CN111333917A - Hydrophobic cellulose-chitosan high-barrier composite film and preparation method thereof - Google Patents
Hydrophobic cellulose-chitosan high-barrier composite film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of cellulose materials, and discloses a hydrophobic cellulose-chitosan high-barrier composite film which comprises the following formula raw materials and components: chitosan grafted graphene, hydrophobic nano-cellulose and oxidized cellulose. According to the hydrophobic cellulose-chitosan high-barrier composite film, acyl chloride groups of chlorinated graphene react with amino groups of chitosan to obtain chitosan grafted graphene, and then Schiff base condensation reaction is carried out on the chitosan grafted graphene and aldehyde groups of oxidized cellulose to organically combine graphene particles with cellulose, so that the compatibility of graphene nanoparticles and cellulose is improved, graphene nanoparticles are uniformly dispersed in gaps of the cellulose film to form a continuous and compact barrier layer, the oxygen barrier capability of the cellulose film is improved, the contact angle of the cellulose film and water molecules is improved by the long-chain alkylated hydrophobic nano-cellulose, and the hydrophobic property of a film material is enhanced.
Description
Technical Field
The invention relates to the technical field of cellulose materials, in particular to a hydrophobic cellulose-chitosan high-barrier composite film and a preparation method thereof.
Background
The high-barrier material has strong capability of blocking moisture and gas, such as polyvinylidene chloride films, polyethylene films, ethylene/vinyl alcohol copolymers and other materials, and is widely applied to the aspects of food packaging, biological medicines, antibacterial materials and the like.
Cellulose is a polysaccharide compound which is most widely distributed and contains most in nature, cellulose molecules have polarity, the interaction force between molecular chains is very strong, hydrogen bonds can be formed in the cellulose molecules and among the molecules, the cellulose has very strong rigidity, the cellulose is the most abundant natural polymers and natural renewable resources, and the cellulose has good biocompatibility and biodegradability, so materials such as cellulose-based functional composite films have wide application prospects in the aspects of packaging materials, drug carriers and the like, but the traditional cellulose films have low performance of blocking gases such as oxygen and the like, and are very easy to absorb water, so that the hydrophobic performance and the water blocking capacity are poor, and the application field of the cellulose-based films is limited.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a hydrophobic cellulose-chitosan high-barrier composite film and a preparation method thereof, and solves the problems of poor oxygen barrier property and poor hydrophobic property of the cellulose film.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a hydrophobic cellulose-chitosan high-barrier composite film comprises the following raw materials and components: the chitosan grafted graphene, the hydrophobic nano-cellulose and the oxidized cellulose are mixed according to the mass ratio of 5-40:50-120: 100.
Preferably, the preparation method of the hydrophobic cellulose-chitosan high-barrier composite film comprises the following steps:
(1) adding an absolute ethyl alcohol solvent and carboxylated graphene into a reaction bottle, placing the reaction bottle in an ultrasonic separation treatment instrument for ultrasonic dispersion, then slowly dropwise adding thionyl chloride, stirring at a constant speed at 50-70 ℃ for reaction for 4-10 hours, filtering the solution to remove the solvent, washing a solid product by using absolute ethyl alcohol, and fully drying to prepare the acyl chlorinated graphene.
(2) Adding an absolute ethanol solvent and chitosan into a reaction bottle, slowly adding glacial acetic acid until the chitosan is dissolved, then adding acylchlorinated graphene, uniformly dispersing by ultrasonic wave, heating to 100 ℃ and 110 ℃, uniformly stirring for reaction for 24-48h, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the chitosan grafted graphene.
(3) Adding distilled water solvent and nano-cellulose into a reaction bottle, adding aqueous solution of sodium bromide and sodium hypochlorite and 2,2,6, 6-tetramethylpiperidine oxide after uniform ultrasonic dispersion, wherein the mass ratio of the four is 100:30-35:70-80:6-7, stirring at a constant speed at 20-30 ℃ for reaction for 2-6h, slowly adding sodium hydroxide during the reaction process, controlling the pH of the solution to 10, placing the solution in an ice water bath for cooling, adding ethanol solvent until a large amount of precipitate is separated out, filtering the solution to remove the solvent, and washing and dialyzing a solid product to prepare the carboxylated nano-cellulose.
(4) Adding a distilled water solvent and aldehyde nano-cellulose into a reaction bottle, uniformly dispersing by ultrasonic, adding octadecylamine, an activator diisopropylcarbodiimide and a catalyst N-hydroxysuccinimide, reacting for 20-30h at a constant speed under stirring at 20-30 ℃, and centrifugally separating and washing the solution to prepare the long-chain alkylated hydrophobic nano-cellulose.
(5) Adding distilled water and cellulose into a reaction bottle, adding sodium periodate serving as an oxidant after uniform ultrasonic dispersion, heating to 40-60 ℃, uniformly stirring for reaction for 3-8 hours, filtering, washing and drying the solution to prepare the oxidized cellulose.
(6) Adding an acetic acid solution with the mass fraction of 2-4% into a reaction bottle, adding chitosan grafted graphene, oxidized cellulose and hydrophobic nano-cellulose, uniformly dispersing by ultrasonic, heating to 50-80 ℃, stirring at a constant speed for reaction for 4-10h, filtering, washing and drying the solution, placing the solid mixture into an ethanol solvent, uniformly dispersing by ultrasonic, stirring at a constant speed for 10-20h, pouring into a film-forming mold, naturally drying to form a film, and preparing to obtain the hydrophobic cellulose-chitosan high-barrier composite film.
Preferably, the ultrasonic branch treatment instrument comprises an ultrasonic device and an ultrasonic probe fixedly connected below the ultrasonic device, the ultrasonic probe is movably connected with an ultrasonic treatment chamber, a reaction bottle is arranged in the ultrasonic treatment chamber, grooves are formed in two sides of the ultrasonic treatment chamber, the grooves are movably connected with a clamping block, the clamping block is fixedly connected with a moving block, the moving block is movably connected with a spring, and the spring is movably connected with a limiting block.
Preferably, the carboxyl content of the carboxylated graphene is 3-5%, and the mass ratio of the carboxylated graphene to the thionyl chloride is 1: 80-150.
Preferably, the mass fraction of the glacial acetic acid is more than or equal to 99.99%, and the water content is less than or equal to 0.01%.
Preferably, the mass ratio of the aldehyde nanocellulose, octadecylamine, diisopropylcarbodiimide and N-hydroxysuccinimide is 10:8.5-9.5:6-7: 3.5-4.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the hydrophobic cellulose-chitosan high-barrier composite film, thionyl chloride reacts with rich carboxyl on the surface of carboxylated graphene to obtain acylchlorinated graphene, acyl chloride groups react with amino of chitosan to obtain chitosan grafted graphene, hydroxyl groups of cellulose are partially oxidized into aldehyde groups through sodium periodate, and Schiff base condensation reaction is carried out on the aldehyde groups and the chitosan amino groups, so that graphene particles are organically combined with the cellulose, the compatibility of graphene nanoparticles and the cellulose is improved, the phenomenon of graphene in the cellulose film is greatly reduced, graphene nanoparticles are uniformly dispersed in gaps of the cellulose film to form a continuous and compact barrier layer, and the oxygen barrier capability of the cellulose film is improved.
According to the hydrophobic cellulose-chitosan high-barrier composite film, an activating agent and a catalyst are used for activating the carboxyl of the carboxylated nano-cellulose, then the carboxyl is subjected to condensation reaction with the amino of octadecylamine with strong hydrophobicity to obtain long-chain alkylated hydrophobic nano-cellulose, and the long-chain alkylated hydrophobic nano-cellulose is blended with chitosan grafted graphene and oxidized cellulose to obtain the composite cellulose film, so that the contact angle between the cellulose film and water molecules is improved, the hydrophobic property of the film material is enhanced, and the phenomenon that water molecules penetrate through the film is reduced.
Drawings
FIG. 1 is a schematic front view of an ultrasound machine;
FIG. 2 is an enlarged schematic view of the moving block;
figure 3 is a schematic diagram of movement block adjustment.
1. An ultrasonic device; 2. an ultrasonic probe; 3. an ultrasonic treatment chamber; 4. an ultrasonic treatment chamber; 5. a reaction bottle; 6. a groove; 7. a clamping block; 8. a moving block; 9. a spring; 10. and a limiting block.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a hydrophobic cellulose-chitosan high-barrier composite film comprises the following raw materials and components: the chitosan grafted graphene, the hydrophobic nano-cellulose and the oxidized cellulose are mixed according to the mass ratio of 5-40:50-120: 100.
The preparation method of the hydrophobic cellulose-chitosan high-barrier composite film comprises the following steps:
(1) adding an absolute ethyl alcohol solvent and carboxylated graphene with the carboxyl content of 3-5% into a reaction bottle, placing the reaction bottle in an ultrasonic treatment apparatus for ultrasonic dispersion, wherein the ultrasonic treatment apparatus comprises an ultrasonic device, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic probe is movably connected with an ultrasonic treatment chamber, a reaction bottle is arranged in the ultrasonic treatment chamber, grooves are arranged on two sides of the ultrasonic treatment chamber and movably connected with a fixture block, the fixture block is fixedly connected with a moving block, the moving block is movably connected with a spring, the spring is movably connected with a limiting block, then slowly dropwise adding thionyl chloride, the mass ratio of the thionyl chloride to the carboxylated graphene is 80-150:1, stirring and reacting at a constant speed of 50-70 ℃ for 4-10 hours, filtering the solution to remove the solvent, washing a solid product with absolute ethyl alcohol, and fully drying to prepare the acyl chlorinated graphene.
(2) Adding an absolute ethanol solvent and chitosan into a reaction bottle, slowly adding glacial acetic acid until the chitosan is dissolved, then adding acylchlorinated graphene, uniformly dispersing by ultrasonic wave, heating to 100 ℃ and 110 ℃, uniformly stirring for reaction for 24-48h, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the chitosan grafted graphene.
(3) Adding distilled water solvent and nano-cellulose into a reaction bottle, adding aqueous solution of sodium bromide and sodium hypochlorite and 2,2,6, 6-tetramethylpiperidine oxide after uniform ultrasonic dispersion, wherein the mass ratio of the four is 100:30-35:70-80:6-7, stirring at a constant speed at 20-30 ℃ for reaction for 2-6h, slowly adding sodium hydroxide during the reaction process, controlling the pH of the solution to 10, placing the solution in an ice water bath for cooling, adding ethanol solvent until a large amount of precipitate is separated out, filtering the solution to remove the solvent, and washing and dialyzing a solid product to prepare the carboxylated nano-cellulose.
(4) Adding a distilled water solvent and aldehyde nano-cellulose into a reaction bottle, uniformly dispersing by ultrasonic, adding octadecylamine, an activator diisopropylcarbodiimide and a catalyst N-hydroxysuccinimide in a mass ratio of 10:8.5-9.5:6-7:3.5-4, uniformly stirring at a constant speed at 20-30 ℃ for reaction for 20-30h, and centrifugally separating and washing the solution to prepare the long-chain alkylated hydrophobic nano-cellulose.
(5) Adding distilled water and cellulose into a reaction bottle, adding sodium periodate serving as an oxidant after uniform ultrasonic dispersion, heating to 40-60 ℃, uniformly stirring for reaction for 3-8 hours, filtering, washing and drying the solution to prepare the oxidized cellulose.
(6) Adding an acetic acid solution with the mass fraction of 2-4% into a reaction bottle, adding chitosan grafted graphene, oxidized cellulose and hydrophobic nano-cellulose, uniformly dispersing by ultrasonic, heating to 50-80 ℃, stirring at a constant speed for reaction for 4-10h, filtering, washing and drying the solution, placing the solid mixture into an ethanol solvent, uniformly dispersing by ultrasonic, stirring at a constant speed for 10-20h, pouring into a film-forming mold, naturally drying to form a film, and preparing to obtain the hydrophobic cellulose-chitosan high-barrier composite film.
Example 1
(1) Preparing an acylchlorinated graphene component 1: adding an absolute ethyl alcohol solvent and carboxylated graphene with the carboxyl content of 3% into a reaction bottle, placing the reaction bottle in an ultrasonic treatment apparatus for ultrasonic dispersion, wherein the ultrasonic treatment apparatus comprises an ultrasonic device, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic probe is movably connected with an ultrasonic treatment chamber, a reaction bottle is arranged in the ultrasonic treatment chamber, grooves are formed in two sides of the ultrasonic treatment chamber and movably connected with a clamping block, the clamping block is fixedly connected with a moving block, the moving block is movably connected with a spring, the spring is movably connected with a limiting block, thionyl chloride is slowly dripped into the reaction chamber, the mass ratio of the solution to the carboxylated graphene is 80:1, stirring and reacting the reaction solution at a constant speed of 50 ℃ for 4 hours, filtering the solution to remove the solvent, washing a solid product by using absolute ethyl alcohol and fully drying the solid product to prepare the component 1 of the acyl.
(2) Preparing a chitosan grafted graphene component 1: adding an absolute ethanol solvent and chitosan into a reaction bottle, slowly adding glacial acetic acid until the chitosan is dissolved, then adding the acylchlorinated graphene component 1, uniformly dispersing by ultrasonic, heating to 100 ℃, uniformly stirring for reaction for 24 hours, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the chitosan grafted graphene component 1.
(3) Preparation of carboxylated nanocellulose component 1: adding a distilled water solvent and nano-cellulose into a reaction bottle, uniformly dispersing by ultrasonic, adding an aqueous solution of sodium bromide and sodium hypochlorite and 2,2,6, 6-tetramethylpiperidine oxide in a mass ratio of 100:30:70:6, uniformly stirring at 20 ℃ for reaction for 2 hours, slowly adding sodium hydroxide in the reaction process, controlling the pH of the solution to be 10, placing the solution in an ice water bath for cooling, adding an ethanol solvent until a large amount of precipitate is separated out, filtering the solution to remove the solvent, and washing and dialyzing a solid product to prepare the carboxylated nano-cellulose component 1.
(4) Preparation of hydrophobic nanocellulose component 1: adding a distilled water solvent and an aldehyde nano-cellulose component 1 into a reaction bottle, uniformly dispersing by ultrasonic, adding octadecylamine, an activator namely diisopropylcarbodiimide and a catalyst namely N-hydroxysuccinimide in a mass ratio of 10:8.5:6:3.5, uniformly stirring at a constant speed at 20 ℃ for reaction for 20 hours, and centrifugally separating and washing the solution to prepare the long-chain alkylated hydrophobic nano-cellulose component 1.
(5) Preparation of oxidized cellulose component 1: adding distilled water and cellulose into a reaction bottle, adding sodium periodate serving as an oxidant after uniform ultrasonic dispersion, heating to 40 ℃, uniformly stirring for reaction for 3 hours, filtering, washing and drying the solution to obtain the oxidized cellulose component 1.
(6) Preparing a hydrophobic cellulose-chitosan high-barrier composite film material 1: adding an acetic acid solution with the mass fraction of 2% into a reaction bottle, adding a chitosan grafted graphene component 1, an oxidized cellulose component 1 and a hydrophobic nano-cellulose component 1 in a mass ratio of 5:50:100, heating to 50 ℃ after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 4 hours, filtering, washing and drying the solution, placing the solid mixture into an ethanol solvent, stirring at a constant speed for 10 hours after uniform ultrasonic dispersion, pouring into a film-forming mold, and naturally drying to form a film to prepare the hydrophobic cellulose-chitosan high-barrier composite film material 1.
Example 2
(1) Preparing an acylchlorinated graphene component 2: adding an absolute ethyl alcohol solvent and carboxylated graphene with the carboxyl content of 5% into a reaction bottle, placing the reaction bottle in an ultrasonic treatment apparatus for ultrasonic dispersion, wherein the ultrasonic treatment apparatus comprises an ultrasonic device, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic probe is movably connected with an ultrasonic treatment chamber, a reaction bottle is arranged in the ultrasonic treatment chamber, grooves are formed in two sides of the ultrasonic treatment chamber and movably connected with a clamping block, the clamping block is fixedly connected with a moving block, the moving block is movably connected with a spring, the spring is movably connected with a limiting block, thionyl chloride is slowly dripped into the reaction chamber, the mass ratio of the solution to the carboxylated graphene is 80:1, stirring and reacting the reaction solution at a constant speed of 50 ℃ for 4 hours, filtering the solution to remove the solvent, washing a solid product by using absolute ethyl alcohol and fully drying the solid product to prepare the acyl chlorinated graphene component 2.
(2) Preparing a chitosan grafted graphene component 2: adding an absolute ethanol solvent and chitosan into a reaction bottle, slowly adding glacial acetic acid until the chitosan is dissolved, then adding the acylchlorinated graphene component 2, uniformly dispersing by ultrasonic, heating to 100 ℃, uniformly stirring for reaction for 48 hours, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the chitosan grafted graphene component 2.
(3) Preparation of carboxylated nanocellulose component 2: adding a distilled water solvent and nano-cellulose into a reaction bottle, uniformly dispersing by ultrasonic, adding an aqueous solution of sodium bromide and sodium hypochlorite and 2,2,6, 6-tetramethylpiperidine oxide in a mass ratio of 100:31:72:6.2, uniformly stirring at 25 ℃ for reaction for 4 hours, slowly adding sodium hydroxide in the reaction process, controlling the pH of the solution to be 10, placing the solution in an ice water bath for cooling, adding an ethanol solvent until a large amount of precipitate is separated out, filtering the solution to remove the solvent, and washing and dialyzing a solid product to prepare the carboxylated nano-cellulose component 2.
(4) Preparation of hydrophobic nanocellulose component 2: adding a distilled water solvent and an aldehyde nano-cellulose component 2 into a reaction bottle, uniformly dispersing by ultrasonic, adding octadecylamine, an activator namely diisopropylcarbodiimide and a catalyst namely N-hydroxysuccinimide in a mass ratio of 10:8.8:6.3:3.6, uniformly stirring and reacting for 30 hours at 30 ℃, and centrifugally separating and washing the solution to prepare the long-chain alkylated hydrophobic nano-cellulose component 2.
(5) Preparation of oxidized cellulose component 2: adding distilled water and cellulose into a reaction bottle, adding sodium periodate serving as an oxidant after uniform ultrasonic dispersion, heating to 60 ℃, uniformly stirring for reaction for 3 hours, filtering, washing and drying the solution to obtain an oxidized cellulose component 2.
(6) Preparing a hydrophobic cellulose-chitosan high-barrier composite film material 2: adding an acetic acid solution with the mass fraction of 4% into a reaction bottle, adding the chitosan grafted graphene component 2, the oxidized cellulose component 2 and the hydrophobic nano-cellulose component 2 in a mass ratio of 10:65:100, heating to 80 ℃ after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 10 hours, filtering, washing and drying the solution, placing the solid mixture into an ethanol solvent, stirring at a constant speed for 20 hours after uniform ultrasonic dispersion, pouring into a film-forming mold, and naturally drying to form a film to prepare the hydrophobic cellulose-chitosan high-barrier composite film material 2.
Example 3
(1) Preparing an acylchlorinated graphene component 3: adding an absolute ethyl alcohol solvent and carboxylated graphene with the carboxyl content of 4% into a reaction bottle, placing the reaction bottle in an ultrasonic treatment apparatus for ultrasonic dispersion, wherein the ultrasonic treatment apparatus comprises an ultrasonic device, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic probe is movably connected with an ultrasonic treatment chamber, a reaction bottle is arranged in the ultrasonic treatment chamber, grooves are formed in two sides of the ultrasonic treatment chamber and movably connected with a clamping block, the clamping block is fixedly connected with a moving block, the moving block is movably connected with a spring, the spring is movably connected with a limiting block, thionyl chloride is slowly dripped into the reaction chamber, the mass ratio of the solution to the carboxylated graphene is 110:1, stirring and reacting the reaction solution at a constant speed for 8 hours at 60 ℃, filtering the solution to remove the solvent, washing a solid product by using absolute ethyl alcohol and fully drying the solid product to prepare the acyl chlorinated graphene component 3.
(2) Preparing a chitosan grafted graphene component 3: adding an absolute ethanol solvent and chitosan into a reaction bottle, slowly adding glacial acetic acid until the chitosan is dissolved, then adding the acylchlorinated graphene component 3, uniformly dispersing by ultrasonic, heating to 105 ℃, uniformly stirring for reaction for 36 hours, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the chitosan grafted graphene component 3.
(3) Preparation of carboxylated nanocellulose component 3: adding a distilled water solvent and nano-cellulose into a reaction bottle, uniformly dispersing by ultrasonic, adding an aqueous solution of sodium bromide and sodium hypochlorite and 2,2,6, 6-tetramethylpiperidine oxide in a mass ratio of 100:33:75:6.5, uniformly stirring at 25 ℃ for reaction for 4 hours, slowly adding sodium hydroxide in the reaction process, controlling the pH of the solution to be 10, placing the solution in an ice water bath for cooling, adding an ethanol solvent until a large amount of precipitate is separated out, filtering the solution to remove the solvent, and washing and dialyzing a solid product to prepare the carboxylated nano-cellulose component 3.
(4) Preparation of hydrophobic nanocellulose component 3: adding a distilled water solvent and an aldehyde nano-cellulose component 3 into a reaction bottle, uniformly dispersing by ultrasonic, adding octadecylamine, an activator namely diisopropylcarbodiimide and a catalyst namely N-hydroxysuccinimide in a mass ratio of 10:9:6.5:3.8, reacting for 25 hours at a constant speed at 25 ℃ by stirring, and centrifugally separating and washing the solution to prepare the long-chain alkylated hydrophobic nano-cellulose component 3.
(5) Preparation of oxidized cellulose component 3: adding distilled water and cellulose into a reaction bottle, adding sodium periodate serving as an oxidant after uniform ultrasonic dispersion, heating to 50 ℃, uniformly stirring for reaction for 5 hours, filtering, washing and drying the solution to obtain the oxidized cellulose component 3.
(6) Preparing a hydrophobic cellulose-chitosan high-barrier composite film material 3: adding an acetic acid solution with the mass fraction of 2% into a reaction bottle, adding a chitosan grafted graphene component 3, an oxidized cellulose component 3 and a hydrophobic nano-cellulose component 3 in a mass ratio of 20:90:100, heating to 80 ℃ after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 8 hours, filtering, washing and drying the solution, placing the solid mixture into an ethanol solvent, stirring at a constant speed for 15 hours after uniform ultrasonic dispersion, pouring into a film-forming mold, and naturally drying to form a film, thus preparing the hydrophobic cellulose-chitosan high-barrier composite film material 3.
Example 4
(1) Preparing an acylchlorinated graphene component 4: adding an absolute ethyl alcohol solvent and carboxylated graphene with the carboxyl content of 5% into a reaction bottle, placing the reaction bottle in an ultrasonic treatment apparatus for ultrasonic dispersion, wherein the ultrasonic treatment apparatus comprises an ultrasonic device, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic probe is movably connected with an ultrasonic treatment chamber, a reaction bottle is arranged in the ultrasonic treatment chamber, grooves are formed in two sides of the ultrasonic treatment chamber and movably connected with a clamping block, the clamping block is fixedly connected with a moving block, the moving block is movably connected with a spring, the spring is movably connected with a limiting block, thionyl chloride is slowly dripped, the mass ratio of the thionyl chloride to the carboxylated graphene is 135:1, stirring and reacting at a constant speed for 10 hours at 50 ℃, filtering the solution to remove the solvent, washing a solid product with absolute ethyl alcohol and fully drying to prepare an acylchlorinated graphene component 4.
(2) Preparing a chitosan grafted graphene component 4: adding an absolute ethanol solvent and chitosan into a reaction bottle, slowly adding glacial acetic acid until the chitosan is dissolved, then adding the acylchlorinated graphene component 4, uniformly dispersing by ultrasonic, heating to 10 ℃, uniformly stirring for reaction for 48 hours, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the chitosan grafted graphene component 4.
(3) Preparation of carboxylated nanocellulose component 4: adding a distilled water solvent and nano-cellulose into a reaction bottle, uniformly dispersing by ultrasonic, adding an aqueous solution of sodium bromide and sodium hypochlorite and 2,2,6, 6-tetramethylpiperidine oxide in a mass ratio of 100:34:78:6.7, uniformly stirring at 30 ℃ for reaction for 6 hours, slowly adding sodium hydroxide in the reaction process, controlling the pH of the solution to be 10, placing the solution in an ice water bath for cooling, adding an ethanol solvent until a large amount of precipitate is separated out, filtering the solution to remove the solvent, and washing and dialyzing a solid product to prepare the carboxylated nano-cellulose component 4.
(4) Preparation of hydrophobic nanocellulose component 4: adding a distilled water solvent and an aldehyde nano-cellulose component 4 into a reaction bottle, uniformly dispersing by ultrasonic, adding octadecylamine, an activator diisopropylcarbodiimide and a catalyst N-hydroxysuccinimide in a mass ratio of 10:9.4:6.7:3.9, uniformly stirring at 30 ℃ for reaction for 30 hours, and centrifugally separating and washing the solution to obtain the long-chain alkylated hydrophobic nano-cellulose component 4.
(5) Preparation of oxidized cellulose component 4: adding distilled water and cellulose into a reaction bottle, adding sodium periodate serving as an oxidant after uniform ultrasonic dispersion, heating to 50 ℃, uniformly stirring for reaction for 8 hours, filtering, washing and drying the solution to obtain an oxidized cellulose component 4.
(6) Preparing a hydrophobic cellulose-chitosan high-barrier composite film material 4: adding an acetic acid solution with the mass fraction of 4% into a reaction bottle, adding the chitosan grafted graphene component 4, the oxidized cellulose component 4 and the hydrophobic nano-cellulose component 4 in a mass ratio of 30:110:100, heating to 80 ℃ after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 10 hours, filtering, washing and drying the solution, placing the solid mixture into an ethanol solvent, stirring at a constant speed for 20 hours after uniform ultrasonic dispersion, pouring into a film-forming mold, and naturally drying to form a film, thus preparing the hydrophobic cellulose-chitosan high-barrier composite film material 4.
Example 5
(1) Preparing an acylchlorinated graphene component 5: adding an absolute ethyl alcohol solvent and carboxylated graphene with the carboxyl content of 5% into a reaction bottle, placing the reaction bottle in an ultrasonic treatment apparatus for ultrasonic dispersion, wherein the ultrasonic treatment apparatus comprises an ultrasonic device, an ultrasonic probe is fixedly connected below the ultrasonic device, the ultrasonic probe is movably connected with an ultrasonic treatment chamber, a reaction bottle is arranged in the ultrasonic treatment chamber, grooves are formed in two sides of the ultrasonic treatment chamber and movably connected with a clamping block, the clamping block is fixedly connected with a moving block, the moving block is movably connected with a spring, the spring is movably connected with a limiting block, thionyl chloride is slowly dripped, the mass ratio of the thionyl chloride to the carboxylated graphene is 150:1, stirring and reacting at a constant speed for 10 hours at 70 ℃, filtering the solution to remove the solvent, washing a solid product with absolute ethyl alcohol, and fully drying to prepare the acylchlorinated graphene component 5.
(2) Preparing a chitosan grafted graphene component 5: adding an absolute ethanol solvent and chitosan into a reaction bottle, slowly adding glacial acetic acid until the chitosan is dissolved, then adding the acylchlorinated graphene component 5, uniformly dispersing by using ultrasonic waves, heating to 110 ℃, uniformly stirring for reaction for 48 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the chitosan grafted graphene component 5.
(3) Preparation of carboxylated nanocellulose component 5: adding a distilled water solvent and nano-cellulose into a reaction bottle, uniformly dispersing by ultrasonic, adding an aqueous solution of sodium bromide and sodium hypochlorite and 2,2,6, 6-tetramethylpiperidine oxide in a mass ratio of 100:35:80:7, uniformly stirring at 30 ℃ for reaction for 6 hours, slowly adding sodium hydroxide in the reaction process, controlling the pH of the solution to be 10, placing the solution in an ice water bath for cooling, adding an ethanol solvent until a large amount of precipitate is separated out, filtering the solution to remove the solvent, and washing and dialyzing a solid product to prepare the carboxylated nano-cellulose component 5.
(4) Preparation of hydrophobic nanocellulose component 5: adding a distilled water solvent and an aldehyde nano-cellulose component 5 into a reaction bottle, uniformly dispersing by ultrasonic, adding octadecylamine, an activator diisopropylcarbodiimide and a catalyst N-hydroxysuccinimide in a mass ratio of 10:9.5:7:4, uniformly stirring at 30 ℃ for reaction for 30 hours, and centrifugally separating and washing the solution to prepare the long-chain alkylated hydrophobic nano-cellulose component 5.
(5) Preparation of oxidized cellulose component 5: adding distilled water and cellulose into a reaction bottle, adding sodium periodate serving as an oxidant after uniform ultrasonic dispersion, heating to 60 ℃, uniformly stirring for reaction for 8 hours, filtering, washing and drying the solution to obtain the oxidized cellulose component 5.
(6) Preparing a hydrophobic cellulose-chitosan high-barrier composite film material 5: adding an acetic acid solution with the mass fraction of 4% into a reaction bottle, adding a chitosan grafted graphene component 5, an oxidized cellulose component 5 and a hydrophobic nano-cellulose component 5 in a mass ratio of 40:120:100, heating to 80 ℃ after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 10 hours, filtering, washing and drying the solution, placing the solid mixture into an ethanol solvent, stirring at a constant speed for 20 hours after uniform ultrasonic dispersion, pouring into a film-forming mold, and naturally drying to form a film, thus preparing the hydrophobic cellulose-chitosan high-barrier composite film material 5.
The hydrophobic cellulose-chitosan high-barrier composite film materials of examples 1-5 were tested for water contact angle using a DSA-X Plus optical contact angle measuring instrument.
| Examples | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Water contact angle | 78.9° | 83.0° | 81.8° | 93.6° | 79.2° |
The hydrophobic cellulose-chitosan high barrier composite film materials of examples 1-5 were tested for oxygen barrier properties using an STG-V1 air permeability tester.
In summary, according to the hydrophobic cellulose-chitosan high-barrier composite film, thionyl chloride reacts with rich carboxyl groups on the surface of carboxylated graphene to obtain acylchlorinated graphene, acyl chloride groups perform substitution reaction with amino groups of chitosan to obtain chitosan grafted graphene, sodium periodate is used for oxidizing hydroxyl groups of cellulose into aldehyde groups, and Schiff base condensation reaction is performed with chitosan amino groups, so that graphene particles are organically combined with cellulose, the compatibility of graphene nano particles and cellulose is improved, the agglomeration phenomenon of graphene in the cellulose film is greatly reduced, graphene nanoparticles are uniformly dispersed in gaps of the cellulose film, a continuous and compact barrier layer is formed, and the oxygen barrier capability of the cellulose film is improved.
Activating carboxyl of the carboxylated nanocellulose by using an activating agent and a catalyst, performing condensation reaction with the amino of octadecylamine with strong hydrophobicity to obtain long-chain alkylated hydrophobic nanocellulose, and blending the long-chain alkylated hydrophobic nanocellulose with chitosan grafted graphene and oxidized cellulose to obtain the composite cellulose film, so that the contact angle of the cellulose film and water molecules is improved, the hydrophobic property of the film material is enhanced, and the phenomenon that the water molecules penetrate through the film is greatly reduced.
Claims (6)
1. A hydrophobic cellulose-chitosan high-barrier composite film comprises the following raw materials and components, and is characterized in that: the chitosan grafted graphene, the hydrophobic nano-cellulose and the oxidized cellulose are mixed according to the mass ratio of 5-40:50-120: 100.
2. The hydrophobic cellulose-chitosan high-barrier composite film according to claim 1, wherein: the preparation method of the hydrophobic cellulose-chitosan high-barrier composite film comprises the following steps:
(1) adding carboxylated graphene into an absolute ethyl alcohol solvent, placing the mixture into an ultrasonic dispersion treatment instrument for ultrasonic dispersion, dropwise adding thionyl chloride, reacting for 4-10 hours at 50-70 ℃, filtering, washing and drying to prepare the acyl chlorinated graphene;
(2) adding chitosan into an absolute ethyl alcohol solvent, adding glacial acetic acid until the chitosan is dissolved, adding acylchlorinated graphene, uniformly dispersing by ultrasonic, heating to the temperature of 100 ℃ and 110 ℃, reacting for 24-48h, filtering, washing and drying to prepare chitosan grafted graphene;
(3) adding nano-cellulose into a distilled water solvent, uniformly dispersing by ultrasonic, adding an aqueous solution of sodium bromide and sodium hypochlorite and 2,2,6, 6-tetramethylpiperidine oxide in a mass ratio of 100:30-35:70-80:6-7, reacting at 20-30 ℃ for 2-6h, slowly adding sodium hydroxide in the reaction process, controlling the pH of the solution to be 10, precipitating, filtering, washing and dialyzing to prepare carboxylated nano-cellulose;
(4) adding aldehyde nanocellulose into a distilled aqueous solvent, uniformly dispersing by ultrasonic, adding octadecylamine, an activator diisopropylcarbodiimide and a catalyst N-hydroxysuccinimide, reacting for 20-30h at 20-30 ℃, and performing centrifugal separation and washing to prepare long-chain alkylated hydrophobic nanocellulose;
(5) adding cellulose into a distilled water solvent, adding sodium periodate serving as an oxidant after uniform ultrasonic dispersion, heating to 40-60 ℃, reacting for 3-8h, filtering, washing and drying to prepare oxidized cellulose;
(6) adding chitosan grafted graphene, oxidized cellulose and hydrophobic nano-cellulose into an acetic acid solution with the mass fraction of 2-4%, uniformly dispersing by ultrasonic, heating to 50-80 ℃, reacting for 4-10h, filtering, washing and drying, placing the solid mixture into an ethanol solvent, uniformly stirring for 10-20h after uniformly dispersing by ultrasonic, pouring into a film-forming mold, naturally drying to form a film, and preparing the hydrophobic cellulose-chitosan high-barrier composite film.
3. The hydrophobic cellulose-chitosan high-barrier composite film according to claim 2, wherein: the ultrasonic branch treatment instrument comprises an ultrasonic device and an ultrasonic probe fixedly connected below the ultrasonic device, wherein the ultrasonic probe is movably connected with an ultrasonic treatment chamber, a reaction bottle is arranged in the ultrasonic treatment chamber, grooves are formed in two sides of the ultrasonic treatment chamber, the grooves are movably connected with a clamping block, the clamping block is fixedly connected with a moving block, the moving block is movably connected with a spring, and the spring is movably connected with a limiting block.
4. The hydrophobic cellulose-chitosan high-barrier composite film according to claim 2, wherein: the carboxyl content of the carboxylated graphene is 3-5%, and the mass ratio of the carboxylated graphene to the thionyl chloride is 1: 80-150.
5. The hydrophobic cellulose-chitosan high-barrier composite film according to claim 2, wherein: the mass fraction of the glacial acetic acid is more than or equal to 99.99 percent, and the water content is less than or equal to 0.01 percent.
6. The hydrophobic cellulose-chitosan high-barrier composite film according to claim 2, wherein: the mass ratio of the aldehyde nanocellulose, the octadecylamine, the diisopropylcarbodiimide and the N-hydroxysuccinimide is 10:8.5-9.5:6-7: 3.5-4.
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