Composite film and preparation method and application thereof

Abstract

The invention relates to a composite film as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing dispersion liquid containing binary transition metal oxide with a platinum compound for reduction reaction; mixing the prepared platinum-doped transition metal oxide with thermoplastic resin and a first solvent to obtain a first suspension, and preparing a first film through a solution casting method; a halogenated phenol compound, tetrakis hydroxymethyl phosphonium sulfate and an activating agent are mixed and reacted in a second solvent, and then mixed and reacted with halogenated alkane and imidazole monomers; carrying out extraction and recrystallization to obtain a quaternary phosphonium salt compound, mixing the quaternary phosphonium salt compound with a perfluorinated compound in a third solvent for reaction, and then adding a photosensitizer and cellulose; and mixing the obtained cellulose mixture with a fourth solvent to obtain a second suspension, and forming a second film on at least one surface of the first film through a solution casting method to obtain the composite film. The composite film has excellent heat resistance, ultraviolet resistance and antibacterial and bactericidal properties, and is biodegradable.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial materials, and in particular to a composite film and a preparation method and application thereof. Background Art

[0002] Foodborne diseases are a globally recognized serious public health problem. Pathogen contamination and the uncontrolled growth of planktonic microorganisms are one of the main causes of food spoilage. Food cling film is an effective barrier to isolate microbial contamination, so people have paid extensive attention to cling film with high sterilization efficiency. However, the single active agent in existing food cling film only has a short-term antibacterial effect and is not suitable for long-term preservation of food. Moreover, during the process of heating food and cling film together, cling film that is not heat-resistant, has poor UV resistance, or is not very safe will decompose harmful substances into food, destroying the nutrients in the food and affecting people's health. In addition, existing food cling film also has disadvantages such as slow degradation, poor biocompatibility, and environmental pollution. Summary of the Invention

[0003] Based on this, it is necessary to provide a composite film and its preparation method and application to address the above problems; the composite film prepared by the preparation method has excellent heat resistance, UV resistance, antibacterial and bactericidal properties, and is biodegradable, and has broad development space and market value.

[0004] A method for preparing a composite film comprises the following steps:

[0005] Mixing a dispersion containing a binary transition metal oxide with a platinum compound, reacting under reducing conditions to obtain a platinum-doped transition metal oxide, and mixing the platinum-doped transition metal oxide with a thermoplastic resin and a first solvent to obtain a first suspension;

[0006] A halogenated phenol compound, tetrakis(hydroxymethyl)phosphonium sulfate, and an activator are mixed and reacted in a second solvent to obtain a mixture, the mixture is further mixed and reacted with a halogenated alkane and an imidazole monomer, after the reaction is completed, a quaternary phosphonium salt compound is obtained by extraction and recrystallization, the quaternary phosphonium salt compound is mixed and reacted with a perfluorinated compound in a third solvent, and then a photosensitizer and cellulose are added to obtain a cellulose mixture, and the cellulose mixture is mixed with a fourth solvent to obtain a second suspension;

[0007] A solution casting method is adopted to prepare a first film from any suspension, and then another suspension is formed into a second film on at least one surface of the first film to obtain a composite film.

[0008] In one embodiment, the step of preparing the platinum-doped transition metal oxide satisfies at least one of the following conditions:

[0009] (1) The mass ratio of the binary transition metal oxide to the platinum compound is 3:2-4:1;

[0010] (2) In the dispersion containing the binary transition metal oxide, the concentration of the binary transition metal oxide is 0.06 g / mL to 0.08 g / mL;

[0011] (3) the binary transition metal oxide is selected from at least one of NiCo2O4, ZnCo2O4 or MnCo2O4;

[0012] (4) The platinum compound is selected from at least one of tetraammineplatinum nitrate and trans-diaminoplatinum tetrachloride.

[0013] In one embodiment, the step of preparing the first suspension satisfies at least one of the following conditions:

[0014] (1) The mass ratio of the platinum-doped transition metal oxide to the thermoplastic resin is 1:4-2:5;

[0015] (2) In the first suspension, the concentration of the thermoplastic resin is 0.125 g / mL to 0.175 g / mL;

[0016] (3) The heat-resistant temperature of the thermoplastic resin is greater than or equal to 200°C;

[0017] (4) The thermoplastic resin is selected from at least one of epoxy acrylate, polyimide, bismaleimide or polyetheretherketone;

[0018] (5) The first solvent is selected from at least one of N,N-dimethylacetamide, acetone or cyclohexane.

[0019] In one embodiment, the preparation step of mixing the halogenated phenol compound, tetrakis(hydroxymethyl)phosphonium sulfate, and the activator in the second solvent satisfies at least one of the following conditions:

[0020] (1) The mass ratio of the halogenated phenol compound, the tetrakis(hydroxymethyl)phosphonium sulfate and the activator is (2-3):(4-5):(5-7);

[0021] (2) In the mixed solution of the halogenated phenol compound, the tetrakis(hydroxymethyl)phosphonium sulfate, the activator, and the second solvent, the concentration of the tetrakis(hydroxymethyl)phosphonium sulfate is 0.1 g / mL-0.2 g / mL;

[0022] (3) the halogenated phenol compound is selected from at least one of p-bromophenol, 2,4,6-tribromophenol, 2-bromo-4-methylphenol or 4-chloro-2-methylphenol;

[0023] (4) the activator is selected from at least one of potassium carbonate, zinc chloride or potassium hydroxide;

[0024] (5) the second solvent is selected from at least one of acetone, dimethyl sulfoxide, and trimethyl phosphate;

[0025] (6) The reaction temperature is 70°C-80°C, and the reaction time is 1h-2h.

[0026] In one embodiment, the preparation step of further mixing the mixture with a halogenated alkane and an imidazole monomer satisfies at least one of the following conditions:

[0027] (1) The volume ratio of the halogenated alkane to the mixture is 3:20-1:3;

[0028] (2) the mass ratio of the imidazole monomer to the tetrakis(hydroxymethyl)phosphonium sulfate is 1:5-1:2;

[0029] (3) The halogenated alkane is selected from at least one of 1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane, 1-chloropentane, 1-bromo-2-chloroethane, and 1,4-dichlorobutane;

[0030] (4) the imidazole monomer is selected from at least one of 1-allylimidazole, 1-vinylimidazole, and 1-allyl-3-methylimidazole chloride;

[0031] (5) The reaction temperature is 70°C-80°C, and the reaction time is 3h-5h.

[0032] In one embodiment, the step of preparing the cellulose mixture satisfies at least one of the following conditions:

[0033] (1) The mass ratio of the quaternary phosphonium salt compound to the perfluorinated compound is 2:1-5:1;

[0034] (2) The perfluorinated compound is at least one selected from perfluorooctyl acrylate, N-ethyl perfluorooctylsulfonamidoethyl acrylate, and perfluorooctyl ethyl acrylate;

[0035] (3) the third solvent is selected from at least one of acetonitrile, dichloromethane or caprolactam;

[0036] (4) The photosensitizer is selected from at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 10-phenylphenothiazine, and 5-aminolevulinic acid;

[0037] (5) the cellulose is selected from at least one of hydroxypropyl methylcellulose, hydroxyethyl cellulose or hydroxymethyl cellulose;

[0038] (6) The temperature for the mixed reaction of the quaternary phosphonium salt compound and the perfluoro compound in the third solvent is 70° C.-80° C.

[0039] In one embodiment, the step of preparing the second suspension satisfies at least one of the following conditions:

[0040] (1) In the second suspension, the concentration of the cellulose mixture is 0.0625 g / mL-0.1 g / mL;

[0041] (2) The fourth solvent is selected from at least one of N,N-dimethylacetamide, acetone or cyclohexane.

[0042] A composite film prepared by the above-mentioned composite film preparation method.

[0043] In one embodiment, when the first film is made of the first suspension and the second film is made of the second suspension, the composite film satisfies at least one of the following conditions:

[0044] (1) The thickness ratio of the first film to the second film is 1:2-1:3;

[0045] (2) the content of platinum-doped transition metal oxide in the first film is 20%-30%;

[0046] (3) The content of the quaternary phosphonium salt compound containing a fluorine chain in the second film is 50%-65%;

[0047] (4) The zeta potential of the quaternary phosphonium salt compound containing a fluorine chain in the second thin film is -18.23 mV to -20.35 mV.

[0048] An application of the composite film as described above in food packaging.

[0049] The preparation method comprises the following steps: obtaining a platinum-doped transition metal oxide through a reduction reaction, blending the platinum-doped transition metal oxide with a thermoplastic resin to obtain a first suspension; introducing an imidazole ring and a fluorine chain of a halogen-loaded compound into a quaternary phosphonium salt compound, blending the quaternary phosphonium salt compound with cellulose to form a second suspension; and using the first suspension and the second suspension respectively to form a laminated composite film by a solution casting method.

[0050] The two-layer or three-layer composite film prepared by the above preparation method, first, has good heat resistance and UV resistance, good chemical stability and high safety under high temperature and UV environment, and is particularly suitable for food packaging and other fields; second, it has a high unit charge density and can adsorb negatively charged bacteria, which can not only effectively kill bacteria and prevent the emergence of drug-resistant bacteria, but also inhibit the formation of bacterial biofilms, thereby having excellent antibacterial and bactericidal properties, which is beneficial to maintaining food quality and ensuring food safety; third, it has excellent film-forming, waterproof and mechanical properties, which is beneficial to further hinder microbial contamination and can preserve food for a long time when used for packaging; fourth, it is biodegradable and is a green and environmentally friendly material with broad development space and market value. DETAILED DESCRIPTION

[0051] To facilitate understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. On the contrary, the purpose of providing these embodiments or examples is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in this specification of the present invention are only for the purpose of describing specific embodiments or examples and are not intended to limit the present invention.

[0053] The method for preparing the composite film provided by the present invention comprises the following steps:

[0054] S1, mixing a dispersion containing a binary transition metal oxide with a platinum compound, reacting under reducing conditions to obtain a platinum-doped transition metal oxide, and mixing the platinum-doped transition metal oxide with a thermoplastic resin and a first solvent to obtain a first suspension;

[0055] S2, mixing a halogenated phenol compound, tetrakis(hydroxymethyl)phosphonium sulfate, and an activator in a second solvent to obtain a mixture, further mixing the mixture with a halogenated alkane and an imidazole monomer to obtain a quaternary phosphonium salt compound after the reaction is completed, extracting and recrystallizing the mixture, mixing the quaternary phosphonium salt compound with a perfluorinated compound in a third solvent to obtain a cellulose mixture, then adding a photosensitizer and cellulose to obtain a cellulose mixture, and mixing the cellulose mixture with a fourth solvent to obtain a second suspension;

[0056] S3, using a solution casting method to form a first film from any one suspension, and then forming a second film from another suspension on at least one surface of the first film to obtain a composite film.

[0057] In step S1, platinum-doped transition metal oxide is obtained by a reduction reaction, and the platinum-doped transition metal oxide is blended with a thermoplastic resin to obtain a first suspension, which effectively improves the UV resistance and antibacterial properties of the composite film, and improves the corrosion resistance, acid and alkali resistance, water resistance and mechanical properties of the composite film.

[0058] It should be noted that the above-mentioned dispersion containing binary transition metal oxide can be prepared by an existing preparation method, which is not limited to the present invention. For example, two soluble metal salts containing different transition metal elements are subjected to a solvent thermal reaction at 140°C-160°C for 30min-70min. After the reaction, the mixture is cooled, washed, and dried to obtain a binary transition metal oxide. The binary transition metal oxide is then added to water and ultrasonicated for 20min-30min to obtain a dispersion containing binary transition metal oxide, wherein the soluble metal salt is but not limited to at least one of nickel salt, zinc salt, and manganese salt. The nickel salt is preferably nickel acetate (Ni(CH3COO)2·4H2O), the zinc salt is preferably zinc acetate (Zn(CH3COO)2·2H2O), and the manganese salt is preferably manganese acetate (Mn(CH3COO)2·4H2O). The reaction solvent is selected from an alcohol organic solvent, including but not limited to at least one of ethylene glycol, triethylene glycol, or triethylene glycol.

[0059] In one embodiment, the step of preparing the platinum-doped transition metal oxide satisfies at least one of the following conditions:

[0060] (1) The mass ratio of the binary transition metal oxide to the platinum compound is 3:2-4:1;

[0061] (2) In the dispersion containing the binary transition metal oxide, the concentration of the binary transition metal oxide is 0.06 g / mL to 0.08 g / mL;

[0062] (3) the binary transition metal oxide is selected from at least one of NiCo2O4, ZnCo2O4 or MnCo2O4;

[0063] (4) The platinum compound is selected from at least one of tetraammineplatinum nitrate and trans-diaminoplatinum tetrachloride.

[0064] By regulating the ratio and type of raw materials, it is beneficial to improve the reaction efficiency of preparing platinum-doped transition metal oxides, thereby further improving the UV resistance, antibacterial properties and mechanical properties of the prepared composite film.

[0065] Specifically, a dispersion containing a binary transition metal oxide is mixed with a platinum compound for 30-40 minutes, and then a reducing agent is added to react for 50-60 minutes. After the reaction is completed, the mixture is cooled, washed, and dried to obtain a platinum-doped transition metal oxide. The ratio of the volume of the mixed liquid formed by the dispersion containing the binary transition metal oxide and the platinum compound to the volume of the reducing agent is 1:60-1:25, and the reducing agent is selected from at least one of sodium borohydride, stannous chloride, or oxalic acid.

[0066] In one embodiment, the step of preparing the first suspension satisfies at least one of the following conditions:

[0067] (1) The mass ratio of the platinum-doped transition metal oxide to the thermoplastic resin is 1:4-2:5;

[0068] (2) In the first suspension, the concentration of the thermoplastic resin is 0.125 g / mL to 0.175 g / mL;

[0069] (3) The heat-resistant temperature of the thermoplastic resin is greater than or equal to 200°C;

[0070] (4) The thermoplastic resin is selected from at least one of epoxy acrylate, polyimide, bismaleimide or polyetheretherketone;

[0071] (5) The first solvent is selected from at least one of N,N-dimethylacetamide, acetone or cyclohexane.

[0072] By regulating the ratio of platinum-doped transition metal oxide to thermoplastic resin and the type of raw materials, it is beneficial to improve the dispersion effect of platinum-doped transition metal oxide in thermoplastic resin, thereby further improving the water resistance, heat resistance, UV resistance, antibacterial resistance, corrosion resistance and acid and alkali resistance of the prepared composite film.

[0073] In step S2, the ionic radius of the phosphorus atom in tetrakis (hydroxymethyl) phosphonium sulfate is large, the polarization effect is strong, and it is more likely to adsorb bacteria with negative ions. At the same time, tetrakis (hydroxymethyl) phosphonium sulfate has strong chemical stability, is not easy to react with redox agents or acids and bases, and is biodegradable, thereby helping to improve the antibacterial properties, bactericidal properties, corrosion resistance, and biodegradability of the composite film obtained. Furthermore, the introduction of an imidazole ring loaded with a halogen compound into tetrakis (hydroxymethyl) phosphonium sulfate can significantly increase the unit charge density of tetrakis (hydroxymethyl) phosphonium sulfate, which is beneficial to its adsorption of negatively charged bacteria and further improves the antibacterial properties of the composite film obtained.

[0074] In one embodiment, the preparation step of mixing the halogenated phenol compound, tetrakis(hydroxymethyl)phosphonium sulfate, and the activator in the second solvent satisfies at least one of the following conditions:

[0075] (1) The mass ratio of the halogenated phenol compound, the tetrakis(hydroxymethyl)phosphonium sulfate and the activator is (2-3):(4-5):(5-7);

[0076] (2) In the mixed solution of the halogenated phenol compound, the tetrakis(hydroxymethyl)phosphonium sulfate, the activator, and the second solvent, the concentration of the tetrakis(hydroxymethyl)phosphonium sulfate is 0.1 g / mL-0.2 g / mL;

[0077] (3) the halogenated phenol compound is selected from at least one of p-bromophenol, 2,4,6-tribromophenol, 2-bromo-4-methylphenol or 4-chloro-2-methylphenol;

[0078] (4) the activator is selected from at least one of potassium carbonate, zinc chloride or potassium hydroxide;

[0079] (5) the second solvent is selected from at least one of acetone, dimethyl sulfoxide, and trimethyl phosphate;

[0080] (6) The reaction temperature is 70°C-80°C, and the reaction time is 1h-2h.

[0081] In one embodiment, the preparation step of further mixing the mixture with the halogenated alkane and the imidazole monomer satisfies at least one of the following conditions:

[0082] (1) The volume ratio of the halogenated alkane to the mixture is 3:20-1:3;

[0083] (2) the mass ratio of the imidazole monomer to the tetrakis(hydroxymethyl)phosphonium sulfate is 1:5-1:2;

[0084] (3) The halogenated alkane is selected from at least one of 1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane, 1-chloropentane, 1-bromo-2-chloroethane, and 1,4-dichlorobutane;

[0085] (4) the imidazole monomer is selected from at least one of 1-allylimidazole, 1-vinylimidazole, and 1-allyl-3-methylimidazole chloride;

[0086] (5) The reaction temperature is 70°C-80°C, and the reaction time is 3h-5h.

[0087] It should be noted that the present invention does not limit the order of adding the alkyl halide and the imidazole monomer. The imidazole monomer can be added first and then the alkyl halide. Preferably, the alkyl halide is added first and stirred for 30-40 minutes, and then the imidazole monomer is added and the reaction is continued for 3-4 hours. The extraction and the recrystallization can adopt existing methods, and the present invention does not limit this.

[0088] In one embodiment, the step of preparing the cellulose mixture satisfies at least one of the following conditions:

[0089] (1) The mass ratio of the quaternary phosphonium salt compound to the perfluorinated compound is 2:1-5:1;

[0090] (2) The perfluorinated compound is at least one selected from perfluorooctyl acrylate, N-ethyl perfluorooctylsulfonamidoethyl acrylate, and perfluorooctyl ethyl acrylate;

[0091] (3) the third solvent is selected from at least one of acetonitrile, dichloromethane or caprolactam;

[0092] (4) The photosensitizer is selected from at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 10-phenylphenothiazine, and 5-aminolevulinic acid;

[0093] (5) the cellulose is selected from at least one of hydroxypropyl methylcellulose, hydroxyethyl cellulose or hydroxymethyl cellulose;

[0094] (6) The temperature for the mixed reaction of the quaternary phosphonium salt compound and the perfluoro compound in the third solvent is 70° C.-80° C.

[0095] Preferably, the concentration of the quaternary phosphonium salt compound in the third solvent is 0.24 g / mL-0.36 g / mL.

[0096] In one embodiment, the mass ratio of the quaternary phosphonium salt compound to the cellulose and the photosensitizer is (4-5):(3-5):(1-2).

[0097] Among them, a fluorine chain is introduced as a side chain into the quaternary phosphonium salt compound, so that under the action of a photosensitizer, when the prepared composite film is irradiated with ultraviolet light, the photosensitizer can be quickly decomposed into an initiator with strong activity, which is beneficial to enhancing the activity of the fluorine chain, thereby effectively improving the ultraviolet resistance and antibacterial properties of the composite film. At the same time, the quaternary phosphonium salt compound has good solubility in cellulose, which is beneficial to improving the stability of the quaternary phosphonium salt compound in the fiber membrane.

[0098] In one embodiment, the step of preparing the second suspension satisfies at least one of the following conditions:

[0099] (1) In the second suspension, the concentration of the cellulose mixture is 0.0625 g / mL-0.1 g / mL;

[0100] (2) The fourth solvent is selected from at least one of N,N-dimethylacetamide, acetone or cyclohexane.

[0101] It should be noted that the present invention does not limit the preparation order of step S1 and step S2. Step S1 can be performed first and then step S2, or step S2 can be performed first and then step S1, or step S1 and step S2 can be performed simultaneously.

[0102] In step S3, any one suspension is made into a first film by solution casting, and then another suspension is formed into a second film on at least one surface of the first film to form a composite film with a two-layer or three-layer structure, so that the composite film has excellent heat resistance, UV resistance and antibacterial and sterilization properties, as well as good mechanical properties and biodegradability.

[0103] Specifically, the solution casting method of the first film in the present invention is to cast any suspension on a hot glass plate, and obtain the first film after drying, and the temperature of the hot glass plate is 80°C-90°C. The solution casting method of the second film is to cast another suspension on at least one surface of the first film, and obtain a composite film after drying.

[0104] A composite film prepared by the above-mentioned composite film preparation method.

[0105] Specifically, the composite film includes a first film and a second film stacked in sequence, or includes a second film, a first film, and a second film stacked in sequence, wherein the first film can be made of a first suspension, and the second film is made of a second suspension; the first film can also be made of a second suspension, and the second film is made of the first suspension, and the present invention does not limit this.

[0106] When the first film is made of a first suspension and the second film is made of a second suspension, the first film includes a thermoplastic resin film and a platinum-doped transition metal oxide distributed in the thermoplastic resin film, and the second film includes a cellulose film and a quaternary phosphonium salt compound containing a fluorine chain distributed in the cellulose film, wherein the quaternary phosphonium salt compound containing a fluorine chain also contains an imidazole ring carrying a halogen compound.

[0107] The composite film has excellent heat resistance, UV resistance, antibacterial and bactericidal properties, and is biodegradable, and has broad development space and market value.

[0108] In one embodiment, when the first film is made of the first suspension and the second film is made of the first suspension, the composite film satisfies at least one of the following conditions:

[0109] (1) The thickness ratio of the first film to the second film is 1:2-1:3;

[0110] (2) the content of platinum-doped transition metal oxide in the first film is 20%-30%;

[0111] (3) The content of the quaternary phosphonium salt compound containing a fluorine chain in the second film is 50%-65%;

[0112] (4) The zeta potential of the quaternary phosphonium salt compound containing a fluorine chain in the second thin film is -18.23 mV to -20.35 mV.

[0113] It should be noted that when the composite film has a three-layer structure, that is, when there is a second film on each of the two surfaces of the first film, the thicknesses of the two second films may be the same or different.

[0114] An application of the composite film as described above in food packaging, such as food packaging bags, food cling film, etc.

[0115] The composite film, its preparation method, and its application are further described below through the following specific examples. However, those skilled in the art will understand that the following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention. Where specific conditions are not specified in the examples, conventional conditions or those recommended by the manufacturer were followed. Reagents or instruments used, for which the manufacturer is not specified, are commercially available conventional products.

[0116] Example 1

[0117] Dissolve 2g of cobalt acetate (Co(CH3COO)2·4H2O) in 100mL of ethylene glycol, stir at 30°C for 20min, add 1g of nickel acetate (Ni(CH3COO)2·4H2O) while stirring continuously, then raise the temperature to 140°C and stir for 30min. After the reaction is completed, cool at room temperature, remove the supernatant, wash the precipitate with anhydrous ethanol, and dry it in an oven at 100°C for 4h to obtain NiCo2O4.

[0118] 3 g of NiCo2O4 was dispersed in 50 mL of deionized water and ultrasonically dispersed for 20 min. Then, 1 g of tetraammineplatinum nitrate was added and stirred for 30 min. Then, 1 mL of sodium borohydride was added and stirred for 50 min. After the reaction was completed, it was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100 ° C for 4 h to obtain NiCo2O4-Pt.

[0119] Dissolve 10g of epoxy acrylate (heat-resistant temperature of 250℃) in 70mL of N,N-dimethylacetamide, add 3g of NiCo2O4-Pt, stir for 20min, and cast the suspension on a glass plate at 80℃. After evaporation of the organic solvent and drying, an epoxy acrylate (EA) film containing metal oxide (NiCo2O4-Pt) is obtained.

[0120] 2 g of p-bromophenol and 4 g of tetrakis(hydroxymethyl)phosphonium sulfate were dissolved in 30 mL of acetone, 5 g of potassium carbonate was added, and the mixture was reacted at 70 ° C for 1 h. Then, 6 mL of 1,6-dibromohexane was added dropwise and stirred for 30 min. Then, 1 g of 1-allylimidazole was added and the reaction was continued for 3 h. 100 mL of water and 100 mL of ethyl acetate were added for extraction, separation, and collection of the organic phase. After concentration, n-hexane was added for recrystallization, filtration, and drying in an oven at 60 ° C for 12 h to obtain a quaternary phosphonium salt compound.

[0121] 4 g of a quaternary phosphonium salt compound was dissolved in 30 mL of acetonitrile, and 1 g of perfluorooctyl acrylate was added under continuous stirring. The temperature was raised to 70°C, and 1 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 3 g of hydroxypropyl methylcellulose were added thereto. The mixture was stirred for 1 hour. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100°C for 4 hours to obtain a quaternary phosphonium salt / cellulose mixture containing a fluorine chain in the side chain.

[0122] 5 g of a quaternary phosphonium salt with a fluorine chain in the side chain / cellulose mixture was dissolved in 70 mL of N,N-dimethylacetamide and stirred for 20 min. The resulting suspension was cast on an epoxy acrylate film of a metal oxide (NiCo2O4-Pt). After evaporation of the organic solvent and drying, a metal oxide (NiCo2O4-Pt) epoxy acrylate-quaternary phosphonium salt with a fluorine chain in the side chain / cellulose composite film was obtained.

[0123] Example 2

[0124] Dissolve 2.5 g of cobalt acetate (Co(CH3COO)2·4H2O) in 110 mL of ethylene glycol, stir at 35°C for 25 minutes, add 1.5 g of nickel acetate (Ni(CH3COO)2·4H2O) while stirring continuously, then raise the temperature to 150°C and stir for 35 minutes. After the reaction is completed, cool at room temperature, remove the supernatant, wash the precipitate with anhydrous ethanol, and dry it in an oven at 100°C for 4 hours to obtain NiCo2O4.

[0125] 3.5 g of NiCo2O4 was dispersed in 55 mL of deionized water and ultrasonicated for 25 min. Then 1.5 g of tetraammineplatinum nitrate was added and stirred for 35 min. Then 1.5 mL of sodium borohydride was added and stirred for 55 min. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, the precipitate was washed with anhydrous ethanol, and dried in an oven at 100 ° C for 4 h to obtain NiCo2O4-Pt.

[0126] Dissolve 11 g of epoxy acrylate (heat-resistant temperature of 250°C) in 75 mL of N,N-dimethylacetamide, add 3.5 g of NiCo2O4-Pt, stir for 25 minutes, cast the suspension on a glass plate at 90°C, allow the organic solvent to evaporate, and dry to obtain an epoxy acrylate (EA) film containing metal oxide (NiCo2O4-Pt).

[0127] Dissolve 2.5 g of p-bromophenol and 5 g of tetrakis(hydroxymethyl)phosphonium sulfate in 35 mL of acetone, add 6 g of potassium carbonate, react at 75 ° C for 1.5 h, then add 8 mL of 1,6-dibromohexane dropwise, stir for 35 min, add 1.5 g of 1-allylimidazole, continue to react for 3.5 h, add 100 mL of water and 100 mL of ethyl acetate for extraction, separate the liquids, collect the organic phase, concentrate, add n-hexane for recrystallization, filter, and dry in an oven at 60 ° C for 12 h to obtain a quaternary phosphonium salt compound.

[0128] 4.5 g of a quaternary phosphonium salt compound was dissolved in 35 mL of acetonitrile, and 1.5 g of perfluorooctyl acrylate was added under continuous stirring. The temperature was raised to 75°C, and 1.5 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 4 g of hydroxypropyl methylcellulose were added thereto. The mixture was stirred for 1.5 h. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100°C for 4 h to obtain a quaternary phosphonium salt / cellulose mixture containing a fluorine chain in the side chain.

[0129] 6 g of a quaternary phosphonium salt with a fluorine chain in the side chain / cellulose mixture was dissolved in 75 mL of N,N-dimethylacetamide and stirred for 25 minutes. The resulting suspension was cast on an epoxy acrylate film of a metal oxide (NiCo2O4-Pt). After evaporation of the organic solvent and drying, a metal oxide (NiCo2O4-Pt) epoxy acrylate-quaternary phosphonium salt with a fluorine chain in the side chain / cellulose composite film was obtained.

[0130] Example 3

[0131] Dissolve 3g of cobalt acetate (Co(CH3COO)2·4H2O) in 120mL of ethylene glycol, stir at 40°C for 30min, add 2g of nickel acetate (Ni(CH3COO)2·4H2O) while stirring continuously, then raise the temperature to 160°C and stir for 40min. After the reaction is completed, cool at room temperature, remove the supernatant, wash the precipitate with anhydrous ethanol, and dry it in an oven at 100°C for 4h to obtain NiCo2O4.

[0132] 4 g of NiCo2O4 was dispersed in 60 mL of deionized water and ultrasonicated for 30 min. Then, 2 g of tetraammineplatinum nitrate was added and stirred for 40 min. Then, 2 mL of sodium borohydride was added and stirred for 60 min. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100 ° C for 4 h to obtain NiCo2O4-Pt.

[0133] Dissolve 12 g of epoxy acrylate (heat-resistant temperature of 250°C) in 80 mL of N,N-dimethylacetamide, add 4 g of NiCo2O4-Pt, stir for 30 minutes, cast the suspension on a 90°C hot glass plate, allow the organic solvent to evaporate, and dry to obtain an epoxy acrylate (EA) film containing metal oxide (NiCo2O4-Pt).

[0134] Dissolve 3 g of p-bromophenol and 5.5 g of tetrakis(hydroxymethyl)phosphonium sulfate in 40 mL of acetone, add 7 g of potassium carbonate, react at 80 ° C for 2 h, then add 10 mL of 1,6-dibromohexane dropwise, stir for 40 min, add 2 g of 1-allylimidazole, continue to react for 4 h, add 100 mL of water and 100 mL of ethyl acetate for extraction, separate the liquids, collect the organic phase, concentrate, add n-hexane for recrystallization, filter, and dry in an oven at 60 ° C for 12 h to obtain a quaternary phosphonium salt compound.

[0135] 5 g of a quaternary phosphonium salt compound was dissolved in 40 mL of acetonitrile, and 2 g of perfluorooctyl acrylate was added under continuous stirring. The temperature was raised to 80°C, and 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 5 g of hydroxypropyl methylcellulose were added thereto. The mixture was stirred for 2 h. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100°C for 4 h to obtain a quaternary phosphonium salt / cellulose mixture containing a fluorine chain in the side chain.

[0136] 7 g of a quaternary phosphonium salt with a fluorine chain in the side chain / cellulose mixture was dissolved in 80 mL of N,N-dimethylacetamide and stirred for 30 min. The suspension was cast on an epoxy acrylate film of a metal oxide (NiCo2O4-Pt). After evaporation of the organic solvent and drying, a metal oxide (NiCo2O4-Pt) epoxy acrylate-quaternary phosphonium salt with a fluorine chain in the side chain / cellulose composite film was obtained.

[0137] Example 4

[0138] 3 g of commercial ZnCo2O4 was dispersed in 50 mL of deionized water and ultrasonically dispersed for 20 min. Then 1 g of tetraammineplatinum nitrate was added and stirred for 30 min. Then 1 mL of sodium borohydride was added and stirred for 50 min. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100 ° C for 4 h to obtain ZnCo2O4-Pt.

[0139] Dissolve 12g of polyimide (heat-resistant temperature of 400℃) in 80mL of acetone, add 3g of ZnCo2O4-Pt, stir for 20min, cast the suspension on a glass plate at 80℃, and after evaporation of the organic solvent and drying, a polyimide film containing metal oxide (ZnCo2O4-Pt) is obtained.

[0140] 2 g of 2,4,6-tribromophenol and 5.5 g of tetrakishydroxymethylphosphonium sulfate were dissolved in 30 mL of acetone, 5 g of zinc chloride was added, and the mixture was reacted at 70 ° C for 1 h. Then, 6 mL of 1-chloropentane was added dropwise and stirred for 30 min. Then, 1 g of 1-allylimidazole was added thereto and the reaction was continued for 3 h. 100 mL of water and 100 mL of ethyl acetate were added for extraction, separation, and collection of the organic phase. After concentration, n-hexane was added for recrystallization, filtration, and drying in an oven at 60 ° C for 12 h to obtain a quaternary phosphonium salt compound.

[0141] 4 g of a quaternary phosphonium salt compound was dissolved in 30 mL of dichloromethane, and 1 g of N-ethyl perfluorooctane sulfonamidoethyl acrylate was added under continuous stirring. The temperature was raised to 70°C, and 1 g of 10-phenylphenothiazine and 5.5 g of hydroxypropyl methylcellulose were added thereto. The mixture was stirred for 1 hour. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100°C for 4 hours to obtain a quaternary phosphonium salt / cellulose mixture containing a fluorine chain in the side chain.

[0142] 5 g of a quaternary phosphonium salt with a fluorine chain in the side chain / cellulose mixture was dissolved in 70 mL of N,N-dimethylacetamide and stirred for 20 min. The resulting suspension was cast on a polyimide membrane of a metal oxide (ZnCo2O4-Pt). After evaporation of the organic solvent and drying, a metal oxide (ZnCo2O4-Pt) polyimide-quaternary phosphonium salt with a fluorine chain in the side chain / cellulose composite membrane was obtained.

[0143] Example 5

[0144] 3 g of commercial ZnCo2O4 was dispersed in 50 mL of deionized water and ultrasonically dispersed for 20 min. Then 1 g of trans-diaminoplatinum tetrachloride was added and stirred for 30 min. Then 1 mL of stannous chloride was added and stirred for 50 min. After the reaction was completed, it was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100 ° C for 4 h to obtain ZnCo2O4-Pt.

[0145] Dissolve 10g of polyimide (heat-resistant temperature of 400℃) in 80mL of acetone, add 3g of ZnCo2O4-Pt, stir for 20min, cast the suspension on a glass plate at 80℃, and after evaporation of the organic solvent and drying, a polyimide film containing metal oxide (ZnCo2O4-Pt) is obtained.

[0146] 2 g of 4-chloro-2-methylphenol and 5 g of tetrakishydroxymethylphosphonium sulfate were dissolved in 25 mL of dimethyl sulfoxide, 5 g of zinc chloride was added, and the mixture was reacted at 70 ° C for 1 h. Then, 6 mL of 1-chloropentane was added dropwise and stirred for 30 min. Then, 1 g of 1-allylimidazole was added thereto and the reaction was continued for 3 h. 100 mL of water and 100 mL of ethyl acetate were added for extraction, separation, and collection of the organic phase. After concentration, n-hexane was added for recrystallization, filtration, and drying in an oven at 70 ° C for 10 h to obtain a quaternary phosphonium salt compound.

[0147] 5.2 g of a quaternary phosphonium salt compound was dissolved in 35 mL of dichloromethane, and 2.2 g of perfluorooctyl ethyl acrylate was added under continuous stirring. The temperature was raised to 70°C, and 1.5 g of 10-phenylphenothiazine and 5 g of hydroxyethyl cellulose were added and stirred for 1.5 h. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100°C for 5 h to obtain a quaternary phosphonium salt / cellulose mixture containing a fluorine chain in the side chain.

[0148] 7.5 g of a quaternary phosphonium salt with a fluorine chain in the side chain / cellulose mixture was dissolved in 80 mL of N,N-dimethylacetamide and stirred for 40 min. The resulting suspension was cast on a polyimide membrane of a metal oxide (ZnCo2O4-Pt). After evaporation of the organic solvent and drying, a metal oxide (ZnCo2O4-Pt) polyimide-quaternary phosphonium salt with a fluorine chain in the side chain / cellulose composite membrane was obtained.

[0149] Example 6

[0150] 2 g of 2,4,6-tribromophenol and 5.5 g of tetrakishydroxymethylphosphonium sulfate were dissolved in 30 mL of acetone, 5 g of zinc chloride was added, and the mixture was reacted at 70 ° C for 1 h. Then, 6 mL of 1-chloropentane was added dropwise and stirred for 30 min. Then, 1 g of 1-vinylimidazole was added thereto and the reaction was continued for 3 h. 100 mL of water and 100 mL of ethyl acetate were added for extraction, separation, and collection of the organic phase. After concentration, n-hexane was added for recrystallization, filtration, and drying in an oven at 60 ° C for 12 h to obtain a quaternary phosphonium salt compound.

[0151] 5 g of a quaternary phosphonium salt compound was dissolved in 40 mL of dichloromethane, and 2 g of perfluorooctyl acrylate was added under continuous stirring. The temperature was raised to 70°C, and 2 g of 10-phenylphenothiazine and 3 g of hydroxypropyl methylcellulose were added thereto. The mixture was stirred for 1 hour. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100°C for 4 hours to obtain a quaternary phosphonium salt / cellulose mixture containing a fluorine chain in the side chain.

[0152] 5 g of a quaternary phosphonium salt with a fluorine chain in the side chain / cellulose mixture was dissolved in 70 mL of N,N-dimethylacetamide and stirred for 20 min. The suspension was cast on a glass plate at 80°C. After evaporation of the organic solvent and drying, a quaternary phosphonium salt with a fluorine chain in the side chain / cellulose membrane was obtained.

[0153] 4 g of commercial MnCo2O4 was dispersed in 50 mL of deionized water and ultrasonically dispersed for 20 min. Then, 1 g of trans-diaminoplatinum tetrachloride was added and stirred for 30 min. Then, 1 mL of sodium borohydride was added and stirred for 1 h. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100 ° C for 4 h to obtain MnCo2O4-Pt.

[0154] 12 g of bismaleimide (heat-resistant temperature of 260°C) was dissolved in 80 mL of acetone, 3 g of MnCo2O4-Pt was added, and the mixture was stirred for 20 minutes. The resulting suspension was cast on a quaternary phosphonium salt with a fluorine chain in the side chain / cellulose membrane. After evaporation of the organic solvent and drying, a metal oxide (MnCo2O4-Pt) bismaleimide-quaternary phosphonium salt with a fluorine chain in the side chain / cellulose composite membrane was obtained.

[0155] Comparative Example 1

[0156] The difference between Comparative Example 1 and Example 3 is that 12 g of epoxy acrylate is dissolved in 80 mL of N,N-dimethylacetamide, 4 g of NiCo2O4 is added, and the mixture is stirred for 30 min. The suspension is cast on a hot glass plate at 80°C, and after the organic solvent is evaporated and dried, an epoxy acrylate (EA) film containing metal oxide NiCo2O4 is obtained as the first thin film.

[0157] Comparative Example 2

[0158] The difference between Comparative Example 2 and Example 3 is that 12 g of epoxy acrylate is dissolved in 80 mL of N,N-dimethylacetamide, 4 g of tetraammineplatinum nitrate is added, and the mixture is stirred for 30 minutes. The suspension is cast on a hot glass plate at 80°C. After evaporation of the organic solvent and drying, an epoxy acrylate (EA) film containing platinum ions is obtained as the first thin film.

[0159] Comparative Example 3

[0160] The difference between Comparative Example 3 and Example 3 is that 2 g of perfluorooctyl acrylate is dissolved in acetonitrile, the temperature is raised to 80°C, 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 5 g of hydroxypropyl methylcellulose are added thereto, and the mixture is stirred for 2 h. After the reaction is completed, the mixture is cooled at room temperature, the supernatant is removed, the precipitate is washed with anhydrous ethanol, and the precipitate is dried in an oven at 100°C for 4 h to obtain a fluoro chain / cellulose mixture.

[0161] 7 g of the fluorochain / cellulose mixture was dissolved in 80 mL of N,N-dimethylacetamide and stirred for 30 min. The suspension was cast on the epoxy acrylate film of the metal oxide (NiCo2O4-Pt). After evaporation of the organic solvent and drying, the epoxy acrylate-fluorochain / cellulose composite film of the metal oxide (NiCo2O4-Pt) was obtained.

[0162] Comparative Example 4

[0163] The difference between Comparative Example 4 and Example 3 is that 5 g of the quaternary phosphonium salt compound was dissolved in 40 mL of acetonitrile, the temperature was raised to 80 ° C, 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 5 g of hydroxypropyl methylcellulose were added thereto, and the mixture was stirred for 2 h. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, and the precipitate was washed with anhydrous ethanol and dried in an oven at 100 ° C for 4 h to obtain a quaternary phosphonium salt / cellulose mixture.

[0164] 7 g of the quaternary phosphonium salt / cellulose mixture was dissolved in 80 mL of N,N-dimethylacetamide and stirred for 30 min. The suspension was cast on the epoxy acrylate film of the metal oxide (NiCo2O4-Pt). After evaporation of the organic solvent and drying, the epoxy acrylate-quaternary phosphonium salt / cellulose composite film of the metal oxide (NiCo2O4-Pt) was obtained.

[0165] Comparative Example 5

[0166] The difference between Comparative Example 5 and Example 3 is that 3 g of p-bromophenol and 5 g of tetrakis(hydroxymethyl)phosphonium sulfate were dissolved in 40 mL of acetone, 7 g of potassium carbonate was added, and the mixture was reacted at 80° C. for 2 h. 100 mL of water and 100 mL of ethyl acetate were added for extraction, the liquids were separated, and the organic phase was collected. After concentration, n-hexane was added for recrystallization, filtered, and dried in an oven at 60° C. for 12 h to obtain a quaternary phosphonium salt compound.

[0167] Comparative Example 6

[0168] The difference between Comparative Example 6 and Example 3 is that 5 g of hydroxypropyl methylcellulose is dissolved in 40 mL of acetonitrile, 4 g of NiCo2O4-Pt is added thereto, and the mixture is stirred for 30 minutes. The suspension is cast on a 90°C hot glass plate, the organic solvent is evaporated, and the mixture is dried to obtain a cellulose film containing metal oxide (NiCo2O4-Pt) as the first film.

[0169] Comparative Example 7

[0170] The difference between Comparative Example 7 and Example 3 is that 5 g of the quaternary phosphonium salt compound was dissolved in 40 mL of acetonitrile, 2 g of perfluorooctyl acrylate was added under continuous stirring, the temperature was raised to 80 ° C, 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 12 g of epoxy acrylate (heat-resistant temperature of 250 ° C) were added thereto, and stirred for 2 h. After the reaction was completed, the mixture was cooled at room temperature, the supernatant was removed, the precipitate was washed with anhydrous ethanol, and dried in an oven at 100 ° C for 4 h to obtain a mixture.

[0171] 7 g of the mixture was dissolved in 80 mL of N,N-dimethylacetamide and stirred for 30 min. The suspension was cast on the epoxy acrylate film of metal oxide (NiCo2O4-Pt) as the second film. After evaporation of the organic solvent and drying, a composite film was obtained.

[0172] Comparative Example 8

[0173] The difference between Comparative Example 8 and Example 3 is that 5.5 g of dioctyldimethylammonium bromide is used instead of 5.5 g of tetrakishydroxymethylphosphonium sulfate.

[0174] The quaternary phosphonium salt compounds, the first thin film and the second thin film prepared in all the examples and comparative examples were characterized and tested. The results are shown in Table 1.

[0175] Table 1

[0176]

[0177] The composite films prepared in all the examples and comparative examples were subjected to performance tests, and the performance indicators and test methods are as follows:

[0178] (1) Mechanical properties: The test was performed using a universal testing machine according to ISO 527-3. The composite film was cut into 5 cm × 2 cm strips and operated in tensile mode with a crosshead speed of 30 mm / min. At least 10 samples were tested in each group.

[0179] (2) UV resistance test: The composite film was cut into 3 cm × 5 cm films and tested using a UV-visible spectrophotometer at 200 nm-800 nm.

[0180] (3) Antibacterial performance test: GB / T 30706-2014 “Test method and evaluation of antibacterial performance of photocatalytic antibacterial materials and products under visible light irradiation” was used to evaluate the antibacterial performance and antibacterial durability of the composite film. First, the composite film was added to the water-based coating at a dosage of 1 wt% to prepare a solution. The solution was prepared at a pressure of 20 g / m 2 The amount of the product was evenly sprayed on a 5cm×5cm acrylic plate, placed in an oven at 60℃ and dried for 24 hours to test the antibacterial effect.

[0181] (4) Heat resistance test: The composite film was placed in an oven at 300 °C for 48 h and then taken out and its mechanical properties, UV resistance and antibacterial properties were tested again.

[0182] (5) Biodegradability: The dried composite film was cut into discs with a diameter of 10 mm, weighed, and placed in a sample tube. 5 mL of potassium hydrogen phthalate buffer solution with a pH of 4.0, sodium tetraborate buffer solution with a pH of 9.18, and mixed phosphate buffer solution with a pH of 6.8 were added in sequence. The degradation experiment was carried out at 37°C. The sample tube was taken out every 5 days, centrifuged, and the sample was taken out. After rinsing with distilled water, it was dried in a vacuum oven at 5°C to constant weight. The weighing data was recorded and the experiment was repeated to calculate the weight loss rate of the composite film.

[0183] The test results of all embodiments and comparative examples are shown in Table 2 and Table 3.

[0184] Table 2

[0185]

[0186]

[0187] Table 3

[0188] Weight loss rate after 5 days Weight loss rate after 10 days Weight loss rate after 15 days Weight loss rate after 20 days Weight loss rate after 25 days Example 1 20.3％ 34.6％ 59.4％ 78.5％ 98.3％ Example 2 21.4％ 36.7％ 58.6％ 80.3％ 99.3％ Example 3 23.4％ 38.5％ 69.2％ 83.3％ 99.7％ Example 4 24.5％ 39.4％ 68.4％ 84.5％ 99.1％ Example 5 28.3％ 37.5％ 67.4％ 84.6％ 98.3％ Example 6 24.5％ 36.7％ 66.3％ 83.5％ 97.3％ Comparative Example 1 19.3％ 23.4％ 54.3％ 65.2％ 78.3％ Comparative Example 2 19.7％ 22.5％ 45.6％ 56.7％ 56.9％ Comparative Example 3 20.1％ 25.6％ 43.5％ 55.6％ 78.3％ Comparative Example 4 20.1％ 22.3％ 42.4％ 52.2％ 65.9％ Comparative Example 5 20.2％ 25.5％ 43.6％ 50.3％ 62.4％ Comparative Example 6 18.3％ 23.5％ 42.4％ 52.4％ 60.4％ Comparative Example 7 17.8％ 22.6％ 47.8％ 50.3％ 79.4％ Comparative Example 8 20.4％ 30.2％ 57.8％ 67.4％ 78.1％

[0189] The results in the table show that, under the same test conditions, the composite film prepared in the embodiment has higher tensile strength, lower ultraviolet transmittance, and higher Escherichia coli and Staphylococcus aureus removal rates than the composite film prepared in the comparative example. Furthermore, after heat treatment, the composite film still outperforms the comparative example in all aspects. Furthermore, the composite film prepared in the embodiment has a weight loss rate of over 98% after 25 days of experimentation, and essentially no residual residue will cause environmental pollution, exhibiting good biodegradability. Therefore, the composite film provided by the present invention has good mechanical strength, heat resistance, ultraviolet resistance, antibacterial and bactericidal properties, and is biodegradable, possessing broad development potential and market value.

[0190] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0191] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A method for preparing a composite film, characterized in that: The steps include: Mixing a dispersion containing a binary transition metal oxide with a platinum compound, reacting under reducing conditions to obtain a platinum-doped transition metal oxide, and mixing the platinum-doped transition metal oxide with a thermoplastic resin and a first solvent to obtain a first suspension; A halogenated phenol compound, tetrakis(hydroxymethyl)phosphonium sulfate, and an activator are mixed and reacted in a second solvent to obtain a mixture, the mixture is further mixed and reacted with a halogenated alkane and an imidazole monomer, and after the reaction is completed, a quaternary phosphonium salt compound is obtained by extraction and recrystallization, the quaternary phosphonium salt compound is mixed and reacted with a perfluorinated compound in a third solvent, and then a photosensitizer and cellulose are added to obtain a cellulose mixture, and the cellulose mixture is mixed with a fourth solvent to obtain a second suspension; A solution casting method is adopted to prepare a first film from any suspension, and then another suspension is formed into a second film on at least one surface of the first film to obtain a composite film.

2. The method for preparing a composite film according to claim 1, wherein: The step of preparing the platinum-doped transition metal oxide satisfies at least one of the following conditions: (1) The mass ratio of the binary transition metal oxide to the platinum compound is 3:2-4:1; (2) In the dispersion containing the binary transition metal oxide, the concentration of the binary transition metal oxide is 0.06 g / mL to 0.08 g / mL; (3) the binary transition metal oxide is selected from at least one of NiCo2O4, ZnCo2O4 or MnCo2O4; (4) The platinum compound is selected from at least one of tetraammineplatinum nitrate and trans-diaminoplatinum tetrachloride.

3. The method for preparing a composite film according to claim 1, wherein: The step of preparing the first suspension satisfies at least one of the following conditions: (1) The mass ratio of the platinum-doped transition metal oxide to the thermoplastic resin is 1:4-2:5; (2) In the first suspension, the concentration of the thermoplastic resin is 0.125 g / mL to 0.175 g / mL; (3) The heat-resistant temperature of the thermoplastic resin is greater than or equal to 200°C; (4) The thermoplastic resin is selected from at least one of epoxy acrylate, polyimide, bismaleimide or polyetheretherketone; (5) The first solvent is selected from at least one of N,N-dimethylacetamide, acetone or cyclohexane.

4. The method for preparing a composite film according to claim 1, wherein: The preparation step of mixing the halogenated phenol compound, tetrakis(hydroxymethyl)phosphonium sulfate, and the activator in the second solvent for reaction satisfies at least one of the following conditions: (1) The mass ratio of the halogenated phenol compound, the tetrakis(hydroxymethyl)phosphonium sulfate and the activator is (2-3):(4-5):(5-7); (2) In the mixed solution of the halogenated phenol compound, the tetrakis(hydroxymethyl)phosphonium sulfate, the activator, and the second solvent, the concentration of the tetrakis(hydroxymethyl)phosphonium sulfate is 0.1 g / mL-0.2 g / mL; (3) the halogenated phenol compound is selected from at least one of p-bromophenol, 2,4,6-tribromophenol, 2-bromo-4-methylphenol or 4-chloro-2-methylphenol; (4) the activator is selected from at least one of potassium carbonate, zinc chloride or potassium hydroxide; (5) the second solvent is selected from at least one of acetone, dimethyl sulfoxide, and trimethyl phosphate; (6) The reaction temperature is 70°C-80°C, and the reaction time is 1h-2h.

5. The method for preparing a composite film according to claim 1, wherein: The preparation step of continuing to mix the mixture with the halogenated alkane and the imidazole monomer to react satisfies at least one of the following conditions: (1) The volume ratio of the halogenated alkane to the mixture is 3:20-1:3; (2) the mass ratio of the imidazole monomer to the tetrakis(hydroxymethyl)phosphonium sulfate is 1:5-1:2; (3) The halogenated alkane is selected from at least one of 1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane, 1-chloropentane, 1-bromo-2-chloroethane, and 1,4-dichlorobutane; (4) the imidazole monomer is selected from at least one of 1-allylimidazole, 1-vinylimidazole, and 1-allyl-3-methylimidazole chloride; (5) The reaction temperature is 70°C-80°C, and the reaction time is 3h-5h.

6. The method for preparing a composite film according to claim 1, wherein: The preparation step of the cellulose mixture satisfies at least one of the following conditions: (1) The mass ratio of the quaternary phosphonium salt compound to the perfluorinated compound is 2:1-5:1; (2) The perfluorinated compound is at least one selected from perfluorooctyl acrylate, N-ethyl perfluorooctylsulfonamidoethyl acrylate, and perfluorooctyl ethyl acrylate; (3) the third solvent is selected from at least one of acetonitrile, dichloromethane or caprolactam; (4) The photosensitizer is selected from at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 10-phenylphenothiazine, and 5-aminolevulinic acid; (5) the cellulose is selected from at least one of hydroxypropyl methylcellulose, hydroxyethyl cellulose or hydroxymethyl cellulose; (6) The temperature for the mixed reaction of the quaternary phosphonium salt compound and the perfluoro compound in the third solvent is 70° C.-80° C.

7. The method for preparing a composite film according to claim 1, wherein: The step of preparing the second suspension satisfies at least one of the following conditions: (1) In the second suspension, the concentration of the cellulose mixture is 0.0625 g / mL-0.1 g / mL; (2) The fourth solvent is selected from at least one of N,N-dimethylacetamide, acetone or cyclohexane.

8. A composite film produced by the method for producing a composite film according to any one of claims 1 to 7.

9. The composite film according to claim 8, characterized in that When the first film is made of the first suspension and the second film is made of the second suspension, the composite film satisfies at least one of the following conditions: (1) The thickness ratio of the first film to the second film is 1:2-1:3; (2) the content of platinum-doped transition metal oxide in the first film is 20%-30%; (3) The content of the quaternary phosphonium salt compound containing a fluorine chain in the second film is 50%-65%; (4) The zeta potential of the quaternary phosphonium salt compound containing a fluorine chain in the second thin film is -18.23 mV to -20.35 mV.

10. Use of the composite film according to claim 8 or 9 in food packaging.

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