CN116082913A - Urethane-acrylic ester/nano metal wear-resistant antibacterial coating and preparation method thereof - Google Patents
Urethane-acrylic ester/nano metal wear-resistant 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/0806—Silver
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- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a urethane-acrylate/nano metal wear-resistant antibacterial coating and a preparation method thereof. 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 urethane-acrylic ester/nano metal floor wear-resistant antibacterial coating prepared by the invention solves the problems of easy agglomeration, oxidization, color change and the like of nano metal, has long-term antibacterial property and wear resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a urethane-acrylate/nano metal wear-resistant antibacterial coating and a preparation method thereof.
Background
With the improvement of the living standard of people, the functionalized floors are later development trend, such as imparting the floor with antibacterial paint. At present, although composite floors with antibacterial performance appear in the market of wood floors, the antibacterial performance of the composite floors is generally not ideal, and the requirements of people on the antibacterial performance cannot be met. Patent CN101555380a provides an antibacterial two-component polyurethane coating for wood floors, which achieves the antibacterial purpose by adding an organic antibacterial agent into the polyurethane coating, but the organic antibacterial agent can cause bacteria to develop drug resistance and can generate super bacteria. Patent CN 104017410B provides an antibacterial composite floor based on nano zinc particles, which achieves the antibacterial purpose by adding nano zinc particles into acrylic paint, but externally added nano zinc particles are unstable, a thinner is needed, and the VOC content is high.
Disclosure of Invention
The invention aims to solve the technical problem of providing the urethane-acrylic ester/nano metal wear-resistant 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 wear-resistant 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 wear-resistant 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 agents 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 wear-resistant filler is boron nitride.
A preparation method of urethane-acrylic ester/nano metal wear-resistant 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, an abrasion-resistant 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 floor abrasion-resistant antibacterial coating.
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 25 ℃.
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) The invention provides a urethane-acrylic ester/nano metal wear-resistant antibacterial coating and a preparation method thereof, wherein an aqueous polyurethane modified acrylic ester resin is synthesized, a metal ion aqueous solution is used for in-situ emulsification of carboxyl-containing polyurethane prepolymer modified and hydroxyl-containing acrylic ester monomer resin is used as a liquid phase, and a 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 wear-resistant 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 wear-resistant 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 wear-resistant 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 wear-resistant 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 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 wear-resistant filler is boron nitride.
The invention provides a preparation method of urethane-acrylic ester/nano metal wear-resistant 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, an abrasion-resistant 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 abrasion-resistant antibacterial coating for the floor.
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 to obtain a 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 boron nitride 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 polyurethane-acrylic ester/nano silver wear-resistant antibacterial coating for floors.
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 flash rust inhibitor, 0.3g of Tego-4100 flatting agent, 7.5g of boron nitride and 0.45g of T-1550 thickener, stirring for 15min to completely disperse the materials, filtering with 200-mesh filter cloth, and packaging to obtain the polyurethane-acrylic ester/nano copper wear-resistant antibacterial coating for floors.
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;
step 304, introducing nitrogen into the emulsion particles in 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 nano zinc is 5-10 nm;
and 305, cooling to room temperature, adding 0.3g of BYK-028 defoamer, 0.01gED-617F anti-flash rust agent, 0.5g of Tego-4100 flatting agent, 10g of boron nitride and 0.6g of T-1550 thickener, stirring for 15min to completely disperse the materials, filtering with 200-mesh filter cloth, and packaging to obtain the polyurethane-acrylic ester/nano zinc wear-resistant antibacterial coating for floors.
The urethane-acrylate/nano metal wear-resistant antibacterial coating prepared in examples 1-3 was sprayed on the floor surface and placed in an 80 ℃ oven for baking for 1 hour, and the coating properties were as follows:
table 1 coating properties comparison table
| Adhesion force | Hardness of | Wear resistance (750 g/500 r/g) | Antibacterial ratio (%) | |
| Example 1 | 0 | 4H | 0.0015 | 99.99 |
| Example 2 | 0 | 4H | 0.0020 | 99.99 |
| Example 3 | 0 | 4H | 0.0025 | 99.99 |
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 urethane-acrylic ester/nano metal floor wear-resistant antibacterial coating prepared by the invention solves the problems of easy agglomeration, oxidization, color change 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 wear-resistant 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 wear-resistant 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 abrasion resistant antimicrobial 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 agents 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 abrasion-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 abrasion-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 wear-resistant filler is boron nitride.
5. A method for preparing the urethane-acrylate/nano-metal abrasion-resistant antibacterial paint according to any one of claims 1 to 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, an abrasion-resistant 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 floor abrasion-resistant antibacterial coating.
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 25 ℃.
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 method of claim 5, wherein the equivalent ratio of isocyanate to hydroxyl in step 1 is between 1.4 and 2 and the equivalent ratio of isocyanate to hydroxyl in step 2 is between 0.8 and 0.95.
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