CN113789114A - Self-repairing antibacterial polyurethane coating and preparation method thereof - Google Patents
Self-repairing antibacterial polyurethane coating and preparation method thereof Download PDFInfo
- Publication number
- CN113789114A CN113789114A CN202111091899.9A CN202111091899A CN113789114A CN 113789114 A CN113789114 A CN 113789114A CN 202111091899 A CN202111091899 A CN 202111091899A CN 113789114 A CN113789114 A CN 113789114A
- Authority
- CN
- China
- Prior art keywords
- self
- polyurethane coating
- modified graphene
- antibacterial polyurethane
- silicone oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C09D5/08—Anti-corrosive paints
-
- 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
-
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
- Carbon And Carbon Compounds (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a self-repairing antibacterial polyurethane coating and a preparation method thereof, and relates to the field of polyurethane coatings. When the self-repairing antibacterial polyurethane coating is prepared, amino silicone oil, polyester polyol and isocyanate are used for preparing a polyurethane coating material, modified graphene is added for preparing the self-repairing antibacterial polyurethane coating material, and finally coating is carried out; the amino silicone oil is prepared by adding 2, 3-epoxypropyl trimethyl ammonium chloride for reaction when the amino silicone oil is prepared; the modified graphene is prepared by grafting 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid on graphene oxide and then reducing the graphene oxide. The self-repairing antibacterial polyurethane coating prepared by the invention not only has self-repairing antibacterial capability, but also has better water resistance and hydrophobicity.
Description
Technical Field
The invention relates to the field of polyurethane coatings, in particular to a self-repairing antibacterial polyurethane coating and a preparation method thereof.
Background
Polyurethane is a general name of a high molecular compound with a main chain containing a urethane group unit, and is a multi-block polymer formed by gradually polymerizing polyol, a small molecular chain extender and polyisocyanate. The polyol forms a soft segment, the micromolecular chain extender and the polyisocyanate form a hard segment, and the molecular structure and the physical and chemical properties of the polyurethane can be effectively controlled by adjusting the components and the proportion in the soft segment.
At present, self-repairing polyurethane materials have been reported, and the self-repairing mechanism mainly comprises: thermoreversible repair, photoreversible repair, and microencapsulated repair. The microcapsule repairing method has complex preparation process and higher cost, has larger limitation on the application of the coating, and can not realize multiple times of repairing; the thermoreversible repair method requires a specific repair environment or condition, and the transparency and film forming property of the coating are easily affected. Accordingly, the present application is directed to water resistant polyurethane coatings that self-heal at moderate temperatures and have an antimicrobial effect.
Disclosure of Invention
The invention aims to provide a self-repairing antibacterial polyurethane coating and a preparation method thereof, and aims to solve the problems in the background art.
A self-repairing antibacterial polyurethane coating mainly comprises the following raw material components in parts by weight: 19-38 parts of amino silicone oil, 3.04-6.46 parts of polyethylene glycol, 11-22.6 parts of isophorone diisocyanate, 1-2 parts of hydrogen peroxide, 19-38 parts of N, N-dimethylformamide and 5-10 parts of modified graphene.
Preferably, the amino silicone oil is prepared by adding 2, 3-epoxypropyltrimethylammonium chloride during preparation of the amino silicone oil.
Preferably, the modified graphene is prepared by grafting 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid on graphene oxide and then reducing the graphene oxide.
Preferably, the preparation method of the self-repairing antibacterial polyurethane coating comprises the following steps: preparing amino silicone oil, preparing a polyurethane coating material, preparing modified graphene and preparing a self-repairing antibacterial polyurethane coating.
Preferably, the preparation method of the self-repairing antibacterial polyurethane coating comprises the following specific steps:
(1) mixing alpha, omega dihydroxy polydimethylsiloxane and 2, 3-epoxypropyl trimethyl ammonium chloride with the mass of 0.3-0.5 time of that of the alpha, omega dihydroxy polydimethylsiloxane, placing the mixture in a three-necked bottle, uniformly stirring, heating to 80-120 ℃, preserving heat for 20-30 min, adding N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane and triethylamine with the mass fraction of 2-3% of that of the alpha, omega dihydroxy polydimethylsiloxane being 8-10 times of that of the alpha, omega dihydroxy polydimethylsiloxane, uniformly stirring, heating to 120 ℃, preserving heat for 10h, adjusting the pressure to 0.01MPa, and continuously reacting for 0.5-1 h to prepare amino silicone oil;
(2) mixing isophorone diisocyanate and amino silicone oil according to a mass ratio of 11: 19-11.3: 19, mixing and placing the mixture in a round-bottom flask, adding N, N-dimethylformamide with the mass of amino silicone oil and the like, reacting for 2.5-3 h at 40-50 ℃ and 800-1200 rpm, adding polyethylene glycol with the mass of 0.16-0.17 time that of the amino silicone oil, and continuing to react for 1-1.5 h to prepare a polyurethane coating material;
(3) mixing the graphene oxide dispersion liquid and 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid with the mass of 0.5-0.6 time that of the graphene oxide dispersion liquid, placing the mixture in a three-neck flask, heating the mixture to 50-60 ℃ in a nitrogen atmosphere, adjusting the pH to 8-9 by using 10% sodium hydroxide, preserving the temperature, reacting for 10-20 min, cooling the mixture to room temperature to obtain pre-modified graphene, and reducing the pre-modified graphene to obtain modified graphene;
(4) mixing modified graphene with hydrogen peroxide with the mass fraction of 20% and the mass fraction of 0.2-0.4 times that of the modified graphene and a polyurethane coating material with the mass fraction of 9.5-13 times that of the modified graphene, stirring at room temperature and 1500-2000 rpm for 3-5 h, transferring to a water bath with the temperature of 80 ℃ and preserving heat for 30min to prepare self-repairing antibacterial polyurethane;
(5) and washing the substrate with deionized water for 3-5 times, drying, coating the self-repairing antibacterial polyurethane on the surface of the substrate, and curing at 60-80 ℃ for 5-8 h to prepare the self-repairing antibacterial polyurethane coating.
Preferably, in the step (1): the mass ratio of the alpha, omega dihydroxy polydimethyl siloxane to the N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane is 1: 2-1: 2.2.
preferably, in the step (2): the preparation method of the mixed solution comprises the following steps: mixing 1mol/L ferric chloride solution and 1mol/L copper chloride solution according to a volume ratio of 5: 1-8: 1, mixing and stirring uniformly, and preparing the mixture in situ.
Preferably, in the step (3): the preparation method of the graphene oxide dispersion liquid comprises the following steps: putting graphite into a reaction vessel, slowly adding fuming nitric acid, then slowly adding sodium fluosilicate to react for 24 hours, washing with 5% hydrochloric acid for 5 times after the reaction is finished, and then washing with distilled water until the solution is neutral to prepare the graphene oxide dispersion liquid.
Preferably, in the step (3): the reduction process comprises the following steps: peeling the pre-modified graphene for 1h by ultrasonic equipment under 200W, adding sodium hydroxide which is 0.2 time of the mass of the pre-modified graphene and polyvinylpyrrolidone which is 0.05 time of the mass of the pre-modified graphene, and placing the mixture in a water bath at 95 ℃ for heating for 12h to obtain the modified graphene.
Preferably, in the step (5): the thickness of the self-repairing antibacterial polyurethane coating on the surface of the machine body is 0.2-0.5 nm.
Compared with the prior art, the invention has the following beneficial effects:
when the self-repairing antibacterial polyurethane coating is prepared, amino silicone oil, polyester polyol and isocyanate are used for preparing a polyurethane coating material, modified graphene is added for preparing the self-repairing antibacterial polyurethane coating material, and finally coating is carried out; the amino silicone oil is prepared by adding 2, 3-epoxypropyl trimethyl ammonium chloride for reaction when the amino silicone oil is prepared; the modified graphene is prepared by grafting 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid on graphene oxide and then reducing the graphene oxide;
2, 3-epoxypropyl trimethyl ammonium chloride is added when amino silicone oil is prepared, so that epoxy groups are introduced on side chains of the silicone oil to regenerate the amino silicone oil, the end groups of the amino silicone oil are hydroxyl groups, the side groups are methoxyl, amino and epoxy groups, and quaternary ammonium salt is introduced at the same time, so that the image layer has an antibacterial effect; the epoxy functional group can react with isocyanate in polyurethane to form a network structure, so that the internal crosslinking of the polyurethane is tighter, the adhesion is enhanced, and meanwhile, the siloxane chain segment can migrate and be enriched to the surface of the coating, so that the surface free energy of the polyurethane coating material is reduced, the surface hydrophobicity is improved, and the degree of migration of the siloxane chain segment to the surface of the coating is staggered due to the internal crosslinking of the polyurethane, so that a nano-scale protruding structure is formed on the surface, and the water resistance of the coating is enhanced;
reacting amino on 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid with hydroxyl and epoxy groups on graphene oxide, grafting the amino on the graphene oxide, and reducing to obtain modified graphene; the modified graphene is introduced into a cross-linked reticular structure by adding the modified graphene into a polyurethane coating material, wherein the amino group on the 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid reacts with the terminal group of amino silicone oil to form hydroxyl, so that the corrosion resistance of the coating is enhanced, meanwhile, the sulfydryl on the 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid is oxidized to form a disulfide bond, the cross-linking density of the polyurethane coating material is increased, and the reversible disulfide bond enables the self-repairing capability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to illustrate the method for testing each index of the self-healing antibacterial polyurethane coating prepared in the examples and comparative examples as follows:
hydrophobicity: the self-repairing antibacterial polyurethane coatings prepared in the examples and the comparative examples are subjected to a water contact angle test by using a contact angle meter.
And (3) antibacterial property: the self-repairing antibacterial polyurethane coatings prepared in the examples and the comparative examples are tested according to GB/T31402 for antibacterial performance.
Self-repairability: the self-healing antibacterial polyurethane coatings prepared in examples and comparative examples were scratched with a blade having a length of 20 μm and a depth of 50 μm, and the scratch recovery time was recorded at room temperature.
Example 1
A self-repairing antibacterial polyurethane coating mainly comprises the following components in parts by weight:
19 parts of amino silicone oil, 3.04 parts of polyethylene glycol, 11 parts of isophorone diisocyanate, 1 part of hydrogen peroxide, 19 parts of N, N-dimethylformamide and 5 parts of modified graphene.
A preparation method of a self-repairing antibacterial polyurethane coating comprises the following steps:
(1) mixing alpha, omega dihydroxy polydimethylsiloxane and 2, 3-epoxypropyl trimethyl ammonium chloride with the mass of 0.3 time of that of the alpha, omega dihydroxy polydimethylsiloxane, putting the mixture into a three-necked bottle, uniformly stirring the mixture, heating the mixture to 80 ℃, preserving the heat for 20min, adding N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane and triethylamine with the mass fraction of 3 percent of that of 8 times of the mass of the alpha, omega dihydroxy polydimethylsiloxane, uniformly stirring the mixture, heating the mixture to 120 ℃, preserving the heat for 10h, adjusting the pressure to 0.01MPa, and continuously reacting the mixture for 0.5h to prepare amino silicone oil;
(2) mixing isophorone diisocyanate and amino silicone oil according to a mass ratio of 11: 19 mixing and placing the mixture in a round-bottom flask, adding N, N-dimethylformamide with the mass of amino silicone oil and the like, reacting for 2.5 hours at 40 ℃ and 800rpm, adding polyethylene glycol with the mass of 0.16 time of the amino silicone oil, and continuing to react for 1 hour to obtain a polyurethane coating material;
(3) mixing the graphene oxide dispersion liquid and 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid with the mass of 0.5 time that of the graphene oxide dispersion liquid, placing the mixture in a three-neck flask, heating the mixture to 50 ℃ in a nitrogen atmosphere, adjusting the pH to 8 by using sodium hydroxide with the mass fraction of 10%, performing heat preservation reaction for 10min, cooling the mixture to room temperature to obtain pre-modified graphene, and reducing the pre-modified graphene to obtain modified graphene;
(4) mixing modified graphene with hydrogen peroxide with the mass fraction of 20% and the mass fraction of the modified graphene being 0.2 times that of the modified graphene and a polyurethane coating material with the mass fraction of 9.5 times that of the modified graphene, stirring for 3 hours at room temperature and 1500rpm, transferring the mixture into a water bath with the temperature of 80 ℃ and preserving the heat for 30 minutes to prepare self-repairing antibacterial polyurethane;
(5) and washing the substrate with deionized water for 3 times, drying, coating the self-repairing antibacterial polyurethane on the surface of the substrate, and curing at 60 ℃ for 8 hours to obtain the self-repairing antibacterial polyurethane coating.
Preferably, in the step (1): the mass ratio of the alpha, omega dihydroxy polydimethyl siloxane to the N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane is 1: 2.
preferably, in the step (3): the preparation method of the graphene oxide dispersion liquid comprises the following steps: putting graphite into a reaction vessel, slowly adding fuming nitric acid, then slowly adding sodium fluosilicate to react for 24 hours, washing with 5% hydrochloric acid for 5 times after the reaction is finished, and then washing with distilled water until the solution is neutral to prepare the graphene oxide dispersion liquid.
Preferably, in the step (3): the reduction process comprises the following steps: peeling the pre-modified graphene for 1h by ultrasonic equipment under 200W, adding sodium hydroxide which is 0.2 time of the mass of the pre-modified graphene and polyvinylpyrrolidone which is 0.05 time of the mass of the pre-modified graphene, and placing the mixture in a water bath at 95 ℃ for heating for 12h to obtain the modified graphene.
Preferably, in the step (5): the thickness of the self-repairing antibacterial polyurethane coated on the surface of an organism is 0.2 nm.
Example 2
A self-repairing antibacterial polyurethane coating mainly comprises the following components in parts by weight:
38 parts of amino silicone oil, 6.46 parts of polyethylene glycol, 22.6 parts of isophorone diisocyanate, 2 parts of hydrogen peroxide, 38 parts of N, N-dimethylformamide and 10 parts of modified graphene.
A preparation method of a self-repairing antibacterial polyurethane coating comprises the following steps:
(1) mixing alpha, omega dihydroxy polydimethylsiloxane and 2, 3-epoxypropyl trimethyl ammonium chloride with the mass of 0.5 time of that of the alpha, omega dihydroxy polydimethylsiloxane, placing the mixture into a three-necked bottle, uniformly stirring the mixture, heating the mixture to 120 ℃, preserving the heat for 20min, adding N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane and triethylamine with the mass fraction of 2 percent of that of the alpha, omega dihydroxy polydimethylsiloxane being 10 times that of the alpha, omega dihydroxy polydimethylsiloxane, uniformly stirring the mixture, heating the mixture to 120 ℃, preserving the heat for 10h, adjusting the pressure to 0.01MPa, and continuously reacting the mixture for 1h to prepare amino silicone oil;
(2) mixing isophorone diisocyanate and amino silicone oil according to a mass ratio of 11: 19 mixing and placing the mixture in a round-bottom flask, adding N, N-dimethylformamide with the mass of amino silicone oil and the like, reacting for 2.5 hours at 50 ℃ and 1200rpm, adding polyethylene glycol with the mass of 0.16 time of the amino silicone oil, and continuing to react for 1.5 hours to obtain a polyurethane coating material;
(3) mixing the graphene oxide dispersion liquid and 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid with the mass of 0.6 time that of the graphene oxide dispersion liquid, placing the mixture in a three-neck flask, heating the mixture to 60 ℃ in a nitrogen atmosphere, adjusting the pH to 9 by using sodium hydroxide with the mass fraction of 10%, performing heat preservation reaction for 20min, cooling the mixture to room temperature to obtain pre-modified graphene, and reducing the pre-modified graphene to obtain modified graphene;
(4) mixing modified graphene with hydrogen peroxide with the mass fraction of 20% and the mass fraction of 0.4 times that of the modified graphene and a polyurethane coating material with the mass fraction of 13 times that of the modified graphene, stirring for 5 hours at room temperature and 1500rpm, transferring to a water bath with the temperature of 80 ℃ and preserving heat for 30 minutes to prepare self-repairing antibacterial polyurethane;
(5) and washing the substrate with deionized water for 5 times, drying, coating the self-repairing antibacterial polyurethane on the surface of the substrate, and curing at 80 ℃ for 5 hours to obtain the self-repairing antibacterial polyurethane coating.
Preferably, in the step (1): the mass ratio of the alpha, omega dihydroxy polydimethyl siloxane to the N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane is 1: 2.
preferably, in the step (3): the preparation method of the graphene oxide dispersion liquid comprises the following steps: putting graphite into a reaction vessel, slowly adding fuming nitric acid, then slowly adding sodium fluosilicate to react for 24 hours, washing with 5% hydrochloric acid for 5 times after the reaction is finished, and then washing with distilled water until the solution is neutral to prepare the graphene oxide dispersion liquid.
Preferably, in the step (3): the reduction process comprises the following steps: peeling the pre-modified graphene for 1h by ultrasonic equipment under 200W, adding sodium hydroxide which is 0.2 time of the mass of the pre-modified graphene and polyvinylpyrrolidone which is 0.05 time of the mass of the pre-modified graphene, and placing the mixture in a water bath at 95 ℃ for heating for 12h to obtain the modified graphene.
Preferably, in the step (5): the thickness of the self-repairing antibacterial polyurethane coated on the surface of an organism is 0.5 nm.
Comparative example 1
A self-repairing antibacterial polyurethane coating mainly comprises the following components in parts by weight:
19 parts of amino silicone oil, 5.7 parts of 2, 3-epoxypropyltrimethylammonium chloride, 3.04 parts of polyethylene glycol, 11 parts of isophorone diisocyanate, 1 part of hydrogen peroxide, 19 parts of N, N-dimethylformamide and 5 parts of modified graphene.
A preparation method of a self-repairing antibacterial polyurethane coating comprises the following steps:
(1) mixing amino silicone oil with 2, 3-epoxypropyltrimethylammonium chloride 19: mixing the materials in a mass ratio of 5.7, placing the mixture in a round-bottom flask, adding triethylamine with the mass fraction of 3 percent which is 8 times that of the amino silicone oil, uniformly stirring, heating to 120 ℃, preserving the temperature for 10 hours, adjusting the pressure to 0.01MPa, and continuously reacting for 0.5 hour to obtain modified amino silicone oil;
(2) mixing isophorone diisocyanate and amino silicone oil according to a mass ratio of 11: 19 mixing and placing the mixture in a round-bottom flask, adding N, N-dimethylformamide with the mass of modified amino silicone oil and the like, reacting for 2.5 hours at 40 ℃ and 800rpm, adding polyethylene glycol with the mass of 0.16 time of the modified amino silicone oil, and continuing to react for 1 hour to prepare a polyurethane coating material;
(3) mixing the graphene oxide dispersion liquid and 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid with the mass of 0.5 time that of the graphene oxide dispersion liquid, placing the mixture in a three-neck flask, heating the mixture to 50 ℃ in a nitrogen atmosphere, adjusting the pH to 8 by using sodium hydroxide with the mass fraction of 10%, performing heat preservation reaction for 10min, cooling the mixture to room temperature to obtain pre-modified graphene, and reducing the pre-modified graphene to obtain modified graphene;
(4) mixing modified graphene with hydrogen peroxide with the mass fraction of 20% and the mass fraction of the modified graphene being 0.2 times that of the modified graphene and a polyurethane coating material with the mass fraction of 9.5 times that of the modified graphene, stirring for 3 hours at room temperature and 1500rpm, transferring the mixture into a water bath with the temperature of 80 ℃ and preserving the heat for 30 minutes to prepare self-repairing antibacterial polyurethane;
(5) and washing the substrate with deionized water for 3 times, drying, coating the self-repairing antibacterial polyurethane on the surface of the substrate, and curing at 60 ℃ for 8 hours to obtain the self-repairing antibacterial polyurethane coating.
Preferably, in the step (3): the preparation method of the graphene oxide dispersion liquid comprises the following steps: putting graphite into a reaction vessel, slowly adding fuming nitric acid, then slowly adding sodium fluosilicate to react for 24 hours, washing with 5% hydrochloric acid for 5 times after the reaction is finished, and then washing with distilled water until the solution is neutral to prepare the graphene oxide dispersion liquid.
Preferably, in the step (3): the reduction process comprises the following steps: peeling the pre-modified graphene for 1h by ultrasonic equipment under 200W, adding sodium hydroxide which is 0.2 time of the mass of the pre-modified graphene and polyvinylpyrrolidone which is 0.05 time of the mass of the pre-modified graphene, and placing the mixture in a water bath at 95 ℃ for heating for 12h to obtain the modified graphene.
Preferably, in the step (5): the thickness of the self-repairing antibacterial polyurethane coated on the surface of an organism is 0.2 nm.
Comparative example 2
A self-repairing antibacterial polyurethane coating mainly comprises the following components in parts by weight:
19 parts of amino silicone oil, 3.04 parts of polyethylene glycol, 11 parts of isophorone diisocyanate, 1 part of hydrogen peroxide, 19 parts of N, N-dimethylformamide and 5 parts of graphene.
A preparation method of a self-repairing antibacterial polyurethane coating comprises the following steps:
(1) mixing alpha, omega dihydroxy polydimethylsiloxane and 2, 3-epoxypropyl trimethyl ammonium chloride with the mass of 0.3 time of that of the alpha, omega dihydroxy polydimethylsiloxane, putting the mixture into a three-necked bottle, uniformly stirring the mixture, heating the mixture to 80 ℃, preserving the heat for 20min, adding N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane and triethylamine with the mass fraction of 3 percent of that of 8 times of the mass of the alpha, omega dihydroxy polydimethylsiloxane, uniformly stirring the mixture, heating the mixture to 120 ℃, preserving the heat for 10h, adjusting the pressure to 0.01MPa, and continuously reacting the mixture for 0.5h to prepare amino silicone oil;
(2) mixing isophorone diisocyanate and amino silicone oil according to a mass ratio of 11: 19 mixing and placing the mixture in a round-bottom flask, adding N, N-dimethylformamide with the mass of amino silicone oil and the like, reacting for 2.5 hours at 40 ℃ and 800rpm, adding polyethylene glycol with the mass of 0.16 time of the amino silicone oil, and continuing to react for 1 hour to obtain a polyurethane coating material;
(3) mixing graphene, hydrogen peroxide with the mass fraction of 20% and the mass fraction of 0.2 times that of graphene and a polyurethane coating material with the mass fraction of 9.5 times that of graphene, stirring for 3 hours at room temperature and 1500rpm, transferring to a water bath with the temperature of 80 ℃ and preserving heat for 30 minutes to prepare self-repairing antibacterial polyurethane;
(4) and washing the substrate with deionized water for 3 times, drying, coating the self-repairing antibacterial polyurethane on the surface of the substrate, and curing at 60 ℃ for 8 hours to obtain the self-repairing antibacterial polyurethane coating.
Preferably, in the step (1): the mass ratio of the alpha, omega dihydroxy polydimethyl siloxane to the N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane is 1: 2.
preferably, in the step (3): the preparation method of the graphene oxide dispersion liquid comprises the following steps: putting graphite into a reaction vessel, slowly adding fuming nitric acid, then slowly adding sodium fluosilicate to react for 24 hours, washing with 5% hydrochloric acid for 5 times after the reaction is finished, and then washing with distilled water until the solution is neutral to prepare the graphene oxide dispersion liquid.
Preferably, in the step (4): the thickness of the self-repairing antibacterial polyurethane coated on the surface of an organism is 0.2 nm.
Comparative example 3
A self-repairing antibacterial polyurethane coating mainly comprises the following components in parts by weight:
19 parts of amino silicone oil, 3.04 parts of polyethylene glycol, 11 parts of isophorone diisocyanate, 1 part of hydrogen peroxide and 19 parts of N, N-dimethylformamide.
A preparation method of a self-repairing antibacterial polyurethane coating comprises the following steps:
(1) mixing alpha, omega dihydroxy polydimethylsiloxane and 2, 3-epoxypropyl trimethyl ammonium chloride with the mass of 0.3 time of that of the alpha, omega dihydroxy polydimethylsiloxane, putting the mixture into a three-necked bottle, uniformly stirring the mixture, heating the mixture to 80 ℃, preserving the heat for 20min, adding N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane and triethylamine with the mass fraction of 3 percent of that of 8 times of the mass of the alpha, omega dihydroxy polydimethylsiloxane, uniformly stirring the mixture, heating the mixture to 120 ℃, preserving the heat for 10h, adjusting the pressure to 0.01MPa, and continuously reacting the mixture for 0.5h to prepare amino silicone oil;
(2) mixing isophorone diisocyanate and amino silicone oil according to a mass ratio of 11: 19, mixing and placing the mixture in a round-bottom flask, adding N, N-dimethylformamide with the mass of amino silicone oil and the like, reacting for 2.5 hours at 40 ℃ and 800rpm, adding polyethylene glycol with the mass of 0.16 time of the amino silicone oil, and continuing to react for 1 hour to prepare the self-repairing antibacterial polyurethane;
(3) and washing the substrate with deionized water for 3 times, drying, coating the self-repairing antibacterial polyurethane on the surface of the substrate, and curing at 60 ℃ for 8 hours to obtain the self-repairing antibacterial polyurethane coating.
Preferably, in the step (1): the mass ratio of the alpha, omega dihydroxy polydimethyl siloxane to the N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane is 1: 2.
preferably, in the step (3): the thickness of the self-repairing antibacterial polyurethane coated on the surface of an organism is 0.2 nm.
Comparative example 4
A self-repairing antibacterial polyurethane coating mainly comprises the following components in parts by weight:
3.04 parts of polyethylene glycol, 11 parts of isophorone diisocyanate, 1 part of hydrogen peroxide, 19 parts of N, N-dimethylformamide and 5 parts of modified graphene.
A preparation method of a self-repairing antibacterial polyurethane coating comprises the following steps:
(1) mixing isophorone diisocyanate and N, N-dimethylformamide according to a mass ratio of 11: 19 mixing and placing in a round-bottom flask, reacting for 2.5h at 40 ℃ and 800rpm, adding polyethylene glycol with the mass of 0.16 time of that of the N, N-dimethylformamide, and continuing to react for 1h to obtain a polyurethane coating material;
(2) mixing the graphene oxide dispersion liquid and 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid with the mass of 0.5 time that of the graphene oxide dispersion liquid, placing the mixture in a three-neck flask, heating the mixture to 50 ℃ in a nitrogen atmosphere, adjusting the pH to 8 by using sodium hydroxide with the mass fraction of 10%, performing heat preservation reaction for 10min, cooling the mixture to room temperature to obtain pre-modified graphene, and reducing the pre-modified graphene to obtain modified graphene;
(3) mixing modified graphene with hydrogen peroxide with the mass fraction of 20% and the mass fraction of the modified graphene being 0.2 times that of the modified graphene and a polyurethane coating material with the mass fraction of 9.5 times that of the modified graphene, stirring for 3 hours at room temperature and 1500rpm, transferring the mixture into a water bath with the temperature of 80 ℃ and preserving the heat for 30 minutes to prepare self-repairing antibacterial polyurethane;
(4) and washing the substrate with deionized water for 3 times, drying, coating the self-repairing antibacterial polyurethane on the surface of the substrate, and curing at 60 ℃ for 8 hours to obtain the self-repairing antibacterial polyurethane coating.
Preferably, in the step (2): the preparation method of the graphene oxide dispersion liquid comprises the following steps: putting graphite into a reaction vessel, slowly adding fuming nitric acid, then slowly adding sodium fluosilicate to react for 24 hours, washing with 5% hydrochloric acid for 5 times after the reaction is finished, and then washing with distilled water until the solution is neutral to prepare the graphene oxide dispersion liquid.
Preferably, in the step (3): the reduction process comprises the following steps: peeling the pre-modified graphene for 1h by ultrasonic equipment under 200W, adding sodium hydroxide which is 0.2 time of the mass of the pre-modified graphene and polyvinylpyrrolidone which is 0.05 time of the mass of the pre-modified graphene, and placing the mixture in a water bath at 95 ℃ for heating for 12h to obtain the modified graphene.
Preferably, in the step (4): the thickness of the self-repairing antibacterial polyurethane coated on the surface of an organism is 0.2 nm.
Examples of effects
Table 1 below gives the results of various performance analyses of the self-healing antibacterial polyurethane coatings using examples 1, 2 of the present invention and comparative examples 1, 2,3, 4.
TABLE 1
| Water contact Angle (°) | Reduction rate of Escherichia coli after 24h of action | Scratch recovery time(s) | |
| Example 1 | 161 | 99.5 | 33 |
| Example 2 | 157 | 99.7 | 36 |
| Comparative example 1 | 118 | 98.6 | 41 |
| Comparative example 2 | 155 | 97.5 | Without recovery |
| Comparative example 3 | 153 | 99.2 | Without recovery |
| Comparative example 4 | 94 | 38.6 | 39 |
Compared with experimental data of comparative examples in the table 1, it can be obviously found that the self-repairing antibacterial polyurethane coatings prepared in the examples 1, 2 and 3 have large water contact angles, high escherichia coli reduction rate after 24 hours of action and quick scratch recovery time, and the self-repairing antibacterial polyurethane coatings prepared by the method have good hydrophobicity, antibacterial property and self-repairing capability;
from the comparison of experimental data of example 1 and example 2 and comparative example 1 and comparative example 4, it can be found that 2, 3-epoxypropyltrimethylammonium chloride is added in the process of preparing amino silicone oil, epoxy groups can be retained, quaternary ammonium salt enables the coating to have antibacterial property, epoxy functional groups enable internal crosslinking of polyurethane to be tighter, siloxane chain segments improve surface hydrophobicity, and amino silicone oil and 2, 3-epoxypropyltrimethylammonium chloride are directly used for reaction, so that epoxy groups cannot be retained, the internal crosslinking degree of polyurethane is reduced, introduction of modified graphene is influenced, the hydrophobicity of the coating is weaker, and scratching time is prolonged;
from the comparison of the experimental data of the embodiment 1 and the embodiment 2 and the comparative examples 2 and 3, it can be found that the 2- (N, N-dimethylamino) ethylamine dithiocarboxylic acid modified graphene is oxidized by sulfydryl to form a disulfide bond, so that the crosslinking density of the polyurethane coating material is increased, and the coating has self-repairing capability.
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 attributes 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. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. The self-repairing antibacterial polyurethane coating is characterized by mainly comprising the following raw material components in parts by weight: 19-38 parts of amino silicone oil, 3.04-6.46 parts of polyethylene glycol, 11-22.6 parts of isophorone diisocyanate, 1-2 parts of hydrogen peroxide, 19-38 parts of N, N-dimethylformamide and 5-10 parts of modified graphene.
2. The self-repairing antibacterial polyurethane coating of claim 1, wherein the amino silicone oil is prepared by adding 2, 3-epoxypropyltrimethylammonium chloride during the preparation of the amino silicone oil.
3. The self-repairing antibacterial polyurethane coating of claim 2, wherein the modified graphene is prepared by grafting 2- (N, N-dimethylamino) ethylamine dithiocarboxylic acid on graphene oxide and then reducing the graphene oxide.
4. A preparation method of a self-repairing antibacterial polyurethane coating is characterized by comprising the following steps: preparing amino silicone oil, preparing a polyurethane coating material, preparing modified graphene and preparing a self-repairing antibacterial polyurethane coating.
5. The preparation method of the self-repairing antibacterial polyurethane coating of claim 4, which is characterized by comprising the following specific steps:
(1) mixing alpha, omega dihydroxy polydimethylsiloxane and 2, 3-epoxypropyl trimethyl ammonium chloride with the mass of 0.3-0.5 time of that of the alpha, omega dihydroxy polydimethylsiloxane, placing the mixture in a three-necked bottle, uniformly stirring, heating to 80-120 ℃, preserving heat for 20-30 min, adding N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane and triethylamine with the mass fraction of 2-3% of that of the alpha, omega dihydroxy polydimethylsiloxane being 8-10 times of that of the alpha, omega dihydroxy polydimethylsiloxane, uniformly stirring, heating to 120 ℃, preserving heat for 10h, adjusting the pressure to 0.01MPa, and continuously reacting for 0.5-1 h to prepare amino silicone oil;
(2) mixing isophorone diisocyanate and amino silicone oil according to a mass ratio of 11: 19-11.3: 19, mixing and placing the mixture in a round-bottom flask, adding N, N-dimethylformamide with the mass of amino silicone oil and the like, reacting for 2.5-3 h at 40-50 ℃ and 800-1200 rpm, adding polyethylene glycol with the mass of 0.16-0.17 time that of the amino silicone oil, and continuing to react for 1-1.5 h to prepare a polyurethane coating material;
(3) mixing the graphene oxide dispersion liquid and 2- (N, N-dimethylamino) ethylamino dithiocarboxylic acid with the mass of 0.5-0.6 time that of the graphene oxide dispersion liquid, placing the mixture in a three-neck flask, heating the mixture to 50-60 ℃ in a nitrogen atmosphere, adjusting the pH to 8-9 by using 10% sodium hydroxide, preserving the temperature, reacting for 10-20 min, cooling the mixture to room temperature to obtain pre-modified graphene, and reducing the pre-modified graphene to obtain modified graphene;
(4) mixing modified graphene with hydrogen peroxide with the mass fraction of 20% and the mass fraction of 0.2-0.4 times that of the modified graphene and a polyurethane coating material with the mass fraction of 9.5-13 times that of the modified graphene, stirring at room temperature and 1500-2000 rpm for 3-5 h, transferring to a water bath with the temperature of 80 ℃ and preserving heat for 30min to prepare self-repairing antibacterial polyurethane;
(5) and washing the substrate with deionized water for 3-5 times, drying, coating the self-repairing antibacterial polyurethane on the surface of the substrate, and curing at 60-80 ℃ for 5-8 h to prepare the self-repairing antibacterial polyurethane coating.
6. The method for preparing the self-repairing antibacterial polyurethane coating of claim 5, wherein in the step (1): the mass ratio of the alpha, omega dihydroxy polydimethyl siloxane to the N-beta-aminoethyl gamma-aminopropyl trimethyl siloxane is 1: 2-1: 2.2.
7. the method for preparing a self-repairing antibacterial polyurethane coating according to claim 5, wherein in the step (3): the preparation method of the graphene oxide dispersion liquid comprises the following steps: putting graphite into a reaction vessel, slowly adding fuming nitric acid, then slowly adding sodium fluosilicate to react for 24 hours, washing with 5% hydrochloric acid for 5 times after the reaction is finished, and then washing with distilled water until the solution is neutral to prepare the graphene oxide dispersion liquid.
8. The method for preparing a self-repairing antibacterial polyurethane coating according to claim 5, wherein in the step (3): the reduction process comprises the following steps: peeling the pre-modified graphene for 1h by ultrasonic equipment under 200W, adding sodium hydroxide which is 0.2 time of the mass of the pre-modified graphene and polyvinylpyrrolidone which is 0.05 time of the mass of the pre-modified graphene, and placing the mixture in a water bath at 95 ℃ for heating for 12h to obtain the modified graphene.
9. The method for preparing a self-repairing antibacterial polyurethane coating according to claim 5, wherein in the step (4): the thickness of the self-repairing antibacterial polyurethane coating on the surface of the machine body is 0.2-0.5 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111091899.9A CN113789114A (en) | 2021-09-17 | 2021-09-17 | Self-repairing antibacterial polyurethane coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111091899.9A CN113789114A (en) | 2021-09-17 | 2021-09-17 | Self-repairing antibacterial polyurethane coating and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113789114A true CN113789114A (en) | 2021-12-14 |
Family
ID=79183784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111091899.9A Pending CN113789114A (en) | 2021-09-17 | 2021-09-17 | Self-repairing antibacterial polyurethane coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113789114A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989652A (en) * | 2022-07-04 | 2022-09-02 | 佛山市建春友金属科技有限公司 | Antibacterial coating for surface protection of stainless steel structure |
| CN115160911A (en) * | 2022-08-17 | 2022-10-11 | 漳州市恩扬工艺品有限公司 | Polyurethane finish composition and preparation method thereof |
| CN116355388A (en) * | 2023-04-10 | 2023-06-30 | 江西龙正科技发展有限公司 | Polyurethane anticorrosion composite material bracket |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073987A (en) * | 2013-01-17 | 2013-05-01 | 杭州电子科技大学 | Preparation method for organic silicon modified polyester type polyurethane emulsion leather finishing agent |
| CN105400405A (en) * | 2015-10-30 | 2016-03-16 | 华南理工大学 | Self-repairing organic silicon polyurethane/polyurea anti-pollution material as well as method and application thereof |
| CN107815232A (en) * | 2017-11-16 | 2018-03-20 | 广东华兹卜新材料科技有限公司 | A kind of high-performance water-based polyurethane woodwork coating |
| CN109486280A (en) * | 2018-11-14 | 2019-03-19 | 鳄鱼制漆(上海)有限公司 | A kind of double-component aqueous anti-white board marker graffiti coating of containing water-soluble amido silicon oil |
| WO2020177068A1 (en) * | 2019-03-05 | 2020-09-10 | Dow Global Technologies Llc | Waterborne polyurethane dispersion and method for preparing the same |
| CN112225861A (en) * | 2020-10-30 | 2021-01-15 | 常州大学 | Visible light self-repairing high-strength waterborne polyurethane and preparation method thereof |
| CN112625599A (en) * | 2020-12-11 | 2021-04-09 | 中国科学院海洋研究所 | Rapid self-repairing super-tough organic silicon modified polyurea thiourea antifouling coating and preparation method thereof |
| CN112679689A (en) * | 2020-12-25 | 2021-04-20 | 广州城市职业学院 | Organosilicon quaternary ammonium salt modified polyurethane and preparation method and application thereof |
-
2021
- 2021-09-17 CN CN202111091899.9A patent/CN113789114A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073987A (en) * | 2013-01-17 | 2013-05-01 | 杭州电子科技大学 | Preparation method for organic silicon modified polyester type polyurethane emulsion leather finishing agent |
| CN105400405A (en) * | 2015-10-30 | 2016-03-16 | 华南理工大学 | Self-repairing organic silicon polyurethane/polyurea anti-pollution material as well as method and application thereof |
| CN107815232A (en) * | 2017-11-16 | 2018-03-20 | 广东华兹卜新材料科技有限公司 | A kind of high-performance water-based polyurethane woodwork coating |
| CN109486280A (en) * | 2018-11-14 | 2019-03-19 | 鳄鱼制漆(上海)有限公司 | A kind of double-component aqueous anti-white board marker graffiti coating of containing water-soluble amido silicon oil |
| WO2020177068A1 (en) * | 2019-03-05 | 2020-09-10 | Dow Global Technologies Llc | Waterborne polyurethane dispersion and method for preparing the same |
| CN112225861A (en) * | 2020-10-30 | 2021-01-15 | 常州大学 | Visible light self-repairing high-strength waterborne polyurethane and preparation method thereof |
| CN112625599A (en) * | 2020-12-11 | 2021-04-09 | 中国科学院海洋研究所 | Rapid self-repairing super-tough organic silicon modified polyurea thiourea antifouling coating and preparation method thereof |
| CN112679689A (en) * | 2020-12-25 | 2021-04-20 | 广州城市职业学院 | Organosilicon quaternary ammonium salt modified polyurethane and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| VIERA SKAKALOVA等: "《石墨深加工技术与石墨烯材料系列 石墨烯的性能、制备、表征及器件》", 31 August 2019 * |
| 孟令熹: "新型聚氨酯改性嵌段聚醚氨基硅油的合成及应用", 《有机硅材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989652A (en) * | 2022-07-04 | 2022-09-02 | 佛山市建春友金属科技有限公司 | Antibacterial coating for surface protection of stainless steel structure |
| CN115160911A (en) * | 2022-08-17 | 2022-10-11 | 漳州市恩扬工艺品有限公司 | Polyurethane finish composition and preparation method thereof |
| CN116355388A (en) * | 2023-04-10 | 2023-06-30 | 江西龙正科技发展有限公司 | Polyurethane anticorrosion composite material bracket |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113789114A (en) | Self-repairing antibacterial polyurethane coating and preparation method thereof | |
| CN106589281B (en) | Carbon dioxide-based waterborne polyurethane-polyurea, preparation method and coating/adhesive | |
| CN112375459B (en) | Graphene/water-based epoxy zinc-rich coating with high corrosion resistance and strong adhesive force and preparation method thereof | |
| CN116875169B (en) | Waterproof corrosion-resistant water paint and preparation method thereof | |
| CN114057953A (en) | Preparation method of polyurethane-fluorinated acrylic hybrid emulsion coating film | |
| CN116622270B (en) | Modified graphene antirust anticorrosive paint and preparation method thereof | |
| CN116463046B (en) | Functional carbon-point polyurethane urea composite marine anti-corrosion coating with self-repairing performance and preparation method thereof | |
| KR101656267B1 (en) | Optical film | |
| CN113801504B (en) | Tough anti-permeability antifouling water-based silicate coating for seawater tidal range zone and preparation method thereof | |
| CN111073498A (en) | UV (ultraviolet) curing self-repairing antistatic coating | |
| CN115612330A (en) | Preparation and application of sulfydryl modified nano silver particle dispersion liquid | |
| CN115287012A (en) | Preparation method of super-hydrophobic self-repairing thermosetting PU (polyurethane) adhesive film and automobile protective film | |
| JP2023032463A (en) | Conductive polymer-containing liquid and conductive laminate | |
| CN112341906A (en) | High-strength corrosion-resistant titanium alloy and preparation method thereof | |
| CN113930154B (en) | Self-healing anti-pollution flashover coating and preparation method and application thereof | |
| CN111690366A (en) | Hybrid polyurethane resin glue and preparation method thereof | |
| CN118165598B (en) | Oleophylic self-repairing anti-fouling paint, preparation method thereof and self-repairing film | |
| JP6165325B2 (en) | Optical film | |
| Kim et al. | Self‐Healing Waterborne Polyurethanes as a Sustainable Gel Electrolyte for Flexible Electrochromic Devices | |
| CN118480287B (en) | Polyvinyl chloride fluorine-containing fluorescent primer and preparation method thereof | |
| CN116285516B (en) | Paint and coating for photovoltaic toughened glass and preparation method thereof | |
| CN118325450B (en) | Ocean anti-corrosion coating based on waterborne graphene and preparation and application thereof | |
| CN117457290B (en) | High-flexibility drag chain cable and forming process thereof | |
| CN118248414B (en) | Processing technology of high-temperature-resistant waterproof cable | |
| CN115477734B (en) | Preparation method of intrinsic type in-situ self-repairing anti-corrosion polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |