CN114231129A - Epoxy resin powder coating and application thereof - Google Patents
Epoxy resin powder coating and application thereof Download PDFInfo
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- CN114231129A CN114231129A CN202210057664.6A CN202210057664A CN114231129A CN 114231129 A CN114231129 A CN 114231129A CN 202210057664 A CN202210057664 A CN 202210057664A CN 114231129 A CN114231129 A CN 114231129A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses an epoxy resin powder coating which comprises the following raw materials in parts by weight: 40-50 parts of epoxy resin, 5-10 parts of curing agent, 0.8-1 part of accelerant, 0.5-0.7 part of flatting agent, 15-40 parts of silica powder, 10-20 parts of pigment and filler and 3-5 parts of antibacterial agent; the epoxy resin powder coating is prepared by the following steps: firstly, mixing 80% of epoxy resin, curing agent, accelerator, flatting agent and silicon micropowder to obtain a first component; secondly, mixing 20% of epoxy resin, pigment and filler and an antibacterial agent to obtain a second component; and thirdly, mixing the first component and the second component, premixing for 5-10min to obtain a premix, performing melt extrusion on the premix, putting the extruded sheet-shaped object into a ball mill for grinding, wherein the rotating speed of the ball mill is 1600-2000r/min, and sieving the ground coarse powder with a 200-mesh sieve to obtain the epoxy resin powder coating.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to an epoxy resin powder coating and application thereof.
Background
The epoxy powder coating is a thermosetting powder coating with corrosion resistance and toughness, is applied earliest and developed quickly, and consists of epoxy resin, pigment and filler, additives and a curing agent. Some electronic components, or transportation pipelines, etc. have high requirements for antibacterial properties. However, the existing antibacterial powder coating mainly applies the bactericidal effect of silver ions in the silver antibacterial agent, but has the defects that the silver ions in the silver antibacterial agent are easy to dissolve out and have poor durability, and the silver ions are gradually released to play a bactericidal effect after a coating film is cured for 24 hours, so that the antibacterial powder coating has slow antibacterial effect; in addition, silver ions can be released from the nano-silver continuously, heavy metal pollution can be caused if the silver ions are released into a water body, huge damage can be caused to the water body, and the nano-silver antibacterial agent can be accumulated to cause pathological changes if the nano-silver antibacterial agent is absorbed by internal organs of a human body, so that the health of the human body is damaged.
Disclosure of Invention
The invention provides an epoxy resin powder coating and application thereof.
The technical problems to be solved by the invention are as follows:
some electronic components, or transportation pipelines, etc. have high requirements for antibacterial properties. However, the existing antibacterial powder coating mainly applies the bactericidal effect of silver ions in the silver antibacterial agent, but has the defects that the silver ions in the silver antibacterial agent are easy to dissolve out and have poor durability, and the silver ions are gradually released to play the bactericidal effect after a coating film is cured for 24 hours, so that the antibacterial powder coating has slow antibacterial effect and pollutes the environment.
The purpose of the invention can be realized by the following technical scheme:
an epoxy resin powder coating comprises the following raw materials in parts by weight:
40-50 parts of epoxy resin, 5-10 parts of curing agent, 0.8-1 part of accelerant, 0.5-0.7 part of flatting agent, 15-40 parts of silica powder, 10-20 parts of pigment and filler and 3-5 parts of antibacterial agent;
the epoxy resin powder coating is prepared by the following steps:
firstly, mixing 80% of epoxy resin, curing agent, accelerator, flatting agent and silicon micropowder to obtain a first component;
secondly, mixing 20% of epoxy resin, pigment and filler and an antibacterial agent to obtain a second component;
and thirdly, mixing the first component and the second component, pouring the mixture into a mixing cylinder for premixing for 5-10min to obtain a premix, carrying out melt extrusion on the premix, putting the extruded sheet-shaped object into a ball mill for grinding, wherein the rotating speed of the ball mill is 1600-2000r/min, and sieving the ground coarse powder with a 200-mesh sieve to obtain the epoxy resin powder coating.
Further, the epoxy resin is E12 type bisphenol A type epoxy resin; the grain diameter of the silicon micro powder is 200 meshes; the curing agent is organic acid or anhydride curing agent; the accelerant is dimethyl imidazole; the leveling agent is one of leveling agents H88 or H99; the pigment and the filler are conventional solid pigments and can be selected and matched according to actual color requirements; the temperature of melt extrusion is 100 ℃ in the first zone and 110 ℃ in the second zone, and the rotating speed of an extrusion screw is 50 Hz.
Further, the antibacterial agent is prepared by the steps of:
step A1, adding the component A and gamma-aminoethyl aminopropyltrimethoxysilane into a three-neck flask, setting the temperature to be 60 ℃, stirring for 5-10min, then heating to 90 ℃, adding a tetramethylammonium hydroxide aqueous solution, reacting for 5h, after the reaction is finished, mixing with toluene with the same volume, then carrying out reduced pressure distillation at 60 ℃ until the volume is unchanged, and then drying under the vacuum condition of 25 ℃ to constant weight to obtain a component B;
step A2, adding an auxiliary agent and toluene into a three-neck flask, then adding a toluene solution of a component B, stirring for 5-10min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 5-10min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyldiimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with anhydrous ethanol with the same volume, carrying out reduced pressure distillation, removing the ethanol, repeating for three times, removing the toluene in the system, and then carrying out vacuum drying at the temperature of 25 ℃ to constant weight to obtain the antibacterial agent.
Further, in the step A1, the mass fraction of the aqueous solution of tetramethylammonium hydroxide is 25%, and the use ratio of the component A, the gamma-aminoethyl aminopropyltrimethoxysilane and the aqueous solution of tetramethylammonium hydroxide is 1 g: 1 g: 20 mL; the toluene solution of the component B in the step A2 is prepared by mixing the component B and toluene according to the dosage ratio of 1 g: 15mL of the mixture is obtained by mixing, wherein the dosage ratio of the auxiliary agent, the toluene solution of the component B, the sodium bisulfite, the sodium borohydride, the 4-dimethylpyridine and the N, N-dicyclohexyl diimine is 4 g: 20mL of: 45mL of: 1 g: 0.24 g: 0.12 g: 1.24 g.
Further, component a was prepared by the following steps:
step S11, adding DL-1, 2-isopropylidene glycerol into a round-bottom flask, adding p-toluenesulfonyl chloride under the condition of ice-water bath, then adding pyridine, stirring and reacting for 24 hours, removing the pyridine by reduced pressure distillation after the reaction is finished, then diluting with dichloromethane with the same volume, then washing with distilled water, saturated sodium bicarbonate and 0.1mol/L hydrochloric acid solution for three times in sequence, drying with anhydrous sodium sulfate after the washing is finished, then transferring into a rotary evaporator, and concentrating under reduced pressure until a solid is precipitated to obtain an intermediate 1;
the reaction process is as follows:
step S12, adding the intermediate 1 and sodium p-bromophenolate into a round-bottom flask, then adding N, N-dimethylformamide, stirring and reacting for 36 hours at the temperature of 85 ℃, diluting with ethyl acetate with the same volume after the reaction is finished, then washing with distilled water, 0.1mol/L sodium hydroxide solution and distilled water for three times in sequence, drying with anhydrous magnesium sulfate after the washing is finished, transferring to a rotary evaporator, and concentrating under reduced pressure until a solid is separated out to obtain an intermediate 2;
the reaction process is as follows:
step S13, adding the intermediate 2 and acetonitrile into a round-bottom flask, setting the temperature to 65 ℃, then adding zinc nitrate hexahydrate for reaction for 12 hours, after the reaction is finished, diluting the mixture with equal volume of ethyl acetate, washing the mixture with distilled water for three times, finally drying the mixture with anhydrous magnesium sulfate, transferring the dried mixture to a rotary evaporator, and concentrating the dried mixture under reduced pressure until solid is separated out to obtain an intermediate 3;
the reaction process is as follows:
and step S14, adding the intermediate 3 and triphenylphosphine into a three-neck flask, adding ethylene glycol and nickel bromide, heating to 185 ℃ under the protection of nitrogen, reacting for 24 hours, cooling to room temperature after the reaction is finished, diluting with dichloromethane with the same volume, washing with distilled water for three times, drying with anhydrous sodium sulfate, transferring to a rotary evaporator, and concentrating under reduced pressure to separate out a solid to obtain the component A.
The reaction process is as follows:
further, the amount ratio of DL-1, 2-isopropylidene glycerol, p-toluenesulfonyl chloride and pyridine in step S11 was 13 g: 24 g: 25 mL; in the step S12, the dosage ratio of the intermediate 1 to the sodium p-bromophenolate to the N, N-dimethylformamide is 14 g: 14 g: 200 mL; in step S13, the ratio of the amounts of intermediate 2, acetonitrile and zinc nitrate hexahydrate was 7 g: 30mL of: 15g of the total weight of the mixture; in step S14, the amount ratio of intermediate 3 to triphenylphosphine to ethylene glycol to nickel bromide was 1.9 g: 1.5 g: 5mL of: 1.3 g.
Further, the auxiliary agent is prepared by the following steps:
step S21, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing succinic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature at 60 ℃ and the rotating speed at 200r/min, stirring for 15-20min, then heating the temperature to 90 ℃, adding 4-dimethylaminopyridine, and stirring for reacting for 8 h;
step S22, after the reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, standing after stirring, removing supernatant, adding equal volume of deionized water, stirring for 15 minutes, standing, removing supernatant, performing vacuum filtration, and drying the obtained filter cake for 72 hours at 25 ℃ under vacuum to obtain the auxiliary agent.
The reaction process is as follows:
further, in the mixed solution a in the step S21, the dosage ratio of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide to the N, N-dimethylformamide is 0.02 mol: 100mL, wherein the dosage ratio of succinic anhydride to N, N-dimethylformamide in the mixed solution b is 0.08 moL: 100 mL; wherein the mixed solution a and the mixed solution b are mixed in equal volume, and the dosage of the 4-dimethylamino pyridine is 4 percent of the total mass of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and the succinic anhydride.
Further, the application of the epoxy resin powder coating is applied to the surfaces of medical appliances, indoor electric appliances, kitchen utensils and food processing equipment.
The invention has the beneficial effects that:
DL-1, 2-isopropylidene glycerol is used as a raw material to synthesize a component A, hydroxyl on the component A and alkoxy on gamma-aminoethyl aminopropyl trimethoxy silane are subjected to ester exchange under the catalysis of tetramethyl ammonium hydroxide to obtain a component B, the gamma-aminoethyl aminopropyl trimethoxy silane and the component A are combined, and N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and succinic anhydride are subjected to esterification reaction under the catalysis of 4-dimethylamino pyridine to generate an auxiliary agent.
The obtained component B reacts with an auxiliary agent, amino groups on the component B and carboxyl groups on the auxiliary agent undergo amidation reaction to obtain the antibacterial agent, the antibacterial agent contains a quaternary phosphonium salt cation structure, the antibacterial property of the quaternary phosphonium salt cation is superior to that of a quaternary ammonium salt cation, and cells lose activity until die due to the interaction of the quaternary phosphonium cation with positive charges on the quaternary phosphonium salt cation and a phosphoric acid bimolecular group with negative charges on cell membranes.
The antibacterial agent contains siloxane chain segment silicon-oxygen bond with bond energy higher than carbon-carbon bond, thus increasing the thermal stability of the antibacterial auxiliary agent, widening the application range of the powder coating, leading the antibacterial action to be more long-acting, simultaneously containing the fluorocarbon bond in the auxiliary agent, improving the heat resistance, reducing the surface energy after film forming after introducing fluorine element, leading the powder coating to have lower surface energy, endowing the powder coating with certain hydrophobic property, and further improving the corrosion resistance of the powder coating.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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
An epoxy resin powder coating comprises the following raw materials in parts by weight:
40 parts of epoxy resin, 5 parts of curing agent, 0.8 part of accelerator, 0.5 part of flatting agent, 15 parts of silica powder, 10 parts of pigment and filler and 3 parts of antibacterial agent;
the epoxy resin powder coating is prepared by the following steps:
firstly, mixing 80% of epoxy resin, curing agent, accelerator, flatting agent and silicon micropowder to obtain a first component;
secondly, mixing 20% of epoxy resin, pigment and filler and an antibacterial agent to obtain a second component;
and thirdly, mixing the first component and the second component, pouring the mixture into a mixing tank for premixing for 5min to obtain a premix, carrying out melt extrusion on the premix, putting the extruded sheet-shaped object into a ball mill for grinding, wherein the rotating speed of the ball mill is 1600r/min, and sieving the ground coarse powder with a 200-mesh sieve to obtain the epoxy resin powder coating.
Wherein the epoxy resin is E12 type bisphenol A type epoxy resin; the grain diameter of the silicon micro powder is 200 meshes; the curing agent is organic acid curing agent; the accelerant is dimethyl imidazole; the leveling agent is leveling agent H88; the pigment and filler is titanium dioxide; the temperature of melt extrusion is 100 ℃ in the first zone and 110 ℃ in the second zone, and the rotating speed of an extrusion screw is 50 Hz.
Wherein the antibacterial agent is prepared by the following steps:
step A1, adding the component A and gamma-aminoethyl aminopropyl trimethoxysilane into a three-neck flask, setting the temperature to be 60 ℃, stirring for 5min, then heating to 90 ℃, adding a tetramethyl ammonium hydroxide aqueous solution, reacting for 5h, after the reaction is finished, mixing with equal volume of toluene, then carrying out reduced pressure distillation at 60 ℃ until the volume is unchanged, and then drying under the vacuum condition of 25 ℃ until the weight is constant to obtain a component B;
step A2, adding an auxiliary agent and toluene into a three-neck flask, then adding a toluene solution of a component B, stirring for 5min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 5min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyl diimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with anhydrous ethanol with the same volume, carrying out reduced pressure distillation, removing ethanol, repeating for three times, removing the toluene in the system, and then carrying out vacuum drying to constant weight at the temperature of 25 ℃ to obtain the antibacterial agent.
Wherein, the mass fraction of the tetramethylammonium hydroxide aqueous solution in the step A1 is 25%, and the dosage ratio of the component A, the gamma-aminoethyl aminopropyltrimethoxysilane and the tetramethylammonium hydroxide aqueous solution is 1 g: 1 g: 20 mL; the toluene solution of the component B in the step A2 is prepared by mixing the component B and toluene according to the dosage ratio of 1 g: 15mL of the mixture is obtained by mixing; the dosage ratio of the auxiliary agent, toluene solution of the component B, sodium bisulfite, sodium borohydride, 4-dimethylpyridine and N, N-dicyclohexyldiimine is 4 g: 20mL of: 45mL of: 1 g: 0.24 g: 0.12 g: 1.24 g.
Wherein, the component A is prepared by the following steps:
step S11, adding DL-1, 2-isopropylidene glycerol into a round-bottom flask, adding p-toluenesulfonyl chloride under the condition of ice-water bath, then adding pyridine, stirring and reacting for 24 hours, removing the pyridine by reduced pressure distillation after the reaction is finished, then diluting with dichloromethane with the same volume, then washing with distilled water, saturated sodium bicarbonate and 0.1mol/L hydrochloric acid solution for three times in sequence, drying with anhydrous sodium sulfate after the washing is finished, then transferring into a rotary evaporator, and concentrating under reduced pressure until a solid is precipitated to obtain an intermediate 1;
step S12, adding the intermediate 1 and sodium p-bromophenolate into a round-bottom flask, then adding N, N-dimethylformamide, stirring and reacting for 36 hours at the temperature of 85 ℃, diluting with ethyl acetate with the same volume after the reaction is finished, then washing with distilled water, 0.1mol/L sodium hydroxide solution and distilled water for three times in sequence, drying with anhydrous magnesium sulfate after the washing is finished, transferring to a rotary evaporator, and concentrating under reduced pressure until a solid is separated out to obtain an intermediate 2;
step S13, adding the intermediate 2 and acetonitrile into a round-bottom flask, setting the temperature to 65 ℃, then adding zinc nitrate hexahydrate for reaction for 12 hours, after the reaction is finished, diluting the mixture with equal volume of ethyl acetate, washing the mixture with distilled water for three times, finally drying the mixture with anhydrous magnesium sulfate, transferring the dried mixture to a rotary evaporator, and concentrating the dried mixture under reduced pressure until solid is separated out to obtain an intermediate 3;
and step S14, adding the intermediate 3 and triphenylphosphine into a three-neck flask, adding ethylene glycol and nickel bromide, heating to 185 ℃ under the protection of nitrogen, reacting for 24 hours, cooling to room temperature after the reaction is finished, diluting with dichloromethane with the same volume, washing with distilled water for three times, drying with anhydrous sodium sulfate, transferring to a rotary evaporator, and concentrating under reduced pressure to separate out a solid to obtain the component A.
Wherein the dosage ratio of DL-1, 2-isopropylidene glycerol, p-toluenesulfonyl chloride and pyridine in the step S11 is 13 g: 24 g: 25 mL; in the step S12, the dosage ratio of the intermediate 1 to the sodium p-bromophenolate to the N, N-dimethylformamide is 14 g: 14 g: 200 mL; in step S13, the ratio of the amounts of intermediate 2, acetonitrile and zinc nitrate hexahydrate was 7 g: 30mL of: 15g of the total weight of the mixture; in step S14, the amount ratio of intermediate 3 to triphenylphosphine to ethylene glycol to nickel bromide was 1.9 g: 1.5 g: 5mL of: 1.3 g.
The auxiliary agent is prepared by the following steps:
step S21, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing succinic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature at 60 ℃ and the rotating speed at 200r/min, stirring for 15min, then heating the temperature to 90 ℃, adding 4-dimethylaminopyridine, and stirring and reacting for 8 h;
step S22, after the reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, standing after stirring, removing supernatant, adding equal volume of deionized water, stirring for 15 minutes, standing, removing supernatant, performing vacuum filtration, and drying the obtained filter cake for 72 hours at 25 ℃ under vacuum to obtain the auxiliary agent.
Wherein the dosage ratio of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide to the N, N-dimethylformamide in the mixed solution a is 0.02 mol: 100mL, wherein the dosage ratio of succinic anhydride to N, N-dimethylformamide in the mixed solution b is 0.08 moL: 100 mL; wherein the mixed solution a and the mixed solution b are mixed in equal volume, and the dosage of the 4-dimethylamino pyridine is 4 percent of the total mass of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and the succinic anhydride.
Example 2
An epoxy resin powder coating comprises the following raw materials in parts by weight:
45 parts of epoxy resin, 8 parts of curing agent, 0.9 part of accelerator, 0.6 part of flatting agent, 20 parts of silica micropowder, 15 parts of pigment and filler and 4 parts of antibacterial agent;
the epoxy resin powder coating is prepared by the following steps:
firstly, mixing 80% of epoxy resin, curing agent, accelerator, flatting agent and silicon micropowder to obtain a first component;
secondly, mixing 20% of epoxy resin, pigment and filler and an antibacterial agent to obtain a second component;
and thirdly, mixing the first component and the second component, pouring the mixture into a mixing tank for premixing for 8min to obtain a premix, carrying out melt extrusion on the premix, putting the extruded sheet-shaped object into a ball mill for grinding, wherein the rotating speed of the ball mill is 18000r/min, and sieving the ground coarse powder with a 200-mesh sieve to obtain the epoxy resin powder coating.
Wherein the epoxy resin is E12 type bisphenol A type epoxy resin; the grain diameter of the silicon micro powder is 200 meshes; the curing agent is an anhydride curing agent; the accelerant is dimethyl imidazole; the leveling agent is one of leveling agents H99; the pigment and filler is titanium dioxide; the temperature of melt extrusion is 100 ℃ in the first zone and 110 ℃ in the second zone, and the rotating speed of an extrusion screw is 50 Hz.
Wherein the antibacterial agent is prepared by the following steps:
step A1, adding the component A and gamma-aminoethyl aminopropyl trimethoxysilane into a three-neck flask, setting the temperature to be 60 ℃, stirring for 8min, then heating to 90 ℃, adding a tetramethyl ammonium hydroxide aqueous solution, reacting for 5h, after the reaction is finished, mixing with equal volume of toluene, then carrying out reduced pressure distillation at 60 ℃ until the volume is unchanged, and then drying under the vacuum condition of 25 ℃ until the weight is constant to obtain a component B;
step A2, adding an auxiliary agent and toluene into a three-neck flask, then adding a toluene solution of a component B, stirring for 8min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 8min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyl diimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with anhydrous ethanol with the same volume, carrying out reduced pressure distillation, removing ethanol, repeating for three times, removing the toluene in the system, and then carrying out vacuum drying to constant weight at the temperature of 25 ℃ to obtain the antibacterial agent.
Wherein, the mass fraction of the tetramethylammonium hydroxide aqueous solution in the step A1 is 25%, and the dosage ratio of the component A, the gamma-aminoethyl aminopropyltrimethoxysilane and the tetramethylammonium hydroxide aqueous solution is 1 g: 1 g: 20 mL; the toluene solution of the component B in the step A2 is prepared by mixing the component B and toluene according to the dosage ratio of 1 g: 15mL of the mixture is obtained by mixing; the dosage ratio of the auxiliary agent, toluene solution of the component B, sodium bisulfite, sodium borohydride, 4-dimethylpyridine and N, N-dicyclohexyldiimine is 4 g: 20mL of: 45mL of: 1 g: 0.24 g: 0.12 g: 1.24 g.
Wherein, the component A is prepared by the following steps:
step S11, adding DL-1, 2-isopropylidene glycerol into a round-bottom flask, adding p-toluenesulfonyl chloride under the condition of ice-water bath, then adding pyridine, stirring and reacting for 24 hours, removing the pyridine by reduced pressure distillation after the reaction is finished, then diluting with dichloromethane with the same volume, then washing with distilled water, saturated sodium bicarbonate and 0.1mol/L hydrochloric acid solution for three times in sequence, drying with anhydrous sodium sulfate after the washing is finished, then transferring into a rotary evaporator, and concentrating under reduced pressure until a solid is precipitated to obtain an intermediate 1;
step S12, adding the intermediate 1 and sodium p-bromophenolate into a round-bottom flask, then adding N, N-dimethylformamide, stirring and reacting for 36 hours at the temperature of 85 ℃, diluting with ethyl acetate with the same volume after the reaction is finished, then washing with distilled water, 0.1mol/L sodium hydroxide solution and distilled water for three times in sequence, drying with anhydrous magnesium sulfate after the washing is finished, transferring to a rotary evaporator, and concentrating under reduced pressure until a solid is separated out to obtain an intermediate 2;
step S13, adding the intermediate 2 and acetonitrile into a round-bottom flask, setting the temperature to 65 ℃, then adding zinc nitrate hexahydrate for reaction for 12 hours, after the reaction is finished, diluting the mixture with equal volume of ethyl acetate, washing the mixture with distilled water for three times, finally drying the mixture with anhydrous magnesium sulfate, transferring the dried mixture to a rotary evaporator, and concentrating the dried mixture under reduced pressure until solid is separated out to obtain an intermediate 3;
and step S14, adding the intermediate 3 and triphenylphosphine into a three-neck flask, adding ethylene glycol and nickel bromide, heating to 185 ℃ under the protection of nitrogen, reacting for 24 hours, cooling to room temperature after the reaction is finished, diluting with dichloromethane with the same volume, washing with distilled water for three times, drying with anhydrous sodium sulfate, transferring to a rotary evaporator, and concentrating under reduced pressure to separate out a solid to obtain the component A.
Wherein the dosage ratio of DL-1, 2-isopropylidene glycerol, p-toluenesulfonyl chloride and pyridine in the step S11 is 13 g: 24 g: 25 mL; in the step S12, the dosage ratio of the intermediate 1 to the sodium p-bromophenolate to the N, N-dimethylformamide is 14 g: 14 g: 200 mL; in step S13, the ratio of the amounts of intermediate 2, acetonitrile and zinc nitrate hexahydrate was 7 g: 30mL of: 15g of the total weight of the mixture; in step S14, the amount ratio of intermediate 3 to triphenylphosphine to ethylene glycol to nickel bromide was 1.9 g: 1.5 g: 5mL of: 1.3 g.
The auxiliary agent is prepared by the following steps:
step S21, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing succinic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature at 60 ℃ and the rotating speed at 200r/min, stirring for 18min, then heating the temperature to 90 ℃, adding 4-dimethylaminopyridine, and stirring and reacting for 8 h;
step S22, after the reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, standing after stirring, removing supernatant, adding equal volume of deionized water, stirring for 15 minutes, standing, removing supernatant, performing vacuum filtration, and drying the obtained filter cake for 72 hours at 25 ℃ under vacuum to obtain the auxiliary agent.
Wherein the dosage ratio of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide to the N, N-dimethylformamide in the mixed solution a is 0.02 mol: 100mL, wherein the dosage ratio of succinic anhydride to N, N-dimethylformamide in the mixed solution b is 0.08 moL: 100 mL; wherein the mixed solution a and the mixed solution b are mixed in equal volume, and the dosage of the 4-dimethylamino pyridine is 4 percent of the total mass of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and the succinic anhydride.
Example 3
An epoxy resin powder coating comprises the following raw materials in parts by weight:
50 parts of epoxy resin, 10 parts of curing agent, 1 part of accelerator, 0.7 part of flatting agent, 40 parts of silica micropowder, 20 parts of pigment and filler and 5 parts of antibacterial agent;
the epoxy resin powder coating is prepared by the following steps:
firstly, mixing 80% of epoxy resin, curing agent, accelerator, flatting agent and silicon micropowder to obtain a first component;
secondly, mixing 20% of epoxy resin, pigment and filler and an antibacterial agent to obtain a second component;
and thirdly, mixing the first component and the second component, pouring the mixture into a mixing tank for premixing for 10min to obtain a premix, carrying out melt extrusion on the premix, putting the extruded sheet-shaped object into a ball mill for grinding, wherein the rotating speed of the ball mill is 2000r/min, and sieving the ground coarse powder with a 200-mesh sieve to obtain the epoxy resin powder coating.
Wherein the epoxy resin is E12 type bisphenol A type epoxy resin; the grain diameter of the silicon micro powder is 200 meshes; the curing agent is an organic acid curing agent; the accelerant is dimethyl imidazole; the leveling agent is leveling agent H88; the pigment and filler is titanium dioxide; the temperature of melt extrusion is 100 ℃ in the first zone and 110 ℃ in the second zone, and the rotating speed of an extrusion screw is 50 Hz.
Wherein the antibacterial agent is prepared by the following steps:
step A1, adding the component A and gamma-aminoethyl aminopropyl trimethoxysilane into a three-neck flask, setting the temperature to be 60 ℃, stirring for 5min, then heating to 90 ℃, adding a tetramethyl ammonium hydroxide aqueous solution, reacting for 5h, after the reaction is finished, mixing with equal volume of toluene, then carrying out reduced pressure distillation at 60 ℃ until the volume is unchanged, and then drying under the vacuum condition of 25 ℃ until the weight is constant to obtain a component B;
step A2, adding an auxiliary agent and toluene into a three-neck flask, then adding a toluene solution of a component B, stirring for 5min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 5min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyl diimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with anhydrous ethanol with the same volume, carrying out reduced pressure distillation, removing ethanol, repeating for three times, removing the toluene in the system, and then carrying out vacuum drying to constant weight at the temperature of 25 ℃ to obtain the antibacterial agent.
Wherein, the mass fraction of the tetramethylammonium hydroxide aqueous solution in the step A1 is 25%, and the dosage ratio of the component A, the gamma-aminoethyl aminopropyltrimethoxysilane and the tetramethylammonium hydroxide aqueous solution is 1 g: 1 g: 20 mL; the toluene solution of the component B in the step A2 is prepared by mixing the component B and toluene according to the dosage ratio of 1 g: 15mL of the mixture is obtained by mixing; the dosage ratio of the auxiliary agent, toluene solution of the component B, sodium bisulfite, sodium borohydride, 4-dimethylpyridine and N, N-dicyclohexyldiimine is 4 g: 20mL of: 45mL of: 1 g: 0.24 g: 0.12 g: 1.24 g.
Wherein, the component A is prepared by the following steps:
step S11, adding DL-1, 2-isopropylidene glycerol into a round-bottom flask, adding p-toluenesulfonyl chloride under the condition of ice-water bath, then adding pyridine, stirring and reacting for 24 hours, removing the pyridine by reduced pressure distillation after the reaction is finished, then diluting with dichloromethane with the same volume, then washing with distilled water, saturated sodium bicarbonate and 0.1mol/L hydrochloric acid solution for three times in sequence, drying with anhydrous sodium sulfate after the washing is finished, then transferring into a rotary evaporator, and concentrating under reduced pressure until a solid is precipitated to obtain an intermediate 1;
step S12, adding the intermediate 1 and sodium p-bromophenolate into a round-bottom flask, then adding N, N-dimethylformamide, stirring and reacting for 36 hours at the temperature of 85 ℃, diluting with ethyl acetate with the same volume after the reaction is finished, then washing with distilled water, 0.1mol/L sodium hydroxide solution and distilled water for three times in sequence, drying with anhydrous magnesium sulfate after the washing is finished, transferring to a rotary evaporator, and concentrating under reduced pressure until a solid is separated out to obtain an intermediate 2;
step S13, adding the intermediate 2 and acetonitrile into a round-bottom flask, setting the temperature to 65 ℃, then adding zinc nitrate hexahydrate for reaction for 12 hours, after the reaction is finished, diluting the mixture with equal volume of ethyl acetate, washing the mixture with distilled water for three times, finally drying the mixture with anhydrous magnesium sulfate, transferring the dried mixture to a rotary evaporator, and concentrating the dried mixture under reduced pressure until solid is separated out to obtain an intermediate 3;
and step S14, adding the intermediate 3 and triphenylphosphine into a three-neck flask, adding ethylene glycol and nickel bromide, heating to 185 ℃ under the protection of nitrogen, reacting for 24 hours, cooling to room temperature after the reaction is finished, diluting with dichloromethane with the same volume, washing with distilled water for three times, drying with anhydrous sodium sulfate, transferring to a rotary evaporator, and concentrating under reduced pressure to separate out a solid to obtain the component A.
Wherein the dosage ratio of DL-1, 2-isopropylidene glycerol, p-toluenesulfonyl chloride and pyridine in the step S11 is 13 g: 24 g: 25 mL; in the step S12, the dosage ratio of the intermediate 1 to the sodium p-bromophenolate to the N, N-dimethylformamide is 14 g: 14 g: 200 mL; in step S13, the ratio of the amounts of intermediate 2, acetonitrile and zinc nitrate hexahydrate was 7 g: 30mL of: 15g of the total weight of the mixture; in step S14, the amount ratio of intermediate 3 to triphenylphosphine to ethylene glycol to nickel bromide was 1.9 g: 1.5 g: 5mL of: 1.3 g.
The auxiliary agent is prepared by the following steps:
step S21, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing succinic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature to be 60 ℃ and the rotating speed to be 200r/min, stirring for 20min, then heating the temperature to be 90 ℃, adding 4-dimethylaminopyridine, and stirring and reacting for 8 h;
step S22, after the reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, standing after stirring, removing supernatant, adding equal volume of deionized water, stirring for 15 minutes, standing, removing supernatant, performing vacuum filtration, and drying the obtained filter cake for 72 hours at 25 ℃ under vacuum to obtain the auxiliary agent.
Wherein the dosage ratio of the N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide to the N, N-dimethylformamide in the mixed solution a is 0.02 mol: 100mL, wherein the dosage ratio of succinic anhydride to N, N-dimethylformamide in the mixed solution b is 0.08 moL: 100 mL; wherein the mixed solution a and the mixed solution b are mixed in equal volume, and the dosage of the 4-dimethylamino pyridine is 4 percent of the total mass of the N-ethyl, N-ethoxyl perfluorooctyl sulfonamide and the succinic anhydride
Comparative example 1
The antimicrobial agent of example 1 was replaced with a commercially available quaternary phosphonium salt antimicrobial agent, and the remaining raw materials and preparation process were kept unchanged.
And (3) testing thermal stability: 5mg of the powder coating samples of examples 1 to 3 and comparative example 1 were weighed respectively, placed in a nitrogen atmosphere, and heated from room temperature to 800 ℃ at a rate of 10 ℃/min to test the stability;
spraying a sample plate on the powder coatings prepared in the examples 1-3 and the comparative example 1, wherein the thickness of the sample plate is controlled to be 60-80 microns, and the sample plate is placed in a 180-DEG C constant-temperature drying oven to be baked for 15 minutes, taken out, kept at a constant temperature for 24 hours and then tested for performance;
and (3) corrosion resistance testing: referring to CB/T9286-1998, the test sample is soaked in a sodium chloride aqueous solution with the temperature of 25 ℃ and the mass concentration of 3.5 percent, after being soaked for one week, deionized water is adopted for washing, and the falling condition of each coating is observed; and (3) antibacterial property test: the powder coatings of examples 1-3 and comparative example 1 were subjected to an antibacterial property test according to the antibacterial property test method and antibacterial effect of the antibacterial coating (paint film) of the national standard CB/T21866-2008;
the test results are shown in table 1 below:
TABLE 1
As can be seen from the above table 1, the epoxy resin powder coating prepared by the invention has the excellent characteristics of heat resistance, antibacterial property, corrosion resistance and the like, and has application value and popularization prospect.
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 illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (4)
1. The epoxy resin powder coating is characterized by comprising the following raw materials in parts by weight:
40-50 parts of epoxy resin, 5-10 parts of curing agent, 0.8-1 part of accelerant, 0.5-0.7 part of flatting agent, 15-40 parts of silica powder, 10-20 parts of pigment and filler and 3-5 parts of antibacterial agent;
the antibacterial agent is prepared by the following steps:
step A1, adding the component A and gamma-aminoethyl aminopropyltrimethoxysilane into a three-neck flask, setting the temperature to be 60 ℃, stirring for 5-10min, then heating to 90 ℃, adding a tetramethylammonium hydroxide aqueous solution, reacting for 5h, after the reaction is finished, mixing with toluene with the same volume, then carrying out reduced pressure distillation at 60 ℃ until the volume is unchanged, and then drying under the vacuum condition of 25 ℃ to constant weight to obtain a component B;
step A2, adding an auxiliary agent and toluene into a three-neck flask, then adding a toluene solution of the component B, stirring for 5-10min at the temperature of 60 ℃, then adding sodium bisulfite and sodium borohydride, stirring for 5-10min, raising the temperature to 80 ℃, adding 4-dimethylpyridine and N, N-dicyclohexyldiimine, stirring for reaction for 7h, filtering while hot after the reaction is finished, retaining the filtrate, mixing the filtrate with equal volume of anhydrous ethanol, distilling under reduced pressure, and then drying in vacuum to constant weight at the temperature of 25 ℃ to obtain the antibacterial agent.
2. The epoxy resin powder coating of claim 1, wherein component a is prepared by the steps of:
step S11, adding DL-1, 2-isopropylidene glycerol into a round-bottom flask, adding p-toluenesulfonyl chloride under the condition of ice-water bath, then adding pyridine, stirring and reacting for 24 hours, removing the pyridine by reduced pressure distillation after the reaction is finished, then diluting with dichloromethane with the same volume, then washing with distilled water, saturated sodium bicarbonate and 0.1mol/L hydrochloric acid solution for three times in sequence, drying with anhydrous sodium sulfate after the washing is finished, then transferring into a rotary evaporator, and concentrating under reduced pressure until a solid is precipitated to obtain an intermediate 1;
step S12, adding the intermediate 1 and sodium p-bromophenolate into a round-bottom flask, then adding N, N-dimethylformamide, stirring and reacting for 36 hours at the temperature of 85 ℃, diluting with ethyl acetate with the same volume after the reaction is finished, then washing with distilled water, 0.1mol/L sodium hydroxide solution and distilled water for three times in sequence, drying with anhydrous magnesium sulfate after the washing is finished, transferring to a rotary evaporator, and concentrating under reduced pressure until a solid is separated out to obtain an intermediate 2;
step S13, adding the intermediate 2 and acetonitrile into a round-bottom flask, setting the temperature to 65 ℃, then adding zinc nitrate hexahydrate for reaction for 12 hours, after the reaction is finished, diluting the mixture with equal volume of ethyl acetate, washing the mixture with distilled water for three times, finally drying the mixture with anhydrous magnesium sulfate, transferring the dried mixture to a rotary evaporator, and concentrating the dried mixture under reduced pressure until solid is separated out to obtain an intermediate 3;
and step S14, adding the intermediate 3 and triphenylphosphine into a three-neck flask, adding ethylene glycol and nickel bromide, heating to 185 ℃ under the protection of nitrogen, reacting for 24 hours, cooling to room temperature after the reaction is finished, diluting with dichloromethane with the same volume, washing with distilled water for three times, drying with anhydrous sodium sulfate, transferring to a rotary evaporator, and concentrating under reduced pressure to separate out a solid to obtain the component A.
3. The epoxy resin powder coating as claimed in claim 1, wherein the auxiliary is prepared by the steps of:
step S21, mixing N-ethyl, N-hydroxyethyl perfluorooctyl sulfonamide and N, N-dimethylformamide to prepare a mixed solution a, mixing succinic anhydride and N, N-dimethylformamide to prepare a mixed solution b, mixing the mixed solution a and the mixed solution b, setting the temperature to be 60 ℃, reacting for 15-20min, then heating the temperature to 90 ℃, adding 4-dimethylaminopyridine, and stirring and reacting for 8 hours;
step S22, after the reaction is finished, mixing the obtained reaction solution and deionized water according to the volume ratio of 1: 2, mixing, precipitating, stirring for 2 hours at room temperature, standing after stirring, removing supernatant, adding deionized water with the same volume, stirring for 15 minutes, standing, removing supernatant, carrying out vacuum filtration, and drying the obtained filter cake for 72 hours at 25 ℃ under vacuum to obtain the auxiliary agent.
4. Use of an epoxy resin powder coating according to claim 1, characterized in that it is applied to surfaces of medical instruments, indoor electric appliances, kitchen appliances and food processing equipment.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107641428A (en) * | 2017-10-26 | 2018-01-30 | 浙江华彩新材料有限公司 | A kind of antibacterial powder paint and preparation method thereof |
| CN113621213A (en) * | 2021-08-19 | 2021-11-09 | 安徽成龙塑业科技有限公司 | Plastic particle with high impact resistance |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107641428A (en) * | 2017-10-26 | 2018-01-30 | 浙江华彩新材料有限公司 | A kind of antibacterial powder paint and preparation method thereof |
| CN113621213A (en) * | 2021-08-19 | 2021-11-09 | 安徽成龙塑业科技有限公司 | Plastic particle with high impact resistance |
Non-Patent Citations (1)
| Title |
|---|
| 孙明慧: ""氟硅油的合成及其环氧复合物的研究"", 《中国优秀博硕士学位论文全文数据库（硕士）》 * |
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