Alpha-zirconium phosphate / bacterial cellulose reinforced PP composite film and preparation method thereof

Abstract

The invention provides a preparation method of an alpha-zirconium phosphate / bacterial cellulose reinforced PP composite film, which comprises the following steps: S1, adding an alpha-zirconium phosphate / bacterial cellulose composite film into a sodium laurate solution, dropwise adding an acid to adjust the pH value of the solution to 5.5, heating and stirring for reaction, washing and drying to obtain an alpha-zirconium phosphate / bacterial cellulose reinforced PP composite film; the modified alpha-zirconium phosphate / bacterial cellulose composite film is obtained; s2, heating and dissolving polypropylene in xylene to obtain a polypropylene solution; s3, adding the modified alpha-zirconium phosphate / bacterial cellulose composite membrane prepared in the step S1 into the polypropylene solution prepared in the step S2, and performing ultrasonic shearing to enable the composite membrane to fully adsorb the polypropylene solution; and S4, pressing, drying and drafting the material prepared in the step S3 to obtain the alpha-zirconium phosphate / bacterial cellulose reinforced PP composite film. According to the invention, alpha-zirconium phosphate is loaded on the bacterial cellulose membrane, and the fiber membrane is compounded with PP, so that the mechanical strength of the PP composite membrane is improved.

Description

Technical Field

[0001] The invention relates to the field of PP films, and in particular to an alpha-zirconium phosphate / bacterial cellulose reinforced PP composite film and a preparation method thereof. Background Art

[0002] Polypropylene (PP) composite film is a high-performance polymer material that combines the good processing properties of polypropylene with the high strength characteristics of other reinforcing materials. This material has potential application prospects in many fields, especially in situations where lightweight and high-strength materials are required, such as the automotive, aerospace and packaging industries. At present, the research and development of high-performance polymer materials is an important direction in the field of materials science. These materials usually have the characteristics of high strength, high modulus, high insulation, corrosion resistance, and radiation resistance. The strength of polypropylene composite films can be improved by a variety of methods. One method is to improve the strength of the film by changing the molecular structure of the polymer, such as by copolymerization or adding high-melting-point polypropylene fibers. In the PE / PP skin-core composite fiber, the low-melting-point polyethylene melts to form a film, while the high-melting-point polypropylene fiber remains unchanged, becoming a strong rib frame of the film and increasing the strength of the film. Another method is to introduce nanofillers such as graphene to improve the mechanical properties of polypropylene composites. Studies have shown that the addition of graphene to polypropylene can significantly improve tensile strength, tensile modulus and interface strength. The addition of graphene helps to improve the interface properties of the composite material, thereby improving the overall mechanical properties. Although the strength of PP composite films can be improved by the above methods, there are still some problems in practical applications. For example, although the barrier film prepared by multi-layer composite combines the advantages of multiple materials, bubbles and cracks are easily generated between the film layers, which affects the barrier properties and other packaging effects. There are also certain technical requirements for equipment, and the cost is relatively high. In addition, the dispersion and interfacial compatibility of nanofillers such as graphene are also challenges that need to be overcome when improving the performance of composite materials. Summary of the invention

[0003] Technical problem to be solved: The purpose of the present invention is to provide an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, by loading α-zirconium phosphate on the bacterial cellulose membrane, and compounding the fiber membrane with PP to improve the mechanical strength of the PP composite film.

[0004] Technical solution: An α-zirconium phosphate / bacterial cellulose reinforced PP composite membrane, wherein the PP composite membrane is composited with a modified α-zirconium phosphate / bacterial cellulose composite membrane and PP, wherein the modified α-zirconium phosphate / bacterial cellulose membrane uses bacterial cellulose as a support, and the α-zirconium phosphate is attached to the fiber or wrapped in a fiber membrane grid. The preparation method of the above-mentioned α-zirconium phosphate / bacterial cellulose reinforced PP composite film comprises the following steps: S1. The α-zirconium phosphate / bacterial cellulose composite membrane is added to a sodium laurate solution having a concentration of 0.5-1.5 g / L, an acid is added dropwise to adjust the pH of the solution to 5.5, the reaction is heated and stirred, and the mixture is washed and dried to obtain a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene is heated and dissolved in xylene to obtain a polypropylene solution; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Press, dry and stretch the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film. Preferably, the method for preparing the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. dissolving ZrOCl2·8H2O in hydrochloric acid, stirring and mixing evenly, and then dropping into phosphoric acid, stirring and reacting continuously, collecting the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.2-0.5 mg / mL, and after ultrasonic dispersion, the dispersion was sterilized by ultraviolet to obtain an α-zirconium phosphate dispersion; S14. The α-zirconium phosphate dispersion and the bacterial cellulose culture solution containing Acetobacter xylinum are mixed, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution is 1:10-20, the mixed liquid is mixed evenly and cultured at a constant temperature to obtain an α-zirconium phosphate / bacterial cellulose composite material; S15. After washing the α-zirconium phosphate / bacterial cellulose composite material, dry it to obtain an α-zirconium phosphate / bacterial cellulose composite film. Preferably, the temperature of the heating and stirring reaction in step S1 is 50-60° C. and the time is 1-2 hours. Preferably, the concentration of the polypropylene solution in step S1 is 6-11 wt %. Preferably, in step S11, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 5-10:80-95:45-50. Preferably, the concentration of Acetobacter xylinum in the bacterial cellulose culture solution containing Acetobacter xylinum in step S14 is 3.8-4.5×10 5 cfu / mL. Preferably, the constant temperature culture time in step S14 is 8-10 days. Beneficial effects: The α-zirconium phosphate / bacterial cellulose reinforced PP composite film of the present invention has the following advantages: 1. In the present invention, bacterial cellulose is used to directly reinforce the PP material. The bacterial cellulose membrane has a regular three-dimensional network structure. The hydroxyl groups of the bacterial cellulose membrane are interconnected with the surface of α-zirconium phosphate to bond the α-zirconium phosphate sheets together. Due to the strong hydrogen bonding between the bacterial fibers and the α-zirconium phosphate sheets, the mechanical properties of the composite membrane are significantly improved. The hydrogen bonding interaction force can not only enhance the mechanical connection, but also effectively transfer stress. The effective intercalation of the bacterial nanofibers prevents the agglomeration of the α-zirconium phosphate sheets, and is also a cross-linking agent for the three-dimensionally arranged α-zirconium phosphate sheets. The network structure formed by the bacterial cellulose and α-zirconium phosphate can improve the mechanical properties of the PP material. 2. In order to improve the compatibility of the α-zirconium phosphate / bacterial cellulose composite film with PP in the present invention, the α-zirconium phosphate / bacterial cellulose composite film is reacted with sodium laurate, which can improve the compatibility of the α-zirconium phosphate / bacterial cellulose composite film with PP, thereby improving the mechanical properties. DETAILED DESCRIPTION The present invention will be further described below in conjunction with embodiments, which are explanations of the present invention and are not limited to the following embodiments: Example 1 A method for preparing an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. Adding the α-zirconium phosphate / bacterial cellulose composite membrane to a sodium laurate solution with a concentration of 0.5 g / L, adding acid to adjust the pH of the solution to 5.5, heating and stirring the reaction, the temperature of the heating and stirring reaction is 50°C, the time is 2h, washing and drying, and obtaining a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 6 wt%; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Pressing, drying and stretching the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film; wherein the preparation method of the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. Dissolve ZrOCl2·8H2O in hydrochloric acid, stir well and then add dropwise to phosphoric acid, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 5:80:45, continue stirring the reaction, collect the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.5 mg / mL, and after being uniformly dispersed by ultrasonication, sterilized by ultraviolet light to obtain an α-zirconium phosphate dispersion; S14. The α-zirconium phosphate dispersion was mixed with a bacterial cellulose culture solution containing Acetobacter xylinum, wherein the concentration of Acetobacter xylinum in the culture solution was 4.2×10 5 cfu / mL, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution was 1:10, the mixed liquid was mixed evenly and then cultured at a constant temperature for 8 days to obtain an α-zirconium phosphate / bacterial cellulose composite material; S15. After washing the α-zirconium phosphate / bacterial cellulose composite material, drying is performed to obtain an α-zirconium phosphate / bacterial cellulose composite membrane. Example 2 A method for preparing an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. Adding the α-zirconium phosphate / bacterial cellulose composite membrane to a sodium laurate solution having a concentration of 1.5 g / L, adding acid to adjust the pH of the solution to 5.5, heating and stirring the reaction, the temperature of the heating and stirring reaction is 60°C, the time is 1 h, washing and drying, and obtaining a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 11 wt%; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Pressing, drying and stretching the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film; wherein the preparation method of the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. Dissolve ZrOCl2·8H2O in hydrochloric acid, stir well and then add dropwise to phosphoric acid, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 10:95:50, continue stirring the reaction, collect the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.2 mg / mL, and after being uniformly dispersed by ultrasonication, sterilized by ultraviolet light to obtain an α-zirconium phosphate dispersion; S14. The α-zirconium phosphate dispersion was mixed with a bacterial cellulose culture solution containing Acetobacter xylinum, wherein the concentration of Acetobacter xylinum in the culture solution was 3.88×105 cfu / mL, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution was 1:20, the mixed liquid was mixed evenly and then cultured at a constant temperature for 10 days to obtain an α-zirconium phosphate / bacterial cellulose composite material; S15. After washing the α-zirconium phosphate / bacterial cellulose composite material, drying is performed to obtain an α-zirconium phosphate / bacterial cellulose composite membrane. Example 3 A method for preparing an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. Adding the α-zirconium phosphate / bacterial cellulose composite membrane to a sodium laurate solution with a concentration of 0.8 g / L, adding acid to adjust the pH of the solution to 5.5, heating and stirring the reaction, the temperature of the heating and stirring reaction is 52°C, the time is 2h, washing and drying, and obtaining a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 10wt%; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Pressing, drying and stretching the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film; wherein the preparation method of the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. Dissolve ZrOCl2·8H2O in hydrochloric acid, stir well and then add dropwise to phosphoric acid, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 9:90:48, continue stirring the reaction, collect the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.5 mg / mL, and after being uniformly dispersed by ultrasonication, sterilized by ultraviolet light to obtain an α-zirconium phosphate dispersion; S14. The α-zirconium phosphate dispersion was mixed with a bacterial cellulose culture solution containing Acetobacter xylinum, wherein the concentration of Acetobacter xylinum in the culture solution was 4.12×10 5 cfu / mL, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution was 1:12, the mixed liquid was mixed evenly and then cultured at a constant temperature for 10 days to obtain an α-zirconium phosphate / bacterial cellulose composite material; S15. After washing the α-zirconium phosphate / bacterial cellulose composite material, drying is performed to obtain an α-zirconium phosphate / bacterial cellulose composite membrane. Example 4 A method for preparing an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. Adding the α-zirconium phosphate / bacterial cellulose composite membrane to a sodium laurate solution having a concentration of 1.2 g / L, adding acid to adjust the pH of the solution to 5.5, heating and stirring the reaction, the temperature of the heating and stirring reaction is 58°C, the time is 1 h, washing and drying, and obtaining a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 8 wt%; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Pressing, drying and stretching the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film; wherein the preparation method of the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. Dissolve ZrOCl2·8H2O in hydrochloric acid, stir well and then add dropwise to phosphoric acid, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 6:84:46, continue stirring the reaction, collect the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.2 mg / mL, and after being uniformly dispersed by ultrasonication, sterilized by ultraviolet light to obtain an α-zirconium phosphate dispersion; S14. The α-zirconium phosphate dispersion was mixed with a bacterial cellulose culture solution containing Acetobacter xylinum, wherein the concentration of Acetobacter xylinum in the culture solution was 4.35×10 5 cfu / mL, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution was 1:16, the mixed liquid was mixed evenly and then cultured at a constant temperature for 8 days to obtain an α-zirconium phosphate / bacterial cellulose composite material; S15. After washing the α-zirconium phosphate / bacterial cellulose composite material, drying is performed to obtain an α-zirconium phosphate / bacterial cellulose composite membrane. Example 5 A method for preparing an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. Adding the α-zirconium phosphate / bacterial cellulose composite membrane to a sodium laurate solution with a concentration of 1 g / L, adding acid to adjust the pH of the solution to 5.5, heating and stirring the reaction, the temperature of the heating and stirring reaction is 55°C, the time is 1.5 h, washing and drying, and obtaining a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 9 wt%; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Pressing, drying and stretching the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film; wherein the preparation method of the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. Dissolve ZrOCl2·8H2O in hydrochloric acid, stir well and then add dropwise to phosphoric acid, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 8:88:45, continue stirring the reaction, collect the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.4 mg / mL, and after being uniformly dispersed by ultrasonication, sterilized by ultraviolet light to obtain an α-zirconium phosphate dispersion; S14. The α-zirconium phosphate dispersion was mixed with a bacterial cellulose culture solution containing Acetobacter xylinum, wherein the concentration of Acetobacter xylinum in the culture solution was 3.95×10 5 cfu / mL, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution was 1:15, the mixed liquid was mixed evenly and then cultured at a constant temperature for 9 days to obtain an α-zirconium phosphate / bacterial cellulose composite material; S15. After washing the α-zirconium phosphate / bacterial cellulose composite material, drying is performed to obtain an α-zirconium phosphate / bacterial cellulose composite membrane. Comparative Example 1 A method for preparing an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. Adding the α-zirconium phosphate / bacterial cellulose composite membrane to a sodium laurate solution with a concentration of 1 g / L, adding acid to adjust the pH of the solution to 5.5, heating and stirring the reaction, the temperature of the heating and stirring reaction is 55°C, the time is 1.5 h, washing and drying, and obtaining a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 9 wt%; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Pressing, drying and stretching the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film; wherein the preparation method of the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. Dissolve ZrOCl2·8H2O in hydrochloric acid, stir well and then add dropwise to phosphoric acid, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 8:88:45, continue stirring the reaction, collect the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.4 mg / mL, and after being uniformly dispersed by ultrasonication, sterilized by ultraviolet light to obtain an α-zirconium phosphate dispersion; S14. 5 cfu / mL of bacterial cellulose culture solution of Acetobacter xylinum was mixed and cultured at a constant temperature for 9 days to obtain bacterial cellulose, and the α-zirconium phosphate / bacterial cellulose composite material was washed and dried; S15. Immerse the dried bacterial cellulose membrane in an α-zirconium phosphate dispersion and allow to stand at a constant temperature for 2 weeks to obtain an α-zirconium phosphate / bacterial cellulose composite membrane. Comparative Example 2 A method for preparing an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 9wt%; S2: adding the α-zirconium phosphate / bacterial cellulose composite membrane to the polypropylene solution prepared in step S1, and subjecting the composite membrane to ultrasonic shearing so that the composite membrane fully absorbs the polypropylene solution; S3. Pressing, drying and stretching the material prepared in step S2 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film; wherein the preparation method of the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. Dissolve ZrOCl2·8H2O in hydrochloric acid, stir well and then add dropwise to phosphoric acid, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 8:88:45, continue stirring the reaction, collect the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.4 mg / mL, and after being uniformly dispersed by ultrasonication, sterilized by ultraviolet light to obtain an α-zirconium phosphate dispersion; S14. The α-zirconium phosphate dispersion was mixed with a bacterial cellulose culture solution containing Acetobacter xylinum, wherein the concentration of Acetobacter xylinum in the culture solution was 3.99×10 5 cfu / mL, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution was 1:15, the mixed liquid was mixed evenly and then cultured at a constant temperature for 9 days to obtain an α-zirconium phosphate / bacterial cellulose composite material; S15. After washing the α-zirconium phosphate / bacterial cellulose composite material, drying is performed to obtain an α-zirconium phosphate / bacterial cellulose composite membrane. Comparative Example 3 A method for preparing a bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. The concentration of 4.33×10 5 cfu / mL of bacterial cellulose culture solution of Acetobacter xylinum was mixed and cultured at a constant temperature for 9 days to obtain bacterial cellulose, and the α-zirconium phosphate / bacterial cellulose composite material was washed and dried to obtain a bacterial cellulose film; S2. The bacterial cellulose film was added to a sodium laurate solution having a concentration of 1 g / L, and an acid was added dropwise to adjust the pH of the solution to 5.5, and the mixture was heated and stirred for reaction at a temperature of 55° C. for 1.5 h, and then washed and dried to obtain a modified bacterial cellulose composite film; S3. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 9wt%; S4. adding the modified bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S5. Press, dry and stretch the material prepared in step S3 to obtain a bacterial cellulose reinforced PP composite film. Comparative Example 4 A method for preparing an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. Adding the α-zirconium phosphate / bacterial cellulose composite membrane to a sodium laurate solution with a concentration of 1 g / L, adding acid to adjust the pH of the solution to 5.5, heating and stirring the reaction, the temperature of the heating and stirring reaction is 55°C, the time is 1.5 h, washing and drying, and obtaining a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 9 wt%; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Pressing, drying and stretching the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film; wherein the preparation method of the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. Dissolve ZrOCl2·8H2O in hydrochloric acid, stir well and then add dropwise to phosphoric acid, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 8:88:45, continue stirring the reaction, collect the precipitate to obtain α-zirconium phosphate; S12. Add α-zirconium phosphate to water to prepare a 0.4 mg / mL α-zirconium phosphate dispersion, disperse uniformly by ultrasonication, and sterilize by ultraviolet to obtain an α-zirconium phosphate dispersion; S13. The α-zirconium phosphate dispersion was mixed with a bacterial cellulose culture solution containing Acetobacter xylinum, wherein the concentration of Acetobacter xylinum in the culture solution was 4.18×10 5 cfu / mL, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution was 1:15, the mixed liquid was mixed evenly and then cultured at a constant temperature for 9 days to obtain an α-zirconium phosphate / bacterial cellulose composite material; S14. After washing the α-zirconium phosphate / bacterial cellulose composite material, drying is performed to obtain an α-zirconium phosphate / bacterial cellulose composite membrane. Comparative Example 5 A method for preparing an α-zirconium phosphate / bacterial cellulose reinforced PP composite film, the preparation method comprising the following steps: S1. Adding the α-zirconium phosphate / bacterial cellulose composite membrane to a sodium laurate solution with a concentration of 1 g / L, adding acid to adjust the pH of the solution to 5.5, heating and stirring the reaction, the temperature of the heating and stirring reaction is 55°C, the time is 1.5 h, washing and drying, and obtaining a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene was heated and dissolved in xylene to obtain a polypropylene solution having a concentration of 9 wt%; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Pressing and drying the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film; wherein the preparation method of the α-zirconium phosphate / bacterial cellulose composite film in step S1 comprises the following steps: S11. Dissolve ZrOCl2·8H2O in hydrochloric acid, stir well and then add dropwise to phosphoric acid, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 8:88:45, continue stirring the reaction, collect the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.4 mg / mL, and after being uniformly dispersed by ultrasonication, sterilized by ultraviolet light to obtain an α-zirconium phosphate dispersion; S14. The α-zirconium phosphate dispersion was mixed with a bacterial cellulose culture solution containing Acetobacter xylinum, wherein the concentration of Acetobacter xylinum in the culture solution was 4.09×10 5 cfu / mL, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution was 1:15, the mixed liquid was mixed evenly and then cultured at a constant temperature for 9 days to obtain an α-zirconium phosphate / bacterial cellulose composite material; S15. After washing the α-zirconium phosphate / bacterial cellulose composite material, it is dried to obtain an α-zirconium phosphate / bacterial cellulose composite film. Test of tensile properties: The sample is made into a rectangular shape (2 cm×15 cm) and tested according to GB / T 13022-1991 "Test method for tensile properties of plastic films", with a tensile rate of 200 mm / min. Five identical specimens are made for each sample for testing. Tensile strength MPa Elongation at break % Example 1 56.7 82.6 Example 2 62.8 78.9 Example 3 61.9 82.6 Example 4 59.9 82.4 Example 5 60.5 81.2 Comparative Example 1 50.2 85.1 Comparative Example 2 45.8 65.9 Comparative Example 3 44.7 56.7 Comparative Example 4 52.9 78.2 Comparative Example 5 35.9 86.4 Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. An α-zirconium phosphate / bacterial cellulose reinforced PP composite film, characterized in that: The PP composite membrane is composited by a modified α-zirconium phosphate / bacterial cellulose composite membrane and PP. The modified α-zirconium phosphate / bacterial cellulose membrane uses bacterial cellulose as a support, and the α-zirconium phosphate is attached to the fiber or wrapped in a fiber membrane grid.

2. The method for preparing the α-zirconium phosphate / bacterial cellulose reinforced PP composite film according to claim 1, characterized in that: The preparation method comprises the following steps: S1. The α-zirconium phosphate / bacterial cellulose composite membrane is added to a sodium laurate solution having a concentration of 0.5-1.5 g / L, an acid is added dropwise to adjust the pH of the solution to 5.5, the reaction is heated and stirred, and the mixture is washed and dried to obtain a modified α-zirconium phosphate / bacterial cellulose composite membrane; S2. The polypropylene is heated and dissolved in xylene to obtain a polypropylene solution; S3. adding the modified α-zirconium phosphate / bacterial cellulose composite membrane prepared in step S1 to the polypropylene solution prepared in step S2, and subjecting the composite membrane to ultrasonic shearing so that the polypropylene solution is fully adsorbed; S4. Press, dry and stretch the material prepared in step S3 to obtain an α-zirconium phosphate / bacterial cellulose reinforced PP composite film.

3. The method for preparing the α-zirconium phosphate / bacterial cellulose reinforced PP composite film according to claim 1, characterized in that: The method for preparing the α-zirconium phosphate / bacterial cellulose composite membrane in step S1 comprises the following steps: S11. dissolving ZrOCl2·8H2O in hydrochloric acid, stirring and mixing evenly, and then dropping into phosphoric acid, stirring and reacting continuously, collecting the precipitate to obtain α-zirconium phosphate; S12. α-zirconium phosphate was added to water, and after being evenly dispersed, a Tris solution was added dropwise for reaction, wherein the molar ratio of Tris to α-zirconium phosphate was 1:2, to obtain a stripped α-zirconium phosphate; S13. The stripped α-zirconium phosphate was added to water to prepare an α-zirconium phosphate dispersion having a concentration of 0.2-0.5 mg / mL, and after ultrasonic dispersion, the dispersion was sterilized by ultraviolet to obtain an α-zirconium phosphate dispersion; S14. The α-zirconium phosphate dispersion and the bacterial cellulose culture solution containing Acetobacter xylinum are mixed, the volume ratio of the α-zirconium phosphate dispersion and the bacterial cellulose culture solution is 1:10-20, the mixed liquid is mixed evenly and cultured at a constant temperature to obtain an α-zirconium phosphate / bacterial cellulose composite material; S15. After washing the α-zirconium phosphate / bacterial cellulose composite material, drying is performed to obtain an α-zirconium phosphate / bacterial cellulose composite membrane.

4. The method for preparing the α-zirconium phosphate / bacterial cellulose reinforced PP composite film according to claim 2, characterized in that: The temperature of the heating and stirring reaction in step S1 is 50-60° C. and the time is 1-2 h.

5. The method for preparing the α-zirconium phosphate / bacterial cellulose reinforced PP composite film according to claim 2, characterized in that: The concentration of the polypropylene solution in step S1 is 6-11 wt %.

6. The method for preparing the α-zirconium phosphate / bacterial cellulose reinforced PP composite film according to claim 3, characterized in that: In the step S11, the molar ratio of ZrOCl2·8H2O, hydrochloric acid and phosphoric acid is 5-10:80-95:45-50.

7. The method for preparing the α-zirconium phosphate / bacterial cellulose reinforced PP composite film according to claim 3, characterized in that: The concentration of Acetobacter xylinum in the bacterial cellulose culture solution containing Acetobacter xylinum in step S14 is 3.8-4.5×10 5 cfu / mL.

8. The method for preparing the α-zirconium phosphate / bacterial cellulose reinforced PP composite film according to claim 3, characterized in that: The constant temperature culture time in step S14 is 8-10 days.