CN109021473B - Highly transparent anti-ultraviolet nano cellulose composite film and preparation method thereof - Google Patents
Highly transparent anti-ultraviolet nano cellulose composite film and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
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- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
Abstract
The invention discloses a highly transparent ultraviolet-proof nano cellulose composite film and a preparation method thereof. The matrix of the composite membrane is polyvinyl alcohol, and the reinforcing phase is modified cellulose nanofiber. Firstly, preparing cellulose nano-fiber modified by 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil. And mixing the modified cellulose nano-fiber with a polyvinyl alcohol aqueous solution according to a certain mass ratio, and drying in an oven to obtain the uniform and transparent composite film. The raw materials in the application are derived from biomass, and have the advantages of biodegradability, good biocompatibility and the like. The invention overcomes the defect of poor stability of the micromolecule ultraviolet absorbent, and simultaneously, the epoxidized soybean oil can be used as a plasticizer to increase the flexibility of the composite membrane. The nano particles in the composite film are uniformly dispersed in the matrix, the composite film has high transparency and can provide a remarkable ultraviolet-proof effect, and the ultraviolet-proof effect can be regulated and controlled by controlling the addition amount of the nano particles in the film.
Description
Technical Field
The invention relates to a preparation technology of a biodegradable ultraviolet-proof film, in particular to a highly transparent ultraviolet-proof nano cellulose composite film and a preparation method thereof.
Background
The ultraviolet light mainly includes wavelengths classified into UVC (220 + 280nm), UVB (280 + 320nm) and UVA (320 + 400 nm). UVC is absorbed mainly by the ozone layer before reaching the ground, so its effect is negligible. However, radiation generated by uv can cause serious skin health problems and can activate chromophores in industrial coatings or packaging materials to promote photodegradation of polymers. Therefore, the ultraviolet ray protective material has received much attention, and tin foil and various papers are applied to the package to improve the light scattering ability, which also sacrifices the function and aesthetic sense of the commercial product. The manufacture of optically transparent and UV-shielding polymer composites by the addition of organic and inorganic UV absorbers is a good solution to this problem. Although most conventional organic UV absorbers exhibit good UV blocking properties, they give rise to lightDegradation, migration and aggregation. Inorganic metal oxide nanoparticles (e.g., TiO)2，ZnO，SiO2Ag and Al2O3) UV radiation may also be absorbed. However, possess an inherently wide band gap, rendering its uv absorption incomplete. On the other hand, inorganic nanoparticles always show a significant photocatalytic effect and can degrade polymers.
Currently, commonly used uv absorbers can be classified into: salicylate structure, acrylate structure, benzotriazole-like structure, or benzophenone structure. Benzophenone derivatives have been widely added to plastic packaging as UV blockers to prevent photodegradation of the packaging polymer or its contents. However, benzophenone derivatives are of interest as organic contaminants migrating into solid food matrices. In order to improve the safety of these low molecular weight UV absorbers, researchers have developed various polymeric UV absorbers, which are obtained by grafting or condensing a low molecular weight UV absorber onto a high molecular weight polymer, and the coupling of the UV filter to a high molecular weight polymer can significantly increase the stability thereof.
Recently, cellulose nanofibers with unique advantages have shown great potential in color coating applications due to their high stiffness and low density properties. In addition, the large number of hydroxyl groups on the nanocellulose fibers also facilitates their miscibility with hydrophilic polymers or surface modification of the nanocellulose fibers to improve compatibility with hydrophobic matrices. However, some of the prior surface modification methods have complicated steps and some reaction conditions are harsh. Therefore, it is very important to simplify the chemical surface modification experiment steps, optimize the modification conditions and meet the requirement of green chemistry.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide a highly transparent anti-ultraviolet nano cellulose composite film which is low in raw material price, simple in reaction operation, green and biodegradable in material and has a high-efficiency anti-ultraviolet function. The other purpose of the method is to provide a preparation method of the ultraviolet-proof nano cellulose composite membrane.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the highly transparent ultraviolet-proof nano cellulose composite film is characterized by being prepared by the following steps:
1) centrifuging and washing 0.1-1% cellulose nano-fiber water solution with ethanol and acetone for many times to remove water, and dispersing in dimethyl sulfoxide again;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 5-1: 1, the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1-10 under the condition of continuously introducing nitrogen, the reaction condition is 100-130 ℃, and the reaction time is 1-20 h;
3) after the reaction in the step 2), adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge; washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.1-1%;
4) dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in the solution under high speed stirring to obtain 1-10% polyvinyl alcohol aqueous solution; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1-10: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, and drying in an oven to obtain the highly transparent ultraviolet-proof nano cellulose composite membrane.
In the step 1), the cellulose nano-fiber aqueous solution is 0.1-1% by mass.
In the step 2), the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 5-1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 10-1.
In the step 2), the reaction is carried out under the condition of 100-130 ℃ and the reaction time of 1-20 h, and the nitrogen is continuously introduced.
In the step 3), the mass percentage concentration of the modified cellulose nanofiber aqueous solution is 0.1-1%.
In the step 1 and the step 3), the centrifugation is performed by a desktop centrifuge at the centrifugation rotating speed of 12500 r/min.
In the step 4), the polyvinyl alcohol is 1788 type, and the alcoholysis degree is 87% -89%.
In the step 4), the mass ratio of the modified cellulose nano-fiber to the polyvinyl alcohol in the mixed solution is 1-10: 100, and the concentration of the polyvinyl alcohol aqueous solution is 1-10%.
A method for preparing the highly transparent ultraviolet-proof nano cellulose composite film comprises the following steps:
1) dispersing cellulose nanofibers in dimethyl sulfoxide;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into a cellulose nano-fiber dimethyl sulfoxide solution, wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 5-1: 1, the mass ratio of the cellulose nano-fiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1-10, continuously introducing nitrogen, controlling the temperature to be 100-130 ℃, and reacting for 1-20 h; obtaining a modified cellulose nanofiber mixed solution;
3) adding acetone into the reacted mixture obtained in the step 2), stirring at a high speed, and then centrifuging; washing redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone; dispersing the obtained lower layer precipitate in water again to obtain 0.1-1% modified cellulose nano-fiber aqueous solution;
4) mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a 1% -10% polyvinyl alcohol aqueous solution, and carrying out closed ultrasonic dispersion on the mixed solution in ice water for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, and drying in an oven to obtain the highly transparent ultraviolet-proof nano cellulose composite membrane.
In the step 3), the mass ratio of the modified nano-cellulose to the polyvinyl alcohol is 1-10: 100.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
1) the invention has the characteristics of degradability, high transparency, ultraviolet resistance, excellent mechanical property, mild reaction condition and the like.
2) The related cellulose nanofiber modification method is simple and has strong controllability. From the scanning electron microscope photograph, it can be seen that the modified cellulose nanofibers are uniformly dispersed in the polyvinyl alcohol, and the size is in the nanometer level.
3) Compared with the existing material preparation method, the preparation method of the composite ultraviolet-proof material has the advantages of high efficiency, low cost and easy industrialization.
4) The composite material can be used as a novel packaging material to replace the plastic which is widely used at present, and solves the problems of environmental pollution and safety brought by petrochemical industry. The service life of the ultraviolet sensitive material can be prolonged, the aesthetic feeling is increased, and great economic and social benefits are achieved.
5) Ultraviolet absorption detection proves that the ultraviolet absorption stability is strong, high-efficiency ultraviolet absorption can be realized at low dose, and the practicability is good.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of cellulose nanofibers and modified cellulose nanofibers;
FIG. 2 is a scanning electron micrograph of a modified cellulose nanofiber-polyvinyl alcohol composite film;
FIG. 3 is an ultraviolet transmission spectrum of the modified cellulose nanofiber-polyvinyl alcohol composite membrane;
fig. 4 is an ultraviolet absorption spectrum of the modified cellulose nanofiber-polyvinyl alcohol composite membrane.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.1% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.1%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 1 h; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.1%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 2
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.25% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.25%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 1 h; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.25%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 3
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 1 h; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 4
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 1% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 1%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 1 h; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 1%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 5
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 5 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 6
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 10 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 7
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 15 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 8
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 20 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 9
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 100 ℃, and reacting for 20 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 10
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 110 ℃, and reacting for 20 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 11
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 130 ℃, and reacting for 20 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 12
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 20 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 5: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 5: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane.
Example 13
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 20 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 10: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 10: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 1: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane marked as 1% BE-CNF/PVA.
Example 14
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 20 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 5: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 5: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 5: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane marked as 5% BE-CNF/PVA.
Example 15
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 20 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 5: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 5: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 8: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet nano cellulose composite membrane.
Example 16
A highly transparent anti-ultraviolet nano cellulose composite film is prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber aqueous solution with the mass percentage concentration of 0.5% for many times by using ethanol and acetone to remove water, and dispersing the cellulose nano-fiber aqueous solution in dimethyl sulfoxide again, wherein the mass percentage concentration is 0.5%;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1), continuously introducing nitrogen, controlling the temperature to be 120 ℃, and reacting for 20 hours; wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 5: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 5: 1;
3) and 2) after the reaction is finished, adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging at a high speed of 12500r/min by using a desktop centrifuge. Washing away redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone, taking the lower layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution with the mass percentage concentration of 0.5%;
4) stirring and dissolving 1788 type polyvinyl alcohol with alcoholysis degree of 87% -89% in water at high speed to obtain a polyvinyl alcohol aqueous solution with concentration of 1%; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, wherein the mass ratio of the modified cellulose nanofiber to the polyvinyl alcohol in the mixed solution is 10: 100, and the mixed solution is subjected to closed ultrasonic dispersion in ice water for 100W for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, drying in an oven at 60 ℃ for 12 hours to obtain the highly transparent anti-ultraviolet cellulose nanofiber composite membrane marked as 10% BE-CNF/PVA.
As shown in FIG. 1, the chemical structure of the cellulose nanofibers modified with the coupling solution was measured by infrared, and compared with the infrared pattern of unmodified cellulose nanofibers, both patterns had the presence of hydroxyl groups (at 3450 cm)-1Single peak of (d), there is also C-H stretching vibration (at 2895 cm)-1Monomodal) of cellulose (at 1165 cm)-1Band of (C), C-O stretching movement (at 1118 cm)-1Monomodal) of ethers, C-O-C characteristic of the ethers (at 1061 cm)-1A single peak at (g) and beta-glucose at 897cm-1Characteristic band of (1).
After the cellulose was chemically modified with benzophenone and epoxidized soybean oil, 1601cm-1A new band appears because of the newly appearing C ═ O. It is a characteristic group of the ester formed by the reaction of-OH of cellulose and-COOH of the coupling solution. At 1150, 1240cm-1Bands associated with oils derived from epoxidized soybeans are shown, demonstrating the success of cellulose modification. In addition, 1750cm-1The peak appeared here is the C ═ O stretching vibration peak of epoxidized soybean oil itself.
As can be seen from fig. 2, the polyvinyl alcohol as the matrix material is in a smooth and uniform state, and the modified cellulose is uniformly distributed in the composite film.
The transparency of the composite film is obtained by measuring the transmittance through an ultraviolet detector, and as can be seen from fig. 3, the transparency of the composite film is not obviously affected by the addition of the modified cellulose and is still maintained above 90%.
The ultraviolet absorption measurement shows that as the proportion of the modified cellulose nanofibers is increased, the ultraviolet absorption strength of the composite membrane is increased. The modified cellulose is added into the composite membrane, so that the composite membrane has three obvious absorption peaks in an ultraviolet light wave band, and the success of cellulose modification is proved at the same time. Therefore, the substitution degree of the cellulose is increased by methods such as optimizing reaction conditions and the like, the number of substituent groups on the modified cellulose is increased, and the ultraviolet absorption strength is further increased; the ultraviolet resistance of the composite film can also be changed by adjusting the addition of the modified cellulose.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (8)
1. The highly transparent ultraviolet-proof nano cellulose composite film is characterized by being prepared by the following steps:
1) centrifuging and washing the cellulose nano-fiber water solution with ethanol and acetone for multiple times to remove water, and dispersing in dimethyl sulfoxide again;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into the product obtained in the step 1) to react; the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 5-1: 1, and the mass ratio of the cellulose nanofiber to the 2-hydroxy-4-methoxybenzophenone is 1: 10-1; the reaction temperature is 100-130 ℃, the reaction time is 1-20 h, and the reaction is carried out under the condition of continuously introducing nitrogen;
3) after the reaction in the step 2), adding acetone into the reacted mixture, stirring at a high speed, and then centrifuging; washing unreacted 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil with acetone, taking the lower-layer precipitate, and dispersing in water again to obtain a modified cellulose nanofiber aqueous solution;
4) stirring polyvinyl alcohol at a high speed and dissolving in water to obtain a polyvinyl alcohol aqueous solution; mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a polyvinyl alcohol aqueous solution, and carrying out closed ultrasonic dispersion on the mixed solution in an ice water bath;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, and drying in an oven to obtain the highly transparent ultraviolet-proof nano cellulose composite membrane.
2. The highly transparent ultraviolet-proof nano-cellulose composite film according to claim 1, wherein in the step 1), the cellulose nano-fiber aqueous solution is 0.1-1% by mass.
3. The highly transparent ultraviolet-proof nano-cellulose composite film according to claim 1, wherein in the step 3), the modified cellulose nano-fiber aqueous solution has a mass percentage concentration of 0.1% -1%.
4. The highly transparent ultraviolet-proof nano-cellulose composite membrane according to claim 1, wherein in step 1) and step 3), the centrifugation is performed by a desktop centrifuge at a centrifugation speed of 12500 r/min.
5. The highly transparent ultraviolet-proof nano-cellulose composite film according to claim 1, wherein in the step 4), the polyvinyl alcohol is 1788 type, and the alcoholysis degree is 87% -89%.
6. The highly transparent ultraviolet-proof nano-cellulose composite film according to claim 1, wherein in the step 4), the mass ratio of the modified cellulose nano-fibers to the polyvinyl alcohol in the mixed solution is 1-10: 100, and the concentration of the polyvinyl alcohol aqueous solution is 1-10%.
7. A method for preparing the highly transparent uv-blocking nanocellulose composite membrane of claim 1, characterized by comprising the steps of:
1) dispersing cellulose nanofibers in dimethyl sulfoxide;
2) adding 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil into a cellulose nano-fiber dimethyl sulfoxide solution, wherein the mass ratio of the 2-hydroxy-4-methoxybenzophenone to the epoxidized soybean oil is 5-1: 1, the mass ratio of the cellulose nano-fiber to the 2-hydroxy-4-methoxybenzophenone is 1: 1-10, continuously introducing nitrogen, controlling the temperature to be 100-130 ℃, and reacting for 1-20 h; obtaining a modified cellulose nanofiber mixed solution;
3) adding acetone into the reacted mixture obtained in the step 2), stirring at a high speed, and then centrifuging; washing redundant 2-hydroxy-4-methoxybenzophenone and epoxidized soybean oil by using acetone; dispersing the obtained lower layer precipitate in water again to obtain 0.1-1% modified cellulose nano-fiber aqueous solution;
4) mixing the modified cellulose nanofiber aqueous solution obtained in the step 3) with a 1% -10% polyvinyl alcohol aqueous solution, and carrying out closed ultrasonic dispersion on the mixed solution in ice water for 0.5 h;
5) pouring the mixed solution obtained in the step 4) into an ultra-flat culture dish, and drying in an oven to obtain the highly transparent ultraviolet-proof nano cellulose composite membrane.
8. The method for preparing a highly transparent UV-proof nano-cellulose composite film according to claim 7, wherein in step 4), the mass ratio of the modified nano-cellulose to the polyvinyl alcohol is 1-10: 100.
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