CN116120829A - Urethane-acrylic ester/nano metal flame-retardant antibacterial coating and preparation method thereof - Google Patents
Urethane-acrylic ester/nano metal flame-retardant antibacterial coating and preparation method thereof Download PDFInfo
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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
- 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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- 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
- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/0806—Silver
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/085—Copper
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyurethane-acrylic ester/nano metal flame-retardant antibacterial coating and a preparation method thereof. The invention comprises the following raw materials in parts by mass: 5 to 10 parts of polyether glycol, 10 to 20 parts of diisocyanate, 0.01 to 0.03 part of catalyst, 10 to 15 parts of solvent, 3 to 6 parts of carboxyl-containing chain extender, 5 to 10 parts of hydroxyl-containing end capping agent, 2 to 5 parts of neutralizer, 0.1 to 0.3 part of initiator, 0.3 to 0.7 part of emulsifier, 35 to 55 parts of metal ion aqueous solution, 0.1 to 0.3 part of defoamer, 0.05 to 0.1 part of anti-flash rust agent, 5 to 10 parts of flame retardant filler, 0.3 to 0.6 part of thickener and 0.1 to 0.3 part of flatting agent. The invention provides a polyurethane-acrylic ester/nano metal flame-retardant antibacterial coating and a preparation method thereof, which can solve the problems of easy agglomeration, oxidation, discoloration and the like of nano metal.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyurethane-acrylic ester/nano metal flame-retardant antibacterial coating and a preparation method thereof.
Background
As public facilities, elevators are often contacted by people, sanitary problems cannot be ignored, antibacterial treatment of the elevators is particularly important, and at present, a mode of spraying disinfectant is mainly adopted, so that the problems of high treatment frequency and influence on use exist. Endowing the elevator with an antibacterial function is a trend of development in the future, can realize a long-term antibacterial effect and reduce the frequency of disinfection treatment. The patent CN202897732U provides an epidemic prevention antibacterial freight elevator, is equipped with the photocatalyst coating board that matches with the top of car in the lower part of ventilation board, through the combination of photocatalyst coating board and ultraviolet lamp, can effectively degrade the poisonous and harmful gas in the air, but can not handle the bacterium on elevator surface. The patent CN 110028814A provides a flame-retardant antibacterial coating for an elevator and a preparation method thereof, wherein the antibacterial coating for the elevator is prepared by adopting a mode of combining organic and inorganic antibacterial agents, and can treat bacteria on the surface of the elevator, but the steps of calcining, grinding, ultrasonic cleaning, high-temperature baking and the like are needed, and the preparation process is complicated.
Disclosure of Invention
The invention aims to solve the technical problem of providing the urethane-acrylic ester/nano metal flame-retardant antibacterial coating and the preparation method thereof, which can solve the problems of easy agglomeration, oxidation, discoloration and the like of nano metal.
The invention adopts the technical scheme that:
the urethane-acrylic ester/nano metal flame-retardant antibacterial coating comprises the following raw materials in parts by mass: 5 to 10 parts of polyether glycol, 10 to 20 parts of diisocyanate, 0.01 to 0.03 part of catalyst, 10 to 15 parts of solvent, 3 to 6 parts of carboxyl-containing chain extender, 5 to 10 parts of hydroxyl-containing end capping agent, 2 to 5 parts of neutralizer, 0.1 to 0.3 part of initiator, 0.3 to 0.7 part of emulsifier, 35 to 55 parts of metal ion aqueous solution, 0.1 to 0.3 part of defoamer, 0.05 to 0.1 part of anti-flash rust agent, 5 to 10 parts of flame retardant filler, 0.3 to 0.6 part of thickener and 0.1 to 0.3 part of flatting agent.
The diisocyanate is isophorone diisocyanate or hexamethylene diisocyanate; the catalyst is an organotin catalyst, and is dibutyl tin dilaurate or stannous octoate; the solvent is an active solvent with double bonds, and is butyl acrylate or methyl methacrylate; the carboxyl-containing chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the hydroxyl-containing end-capping agent is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate; the neutralizer is triethylamine, sodium hydroxide or potassium hydroxide; the initiator is ammonium persulfate and potassium persulfate; the emulsifying agent is S-80 and S-60; the metal ion aqueous solution is silver nitrate solution, copper sulfate solution or zinc sulfate solution.
The concentration of the metal ion aqueous solution is 0.01 mol/L-0.5 mol/L.
The defoaming agent is one or two of BYK-028 and BYK-024; the thickening agent is T-1550; the anti-flash rust agent is ED-617F; the leveling agent is Tego-4100, and the flame retardant filler is one or two of aluminum hydroxide and magnesium hydroxide.
A preparation method of urethane-acrylic ester/nano metal flame-retardant antibacterial paint comprises the following steps:
step 1, adding polyether glycol, diisocyanate, a catalyst, a solvent and a carboxyl-containing chain extender into a reaction kettle, and heating to 60-90 ℃ for reaction for 4-8 hours to obtain a carboxyl-containing polyurethane prepolymer solution;
step 2, adding a hydroxyl-containing end capping agent, and reacting for 2-5 hours at 60-90 ℃ to obtain double-bond end capped polyurethane solution;
step 3, cooling to below 30 ℃, adding a neutralizing agent, an initiator and an emulsifying agent, stirring uniformly, adding a metal ion aqueous solution, and emulsifying at a high speed to obtain emulsion particles rich in metal ions, a dispersing agent and a reducing agent;
step 4, introducing nitrogen into the emulsion particles in the step 3, keeping the high-speed stirring speed at 1000-1500 r/min, heating to 45-95 ℃, initiating emulsion polymerization to generate poly (urethane-acrylic ester), and simultaneously carrying out in-situ reduction reaction for 2-6 h to obtain the urethane-acrylic ester/nano metal composite emulsion;
and 5, cooling to normal temperature, adding a defoaming agent, an anti-flash rust agent, a leveling agent, a flame-retardant filler and a thickening agent, stirring for 15min to enable the materials to be completely dispersed, filtering with 200-mesh filter cloth, and packaging to obtain the polyurethane-acrylic ester/nano metal flame-retardant antibacterial coating for the elevator.
And (3) obtaining the carboxyl-containing polyurethane prepolymer serving as a metal ion dispersing agent in the step (1).
In the step 2, the solution obtained in the step 1 is subjected to isocyanate group mass fraction detection, the isocyanate group mass fraction is detected to reach the range, a hydroxyl-containing blocking agent and excessive hydroxypropyl methacrylate are added as a metal ion reducing agent.
In the step 3, the solution obtained in the step 2 is subjected to isocyanate group mass fraction detection, the detected isocyanate group mass fraction reaches 0, and the temperature is reduced to below 30 ℃.
In the step 4, the poly (urethane-acrylate) generated by emulsion polymerization is a nano metal protective agent.
The R value (equivalent ratio of isocyanate groups to hydroxyl groups) in the step 1 is 1.4-2, so that the isocyanate groups are excessive, and the polyurethane prepolymer in the step 1 is reacted with the hydroxyl end capping agent in the step 2 to obtain double-bond end capped polyurethane; and R value in the step 2 is 0.8-0.95, so that the hydroxyl end capping agent in the step 2 is excessive and serves as a reducing agent.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
(1) According to the urethane-acrylic ester/nano metal flame-retardant antibacterial coating and the preparation method thereof, the waterborne polyurethane modified acrylic ester resin is synthesized, the carboxyl-containing polyurethane prepolymer modified by metal ion aqueous solution in-situ emulsification and the hydroxyl-containing acrylic ester monomer resin are used as liquid phases, and the polyurethane chain segment rich in carboxyl is comprehensively utilized as a dispersing agent to adsorb metal ions so as to be uniformly dispersed in emulsion particles; in-situ emulsifying polyurethane modified acrylic resin with metal ion aqueous solution to obtain a liquid phase;
(2) According to the urethane-acrylic ester/nano metal flame-retardant antibacterial coating and the preparation method thereof, provided by the invention, a polyurethane chain segment rich in carboxyl is used as a dispersing agent, and the carboxyl adsorbs metal ions and is uniformly dispersed in emulsion particles; the acrylate monomer chain segment rich in hydroxyl is used as a reducing agent, no external reducing agent is needed, metal ions, a dispersing agent and the reducing agent are uniformly dispersed in latex particles, and the metal ions are reduced in situ in the latex particles to generate nano metal particles;
(3) According to the urethane-acrylate/nano metal flame-retardant antibacterial coating and the preparation method thereof, provided by the invention, the polymer chain in a high-viscosity elastic state is used as a protective agent of nano metal, aggregation of the nano metal is prevented, the generated nano metal has small particle size and narrow distribution, the particle size is 2-10 nm, and the antibacterial rate is up to 99.99%
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a urethane-acrylic ester/nano metal flame-retardant antibacterial coating, which comprises the following raw materials in parts by weight: 5 to 10 parts of polyether glycol, 10 to 20 parts of diisocyanate, 0.01 to 0.03 part of catalyst, 10 to 15 parts of solvent, 3 to 6 parts of carboxyl-containing chain extender, 5 to 10 parts of hydroxyl-containing end capping agent, 2 to 5 parts of neutralizer, 0.1 to 0.3 part of initiator, 0.3 to 0.7 part of emulsifier, 35 to 55 parts of metal ion aqueous solution, 0.1 to 0.3 part of defoamer, 0.05 to 0.1 part of anti-flash rust agent, 5 to 10 parts of flame retardant filler, 0.3 to 0.6 part of thickener and 0.1 to 0.3 part of flatting agent.
The diisocyanate is isophorone diisocyanate or hexamethylene diisocyanate;
the catalyst is an organotin catalyst, and is dibutyl tin dilaurate or stannous octoate;
the solvent is an active solvent with double bonds, and is butyl acrylate or methyl methacrylate;
the carboxyl-containing chain extender is dimethylolpropionic acid or dimethylolbutyric acid;
the hydroxyl-containing end-capping agent is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate;
the neutralizer is triethylamine, sodium hydroxide or potassium hydroxide;
the initiator is ammonium persulfate and potassium persulfate
The emulsifier is S-80, S-60
The metal ion aqueous solution is silver nitrate solution, copper sulfate solution or zinc sulfate solution, and the concentration of the metal ion aqueous solution is 0.01 mol/L-0.5 mol/L.
The defoaming agent is one or two of BYK-028 and BYK-024; the thickening agent is T-1550; the anti-flash rust agent is ED-617F; the leveling agent is Tego-4100, and the flame retardant filler is one or two of aluminum hydroxide and magnesium hydroxide.
The invention provides a preparation method of urethane-acrylic ester/nano metal flame-retardant antibacterial paint, which comprises the following steps:
step 1, adding polyether glycol, diisocyanate, a catalyst, a solvent and a carboxyl-containing chain extender into a reaction kettle, and heating to 60-90 ℃ for reaction for 4-8 hours to obtain a carboxyl-containing polyurethane prepolymer;
step 2, adding a hydroxyl-containing end capping agent, and reacting for 2-5 hours at 60-90 ℃ to obtain double-bond end capped polyurethane;
step 3, cooling to below 30 ℃, adding a neutralizing agent, an initiator and an emulsifying agent, stirring uniformly, adding a metal ion aqueous solution, and emulsifying at a high speed to obtain emulsion particles rich in metal ions, a dispersing agent and a reducing agent;
and 4, introducing nitrogen into the emulsion particles in the step 3, maintaining the high-speed stirring speed at 1000-1500 r/min, heating to 45-95 ℃, initiating emulsion polymerization to generate poly (urethane-acrylate), and simultaneously carrying out in-situ reduction reaction for 2-6 h to obtain the urethane-acrylate/nano metal composite emulsion.
And 5, cooling to normal temperature, adding a defoaming agent, an anti-flash rust agent, a leveling agent, a flame-retardant filler and a thickening agent, stirring for 15min to enable the materials to be completely dispersed, filtering with 200-mesh filter cloth, and packaging to obtain the polyurethane-acrylic ester/nano metal flame-retardant antibacterial coating for the elevator.
Specific:
example 1
Step 101, adding 4.8g of polyether glycol, 10g of isophorone diisocyanate, 0.01g of stannous octoate, 10g of butyl acrylate and 4g of dimethylolpropionic acid into a reaction kettle, and heating to 60 ℃ for reaction for 4 hours; obtaining carboxyl-containing polyurethane prepolymer serving as a metal ion dispersing agent;
102, detecting that the mass fraction of isocyanate groups reaches 3%, cooling to 60 ℃, adding 5g of hydroxypropyl methacrylate, and reacting for 2 hours to obtain double-bond blocked polyurethane, wherein excessive hydroxypropyl methacrylate is used as a metal ion reducing agent;
step 103, detecting that the mass fraction of isocyanate groups reaches 0, cooling to 25 ℃, adding 2g of triethylamine, 0.1g of ammonium persulfate and 0.3g of S-80, uniformly stirring, adding 50g of 0.1mol/L of silver nitrate aqueous solution, and emulsifying at a high speed of 1000r/min for 0.5h to obtain emulsion particles rich in metal ions, dispersing agents and reducing agents thereof;
step 104, introducing nitrogen into the emulsion particles in step 103, keeping the high-speed stirring speed at 1000-1500 r/min, heating to 45 ℃, initiating emulsion polymerization, and reacting for 4 hours to obtain the aqueous poly (urethane-acrylate)/nano-silver composite emulsion, wherein the particle size of the nano-silver is 2-5 nm;
and 105, cooling to room temperature, adding 0.1g of BYK-028 defoamer, 0.05gED-617F anti-flash rust agent, 0.1g of Tego-4100 flatting agent, 5g of aluminum hydroxide and 0.3g of T-1550 thickener, stirring for 15min to completely disperse the materials, filtering with 200-mesh filter cloth, and packaging to obtain the ammonia ester-acrylic ester/nano silver flame-retardant antibacterial coating for the elevator.
Example 2
Step 201, adding 6g of polyether glycol, 12g of isophorone diisocyanate, 0.01g of stannous octoate, 12g of butyl acrylate and 3.5g of dimethylolpropionic acid into a reaction kettle, and heating to 75 ℃ for reaction for 6 hours to obtain a carboxyl-containing polyurethane prepolymer serving as a metal ion dispersing agent;
202, detecting that the mass fraction of isocyanate groups reaches 5.5%, cooling to 75 ℃, adding 7g of hydroxypropyl methacrylate, and reacting for 3.5 hours to obtain double-bond blocked polyurethane, wherein excessive hydroxypropyl methacrylate is used as a metal ion reducing agent;
203, detecting that the mass fraction of isocyanate groups reaches 0, cooling to 25 ℃, adding 3g of triethylamine, 0.2g of ammonium persulfate and 0.45-80, uniformly stirring, adding 40g of 0.05mol/L copper sulfate aqueous solution, and emulsifying at a speed of 1250r/min for 0.5h to obtain emulsion particles rich in metal ions, dispersing agents and reducing agents thereof;
step 204, introducing nitrogen into the emulsion particles in step 203, keeping the high-speed stirring speed at 1000-1500 r/min, heating to 70 ℃, initiating emulsion polymerization, and reacting for 5 hours to obtain the aqueous poly (urethane-acrylate)/nano copper composite emulsion, wherein the particle size of nano copper is 4-8 nm;
and 205, cooling to room temperature, adding 0.2g of BYK-028 defoamer, 0.075gED-617F anti-flash rust agent, 0.3g of Tego-4100 flatting agent, 7.5g of aluminum hydroxide and 0.45g of T-1550 thickener, stirring for 15min to completely disperse materials, filtering with 200-mesh filter cloth, and packaging to obtain the polyurethane-acrylic ester/nano copper flame-retardant antibacterial coating for the elevator.
Example 3
Step 301, adding 8g of polyether glycol, 16g of isophorone diisocyanate, 0.03g of stannous octoate, 16g of butyl acrylate and 5g of dimethylolpropionic acid into a reaction kettle, and heating to 90 ℃ for reaction for 8 hours to obtain a carboxyl-containing polyurethane prepolymer serving as a metal ion dispersing agent;
step 302, detecting that the mass fraction of isocyanate groups reaches 5%, cooling to 90 ℃, adding 9g of hydroxypropyl methacrylate, and reacting for 5 hours to obtain double-bond blocked polyurethane, wherein excessive hydroxypropyl methacrylate is used as a metal ion reducing agent;
step 303, detecting that the mass fraction of isocyanate groups reaches 0, cooling to 25 ℃, adding 4.5g of triethylamine, 0.3g of ammonium persulfate and 0.45g S-80, uniformly stirring, adding 30g of 0.01mol/L zinc sulfate aqueous solution, and emulsifying at a high speed of 1500r/min for 0.5h to obtain emulsion particles rich in metal ions, dispersing agents and reducing agents thereof;
and 304, introducing nitrogen into the emulsion particles in the step 203, keeping the high-speed stirring speed at 1000-1500 r/min, heating to 95 ℃, initiating emulsion polymerization, and reacting for 6 hours to obtain the aqueous poly (urethane-acrylate)/nano zinc composite emulsion, wherein the particle size of the nano zinc is 5-10 nm. After cooling to room temperature, adding 0.3g BYK-028 defoamer, 0.01gED-617F anti-flash rust agent, 0.5g Tego-4100 flatting agent, 10g aluminum hydroxide and 0.6g T-1550 thickener, stirring for 15min to disperse the materials completely, filtering with 200 mesh filter cloth, and packaging to obtain the polyurethane-acrylic ester/nano zinc flame-retardant antibacterial coating for the elevator.
The urethane-acrylate/nano metal flame-retardant antibacterial coating prepared in examples 1-3 was sprayed on the elevator surface and baked with a heat gun for 1h, and the coating properties were as follows:
table 1 coating properties comparison table
According to the invention, the polyurethane chain segment rich in carboxyl is used as a dispersing agent, metal ions are adsorbed by carboxyl, and the acrylate monomer rich in hydroxyl is used as a reducing agent, so that no external reducing agent is needed; the metal ions, the dispersing agent and the reducing agent are uniformly dispersed in the emulsion particles, and in the emulsion polymerization process, the metal ions are reduced to nano metal in situ, and the generated polymer chain with viscoelasticity can also serve as a nano metal protective agent, so that aggregation of the nano metal is hindered, and the formed nano metal has small particle size and narrow distribution. The invention solves the problems of easy agglomeration, oxidation, discoloration and the like of nano metal, has long-term antibacterial property and wear resistance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. The urethane-acrylic ester/nano metal flame-retardant antibacterial coating is characterized by comprising the following raw materials in parts by weight: 5 to 10 parts of polyether glycol, 10 to 20 parts of diisocyanate, 0.01 to 0.03 part of catalyst, 10 to 15 parts of solvent, 3 to 6 parts of carboxyl-containing chain extender, 5 to 10 parts of hydroxyl-containing end capping agent, 2 to 5 parts of neutralizer, 0.1 to 0.3 part of initiator, 0.3 to 0.7 part of emulsifier, 35 to 55 parts of metal ion aqueous solution, 0.1 to 0.3 part of defoamer, 0.05 to 0.1 part of anti-flash rust agent, 5 to 10 parts of flame retardant filler, 0.3 to 0.6 part of thickener and 0.1 to 0.3 part of flatting agent.
2. The urethane-acrylate/nano-metal floor wear-resistant antibacterial coating according to claim 1, wherein the diisocyanate is isophorone diisocyanate or hexamethylene diisocyanate; the catalyst is an organotin catalyst, and is dibutyl tin dilaurate or stannous octoate; the solvent is an active solvent with double bonds, and is butyl acrylate or methyl methacrylate; the carboxyl-containing chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the hydroxyl-containing end-capping agent is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate; the neutralizer is triethylamine, sodium hydroxide or potassium hydroxide; the initiator is ammonium persulfate and potassium persulfate; the emulsifying agent is S-80 and S-60; the metal ion aqueous solution is silver nitrate solution, copper sulfate solution or zinc sulfate solution.
3. The urethane-acrylate/nano-metal floor wear-resistant antibacterial coating according to claim 2, wherein the concentration of the metal ion aqueous solution is 0.01mol/L to 0.5mol/L.
4. The urethane-acrylate/nano-metal floor wear-resistant antibacterial coating according to claim 1, wherein the defoamer is one or both of BYK-028 or BYK-024; the thickening agent is T-1550; the anti-flash rust agent is ED-617F; the leveling agent is Tego-4100, and the flame retardant filler is one or two of aluminum hydroxide and magnesium hydroxide.
5. A method for preparing the urethane-acrylate/nano-metal flame retardant antimicrobial coating according to any one of claims 1-4, comprising the steps of:
step (1), polyether glycol, diisocyanate, a catalyst, a solvent and a carboxyl-containing chain extender are added into a reaction kettle, and the temperature is raised to 60-90 ℃ to react for 4-8 hours to obtain a carboxyl-containing polyurethane prepolymer solution;
step (2), adding a hydroxyl-containing end capping agent, and reacting for 2-5 hours at 60-90 ℃ to obtain double-bond end capped polyurethane solution;
step (3), cooling to below 30 ℃, adding a neutralizing agent, an initiator and an emulsifying agent, uniformly stirring, adding a metal ion aqueous solution, and emulsifying at a high speed to obtain emulsion particles rich in metal ions, a dispersing agent and a reducing agent;
step (4), introducing nitrogen into the emulsion particles in the step (3), keeping the high-speed stirring speed at 1000-1500 r/min, heating to 45-95 ℃, initiating emulsion polymerization to generate poly (urethane-acrylate), and simultaneously carrying out in-situ reduction reaction for 2-6 h to obtain urethane-acrylate/nano metal composite emulsion;
and (5) cooling to normal temperature, adding a defoaming agent, an anti-flash rust agent, a leveling agent, a flame-retardant filler and a thickening agent, stirring for 15min to enable the materials to be completely dispersed, filtering with 200-mesh filter cloth, and packaging to obtain the polyurethane-acrylic ester/nano metal flame-retardant antibacterial coating for the elevator.
6. The method according to claim 5, wherein the carboxyl group-containing polyurethane prepolymer obtained in the step (1) is used as a metal ion dispersing agent.
7. The method according to claim 5, wherein in the step (2), the solution obtained in the step (1) is subjected to detection of the mass fraction of isocyanate groups, the mass fraction of isocyanate groups is detected to be 3-5.5%, a hydroxyl-containing blocking agent is added, and an excess of hydroxypropyl methacrylate is used as a metal ion reducing agent.
8. The method according to claim 5, wherein in the step (3), the solution obtained in the step (2) is subjected to detection of the mass fraction of isocyanate groups, the detected mass fraction of isocyanate groups reaches 0, and the temperature is lowered to below 30 ℃.
9. The method of claim 5, wherein in step (4), the poly (urethane-acrylate) produced by emulsion polymerization is a nano-metal protectant.
10. The aqueous poly (urethane-acrylate) nano metal wear-resistant antibacterial coating for floors and the preparation method thereof according to claim 5, wherein the equivalent ratio of isocyanate to hydroxyl in the step 1 is 1.4-2, and the equivalent ratio of isocyanate to hydroxyl in the step 2 is 0.8-0.95.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310029406.1A CN116120829A (en) | 2023-01-09 | 2023-01-09 | Urethane-acrylic ester/nano metal flame-retardant antibacterial coating and preparation method thereof |
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| CN101029204A (en) * | 2007-04-12 | 2007-09-05 | 江苏晨光涂料有限公司 | Multifunctional water woodenware pigment and its production |
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| CN111116859A (en) * | 2019-12-31 | 2020-05-08 | 杭州吉华高分子材料股份有限公司 | Preparation method of antibacterial modified waterborne polyurethane |
| CN111454476A (en) * | 2020-04-21 | 2020-07-28 | 苏州达万塑胶电子有限公司 | Antibacterial film and processing technology thereof |
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| CN101029204A (en) * | 2007-04-12 | 2007-09-05 | 江苏晨光涂料有限公司 | Multifunctional water woodenware pigment and its production |
| CN103865373A (en) * | 2014-03-17 | 2014-06-18 | 同济大学 | Preparation method of anionic waterborne polyurethane nano-silver composite coating |
| CN108610937A (en) * | 2016-12-09 | 2018-10-02 | 惠州市海灵岛科技有限公司 | A kind of polyurethane-acrylic ester aquosity coating and preparation method thereof |
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