CN112144294A - Graphene modified waterborne polyurethane antibacterial coating adhesive for fabric and preparation method thereof - Google Patents
Graphene modified waterborne polyurethane antibacterial coating adhesive for fabric and preparation method thereof Download PDFInfo
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- CN112144294A CN112144294A CN202011019663.XA CN202011019663A CN112144294A CN 112144294 A CN112144294 A CN 112144294A CN 202011019663 A CN202011019663 A CN 202011019663A CN 112144294 A CN112144294 A CN 112144294A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
- D06N3/148—(cyclo)aliphatic polyisocyanates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
Abstract
The invention discloses a graphene modified waterborne polyurethane antibacterial coating adhesive for fabrics and a preparation method thereof, wherein the carboxyl groups on original GO and the newly formed hydroxyl groups on the surface of PEI-GO can provide hydrogen ions to protonate amine groups on PEI, the protonated amine groups on PEI have higher binding capacity with bacteria with common negative charges, the long-chain structure of PEI can damage the membrane structure of the bacteria after binding, so that the release of intracellular components and the death of the bacteria are caused, therefore, an antibacterial effect is achieved, on the other hand, under the synergistic effect of GO and PEI, the sharp edge of the graphene oxide nanosheet can be regarded as a cutter of a cell membrane as a tool to release contents in the cell, firstly, GO is combined with the cell membrane to cause membrane damage, and then, a large amount of amino groups on PEI are subjected to next sterilization effect, and the graphene modified waterborne polyurethane antibacterial coating adhesive and the cell membrane are matched to enable the graphene modified waterborne polyurethane antibacterial coating adhesive to achieve excellent antibacterial performance.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to graphene modified waterborne polyurethane antibacterial coating adhesive for fabric and a preparation method thereof.
Background
In recent years, microbial contamination has become an important problem that seriously affects human health and safety on a global scale, microbial infection or cross-infection caused by pathogenic microorganisms can occur in various environments and is associated with materials used in hospitals, water purification systems, medical equipment and food packaging, and therefore, antibacterial materials are very important and essential in our daily lives, and antibacterial agents such as quaternary ammonium salts, phosphonium salts, chitosan, metal oxides and metal ions, polyguanidine, N-chloroamine compounds, etc. have been widely used in antibacterial research;
aqueous polyurethane (WPU) dispersions are of particular interest for reducing Volatile Organic Compounds (VOCs) and harmful air pollutants, these environmentally friendly aqueous dispersants have a low viscosity at high molecular weights, and green coatings have good adhesion to different substrates, good abrasion resistance and chemical resistance, however, aqueous polyurethane also has some disadvantages, such as poor water resistance and susceptibility to bacterial growth, and modification of aqueous polyurethane is particularly important;
graphene Oxide (GO) is an attractive material, a two-dimensional honeycomb and an atomic-thin nanostructure and various active oxygen functional groups are combined, researches show that the carbon nanomaterial can cause physical and chemical losses to bacteria, however, the antibacterial effect of the carbon nanomaterial can only be effective under high concentration and long-time exposure, the applicability of the nanomaterial to antibacterial drugs is limited, a novel carbon nanomaterial with strong antibacterial performance is urgently needed to be developed, Polyethyleneimine (PEI) is a weakly alkaline aliphatic polymer and has high-density amine groups which are easy to protonate, PEI can also react with epoxy groups on the surface of graphene oxide through the amine groups to form covalent bonds, some researches are dedicated to the antibacterial performance modification of a GO base membrane, and PEI-GO is introduced into waterborne polyurethane to improve the antibacterial performance of an adhesive membrane and is not explored, in order to solve the problem, the invention provides the following technical scheme.
Disclosure of Invention
The invention aims to provide a graphene modified waterborne polyurethane antibacterial coating adhesive for fabric and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
how to improve the dispersibility of graphene in the waterborne polyurethane antibacterial coating adhesive and enable the prepared coating adhesive for the fabric to have good antibacterial performance.
The purpose of the invention can be realized by the following technical scheme:
the graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric and the preparation method thereof comprise the following steps:
step one, putting graphite into a three-neck flask, uniformly mixing the graphite with mixed acid with a certain mass ratio, adding sodium nitrate and potassium permanganate, moving the three-neck flask into a 35-39 ℃ oil bath kettle, stirring for reaction for 2-3H, adding deionized water into the three-neck flask, heating to 90-95 ℃, stirring for 1-2H, and after the reaction is finished, sequentially adding 30 wt% of H into the three-neck flask2O2Stirring with 30 wt% hydrochloric acid aqueous solution, washing the centrifugal solid until the pH value is neutral, and freeze-drying to obtain solid graphene oxide;
secondly, preparing a graphene oxide aqueous solution and a polyethyleneimine aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 0.9-1mg/mL, the concentration of the polyethyleneimine aqueous solution is 8-10mg/mL, dropwise adding the polyethyleneimine aqueous solution into the graphene oxide aqueous solution for reaction, after the reaction, centrifugally washing a reaction product, and drying to obtain a PEI-GO material;
thirdly, weighing a certain amount of polyether polyol, putting the polyether polyol into a three-neck flask, dehydrating the polyether polyol, adding isophorone diisocyanate (IPDI) into the three-neck flask, reacting at 80-90 ℃ for 1-2h, cooling to 40-50 ℃, sequentially adding dimethylolpropionic acid, 1, 4-butanediol and acetone, reacting at 70-80 ℃ for 1-1.5h, cooling to 50 ℃, adding a catalyst, heating the mixture to 70-75 ℃, reacting for 3-4h, and adding triethylamine and ethylenediamine to obtain a product, namely the Waterborne Polyurethane (WPU);
and fourthly, ultrasonically dispersing the PEI-GO material in deionized water to obtain a PEI-GO aqueous solution, and preparing composite materials with different mass fractions from the PEI-GO aqueous solution and the waterborne polyurethane in the third step by a blending method to obtain the graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric.
As a further scheme of the invention, the mixed acid in the first step is sulfuric acid and phosphoric acid according to a volume ratio of 9: 1-2, and mixing uniformly.
As a further scheme of the invention, the mass ratio of potassium permanganate to graphite in the first step is 4-4.5: 1.
as a further embodiment of the invention, the relative molecular mass of the polyethyleneimine in the second step is selected from one or a mixture of any two of 600, 1800, 10000 and 70000 in any proportion.
As a further embodiment of the present invention, the reaction temperature in the second step is 20 to 80 ℃ and the reaction time is 10 to 24 hours.
As a further scheme of the invention, in the second step, the mass ratio of GO to PEI in the PEI-GO material is 1: 5-5.5.
As a further scheme of the invention, chemical structural formulas of GO and PEI are respectively as follows:
as a further embodiment of the invention, the temperature for dehydrating the polyether polyol in the third step is 120 ℃, the pressure is-0.09 MPa, and the time is 2 hours.
As a further embodiment of the present invention, the polyether polyol in the third step is selected from one or any two of polyoxypropylene diol, polytetrahydrofuran diol and active polyether polyol in any ratio of mixture.
As a further scheme of the invention, the mass fraction of PEI-GO in the composite material in the fourth step is 0-2.0 wt%.
The adhesive film has excellent antibacterial performance for two important reasons, one is that carboxyl groups on original GO and hydroxyl groups newly formed on the surface of PEI-GO can provide hydrogen ions to protonate amine groups on PEI, protonated amine groups on PEI have higher binding capacity with bacteria with common negative charges, long-chain structures of PEI can damage membrane structures of bacteria after binding, so that intracellular components are released and the bacteria die, thereby achieving the antibacterial effect, the other reason is the synergistic effect of GO and PEI, and the sharp edge of a graphene oxide nanosheet can be used as a tool to be regarded as a cutter of a cell membrane, so that intracellular contents are released. Firstly, GO is combined with a cell membrane to cause membrane damage, and then a large amount of amino groups on PEI are used for next sterilization, so that the GO and the PEI are matched to achieve excellent antibacterial performance.
The graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric, which is prepared by the invention, has the characteristic of good dispersibility, has good antibacterial performance, and can be applied to various fields of daily life, industry, medical treatment and the like.
The invention has the beneficial effects that:
1. the method has the characteristics of simple synthesis process, no environmental pollution, easy control of reaction conditions, good stability and the like;
2. compared with other bactericides, the polyethyleneimine has the characteristics of high reaction activity, cheap and easily-obtained raw materials, no pollution and the like, can greatly reduce the production cost when being applied to industrial production, and has development prospect in development and application.
Drawings
The invention is described in further detail below with reference to the figures and specific embodiments.
FIG. 1 is a reaction schematic diagram of polyethyleneimine modified graphene oxide;
fig. 2 is a photograph of an aqueous dispersion of graphene oxide and polyethyleneimine-modified graphene oxide;
FIG. 3 is a graph showing the antibacterial effect of the aqueous polyurethane films of examples 1 to 3 of the present invention after 8 hours of exposure to bacteria.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric and the preparation method thereof are as follows:
step one, putting 2.4g of graphite into a three-neck flask, uniformly mixing with 64.8mL of sulfuric acid and 7.2mL of phosphoric acid, adding 3g of sodium nitrate and 9.6g of potassium permanganate, transferring the three-neck flask into a 39 ℃ oil bath kettle, stirring for 2.5H, adding proper deionized water, heating to 95 ℃, stirring for 1.5H, sequentially adding 30% of H2O2 and a hydrochloric acid aqueous solution, stirring, washing a solid with deionized water until the pH value is neutral, and freeze-drying to obtain solid graphene oxide;
and secondly, dispersing 50mg of GO in 50mL of deionized water, performing ultrasonic treatment in an ultrasonic pot for 1h to obtain a 1mg/mL GO aqueous solution, weighing 0.25g of PEI (Mn 600), adding 25mL of water, and performing ultrasonic treatment for 1h to obtain a 10mg/mL PEI aqueous solution. Slowly dripping a PEI aqueous solution into the GO aqueous solution, stirring for 24 hours at the temperature of 20 ℃, finally washing away redundant PEI through centrifugation, and drying in an oven to obtain a PEI-GO solid product;
thirdly, 34.8g of polyether polyol (N220) is weighed into a three-neck flask, 17.4g of isophorone diisocyanate (IPDI) is added after dehydration, and the reaction is carried out for 2h at 90 ℃. 2.34g dimethylolpropionic acid, 2.734g1, 4-butanediol and a small amount of acetone were added in this order at 50 ℃ and reacted at 80 ℃ for 1h, two drops of catalyst were added when the temperature was lowered to 50 ℃ and the mixture was heated to 75 ℃ and reacted for 4 h. 1.6867g of triethylamine is added at 45 ℃ and stirred for 10min, and a proper amount of deionized water is added to adjust the solid content. Finally, the rotating speed of the stirring paddle is increased, and a proper amount of ethylenediamine is added. The product is Waterborne Polyurethane (WPU);
fourthly, ultrasonically dispersing 5.69mg of PEI-GO in 5mL of deionized water to prepare a water solution with a specific concentration, and preparing the composite material with the mass fraction of 0.2 wt% with 8g of waterborne polyurethane by a blending method. And (3) pouring the mixture into a tetrafluoroethylene mold after ultrasonic treatment to be cured into a film.
Example 2
The graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric and the preparation method thereof are as follows:
step one, putting 2.4g of graphite into a three-neck flask, uniformly mixing with 64mL of sulfuric acid and 8mL of phosphoric acid, adding 3g of sodium nitrate and 9.84g of potassium permanganate, transferring the three-neck flask into a 39 ℃ oil bath kettle, stirring for 2.5H, adding proper deionized water, heating to 95 ℃, stirring for 1.5H, sequentially adding 30% of H2O2 and a hydrochloric acid aqueous solution, stirring, washing a solid (the mass of ethanol: the mass of water is 9: 1) with an ethanol aqueous solution until the pH value is neutral, and freeze-drying to obtain solid graphene oxide;
and secondly, dispersing 50mg of GO in 50mL of deionized water, performing ultrasonic treatment in an ultrasonic pot for 1h to obtain a 1mg/mL GO aqueous solution, weighing 0.26g of PEI (Mn is 1800) and adding 26mL of water to perform ultrasonic treatment for 1h to obtain a 10mg/mL PEI aqueous solution. Slowly dripping a PEI aqueous solution into the GO aqueous solution, stirring for 20h at 40 ℃, finally washing by centrifugation to remove redundant PEI, and drying by an oven to obtain a PEI-GO solid product;
thirdly, 34.8g of polyether polyol (N220) is weighed into a three-neck flask, 17.4g of isophorone diisocyanate (IPDI) is added after dehydration, and the reaction is carried out for 2h at 90 ℃. 2.34g dimethylolpropionic acid, 2.734g1, 4-butanediol and a small amount of acetone were added in this order at 50 ℃ and reacted at 80 ℃ for 1h, two drops of catalyst were added when the temperature was lowered to 50 ℃ and the mixture was heated to 75 ℃ and reacted for 4 h. 1.6867g of triethylamine is added at 45 ℃ and stirred for 10min, and a proper amount of deionized water is added to adjust the solid content. Finally, the rotating speed of the stirring paddle is increased, and a proper amount of ethylenediamine is added. The product is Waterborne Polyurethane (WPU);
fourthly, ultrasonically dispersing 14.27mg of PEI-GO in 5mL of deionized water to prepare an aqueous solution with a specific concentration, and preparing the composite material with the mass fraction of 0.5 wt% with 8g of waterborne polyurethane by a blending method. And (3) pouring the mixture into a tetrafluoroethylene mold after ultrasonic treatment to be cured into a film.
Example 3
The graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric and the preparation method thereof are as follows:
firstly, putting 2.4g of graphite into a three-neck bottle, uniformly mixing with 63mL of sulfuric acid and 9mL of phosphoric acid, adding 3g of sodium nitrate and 10.08g of potassium permanganate, transferring the three-neck bottle into a 39 ℃ oil bath kettle, stirring for 2.5H, adding proper deionized water, heating to 95 ℃, stirring for 1.5H, sequentially adding 30% of H2O2 and a hydrochloric acid aqueous solution, stirring, washing a solid (the mass of ethanol: the mass of water is 9: 1) with an ethanol aqueous solution until the pH value is neutral, and freeze-drying to obtain solid Graphene Oxide (GO);
and secondly, dispersing 50mg of GO in 50mL of deionized water, performing ultrasonic treatment in an ultrasonic pot for 1h to obtain a 1mg/mL GO aqueous solution, weighing 0.27g of PEI (Mn is 10000), adding 27mL of water, and performing ultrasonic treatment for 1h to obtain a 10mg/mL PEI aqueous solution. Slowly dripping a PEI aqueous solution into the GO aqueous solution, stirring for 15h at 60 ℃, finally washing by centrifugation to remove redundant PEI, and drying by an oven to obtain a PEI-GO solid product;
thirdly, 34.8g of polyether polyol (N220) is weighed into a three-neck flask, 17.4g of isophorone diisocyanate (IPDI) is added after dehydration, and the reaction is carried out for 2h at 90 ℃. 2.34g dimethylolpropionic acid, 2.734g1, 4-butanediol and a small amount of acetone were added in this order at 50 ℃ and reacted at 80 ℃ for 1h, two drops of catalyst were added when the temperature was lowered to 50 ℃ and the mixture was heated to 75 ℃ and reacted for 4 h. 1.6867g of triethylamine is added at 45 ℃ and stirred for 10min, and a proper amount of deionized water is added to adjust the solid content. Finally, the rotating speed of the stirring paddle is increased, and a proper amount of ethylenediamine is added. The product is Waterborne Polyurethane (WPU);
fourthly, ultrasonically dispersing 28.69mg of PEI-GO in 5mL of deionized water to prepare an aqueous solution with a specific concentration, and preparing the composite material with the mass fraction of 1.0 wt% with 8g of waterborne polyurethane by a blending method. And (3) pouring the mixture into a tetrafluoroethylene mold after ultrasonic treatment to be cured into a film.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.
Claims (10)
1. The preparation method of the graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric is characterized by comprising the following steps of: the method comprises the following steps:
step one, putting graphite into a three-neck flask, uniformly mixing the graphite with mixed acid with a certain mass ratio, adding sodium nitrate and potassium permanganate, moving the three-neck flask into a 35-39 ℃ oil bath kettle, stirring for reaction for 2-3H, adding deionized water into the three-neck flask, heating to 90-95 ℃, stirring for 1-2H, and after the reaction is finished, sequentially adding 30 wt% of H into the three-neck flask2O2Stirring with 30 wt% hydrochloric acid aqueous solution, washing the centrifugal solid until the pH value is neutral, and freeze-drying to obtain solid graphene oxide;
secondly, preparing a graphene oxide aqueous solution and a polyethyleneimine aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 0.9-1mg/mL, the concentration of the polyethyleneimine aqueous solution is 8-10mg/mL, dropwise adding the polyethyleneimine aqueous solution into the graphene oxide aqueous solution for reaction, after the reaction, centrifugally washing a reaction product, and drying to obtain a PEI-GO material;
thirdly, weighing a certain amount of polyether polyol, putting the polyether polyol into a three-neck flask, dehydrating the polyether polyol at the temperature of 120 ℃, under the pressure of-0.09 MPa for 2 hours, adding isophorone diisocyanate (IPDI) into the three-neck flask after dehydration is finished, reacting at the temperature of 80-90 ℃ for 1-2 hours, cooling to 40-50 ℃, sequentially adding dimethylolpropionic acid, 1, 4-butanediol and acetone, reacting at the temperature of 70-80 ℃ for 1-1.5 hours, cooling to 50 ℃, adding a catalyst, heating the mixture to 70-75 ℃, reacting for 3-4 hours, and adding triethylamine and ethylenediamine to obtain a product, namely the Waterborne Polyurethane (WPU);
and fourthly, ultrasonically dispersing the PEI-GO material in deionized water to obtain a PEI-GO aqueous solution, and preparing composite materials with different mass fractions from the PEI-GO aqueous solution and the waterborne polyurethane in the third step by a blending method to obtain the graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric.
2. The preparation method of the graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric according to claim 1, wherein in the first step, the mixed acid is sulfuric acid and phosphoric acid in a volume ratio of 9: 1-2, and mixing uniformly.
3. The preparation method of the graphene-modified waterborne polyurethane antibacterial coating adhesive for the fabric according to claim 1, wherein in the first step, the mass ratio of potassium permanganate to graphite is 4-4.5: 1.
4. the preparation method of the graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric according to claim 1, wherein in the second step, the relative molecular mass of the polyethyleneimine is one or a mixture of any two of 600, 1800, 10000 and 70000 in any proportion.
5. The preparation method of the graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric according to claim 1, wherein the reaction temperature in the second step is 20-80 ℃ and the reaction time is 10-24 hours.
6. The preparation method of the graphene-modified waterborne polyurethane antibacterial coating adhesive for the fabric according to claim 1, wherein in the second step, the mass ratio of GO to PEI in the PEI-GO material is 1: 5-5.5.
7. The preparation method of the graphene modified waterborne polyurethane antibacterial coating adhesive for the fabric according to claim 1, wherein chemical structural formulas of GO and PEI are respectively as follows:
8. the preparation method of the graphene-modified waterborne polyurethane antibacterial coating glue for the fabric according to claim 1, wherein in the third step, the polyether polyol is selected from one or any two of polyoxypropylene glycol, polytetrahydrofuran glycol and active polyether polyol.
9. The preparation method of the graphene-modified waterborne polyurethane antibacterial coating adhesive for the fabric according to claim 1, wherein in the fourth step, the mass fraction of PEI-GO in the composite material is 0-2.0 wt%.
10. The graphene-modified waterborne polyurethane antibacterial coating adhesive for the fabric is characterized by being prepared according to the preparation method of any one of claims 1 to 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114805722A (en) * | 2022-04-22 | 2022-07-29 | 深圳环能石墨烯科技有限公司 | Graphene modified waterborne polyurethane composite material and preparation method thereof |
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- 2020-09-24 CN CN202011019663.XA patent/CN112144294A/en active Pending
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| CN1931941A (en) * | 2006-09-14 | 2007-03-21 | 华明扬 | Prepn process of antibacterial poromeric paint of water-thinned polyurethane |
| EP2940080A2 (en) * | 2014-05-02 | 2015-11-04 | Ncsr Demokritos | Novel dendritic polymer- functionalized nanostructured carbon-based materials with antibacterial properties and their effect in photosynthetic process |
| CN104861643A (en) * | 2015-05-29 | 2015-08-26 | 安徽大学 | Preparing method of graphene/waterborne polyurethane composite material |
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| CN114805722A (en) * | 2022-04-22 | 2022-07-29 | 深圳环能石墨烯科技有限公司 | Graphene modified waterborne polyurethane composite material and preparation method thereof |
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Application publication date: 20201229 |