CN111978772A - Antibacterial and antivirus powder coating and preparation process thereof - Google Patents
Antibacterial and antivirus powder coating and preparation process thereof Download PDFInfo
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- CN111978772A CN111978772A CN202010728219.9A CN202010728219A CN111978772A CN 111978772 A CN111978772 A CN 111978772A CN 202010728219 A CN202010728219 A CN 202010728219A CN 111978772 A CN111978772 A CN 111978772A
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
Abstract
The invention discloses an antibacterial and antivirus powder coating, which comprises the following raw materials in parts by weight: 60-70 parts of polyester resin, 3-4 parts of antibacterial agent, 4-5 parts of graphene, 1.6-2 parts of coupling agent, 5-6 parts of curing agent and 1-1.2 parts of flatting agent; the invention also discloses a preparation process of the powder coating. According to the invention, polyester resin synthesized by taking different polyhydric alcohols and polybasic acids as raw materials is used as a film forming substrate of the coating, so that the water resistance, weather resistance and mechanical properties of the coating can be effectively improved; by adding the self-made antibacterial agent into the coating, the antibacterial agent is a high-molecular quaternary phosphonium salt antibacterial agent, has high-efficiency antibacterial performance, good compatibility with a coating substrate and high dissolution resistance, and gives the coating good antibacterial effect and antibacterial durability; through the auxiliary matching of other auxiliary agents, the prepared coating has the effects of resisting bacteria and killing viruses on the basis of weather resistance, water resistance and high mechanical property.
Description
Technical Field
The invention belongs to the field of powder coatings, and particularly relates to an antibacterial and antivirus powder coating and a preparation process thereof.
Background
The powder coating is a novel, solvent-free, pure solid powder coating consisting of a polymer, a pigment and an additive; the method has the characteristics of no use of solvent, no pollution, energy and resource saving, labor intensity reduction, high mechanical strength of film coating and the like. The antibacterial function of the paint is mainly realized by adding an antibacterial agent into the paint, and currently, the antibacterial agent mainly comprises three types: natural antibacterial agent, organic antibacterial agent and inorganic antibacterial agent, wherein the natural antibacterial agent is mainly extract of animals and plants such as propolis and garlicin; the organic antibacterial agent is mainly organic compounds such as organic acids, phenols, organic amines, isothiazolinone and the like; inorganic antibacterial agents are those formed by immobilizing metals such as copper and zinc and ions thereof on various carriers, and are classified into two major types, namely metal ion type and metal oxide type.
Powder coating is generally cured by high-temperature baking during use, and natural antibacterial agents such as propolis, garlicin and the like are used. The heat resistance stability and the use durability of the paint are poor, and the paint is not suitable to be used as an antibacterial additive in powder coating; if the organic antibacterial agent is adopted, the thermal stability of the organic antibacterial agent is poor in the process of baking the powder coating, and the organic antibacterial agent is easy to volatilize at high temperature, so that the organic antibacterial agent has obvious poison and pollution to operators and the surrounding environment. And the inorganic oxidation type antibacterial agent can play an antibacterial effect only by ultraviolet irradiation or under the action of oxygen and water. And the common doped antibacterial agent has great defects in uniform dispersibility and durability in the powder coating, thereby influencing the antibacterial and antivirus effects of the powder coating.
Disclosure of Invention
The invention aims to provide an antibacterial and antivirus powder coating and a preparation process thereof, and the polyester resin synthesized by adopting different polyols and polyatomic acid as raw materials is used as a film forming substrate of the coating, so that the water resistance, weather resistance and mechanical property of a coating can be effectively improved; the self-made antibacterial agent is added into the coating, the antibacterial agent is a high-molecular quaternary phosphonium salt antibacterial agent, has high-efficiency antibacterial performance, has good compatibility with a coating matrix and high dissolution resistance, and in addition, the molecules of the antibacterial agent contain a plurality of phenolic hydroxyl groups which can react with a curing agent to participate in the cross-linking and curing reaction of the coating, so that the uniform dispersion and the bonding force of the antibacterial agent in the coating are further improved, and the uniformity and the durability of the antibacterial effect are improved; through the auxiliary matching of other auxiliary agents, the prepared coating has the effects of resisting bacteria and killing viruses on the basis of weather resistance, water resistance and high mechanical property.
The purpose of the invention can be realized by the following technical scheme:
an antibacterial and antivirus powder coating comprises the following raw materials in parts by weight: 60-70 parts of polyester resin, 3-4 parts of antibacterial agent, 4-5 parts of graphene, 1.6-2 parts of coupling agent, 5-6 parts of curing agent and 1-1.2 parts of flatting agent;
the powder coating is prepared by the following steps:
firstly, weighing polyester resin, an antibacterial agent, graphene, a coupling agent, a curing agent and a flatting agent according to the weight parts, putting the polyester resin, the antibacterial agent, the graphene, the coupling agent, the curing agent and the flatting agent into a high-speed mixer, stirring and mixing for 20-25min at 300r/min, and then increasing the rotating speed to 2000r/min, stirring and mixing for 8-10min to obtain a premix;
and secondly, extruding the premix through a double-screw extruder to form a flaky material, and crushing, grinding and sieving the flaky material with a 200-mesh sieve to obtain fine powder so as to prepare the powder coating.
Further, the polyester resin is prepared by the following method:
putting neopentyl glycol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-propanediol, trihydroxyethyl isocyanurate, terephthalic acid and adipic acid into a reaction kettle together according to the formula amount, firstly introducing nitrogen for 15-20min to replace air in the reaction kettle, then raising the temperature under the protection of nitrogen, starting to extract esterified water when the temperature is raised to 160 ℃ of 150-.
Further, the ratio of the amounts of neopentyl glycol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-propanediol, tris (hydroxyethyl) isocyanurate, terephthalic acid and adipic acid used was 10g:5g:3g:2g:12g:8 g.
Further, the antibacterial agent is prepared by the following method:
1) adding 6-bromine hexanol, triethylamine and dichloromethane into a flask together, stirring and dissolving, placing the flask in an ice bath, dropwise adding methacryloyl chloride, reacting for 60-70min after dropwise adding, removing the ice bath, continuing to react for 20-24h at room temperature, removing dichloromethane by rotary evaporation after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ to constant weight to obtain a first intermediate;
2) adding the first intermediate, tri (p-hydroxyphenyl) -phosphine, hydroquinone and a proper amount of acetonitrile into a flask, stirring for dissolving, reacting at 80 ℃ for 66-72h, performing rotary evaporation to remove the acetonitrile after the reaction is finished, then washing with ethyl acetate and absolute ethyl alcohol for 3-4 times respectively, performing rotary evaporation to remove the solvent at 55 ℃ again, and finally drying in a vacuum drying oven at 60 ℃ to constant weight to obtain a second intermediate;
3) adding a photoinitiator into the second intermediate, stirring until the photoinitiator is completely dissolved, initiating polymerization reaction for 60-70min under the irradiation of 254nm ultraviolet light, then ultrasonically washing for 3-4 times by using tetrahydrofuran to remove unreacted monomers and oligomers, and drying in a vacuum drying oven to constant weight to obtain the antibacterial agent.
Further, the amount ratio of the 6-bromine hexanol, the triethylamine, the dichloromethane and the methacryloyl chloride in the step 1) is 23-25g, 18-19g, 100mL and 19.8-20.0 g; the dosage ratio of the first intermediate, the tri (p-hydroxyphenyl) -phosphine, the hydroquinone and the acetonitrile in the step 2) is 25g to 38g to 0.315g to 20 mL; the mass ratio of the second intermediate to the photoinitiator in step 3) is 100: 1.
A preparation process of antibacterial and antivirus powder coating comprises the following steps:
firstly, weighing polyester resin, an antibacterial agent, graphene, a coupling agent, a curing agent and a flatting agent according to the weight parts, putting the polyester resin, the antibacterial agent, the graphene, the coupling agent, the curing agent and the flatting agent into a high-speed mixer, stirring and mixing for 20-25min at 300r/min, and then increasing the rotating speed to 2000r/min, stirring and mixing for 8-10min to obtain a premix;
and secondly, extruding the premix through a double-screw extruder to form a flaky material, and crushing, grinding and sieving the flaky material with a 200-mesh sieve to obtain fine powder so as to prepare the powder coating.
The invention has the beneficial effects that:
the polyester resin is used as a film forming substrate of the coating, different types of polyols and polyacids are adopted to participate in the reaction in the synthesis of the polyester resin, and the two trifunctional group monomers of the trihydroxyethyl isocyanurate are introduced, so that the branching degree and the activity of terminal carboxyl of the polyester resin are effectively improved, the polyester resin meets the condition of low-temperature curing, and meanwhile, the stable structure of a triazine ring of the trihydroxyethyl isocyanurate can improve the water resistance, the weather resistance and the mechanical property of the powder coating; monomers such as adipic acid and methyl propylene glycol are added, so that the flexibility of a chain segment of the polyester resin can be enhanced, and the powder coating is ensured to have good fluidity in the curing process, so that the coating has good appearance and mechanical properties; the isophthalic acid is introduced, and the reactivity and the uniqueness of a molecular structure of the isophthalic acid are utilized, so that the reactivity of the polyester resin and the weather resistance of a coating film are improved, and the problem that the low-temperature cured coating film is easy to bloom can be solved; 2-butyl-2-ethyl-1, 3-propylene glycol is introduced, and the larger side group of the 2-butyl-2-ethyl-1, 3-propylene glycol can effectively improve the weather resistance and water resistance of a polyester resin coating film and can ensure the reaction activity of the polyester resin, so that the coating surface of the powder coating has good weather resistance and good mechanical properties;
the self-made antibacterial agent is added into the powder coating, and the obtained high-molecular quaternary phosphonium salt antibacterial agent contains ionic groups, can adsorb bacteria through electrostatic interaction, and then kills the bacteria by cracking cell membranes, so that the aim of resisting bacteria is fulfilled; after the quaternary ammonium salt is polymerized, the cation density is increased, the adsorption to bacteria is enhanced, and meanwhile, the structure that the main chain of the polymer is hydrophobic and the side chain of the polymer is hydrophilic is similar to the phospholipid bilayer structure of a bacterial cell membrane, and the polymer can more easily penetrate through the cell wall to damage the cell membrane and kill the bacteria, so that the antibacterial property of the polymer antibacterial agent has the advantages of low toxicity, easiness in storage, high antibacterial group density and the like compared with a stronger polymer antibacterial agent before polymerization; in addition, the high molecular quaternary phosphonium salt has good compatibility with a coating substrate (polyester resin) and has a non-dissolution type antibacterial characteristic, and due to the large molecular weight, the high molecular antibacterial agent cannot migrate out of the coating along with the increase of time to cause the antibacterial property of the coating to be reduced, so that the problems of poor antibacterial durability and toxicity caused by dissolution of an inorganic antibacterial agent or an organic small molecular antibacterial agent can be avoided; in addition, phenolic hydroxyl of tri (p-hydroxyphenyl) -phosphine is introduced into the molecules of the obtained antibacterial agent, and the phenolic hydroxyl can generate chemical action with a polyester resin curing agent (the molecules of the curing agent contain a plurality of epoxy groups) and participate in the curing and crosslinking reaction to form a more crosslinked network structure, so that the integrity and compactness of the coating can be enhanced, the dispersion effect of the antibacterial agent in the coating and the binding force with the coating substrate can be promoted, and the antibacterial uniformity and the antibacterial durability can be further improved;
according to the invention, polyester resin synthesized by taking different polyhydric alcohols and polybasic acids as raw materials is used as a film forming substrate of the coating, so that the water resistance, weather resistance and mechanical properties of the coating can be effectively improved; the self-made antibacterial agent is added into the coating, the antibacterial agent is a high-molecular quaternary phosphonium salt antibacterial agent, has high-efficiency antibacterial performance, has good compatibility with a coating matrix and high dissolution resistance, and in addition, the molecules of the antibacterial agent contain a plurality of phenolic hydroxyl groups which can react with a curing agent to participate in the cross-linking and curing reaction of the coating, so that the uniform dispersion and the bonding force of the antibacterial agent in the coating are further improved, and the uniformity and the durability of the antibacterial effect are improved; through the auxiliary matching of other auxiliary agents, the prepared coating has the effects of resisting bacteria and killing viruses on the basis of weather resistance, water resistance and high mechanical property.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood 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.
An antibacterial and antivirus powder coating comprises the following raw materials in parts by weight: 60-70 parts of polyester resin, 3-4 parts of antibacterial agent, 4-5 parts of graphene, 1.6-2 parts of coupling agent, 5-6 parts of curing agent and 1-1.2 parts of flatting agent;
the coupling agent is a silane coupling agent or a titanate coupling agent;
the curing agent is triglycidyl isocyanurate;
the leveling agent is organic silicon modified acrylate polymer or hydrogenated castor oil;
the graphene can be uniformly dispersed in the powder coating under the action of the coupling agent, so that the salt spray resistance of the powder coating is improved, and the weather resistance and the aging corrosion resistance of a coating are improved;
wherein, the polyester resin is prepared by the following method:
putting neopentyl glycol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-propanediol, trihydroxyethyl isocyanurate, terephthalic acid and adipic acid into a reaction kettle together according to the formula amount, firstly introducing nitrogen for 15-20min to replace the air in the reaction kettle, then raising the temperature under the protection of nitrogen, starting to extract esterified water when the temperature is raised to 160 ℃ of 150-;
wherein the dosage ratio of neopentyl glycol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-propanediol, trihydroxyethyl isocyanurate, terephthalic acid and adipic acid is 10g:5g: 2g:12g:8 g;
the introduction of the trihydroxyethyl isocyanurate monomer and the three-functional group monomer effectively improves the branching degree and the carboxyl-terminated activity of the polyester resin, so that the polyester resin meets the low-temperature curing condition, and meanwhile, the stable structure of the triazine ring of the trihydroxyethyl isocyanurate can improve the water resistance, the weather resistance and the mechanical property of the powder coating; monomers such as adipic acid and methyl propylene glycol are added, so that the flexibility of a chain segment of the polyester resin can be enhanced, and the powder coating is ensured to have good fluidity in the curing process, so that the coating has good appearance and mechanical properties; the isophthalic acid is introduced, and the reactivity and the uniqueness of a molecular structure of the isophthalic acid are utilized, so that the reactivity of the polyester resin and the weather resistance of a coating film are improved, and the problem that the low-temperature cured coating film is easy to bloom can be solved; 2-butyl-2-ethyl-1, 3-propylene glycol is introduced, and the larger side group of the 2-butyl-2-ethyl-1, 3-propylene glycol can effectively improve the weather resistance and water resistance of a polyester resin coating film and can ensure the reaction activity of the polyester resin, so that the coating surface of the powder coating has good weather resistance and good mechanical properties;
the antibacterial agent is prepared by the following method:
1) adding 6-bromine hexanol, triethylamine and dichloromethane into a flask together, stirring and dissolving, placing the flask in an ice bath, dropwise adding methacryloyl chloride, reacting for 60-70min after dropwise adding, removing the ice bath, continuing to react for 20-24h at room temperature, removing dichloromethane by rotary evaporation after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ to constant weight to obtain a first intermediate;
the amount ratio of the 6-bromine hexanol to the triethylamine to the dichloromethane to the methacryloyl chloride is 23-25g, 18-19g, 100mL, 19.8-20.0 g;
in the step, a substitution reaction is carried out on-OH on a 6-bromine n-hexanol molecule and an acyl chloride group on a methacryloyl chloride molecule to obtain a first intermediate, wherein the first intermediate contains carbon-carbon double bonds C ═ C and-Br on the molecule;
2) adding the first intermediate, tri (p-hydroxyphenyl) -phosphine, hydroquinone (polymerization inhibitor) and a proper amount of acetonitrile into a flask, stirring for dissolving, reacting at 80 ℃ for 66-72h, performing rotary evaporation to remove the acetonitrile after the reaction is finished, then washing with ethyl acetate and absolute ethyl alcohol for 3-4 times respectively, performing rotary evaporation again at 55 ℃ to remove the solvent, and finally drying in a vacuum drying oven at 60 ℃ to constant weight to obtain a second intermediate;
the dosage ratio of the first intermediate, the tri (p-hydroxyphenyl) -phosphine, the hydroquinone and the acetonitrile is 25g to 38g to 0.315g to 20 mL;
reacting-Br on the molecule of the first intermediate with P on the molecule of tri (P-hydroxyphenyl) -phosphine to generate quaternary phosphonium salt and obtain a second intermediate;
3) adding a photoinitiator (benzoin diethyl ether) into the second intermediate, stirring until the photoinitiator is completely dissolved, initiating polymerization reaction for 60-70min under the irradiation of 254nm ultraviolet light, then ultrasonically washing with tetrahydrofuran for 3-4 times, removing unreacted monomers and oligomers, and drying in a vacuum drying oven to constant weight to obtain the antibacterial agent;
the mass ratio of the second intermediate to the photoinitiator is 100: 1;
the carbon-carbon double bond on the molecule of the second intermediate is subjected to polymerization reaction under the irradiation of ultraviolet light to generate high molecular quaternary phosphonium salt;
the obtained high molecular quaternary phosphonium salt antibacterial agent contains ionic groups, can adsorb bacteria through electrostatic interaction, and then kills the bacteria by cracking cell membranes to achieve the aim of antibacterial; after the quaternary ammonium salt is polymerized, the cation density is increased, the adsorption to bacteria is enhanced, and meanwhile, the structure that the main chain of the polymer is hydrophobic and the side chain of the polymer is hydrophilic is similar to the phospholipid bilayer structure of a bacterial cell membrane, and the polymer can more easily penetrate through the cell wall to damage the cell membrane and kill the bacteria, so that the antibacterial property of the polymer antibacterial agent has the advantages of low toxicity, easiness in storage, high antibacterial group density and the like compared with a stronger polymer antibacterial agent before polymerization; in addition, the high molecular quaternary phosphonium salt has good compatibility with a coating substrate (polyester resin) and has a non-dissolution type antibacterial characteristic, and due to the large molecular weight, the high molecular antibacterial agent cannot migrate out of the coating along with the increase of time to cause the antibacterial property of the coating to be reduced, so that the problems of poor antibacterial durability and toxicity caused by dissolution of an inorganic antibacterial agent or an organic small molecular antibacterial agent can be avoided; in addition, phenolic hydroxyl of tri (p-hydroxyphenyl) -phosphine is introduced into the molecules of the obtained antibacterial agent, and the phenolic hydroxyl can generate chemical action with a polyester resin curing agent (the molecules of the curing agent contain a plurality of epoxy groups) and participate in the curing and crosslinking reaction to form a more crosslinked network structure, so that the integrity and compactness of the coating can be enhanced, the dispersion effect of the antibacterial agent in the coating and the binding force with the coating substrate can be promoted, and the antibacterial uniformity and the antibacterial durability can be further improved;
the preparation process of the powder coating comprises the following steps:
firstly, weighing polyester resin, an antibacterial agent, graphene, a coupling agent, a curing agent and a flatting agent according to the weight parts, putting the polyester resin, the antibacterial agent, the graphene, the coupling agent, the curing agent and the flatting agent into a high-speed mixer, stirring and mixing for 20-25min at 300r/min, and then increasing the rotating speed to 2000r/min, stirring and mixing for 8-10min to obtain a premix;
and secondly, extruding the premix through a double-screw extruder to form a flaky material, and crushing, grinding and sieving the flaky material with a 200-mesh sieve to obtain fine powder so as to prepare the powder coating.
Example 1
An antibacterial and antivirus powder coating comprises the following raw materials in parts by weight: 60 parts of polyester resin, 3 parts of antibacterial agent, 4 parts of graphene, 1.6 parts of coupling agent, 5 parts of curing agent and 1 part of flatting agent;
the powder coating is prepared by the following steps:
firstly, weighing polyester resin, an antibacterial agent, graphene, a coupling agent, a curing agent and a flatting agent according to the weight parts, putting the polyester resin, the antibacterial agent, the graphene, the coupling agent, the curing agent and the flatting agent into a high-speed mixer, stirring and mixing for 20min at 300r/min, and then stirring and mixing for 8min at a rotating speed increased to 2000r/min to obtain a premix;
and secondly, extruding the premix through a double-screw extruder to form a flaky material, and crushing, grinding and sieving the flaky material with a 200-mesh sieve to obtain fine powder so as to prepare the powder coating.
Example 2
An antibacterial and antivirus powder coating comprises the following raw materials in parts by weight: 65 parts of polyester resin, 3.5 parts of antibacterial agent, 4.5 parts of graphene, 1.8 parts of coupling agent, 5.5 parts of curing agent and 1.1 parts of flatting agent;
the powder coating is prepared by the following steps:
firstly, weighing polyester resin, an antibacterial agent, graphene, a coupling agent, a curing agent and a flatting agent according to the weight parts, putting the polyester resin, the antibacterial agent, the graphene, the coupling agent, the curing agent and the flatting agent into a high-speed mixer, stirring and mixing for 23min at 300r/min, and then stirring and mixing for 9min at a rotating speed of 2000r/min to obtain a premix;
and secondly, extruding the premix through a double-screw extruder to form a flaky material, and crushing, grinding and sieving the flaky material with a 200-mesh sieve to obtain fine powder so as to prepare the powder coating.
Example 3
An antibacterial and antivirus powder coating comprises the following raw materials in parts by weight: 70 parts of polyester resin, 4 parts of antibacterial agent, 5 parts of graphene, 2 parts of coupling agent, 6 parts of curing agent and 1.2 parts of flatting agent;
the powder coating is prepared by the following steps:
firstly, weighing polyester resin, an antibacterial agent, graphene, a coupling agent, a curing agent and a flatting agent according to the weight parts, putting the polyester resin, the antibacterial agent, the graphene, the coupling agent, the curing agent and the flatting agent into a high-speed mixer, stirring and mixing the polyester resin, the antibacterial agent, the graphene, the coupling agent, the curing agent and the flatting agent for 25min at a speed of 300r/min, and then stirring and mixing the;
and secondly, extruding the premix through a double-screw extruder to form a flaky material, and crushing, grinding and sieving the flaky material with a 200-mesh sieve to obtain fine powder so as to prepare the powder coating.
Comparative example 1
The polyester resin in the example 1 is changed into the common polyester resin, and the rest raw materials and the preparation process are not changed.
Comparative example 2
The antibacterial agent in the example 1 is replaced by a common micromolecular quaternary phosphonium salt antibacterial agent, and the rest raw materials and the preparation process are unchanged.
The powder coatings obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to the following performance tests:
uniformly spraying the powder coating on a pretreated tinplate (polished by sand paper and cleaned by alcohol) by using an electrostatic spraying device (with the voltage of 50KV, the air pressure of 0.05MPa and the spraying distance of about 15cm), vertically suspending the powder coating in a 115 ℃ oven after the spraying is finished, curing for 15min to form a film, forming a coating with the film thickness of about 80 mu m, naturally cooling to room temperature, taking out the coating, standing for 24h, and determining the performance of the coating;
the hardness of the coating is measured according to GB/T6739-2006; the 60-degree gloss of the coating is tested according to GB/T9754-2007; the coating adhesion was determined according to GB/T9286-1998; impact resistance was determined as described in GB/T1732-1993; grading according to HG/T2006-2006, and determining the grade after 500h of salt spray resistance test (the smaller the number is, the higher the grade is, the better the salt spray resistance is); and (3) determination of antibacterial performance: the antibacterial performance and the antibacterial durability are measured according to the national standard GB/T21866-2008; the test results are shown in the following table:
from the table, after the powder coating prepared in the examples 1 to 3 forms a coating, the 60-degree gloss is 29.6 to 30.2, the pencil hardness reaches H, the coating adhesion reaches level 1, and the performance after 500H of salt spray resistance test reaches level 0, which indicates that the powder coating prepared by the invention has good mechanical property and salt spray resistance; the bacteriostatic rates of the powder coatings prepared in the embodiments 1 to 3 to escherichia coli and staphylococcus aureus are both more than 99.9%, which shows that the powder coatings prepared in the invention have good antibacterial and antivirus performances, and after a durability test, the bacteriostatic rates to escherichia coli and staphylococcus aureus are 93.8-94.4% and 93.6-94.0%, respectively, which shows that the powder coatings prepared in the invention have good antibacterial durability; the invention is demonstrated by combining with comparative example 1 that the mechanical property of the coating can be improved by selecting the polyester resin synthesized by specific raw materials as a film forming substrate; the combination of the comparative example 2 shows that the self-made high molecular quaternary phosphonium salt antibacterial agent has good compatibility with a film-forming matrix and good anti-seepage performance, and can participate in the cross-linking curing reaction of the coating to improve the acting force with the film-forming matrix, thereby improving the antibacterial effect and the antibacterial durability.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (6)
1. The antibacterial and antivirus powder coating is characterized by comprising the following raw materials in parts by weight: 60-70 parts of polyester resin, 3-4 parts of antibacterial agent, 4-5 parts of graphene, 1.6-2 parts of coupling agent, 5-6 parts of curing agent and 1-1.2 parts of flatting agent;
the powder coating is prepared by the following steps:
firstly, weighing polyester resin, an antibacterial agent, graphene, a coupling agent, a curing agent and a flatting agent according to the weight parts, putting the polyester resin, the antibacterial agent, the graphene, the coupling agent, the curing agent and the flatting agent into a high-speed mixer, stirring and mixing for 20-25min at 300r/min, and then increasing the rotating speed to 2000r/min, stirring and mixing for 8-10min to obtain a premix;
and secondly, extruding the premix through a double-screw extruder to form a flaky material, and crushing, grinding and sieving the flaky material with a 200-mesh sieve to obtain fine powder so as to prepare the powder coating.
2. An antibacterial and anti-microbial powder coating according to claim 1, wherein the polyester resin is prepared by the following method:
putting neopentyl glycol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-propanediol, trihydroxyethyl isocyanurate, terephthalic acid and adipic acid into a reaction kettle together according to the formula amount, firstly introducing nitrogen for 15-20min to replace air in the reaction kettle, then raising the temperature under the protection of nitrogen, starting to extract esterified water when the temperature is raised to 160 ℃ of 150-.
3. An antibacterial and disinfectant powder coating as claimed in claim 2, wherein said neopentyl glycol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-propanediol, tris-hydroxyethyl isocyanurate, terephthalic acid and adipic acid are used in a ratio of 10g:5g:3g:2g:12g:8 g.
4. An antibacterial and bactericidal powder coating as claimed in claim 1, wherein the antibacterial agent is prepared by a method comprising:
1) adding 6-bromine hexanol, triethylamine and dichloromethane into a flask together, stirring and dissolving, placing the flask in an ice bath, dropwise adding methacryloyl chloride, reacting for 60-70min after dropwise adding, removing the ice bath, continuing to react for 20-24h at room temperature, removing dichloromethane by rotary evaporation after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ to constant weight to obtain a first intermediate;
2) adding the first intermediate, tri (p-hydroxyphenyl) -phosphine, hydroquinone and a proper amount of acetonitrile into a flask, stirring for dissolving, reacting at 80 ℃ for 66-72h, performing rotary evaporation to remove the acetonitrile after the reaction is finished, then washing with ethyl acetate and absolute ethyl alcohol for 3-4 times respectively, performing rotary evaporation to remove the solvent at 55 ℃ again, and finally drying in a vacuum drying oven at 60 ℃ to constant weight to obtain a second intermediate;
3) adding a photoinitiator into the second intermediate, stirring until the photoinitiator is completely dissolved, initiating polymerization reaction for 60-70min under the irradiation of 254nm ultraviolet light, then ultrasonically washing for 3-4 times by using tetrahydrofuran to remove unreacted monomers and oligomers, and drying in a vacuum drying oven to constant weight to obtain the antibacterial agent.
5. The antibacterial and disinfectant powder coating as claimed in claim 4, wherein the ratio of the amounts of 6-bromo-n-hexanol, triethylamine, dichloromethane and methacryloyl chloride used in step 1) is 23-25g:18-19g:100mL:19.8-20.0 g; the dosage ratio of the first intermediate, the tri (p-hydroxyphenyl) -phosphine, the hydroquinone and the acetonitrile in the step 2) is 25g to 38g to 0.315g to 20 mL; the mass ratio of the second intermediate to the photoinitiator in step 3) is 100: 1.
6. The process for preparing an antibacterial and disinfectant powder coating according to claim 1, comprising the steps of:
firstly, weighing polyester resin, an antibacterial agent, graphene, a coupling agent, a curing agent and a flatting agent according to the weight parts, putting the polyester resin, the antibacterial agent, the graphene, the coupling agent, the curing agent and the flatting agent into a high-speed mixer, stirring and mixing for 20-25min at 300r/min, and then increasing the rotating speed to 2000r/min, stirring and mixing for 8-10min to obtain a premix;
and secondly, extruding the premix through a double-screw extruder to form a flaky material, and crushing, grinding and sieving the flaky material with a 200-mesh sieve to obtain fine powder so as to prepare the powder coating.
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