CN111205427A - Antibacterial foamed plastic and preparation method thereof - Google Patents
Antibacterial foamed plastic and preparation method thereof Download PDFInfo
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- CN111205427A CN111205427A CN202010168903.6A CN202010168903A CN111205427A CN 111205427 A CN111205427 A CN 111205427A CN 202010168903 A CN202010168903 A CN 202010168903A CN 111205427 A CN111205427 A CN 111205427A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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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
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
- C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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Abstract
The invention discloses an antibacterial foam and a preparation method thereof, wherein the antibacterial foam comprises a polyurethane foam matrix, coffee grounds and cuprous oxide, the coffee grounds are loaded with copper hydroxide, the cuprous oxide-loaded coffee grounds are uniformly dispersed in the polyurethane foam matrix, and the mass ratio of the cuprous oxide-loaded coffee grounds to the polyurethane foam matrix is 0.001-0.3: 1. the invention adopts the coffee grounds as the carriers of the antibacterial agent, on one hand, the problem of treatment of the coffee grounds is solved, on the other hand, the coffee grounds contain hydroxyl groups and can be well dispersed in the polyether polyol which is the raw material of polyurethane, and cuprous oxide is loaded by the coffee grounds, so that the problem of dispersion of the cuprous oxide in the polyether polyol is solved, and the antibacterial foamed plastic is obtained.
Description
Technical Field
The invention relates to the field of preparation of polymer-based composite materials, in particular to an antibacterial foam and a preparation method thereof.
Background
Polyether glycol used by the polyurethane high-resilience foam is generally capped by EO, polyether activity is high, the diameters of foam holes of produced sponge are mixed and distributed, frameworks are different in thickness and have high aperture ratio, and rebound force with different supporting force can be generated in different deformation states when the sponge is pressed.
However, the foam for furniture in the current market does not have an antibacterial function, and particularly, when children are enuresis on the mattress, bacteria in the foam are rapidly propagated, so that health hidden troubles are brought to people.
Cuprous oxide is used for ship bottom antifouling paint (killing low-grade marine animals). It is used as bactericide, colorant for ceramics and enamel, red glass colorant, and can be used for preparing various copper salts, analytical reagent, and materials for rectifier plating, bactericide for crops, and rectifier in electrical industry.
Coffee grounds are the residues of coffee beans left after grinding coffee, and with the popularity of coffee, a large amount of coffee grounds need to be harmlessly treated every year. The reuse of coffee grounds is a problem that is urgently faced.
Disclosure of Invention
The invention aims to provide an antibacterial foamed plastic and a preparation method thereof, which solve the problem of treatment of coffee grounds and enable the foamed plastic to have antibacterial property.
The technical purpose of the invention is realized by the following technical scheme:
the antibacterial foam comprises a polyurethane foam matrix, coffee grounds and cuprous oxide, wherein the coffee grounds are loaded with the copper hydroxide, the cuprous oxide-loaded coffee grounds are uniformly dispersed in the polyurethane foam matrix, and the mass ratio of the cuprous oxide-loaded coffee grounds to the polyurethane foam matrix is (0.001-0.3): 1.
by adopting the technical scheme, the coffee grounds are used as carriers of the antibacterial agent, so that the problem of treatment of the coffee grounds is solved, the coffee grounds contain hydroxyl groups and can be well dispersed in the polyether polyol which is used as a raw material of polyurethane, and cuprous oxide is loaded by the coffee grounds so as to solve the problem of dispersion of the cuprous oxide in the polyether polyol. Thereby obtaining the antibacterial foamed plastic.
A preparation method of antibacterial foamed plastic comprises the following steps:
a. dissolving coffee grounds: dispersing coffee grounds into water to form a solution, and violently stirring at room temperature until the coffee grounds are completely dissolved;
b. preparing a cuprous oxide solution: adding a copper chloride solution into a sodium hydroxide solution;
c. mixing: adding the cuprous oxide solution into the aqueous solution of the coffee grounds, mixing, and quickly adding the hydrazine hydrate solution into the mixed solution for stirring;
d. and (3) filtering: filtering the mixed solution to obtain a precipitate;
e. washing: washing the precipitate with deionized water;
f. and (3) drying: drying for 1-10 hours in vacuum at 60 ℃ to obtain cuprous oxide-loaded coffee grounds;
g. dispersing: f, dispersedly adding the cuprous oxide-loaded coffee grounds obtained in the step f into polyether-ethanol serving as a raw material of a polyurethane foam body;
h. foaming: adding a certain amount of TDI, melamine and water for foaming to obtain the antibacterial foamed cotton.
Preferably, in the step a, the volume of the water is 100ml, and the coffee grounds are dispersedly added into the water to form a solution of 0.1-10 g/ml.
Preferably, in the step b, the volume of the copper chloride solution is 50ml, the mass concentration of the copper chloride solution is 0.01-2.0mol/L, the volume of the sodium hydroxide solution is 100ml, and the mass concentration of the copper chloride solution is 0.01-3.0 mol/L.
Preferably, in the step c, the volume of the hydrazine hydrate solution is 0.1-20ml, and the mass concentration of the hydrazine hydrate solution is 0.1-3.0 mol/L.
Preferably, in the step g, the mass ratio of the cuprous oxide-loaded coffee grounds to the polyether polyol is 0.001-0.2: 1.
Preferably, in the step h, the mass part of TDI is 50-100 phr.
Preferably, in the step h, the melamine is 0.1 to 6phr in parts by mass.
Preferably, in the step h, the mass part of the water is 1 to 15 phr.
According to the technical scheme, firstly, a coffee grounds solution is prepared, then a cuprous oxide solution is prepared, the cuprous oxide solution is dissolved into the coffee grounds solution through a hydrazine hydrate solution, a cuprous oxide-loaded coffee grounds precipitate is obtained through filtration, ions on the surface of the precipitate are removed after washing, the cuprous oxide-loaded coffee grounds are obtained after drying, the obtained cuprous oxide-loaded coffee grounds are dispersedly added into polyether polyethanol serving as a raw material of a polyurethane sponge body, a series of additives are added, and foaming is carried out to obtain the foam with the antibacterial effect.
The invention adopts the coffee grounds as the carriers of the antibacterial agent, on one hand, the problem of treatment of the coffee grounds is solved, and on the other hand, the coffee grounds contain hydroxyl groups and can be well dispersed in the polyether polyol which is the raw material of polyurethane, thereby solving the dispersion problem.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a graph showing the effect of copper hydroxide content on inhibition.
Detailed Description
The following embodiments are only a part of the embodiments of the present invention, and not all embodiments of the present invention, and the scope of the present invention is not limited to the following embodiments, and any technical solutions that fall under the spirit of the present invention should fall within the scope of the present invention. It should also be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention.
The following describes the substances used in the invention:
coffee grounds are residues left after coffee beans are ground, and along with the popularity of coffee, a large amount of coffee grounds need to be harmlessly treated every year, so that the recycling of the coffee grounds becomes a problem which is urgently faced.
Cuprous oxide is used for preparing ship bottom antifouling paint, is used as a bactericide, a colorant of ceramics and enamel, a red glass coloring agent, and is also used for preparing various copper salts, analytical reagents, materials for rectification electroplating in the electrical industry, a bactericide of crops, a rectifier and the like.
The polyether polyol is prepared by the polyaddition reaction of an initiator and ethylene oxide, propylene oxide, butylene oxide and the like in the presence of a catalyst, is a polymer of which the main chain contains ether bonds and the terminal group or the side group contains more than 2 hydroxyl groups, and is mainly used as a detergent or an antifoaming agent, an excipient, an emulsifier, a wetting agent, a dispersant, a demulsifier and the like.
Hydrazine hydrate is also called hydrazine, pure product is colorless transparent oily liquid, has light ammonia smell, smokes in wet air, has strong basicity and hygroscopicity, and is generally applied to hydrazine hydrate solution or hydrazine salt with 40% -80% of content in industry. The hydrazine hydrate liquid exists in a dimer form, can be randomly mixed with water and alcohol, is insoluble in trichloromethane and ether, has strong basicity and reducibility, and is a strong reducing agent.
TDI is colorless transparent or light yellow liquid, is an organic compound with strong pungent smell, is an important basic chemical raw material for producing polyurethane materials, is mainly used for manufacturing a curing agent of polyurethane paint and polyurethane coating, and is also used for producing soft polyurethane foam and the like.
Melamine, commonly known as melamine and protamine, is a triazine nitrogen-containing heterocyclic ring organic compound, is used as a chemical raw material, is a white monoclinic crystal, is almost tasteless, is slightly soluble in water, is soluble in methanol, formaldehyde, acetic acid, hot ethylene glycol, glycerol and the like, is insoluble in acetone and ethers, is harmful to a body, cannot be used for food processing or food additives, is nonflammable, has stable properties at normal temperature, and plays a role of a flame retardant during foaming.
Example 1
1. Dispersing coffee grounds in 100mL of aqueous solution to form 0.1g/mL solution, stirring vigorously at room temperature, and adding 50mL of 0.01 mol/L CuCl2Added to 100mL of 0.01 mol/L NaOH. Then 0.1 mL of 0.1 mol/L hydrazine hydrate solution was quickly added to the system and stirred. The resulting precipitate was then filtered offWashing with deionized water, and drying in vacuum at 60 deg.C for 1 hr to obtain coffee residue loaded with cuprous oxide;
2. dispersing the cuprous oxide-loaded coffee grounds obtained in the step 1 into polyether polyol, wherein the mass ratio of the cuprous oxide-loaded coffee grounds to the polyether polyol is 0.1: 1, then adding 80 phr of TDI, 1 phr of melamine and 10 phr of water for foaming to obtain the antibacterial foam.
Example 2
1. Dispersing coffee grounds in 100mL of aqueous solution to form a 1g/mL solution, vigorously stirring at room temperature, and adding 50mL of 0.1 mol/L CuCl2Added to 100mL of 0.1 mol/L NaOH. Then 1 mL of 0.3 mol/L hydrazine hydrate solution was quickly added to the system and stirred. Filtering the obtained precipitate, washing with deionized water, and drying in vacuum at 60 deg.C for 2 hr to obtain coffee residue loaded with cuprous oxide;
2. dispersing the cuprous oxide-loaded coffee grounds obtained in the step 1 into polyether polyol, wherein the mass ratio of the cuprous oxide-loaded coffee grounds to the polyether polyol is 0.1: 1, adding 70 phr of TDI, 1 phr of melamine and 12 phr of water for foaming to obtain the antibacterial foam.
Example 3
1. Dispersing coffee grounds in 100mL of aqueous solution to form a 3 g/mL solution, stirring vigorously at room temperature, and adding 50mL of 1mol/L CuCl2Added to 100mL of 1mol/L NaOH. Then 10mL of 1.0mol/L hydrazine hydrate solution was added to the system quickly and stirred. Filtering the obtained precipitate, washing with deionized water, and drying at 60 deg.C in vacuum for 5 hr to obtain coffee residue loaded with cuprous oxide;
2. dispersing the cuprous oxide-loaded coffee grounds obtained in the step 1 into polyether polyol, wherein the mass ratio of the cuprous oxide-loaded coffee grounds to the polyether polyol is 0.2:1, then 100phr TDI, 6phr melamine, 15phr water are added for foaming to obtain the antibacterial foam.
Example 4
1. Dispersing coffee grounds in 100mL of an aqueous solution to form10g/mL solution, vigorously stirred at room temperature, 50mL 2.0mol/L CuCl2Added to 100mL of 3.0mol/L NaOH. Then 20mL of a 3.0mol/L hydrazine hydrate solution was quickly added to the system and stirred. Filtering the obtained precipitate, washing with deionized water, and drying in vacuum at 60 deg.C for 10 hr to obtain coffee residue loaded with cuprous oxide;
2. dispersing the cuprous oxide-loaded coffee grounds obtained in the step 1 into polyether polyol, wherein the mass ratio of the cuprous oxide-loaded coffee grounds to the polyether polyol is 0.2:1, then 100phr TDI, 6phr melamine, 15phr water are added for foaming to obtain the antibacterial foam.
Example 5
1. Dispersing coffee grounds in 100mL of aqueous solution to form a 5g/mL solution, stirring vigorously at room temperature, and adding 50mL of 1.0mol/L CuCl2Added to 100mL of 1.5 mol/L NaOH. Then 10mL of 1.5 mol/L hydrazine hydrate solution was added to the system quickly and stirred. Filtering the obtained precipitate, washing with deionized water, and drying in vacuum at 60 deg.C for 8 hr to obtain coffee residue loaded with cuprous oxide;
2. dispersing the cuprous oxide-loaded coffee grounds obtained in the step 1 into polyether polyol, wherein the mass ratio of the cuprous oxide-loaded coffee grounds to the polyether polyol is 0.2:1, then 100phr TDI, 3 phr melamine and 10 phr water are added for foaming to obtain the antibacterial foam.
Example 6
1. Dispersing coffee grounds in 100mL of aqueous solution to form 8 g/mL solution, stirring vigorously at room temperature, and adding 50mL of 1.0mol/L CuCl2Added to 100mL of 2.0mol/L NaOH. Then 15 mL of 1.5 mol/L hydrazine hydrate solution was added to the system quickly and stirred. Filtering the obtained precipitate, washing with deionized water, and drying in vacuum at 60 deg.C for 10 hr to obtain coffee residue loaded with cuprous oxide;
2. dispersing the cuprous oxide-loaded coffee grounds obtained in the step 1 into polyether polyol, wherein the mass ratio of the cuprous oxide-loaded coffee grounds to the polyether polyol is 0.1: 1, then adding 100phr of TDI, 5phr of melamine and 12 phr of water for foaming to obtain the antibacterial foam.
According to the multiple detections of the above 6 embodiments and other embodiments, the antibacterial rates of the paulownia on escherichia coli and staphylococcus aureus are obtained when the content of the cuprous oxide in the coffee grounds is different, so as to obtain the attached drawing 2, as shown in the attached drawing 2, when the content of the cuprous oxide in the coffee grounds is 0-10%, the antibacterial rate rapidly increases along with the increase of the cuprous oxide content, when the content of the cuprous oxide in the coffee grounds is 10-30%, the trend that the antibacterial rate increases along with the increase of the cuprous oxide tends to be stable, and when the content of the cuprous oxide in the coffee grounds is 30%, the antibacterial rate basically reaches 80%, so that the cost is low and the antibacterial effect is good when the content of the cuprous oxide in the coffee grounds is 30%, and the antibacterial rate is a proper cuprous oxide content.
In the above 6 embodiments, the cuprous oxide is loaded on the coffee grounds, and the harmless treatment of the coffee grounds can be realized by loading the cuprous oxide on the coffee grounds, but since the coffee grounds do not have the sterilization effect, the antibacterial effect of the foamed plastic cannot be optimal when the coffee grounds are used as the loading body. The nano silver is a metal silver simple substance with the particle size of nano grade, the particle size of the nano silver is mostly about 25 nm, the nano silver has strong inhibiting and killing effects on dozens of pathogenic microorganisms such as escherichia coli, gonococcus, chlamydia trachomatis and the like, drug resistance can not be generated, and the nano silver also has the effect of carrying cuprous oxide on coffee grounds, so that the antibacterial effect can be improved by adopting a method of replacing the coffee grounds with the nano silver or adding a proper amount of nano silver into the coffee grounds.
Example 7
1. Dispersing coffee grounds in 100mL of aqueous solution to form 1g/mL solution, mixing with 100mL of nano-silver solution at room temperature, stirring vigorously, and adding 50mL of 1.0mol/L CuCl2Added to 100mL of 1.0mol/L NaOH. Then 10mL of 0.3 mol/L hydrazine hydrate solution was added to the system quickly and stirred. Filtering the obtained precipitate, washing with deionized water, and drying in vacuum at 60 ℃ for 10 hours to obtain cuprous oxide-loaded coffee grounds doped with nano-silver;
2. dispersing the coffee grounds loaded with cuprous oxide and doped with nano silver obtained in the step 1 into polyether polyol, wherein the mass ratio of the coffee grounds loaded with cuprous oxide and doped with nano silver to the polyether polyol is 0.1: 1, then adding 100phr TDI, 5phr melamine and 12 phr water for foaming to obtain the antibacterial foam.
Example 8
1. 100mL of a 15ppm nanosilver solution was prepared, 50mL of 1.0mol/L CuCl2Added to 100mL of 2.0mol/L NaOH. Then 15 mL of 1.5 mol/L hydrazine hydrate solution was added to the system quickly and stirred. Filtering the obtained precipitate, washing with deionized water, and drying in vacuum at 60 ℃ for 10 hours to obtain cuprous oxide-loaded nano silver;
2. dispersing the cuprous oxide-loaded nano silver obtained in the step 1 into polyether polyol, wherein the mass ratio of the cuprous oxide-loaded nano silver to the polyether polyol is 0.1: 1, then adding 100phr of TDI, 5phr of melamine and 12 phr of water for foaming to obtain the antibacterial foam.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The antibacterial foam is characterized by comprising a polyurethane foam matrix, coffee grounds and cuprous oxide, wherein the coffee grounds are loaded with the copper hydroxide, the cuprous oxide-loaded coffee grounds are uniformly dispersed in the polyurethane foam matrix, and the mass ratio of the cuprous oxide-loaded coffee grounds to the polyurethane foam matrix is 0.001-0.3: 1.
2. the preparation method of the antibacterial foamed plastic is characterized by comprising the following steps:
a. dissolving coffee grounds: dispersing coffee grounds into water to form a solution, and violently stirring at room temperature until the coffee grounds are completely dissolved;
b. preparing a cuprous oxide solution: adding a copper chloride solution into a sodium hydroxide solution;
c. mixing: adding the cuprous oxide solution into the aqueous solution of the coffee grounds, mixing, and quickly adding the hydrazine hydrate solution into the mixed solution for stirring;
d. and (3) filtering: filtering the mixed solution to obtain a precipitate;
e. washing: washing the precipitate with deionized water;
f. and (3) drying: drying for 1-10 hours in vacuum at 60 ℃ to obtain cuprous oxide-loaded coffee grounds;
g. dispersing: f, dispersedly adding the cuprous oxide-loaded coffee grounds obtained in the step f into polyether-ethanol serving as a raw material of a polyurethane foam body;
h. foaming: adding a certain amount of TDI, melamine and water for foaming to obtain the antibacterial foamed cotton.
3. The antibacterial foam cotton and the preparation method thereof as claimed in claim 2, wherein in the step a, the volume of water is 100ml, and the coffee grounds are dispersed and added into the water to form a solution of 0.1-10 g/ml.
4. The antibacterial foamed plastic according to claim 3, wherein in the step b, the volume of the copper chloride solution is 50ml, the mass concentration is 0.01-2.0mol/L, the volume of the sodium hydroxide solution is 100ml, and the mass concentration is 0.01-3.0 mol/L.
5. The antibacterial foamed plastic according to claim 4, wherein in the step c, the volume of the hydrazine hydrate solution is 0.1-20ml, and the concentration of the hydrazine hydrate solution is 0.1-3.0 mol/L.
6. The antibacterial foamed plastic and the preparation method thereof as claimed in claim 4, wherein in the step g, the mass ratio of the cuprous oxide-loaded coffee grounds to the polyether polyol is 0.001-0.2: 1.
7. The antibacterial foamed plastic and the preparation method thereof as claimed in claim 4, wherein in the step h, the mass portion of TDI is 50-100 phr.
8. The antibacterial foamed plastic and the preparation method thereof as claimed in claim 2, wherein in the step h, the mass part of the melamine is 0.1-6 phr.
9. The antibacterial foamed plastic and the preparation method thereof as claimed in claim 2, wherein in the step h, the water is 1-15phr in parts by weight.
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