2,6, 6-tetramethylpiperidinol into the three-neck flask, adjusting the pH value of a reaction system to 7 by using a sodium carbonate solution, and when the dropwise adding of the aqueous solution of 2,2,6, 6-tetramethylpiperidinol is finished, continuously stirring at the speed of 200r/min at a constant temperature for reaction for 1.5h, wherein the solvent is a mixture of methanol and dichloromethane in a volume ratio of 1: 6; the dosage ratio of the cyanuric chloride to the solvent to the aqueous solution of the 2,2,6, 6-tetramethyl piperidinol is 0.02mol:200ml:70 ml; the mass concentration of the aqueous solution of the 2,2,6, 6-tetramethyl piperidinol is 0.4 mol/L;
step B, raising the temperature of the reaction system in the step A to 38 ℃, slowly adding sodium sulfanilate aqueous solution, stirring for 1.5 hours at the speed of 200r/min under the condition, adjusting the pH of the reaction system to 5 by using sodium carbonate solution, after the reaction is finished, carrying out suction filtration on the reaction solution, washing a filter cake for 2 times by using absolute ethyl alcohol, and then placing the filter cake in a constant-temperature drying box at 50 ℃ for 30 hours to obtain the modified antibacterial agent, wherein the adding amount of the sodium sulfanilate aqueous solution is equal to that of the aqueous solution of 2,2,6, 6-tetramethyl piperidinol in the step A; the sodium sulfanilate is prepared from sulfanilic acid, sodium carbonate and deionized water, and the mass ratio of the sulfanilic acid to the sodium carbonate is 2: 1.
Example 7:
a preparation method of antibacterial paint for the surface of a plastic product comprises the following steps:
adding an antibacterial polyurethane acrylate oligomer, an active monomer diluent, a modified antibacterial agent, a photoinitiator and an auxiliary agent into a cleaning container, stirring at normal temperature, and uniformly mixing to obtain the antibacterial coating for the surface of a plastic product, wherein the raw materials comprise, by weight, 40 parts of the antibacterial polyurethane acrylate oligomer, 10 parts of the active monomer diluent, 3 parts of the modified antibacterial agent, 0.3 part of the photoinitiator and 3 parts of the auxiliary agent, wherein the active monomer diluent is trimethylolpropane triacrylate and 1, 6-hexanediol diacrylate which are mixed according to the mass ratio of 1:1: 1; the photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone, the auxiliary agent is a mixture of a leveling agent, an adhesion promoter and a wetting agent which are mixed according to the mass ratio of 1:1:1, wherein the leveling agent is an acrylate leveling agent, the adhesion promoter is a titanate coupling agent, the wetting agent is polyoxyethylene fatty alcohol ether, the antibacterial polyurethane acrylic oligomer is prepared from example 1, and the modified antibacterial agent is prepared from example 4.
Example 8:
a preparation method of antibacterial paint for the surface of a plastic product comprises the following steps:
adding an antibacterial polyurethane acrylate oligomer, an active monomer diluent, a modified antibacterial agent, a photoinitiator and an auxiliary agent into a cleaning container, stirring at normal temperature, and uniformly mixing to obtain the antibacterial coating for the surface of a plastic product, wherein the raw materials comprise, by weight, 60 parts of the antibacterial polyurethane acrylate oligomer, 25 parts of the active monomer diluent, 5 parts of the modified antibacterial agent, 1 part of the photoinitiator and 5 parts of the auxiliary agent, wherein the active monomer diluent is a mixture prepared by mixing 1, 4-butanediol diacrylate and triethylene glycol diacrylate according to a mass ratio of 1: 1; the photoinitiator is a mixture of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone and 2, 4, 6-trimethylbenzoylphenylphosphonic acid ethyl ester mixed according to the mass ratio of 1:1, and the auxiliary agent is a mixture of a leveling agent, an adhesion promoter and a wetting agent in any ratio, wherein the leveling agent is an acrylate leveling agent, the adhesion promoter is a titanate coupling agent, the wetting agent is polyoxyethylene fatty alcohol ether, the antibacterial polyurethane acrylic oligomer is prepared in example 2, and the modified antibacterial agent is prepared in example 5.
Example 6:
a preparation method of antibacterial paint for the surface of a plastic product comprises the following steps:
adding an antibacterial polyurethane acrylate oligomer, an active monomer diluent, a modified antibacterial agent, a photoinitiator and an auxiliary agent into a cleaning container, stirring at normal temperature, and uniformly mixing to obtain the antibacterial coating for the surface of a plastic product, wherein the raw materials comprise, by weight, 80 parts of the antibacterial polyurethane acrylate oligomer, 55 parts of the active monomer diluent, 10 parts of the modified antibacterial agent, 3 parts of the photoinitiator and 10 parts of the auxiliary agent, wherein the active monomer diluent is 1, 6-hexanediol diacrylate; the photoinitiator is a mixture of alpha, alpha' -dimethyl benzil ketal 2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone which are mixed according to the mass ratio of 1:1:1, and the auxiliary agent is a mixture of a flatting agent, an adhesion promoter and a wetting agent in any ratio, wherein the flatting agent is an acrylate flatting agent, the adhesion promoter is a titanate coupling agent, the wetting agent is polyoxyethylene fatty alcohol ether, the antibacterial polyurethane acrylic oligomer is prepared in example 3, and the modified antibacterial agent is prepared in example 6.
Comparative example 1:
preparation method of antibacterial coating for surface of plastic product
The antimicrobial urethane acrylic oligomer in the raw material was deleted compared to example 7, and the rest was the same.
Comparative example 2:
preparation method of antibacterial coating for surface of plastic product
The modified antimicrobial agent in the raw material was deleted compared with example 8, and the rest was the same.
Comparative example 3:
preparation method of antibacterial coating for surface of plastic product
Compared with example 9, the antibacterial urethane acrylic oligomer in the raw material was replaced with urethane acrylate oligomer, and the rest was the same.
The coatings obtained in the above examples 7-9 and comparative examples 1-3 are acted on 6 groups of identical glass sheets, film forming is carried out under the same conditions, and the adhesion, hardness and antibacterial performance of the coating film are tested, wherein the adhesion adopts GB/T1998-1992 as a determination standard, the damage degree among the fine scratches of the coating film is observed according to a circle drawing method, and the grade of the adhesion is judged; the hardness measurement standard was tested according to the GB/T5739-1996 pencil method, and the test results are shown below; the antibacterial performance test is carried out according to the national standard GB/T5979-1995, and the test flora is escherichia coli and staphylococcus aureus; the test results are shown below.
From the above data, it can be seen that the antibacterial performance of examples 1 to 3 is superior to that of comparative examples 1 to 3.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (4)
1. A preparation method of antibacterial paint for the surface of a plastic product is characterized by comprising the following steps:
adding the antibacterial polyurethane acrylate oligomer, the reactive monomer diluent, the modified antibacterial agent, the photoinitiator and the auxiliary agent into a cleaning container, stirring at normal temperature, and uniformly mixing to obtain the antibacterial coating for the surface of the plastic product, wherein the weight parts of the raw materials are 40-80 parts of the antibacterial polyurethane acrylate oligomer, 10-55 parts of the reactive monomer diluent, 3-10 parts of the modified antibacterial agent, 0.3-3 parts of the photoinitiator and 3-10 parts of the auxiliary agent;
the antibacterial urethane acrylate oligomer is prepared by the following steps:
step S1, sequentially adding 1, 8-bis (diphenylphosphino) octane, 8-bromo-1-octanol and anhydrous acetonitrile into a reaction container, uniformly mixing, carrying out reflux reaction at 100 ℃ for 20-30h, carrying out rotary evaporation to remove a solvent after the reaction is finished, adding tetrahydrofuran, stirring, washing, carrying out suction filtration, and placing a filter cake in a vacuum drying oven to dry at 40-60 ℃ for 20-30h to obtain a white solid compound I;
step S2, adding the compound I obtained in the step S1 and anhydrous dichloromethane into a reaction vessel, introducing nitrogen into the reaction vessel at an ice bath temperature of O ℃, stirring the mixture for 8 to 15min, and then slowly injecting PBr3Keeping the temperature of the ice bath O unchanged, removing the ice bath after reacting for 5-7 hours, changing to room temperature, continuing to react for 20-30 hours, removing the solvent by rotary evaporation after the reaction is finished, adding the obtained product into a mixed solution of tetrahydrofuran and diethyl ether, and stirring to separate out a white solid compound II;
step S3, adding the reaction product II obtained in the step S2 and anhydrous acetonitrile into a reaction container, carrying out reflux stirring at the temperature of 100 ℃, adding 1, 8-bis (diphenyl) octane for reacting for 20-30h, carrying out rotary evaporation to remove the solvent after the reaction is finished, adding anhydrous tetrahydrofuran, stirring, washing and carrying out suction filtration, and placing the obtained filter cake in a vacuum drying oven for 20-30h to obtain a compound III;
step S4, sequentially adding the compound III, 8-bromo-1-octanol and anhydrous acetonitrile obtained in the step S3 into a reaction container, heating to 100 ℃ under the condition of nitrogen, stirring and reacting at constant temperature for 24 hours, removing the solvent after the reaction is completely carried out by rotary evaporation, adding anhydrous tetrahydrofuran, stirring, washing and carrying out suction filtration, and then placing the obtained filter cake into a vacuum drying oven for 20-30 hours to obtain a compound IV;
and S5, adding the compound IV obtained in the step S4 and isophorone diisocyanate into a reaction container, stirring and heating to 50-60 ℃, reacting at a constant temperature for 1h, slowly dropwise adding dibutyltin dilaurate serving as a catalyst, heating to 65-70 ℃ after the dibutyltin dilaurate is added, slowly adding polyether polyol, completing dropwise adding within 30min, stirring and reacting for 3h at a constant temperature, stopping heating, adjusting the temperature to 40-45 ℃, dropwise adding 2-hydroxyethyl acrylate into the reaction system when the reaction temperature is reduced to 40-45 ℃, continuing to react at a constant temperature for 3h, and obtaining the antibacterial polyurethane acrylate oligomer after the reaction is completed.
2. The method as claimed in claim 1, wherein the amount ratio of 1, 8-bis (diphenylphosphino) octane, 8-bromo-1-octanol and anhydrous acetonitrile in step S1 is 0.04mol:0.08-0.1mol:250-300 ml; compound one, anhydrous dichloromethane and PBr in step S23The dosage ratio of the components is 1mmol:10-20ml:1-3 ml; in the step S3, the dosage ratio of the reaction product II, anhydrous acetonitrile and 1, 8-bis (diphenyl) octane is 1mmol:10-20ml:3-6 mmol; in the step S4, the dosage ratio of the compound III to the compound 8-bromo-1-octanol to the anhydrous acetonitrile is 1mmol:2-3mmol:10-20 ml; in the step S5, the mass ratio of the compound IV to the isophorone diisocyanate to the dibutyltin dilaurate to the polyether polyol to the 2-hydroxyethyl acrylate is 4-6:12-18:0.03-0.1:80-85: 2.5-3.
3. The method for preparing the antibacterial coating on the surface of the plastic product as claimed in claim 1, wherein the reactive monomer diluent is one or a mixture of any more of trimethylolpropane triacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate and triethylene glycol diacrylate at any ratio.
4. The preparation method of the antibacterial coating for the surface of the plastic product, as claimed in claim 1, is characterized in that the modified antibacterial agent is a modified halamine antibacterial agent, and the preparation method comprises the following steps:
step A, placing cyanuric chloride and a solvent into a reaction container, stirring to obtain a uniform solution, transferring the reaction container into an ice bath, keeping the temperature of the ice bath between 0 and 5 ℃, stirring for 10 to 20 minutes at the speed of 300r/min for 150-;
and step B, raising the temperature of the reaction system in the step A to 38-41 ℃, slowly adding sodium sulfanilate aqueous solution, stirring for 1.5-3h at the speed of 150-300r/min under the condition, adjusting the pH of the reaction system to be 5-6 by using sodium carbonate solution, then carrying out suction filtration on reaction liquid, washing a filter cake for 1-2 times by using absolute ethyl alcohol, and then placing the filter cake in a constant-temperature drying box at the temperature of 45-50 ℃ for 20-30h to obtain the modified antibacterial agent.
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| CN115873522A (en) * | 2023-02-02 | 2023-03-31 | 上海兰庆新材料技术股份有限公司 | Wear-resistant and impact-resistant UV (ultraviolet) photocuring protective film and preparation process thereof |
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