CN113956541B - Cellulose/graphene oxide composite film - Google Patents
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- CN113956541B CN113956541B CN202110869456.1A CN202110869456A CN113956541B CN 113956541 B CN113956541 B CN 113956541B CN 202110869456 A CN202110869456 A CN 202110869456A CN 113956541 B CN113956541 B CN 113956541B
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Abstract
The invention discloses a cellulose/graphene oxide composite membrane. The composite membrane is prepared by blending cellulose solution dissolved in organic alkali and graphene oxide dispersion liquid dissolved in organic solvent, and then vacuum drying, coagulation bath adding and hot press drying. According to the invention, cellulose is dissolved in organic alkali, graphene oxide is dissolved in an organic solvent, and then the cellulose solution and the graphene oxide dispersion liquid are mixed, so that the agglomeration phenomenon is effectively prevented, and meanwhile, the graphene oxide is added into the cellulose with high polymerization degree. Compared with a pure regenerated cellulose film, the cellulose/graphene oxide composite film has higher mechanical property and thermal stability, and the permeability coefficient of the composite film is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of polymer films, and particularly relates to a cellulose/graphene oxide composite film.
Background
In recent years, the use of petroleum-based products has been increasing year by year with the development of society. On the one hand, fossil resources face the phenomenon of exhaustion because of their non-renewable nature. Meanwhile, a large number of petroleum-based products are undegradable and carbon-emission, so that serious pollution is caused, and great influence is brought to the ocean and global ecological systems. Therefore, finding a green renewable natural polymer is a well-established research goal. Cellulose, because of its wide source (e.g., it can be extracted from higher plants, marine organisms), high accumulation, low cost, renewable and degradable properties, is considered to be one of the ideal candidates for replacing petroleum-based films. However, cellulose is difficult to directly use because of indissolvable and infusible unique hydrogen bond network, and is usually treated by searching a proper dissolution system and then is operated.
The more mature dissolution systems in the prior art are as follows: firstly, the traditional NMMO (N-methylmorpholine-N-oxide) and DMAc (dimethylamide)/LiCl dissolution system, secondly, the alkali/urea dissolution system proposed by the university of Wuhan, zhang Lina, and secondly, the ionic liquid of the 1-allyl-3-methylimidazole (BMIMCl) series created by the army of the university of Chinese academy of chemistry. Efficient dissolution of cellulose can be achieved in all of the dissolution systems mentioned above. After the dissolution of cellulose is completed, the cellulose is gelled by a coagulating bath and dried to obtain a cellulose regenerated film. However, the cellulose film after dissolution and regeneration has larger general aperture, higher oxygen transmittance and relatively lower mechanical property, thereby severely limiting the application of the cellulose film on packaging materials.
Therefore, the improvement of the mechanical property of the regenerated cellulose film and the increase of the gas barrier property are key points for breaking the application limit of the regenerated cellulose film, and are also great challenges for research and development, and have important significance for realizing the practical application of the regenerated cellulose film. In the current method for improving the gas barrier property, the preparation of the nano composite film by solution blending is simple and quick to operate, has relatively low cost, and can be applied to the method of industrial production.
Disclosure of Invention
The invention aims to provide a cellulose/graphene oxide composite film with good integrity, good mechanical property, good thermal stability and high barrier property, aiming at the defects of low mechanical property, high oxygen transmittance and the like of the existing pure regenerated cellulose film.
In order to achieve the above object, the technical scheme of the present application is as follows: the cellulose/graphene oxide composite film is prepared by blending a cellulose solution dissolved in organic alkali and a graphene oxide dispersion liquid dissolved in an organic solvent, and then performing vacuum drying, coagulation bath adding and hot press drying.
Cellulose is a natural polymer structure containing polyhydroxy groups, and the internal hydrogen bond network formed in the cellulose divides the cellulose into a crystalline region and an amorphous region, so that the cellulose is difficult to dissolve in a conventional solvent. Generally, cellulose can form a large number of free hydroxyl structures after being dissolved, and after graphene oxide is added, strong intermolecular action can be formed between the cellulose and the free hydroxyl structures, so that the graphene oxide is difficult to disperse in a cellulose matrix, agglomeration phenomenon occurs, and the performance of the composite film is greatly reduced.
According to the invention, the cellulose solution dissolved in organic alkali is selected, the interactive hydrogen bond network is firstly opened, the hydroxyl polar group is converted into the soluble ester, and cellulose dissolution is realized, and simultaneously, cellulose molecular chains can be effectively prevented from being recrystallized in a solvent. Then blending the material with the two-dimensional lamellar nano material graphene oxide, and recovering the derivatized group into hydroxyl again. The oxygen-containing functional groups such as carboxyl, epoxy and the like of the graphene oxide can form better intermolecular action with hydroxyl on cellulose, so that the binding force between the oxygen-containing functional groups and the hydroxyl on cellulose is enhanced, the mechanical property of the composite membrane is enhanced, and meanwhile, the barrier property of the composite membrane is improved due to the extension of a permeation path. According to the invention, cellulose is dissolved in organic alkali, graphene oxide is dissolved in an organic solvent, and then the cellulose solution and the graphene oxide dispersion liquid are mixed, so that the agglomeration phenomenon is effectively prevented, and meanwhile, the graphene oxide is added into the cellulose with high polymerization degree.
The graphene oxide is ultrasonically dispersed in the organic solvent, so that uneven dispersion of the graphene oxide caused by gelation of cellulose in the compounding process can be effectively prevented. Meanwhile, the highly-stripped graphene oxide and cellulose have strong hydrogen bond action, so that the graphene oxide and the cellulose are firmly combined together, and uniform and stable dispersion of the graphene oxide in a cellulose hydrogen bond network is realized.
The method adopts a method of combining vacuum drying and coagulation bath deposition. The cellulose composite membrane obtained by vacuum drying and regeneration can better retain the crystal form structure of the original cellulose, thereby maintaining the good mechanical property of the composite membrane. Second, the use of deionized water as a coagulation bath may be more effective in removing residual solvent. The method is environment-friendly, convenient and feasible.
In the cellulose/graphene oxide composite film, the mass percentage of cellulose in the cellulose solution is 2-5wt% of the total mass of the cellulose solution.
In the cellulose/graphene oxide composite film, the mass concentration of graphene oxide in the graphene oxide dispersion liquid is 0.1-10 mg -1 。
In the cellulose/graphene oxide composite film, the mass ratio of the cellulose solution to the graphene oxide dispersion liquid is 100: (2-40).
In the cellulose/graphene oxide composite film, the organic base is a nitrogen-containing heterocyclic organic base.
Preferably, the organic base is any one or two of 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN) and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU).
In the cellulose/graphene oxide composite film, the organic solvent is one or more of ethanol, propanol, acetone, dimethyl sulfoxide, ethylene glycol, dimethyl acrylamide, chloroform, dichloromethane, ethyl acetate and tetrahydrofuran. Preferably, the organic solvent is one or more of ethanol, propanol, acetone and dimethyl sulfoxide. Further preferably, the organic solvent is dimethyl sulfoxide, and the use of dimethyl sulfoxide can ensure that the formed graphene oxide dispersion liquid is directly separated out without gelation in the process of compounding with the cellulose solution.
In the cellulose/graphene oxide composite membrane, the cellulose is one or two of plant cellulose and bacterial cellulose. Preferably, the cellulose is corncob plant cellulose, which can provide a regenerated cellulose matrix film with high polymerization degree in the preparation process.
In the cellulose/graphene oxide composite film, the mass percentage of graphene oxide in the composite film is 0.1-20%.
In the cellulose/graphene oxide composite membrane, the permeability coefficient of the composite membrane is more than 1.68X10 -15 cm 3 cm•cm - 2 s -1 Pa -1 。
In the cellulose/graphene oxide composite membrane, the cellulose solution is prepared by adding cellulose into organic alkali, introducing gas, and heating and stirring.
Preferably, the gas is O 2 、N 2 、CO 2 Any one of the following. Further preferably, the gas is CO 2 。
Preferably, the pressure of heating and stirring is 0.1-2MPa, the temperature is 30-100 ℃, and the time is 0.5-3 h. Preferably, the pressure of heating and stirring is 0.2-0.6MPa, the temperature is 40-60 ℃, and the time is 0.5-2 h.
In the cellulose/graphene oxide composite film, the vacuum drying temperature is 0-120 ℃, and the vacuum drying time is 0.5-48 h. Preferably, the temperature of the vacuum drying is 50-80 ℃, and the vacuum drying time is 3-8h. Further preferably, the temperature of the vacuum drying is 60 ℃, and the vacuum drying time is 6 hours. The drying treatment is carried out at the temperature and time of the vacuum drying, so that the integrity of the composite film can be ensured at a proper temperature in a short time, and the crystal form structure similar to that of the native cellulose can be retained to the greatest extent after the vacuum drying.
In the cellulose/graphene oxide composite film, the coagulating bath is one or more solvents selected from water, ethanol, methanol and acetone. Preferably, the coagulation bath is water. Pure water is directly used as a coagulating bath, so that the method has the advantages of environmental protection and low cost, and finally, the residual solvent in the composite film can be completely removed.
Compared with the prior art, the invention has the following advantages:
(1) The cellulose/graphene oxide composite film can be loaded with high-content graphene oxide, the tensile strength of the composite film can reach 83.2MPa, and compared with a pure regenerated cellulose film, the mechanical property of the composite film is obviously improved;
(2) Compared with a pure regenerated cellulose film, the cellulose/graphene oxide composite film has the advantages that the thermal stability is gradually improved along with the increase of the content of graphene oxide, wherein the highest thermal decomposition temperature is 274 ℃, and the thermal stability is obviously improved;
(3) According to the invention, cellulose is firstly dissolved in organic alkali, graphene oxide is dissolved in an organic solvent, and then a cellulose solution and graphene oxide dispersion liquid are mixed, so that the interfacial energy between the cellulose solution and the graphene oxide dispersion liquid is effectively reduced, and a cross-sectional morphology with obvious alternate microlayer layers is constructed through strong interaction between oxygen-containing groups of the graphene oxide and a large number of hydroxyl groups on the cellulose, and the permeability coefficient of a cellulose/graphene oxide composite membrane is obviously reduced compared with that of pure regenerated cellulose, wherein the minimum permeability is 1.8x10 -15 cm 3 cm·cm -2 s -1 Pa -1 。
Drawings
Fig. 1 is a digital photograph of a cellulose solution and a cellulose/graphene oxide composite solution in example 1 of the present invention.
Fig. 2 is a digital photograph of a cellulose regenerated cellulose film of comparative example 1 and cellulose/graphene oxide composite films of examples 1, 3, and 4 according to the present invention.
Fig. 3 is a cross-sectional scanning electron microscope image of the cellulose/graphene oxide composite film according to example 1, example 3, and example 4 of the present invention.
Fig. 4 is a graph showing comparison of gas permeation coefficients of the cellulose regenerated cellulose film of comparative example 1 and the cellulose/graphene oxide composite films of examples 1, 3 and 4 according to the present invention.
Description of the embodiments
Example 1
Pre-dispersing graphene oxide in ethanol, and performing ultrasonic treatment for 0.5h to obtain the mass concentration of 3mg.g -1 Is a graphene oxide dispersion liquid.
The corncob cellulose was added to 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), and carbon dioxide gas was introduced thereto, followed by heating and stirring to obtain a cellulose solution having a concentration of 2 wt%.
Taking 0.83g of graphene oxide dispersion liquid, slowly adding the graphene oxide dispersion liquid into 25g of cellulose solution under the stirring condition, sealing a beaker by using a preservative film after the graphene oxide dispersion liquid is completely added, stirring the graphene oxide dispersion liquid at room temperature for about 60min, and continuing to carry out ultrasonic treatment for 2h. Pouring the mixture on tin plate with clean and tidy surface, then placing a sample into a vacuum oven, and vacuum drying at 80 ℃ for 8 hours to obtain a regenerated cellulose/graphene oxide composite film, and after the vacuum stage is finished, completely immersing the preliminarily formed regenerated cellulose/graphene oxide composite film into deionized water for about 5 hours, so as to ensure that the solvent in the cellulose can be removed after exchange. And finally, placing the regenerated cellulose membrane exchanged by deionized water into two glass plates by adopting a hot-pressing method, and drying to obtain the cellulose/graphene oxide composite membrane marked with RC/1GO, wherein the mass fraction of the graphene oxide is 1%. The obtained composite film had a tensile strength of 52.3MPa, a thermal decomposition temperature of 232℃and a permeability coefficient of 4.3X10 -14 cm 3 cm·cm -2 s -1 Pa -1 。
The digital photographs of the cellulose solution and the cellulose/graphene oxide composite solution prepared in the embodiment are shown in fig. 1, the cellulose solution on the left side of the photograph shows transparent, and the clear solution indicates that the cellulose is completely dissolved. After graphene oxide is added, the color of the composite liquid becomes dark black and uniform dispersion liquid, and no obvious gel precipitation and agglomeration exist as shown on the right side.
Example 2
The only difference from example 1 is that 3.33g of graphene oxide dispersion was blended with the cellulose solution in this example. The cellulose/graphene oxide composite membrane in this example is labeled RC/2GO, where the graphene oxide mass fraction is 2%. The obtained composite film had a tensile strength of 54.5MPa, a thermal decomposition temperature of 244℃and a permeability coefficient of 2.9X10 -14 cm 3 cm·cm -2 s -1 Pa -1 。
Example 3
The only difference from example 1 is that in this example 5g of graphene oxide dispersion was blended with the cellulose solution. Fibers in this embodimentThe element/graphene oxide composite film is marked as RC/3GO, wherein the mass fraction of the graphene oxide is 3%. The obtained composite film had a tensile strength of 59.4MPa, a thermal decomposition temperature of 256℃and a permeability coefficient of 1.6X10 -14 cm 3 cm·cm -2 s - 1 Pa -1 。
Example 4
The only difference from example 1 is that 8.33g of graphene oxide dispersion was blended with the cellulose solution in this example. The cellulose/graphene oxide composite membrane in this example is labeled RC/5GO, with a graphene oxide mass fraction of 5%. The obtained composite film had a tensile strength of 83.2MPa, a thermal decomposition temperature of 274℃and a permeability coefficient of 1.8X10 -15 cm 3 cm·cm -2 s -1 Pa -1 。
Example 5
The difference from example 1 is only that the mass concentration of the graphene oxide dispersion in this example is 1mg.g -1 . The obtained composite film had a tensile strength of 41.5MPa, a thermal decomposition temperature of 230℃and a permeability coefficient of 4.8X10 -14 cm 3 cm·cm -2 s - 1 Pa -1 。
Example 6
The difference from example 1 is only that the mass concentration of the graphene oxide dispersion in this example is 5mg -1 . The obtained composite film had a tensile strength of 82.1MPa, a thermal decomposition temperature of 278℃and a permeability coefficient of 1.4X10 -15 cm 3 cm·cm -2 s - 1 Pa -1 。
Example 7
The only difference from example 1 is that the mass percentage of cellulose in the cellulose solution in this example is 5wt%. The obtained composite film had a tensile strength of 51.9MPa, a thermal decomposition temperature of 242℃and a permeability coefficient of 2.3X10 -14 cm 3 cm·cm - 2 s -1 Pa -1 。
Example 8
The only difference from example 1 is that the mass percentage of cellulose in the cellulose solution in this example is 3wt%. Drawing of the resulting composite filmThe tensile strength is 54.5MPa, the thermal decomposition temperature is 244 ℃, and the permeability coefficient is 2.9X10 -14 cm 3 cm·cm - 2 s -1 Pa -1 。
Comparative example 1
That is, in example 1, corncob cellulose was added to 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), and carbon dioxide gas was introduced and then heated and stirred to prepare a cellulose solution (RC) having a concentration of 2 wt%.
Digital photographs of the regenerated cellulose thin films or cellulose/graphene oxide composite films prepared in comparative example 1, example 3 and example 4 are shown in fig. 2. According to the graph, the regenerated cellulose film is characterized by high transparency in the whole position, and in the cellulose/graphene oxide composite film provided by the embodiment of the invention, black graphene oxide is successfully dispersed into a cellulose matrix, and the composite film has good flexibility and a relatively smooth surface.
The regenerated cellulose thin films or cellulose/graphene oxide composite films produced in example 1, example 3 and example 4 were subjected to a cross-sectional electron microscopic scan test, and the results are shown in fig. 3. According to the graph, as the content of graphene oxide increases, the cross section of the cellulose/graphene oxide composite film has obvious ravines and gradually increases, a lamellar structure with alternately arranged microlayers is displayed, and the unique structure is formed so as to be very beneficial to the improvement of gas barrier property.
The regenerated cellulose thin films or cellulose/graphene oxide composite films prepared in comparative example 1, example 3 and example 4 were subjected to oxygen permeation experiments, and the results are shown in fig. 4. As can be seen from the figure, as the content of graphene oxide increases, the barrier ability of the composite film to gas increases, and thus it is known that the performance of the composite film is indeed improved.
In summary, the cellulose is dissolved in the organic alkali, the graphene oxide is dissolved in the organic solvent, and then the cellulose solution and the graphene oxide dispersion are mixed, so that the agglomeration phenomenon is effectively prevented, and meanwhile, the graphene oxide is added to the cellulose with high polymerization degree. Compared with a pure regenerated cellulose film, the cellulose/graphene oxide composite film has higher mechanical property and thermal stability, and the permeability coefficient of the composite film is greatly reduced.
The above description of the embodiments of the invention is not intended to limit the invention, but rather, it is to be understood that the invention is capable of numerous modifications and variations in accordance with the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. The cellulose/graphene oxide composite membrane is characterized by being prepared by the following steps: adding corncob cellulose to 1, 5-diazabicyclo [4.3.0]Introducing carbon dioxide gas into the non-5-alkene, heating and stirring to obtain cellulose solution with the concentration of 2 wt%; pre-dispersing graphene oxide in ethanol, and performing ultrasonic treatment for 0.5h to obtain a graphene oxide solution with a mass concentration of 5mg -1 Is a graphene oxide dispersion liquid; taking 0.83g of graphene oxide dispersion liquid, slowly adding 25g of cellulose solution under the stirring condition, sealing a beaker with a preservative film, stirring at room temperature for 60min, continuing to carry out ultrasonic treatment for 2h, pouring the solution on tin plate, then placing the tin plate into a vacuum oven, vacuum drying the solution at 80 ℃ for 8h to prepare a regenerated cellulose/graphene oxide composite film, immersing the preliminarily formed regenerated cellulose/graphene oxide composite film into deionized water for 5h after the vacuum stage is finished, and finally carrying out hot press drying.
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