CN107586395B - Cellulose-potassium titanate composite membrane, preparation method and application thereof - Google Patents
Cellulose-potassium titanate composite membrane, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cellulose-potassium titanate composite membrane, a preparation method and application thereof, and relates to the technical field of natural high polymer materials. The preparation method of the cellulose-potassium titanate composite membrane comprises the following steps: mixing an alkaline solution and potassium titanate, then carrying out pre-cooling treatment to obtain a mixed solution, and mixing the mixed solution and cellulose to obtain a cellulose-potassium titanate mixed solution, wherein the alkaline solution is a urea alkaline solution or a thiourea alkaline solution; regenerating the cellulose-potassium titanate mixed solution in the solidification solution to obtain the cellulose-potassium titanate composite hydrogel, and drying. The preparation method has simple and easy operation, high process stability, no toxicity and no pollution. The prepared cellulose-potassium titanate composite film has the tensile strength of more than or equal to 106.5MPa, has good mechanical property, light transmittance and biodegradability, and can be applied to the preparation of packaging materials or electrode materials of capacitors.
Description
Technical Field
The invention relates to the technical field of natural polymer materials, and particularly relates to a cellulose-potassium titanate composite film, and a preparation method and application thereof.
Background
Since the widely used plastic bags and packaging film materials have the problem of non-degradability, causing great harm to the environment, the european union is considering to prohibit the use of non-degradable plastic bags in the european union range in an all-round manner to prevent the ecological environment from further deteriorating. Meanwhile, the energy and sustainable development problems have been gradually attracted, and the research on renewable resources has been listed as one of 24 international leading fields, in which natural polymers with biodegradability have become a research hotspot, governments, research institutions and entrepreneurs have focused on the research and development of related materials, and have accelerated the industrial development of products.
However, the conventional biodegradable natural polymer materials have problems of high production cost and poor toughness and strength of the materials.
Disclosure of Invention
The invention aims to provide a preparation method of a cellulose-potassium titanate composite membrane, which is simple to operate, stable in process and easy for industrial application.
Another object of the present invention is to provide a novel cellulose-potassium titanate nanocomposite film having excellent mechanical properties and having both excellent light transmittance and biodegradability.
The third purpose of the invention is to provide the application of the cellulose-potassium titanate composite film, so that the cellulose-potassium titanate composite film with excellent mechanical property, light transmittance and biodegradability can be widely applied.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of a cellulose-potassium titanate composite film, which comprises the following steps:
mixing an alkaline solution and potassium titanate, then carrying out pre-cooling treatment to obtain a mixed solution, and mixing the mixed solution and cellulose to obtain a cellulose-potassium titanate mixed solution, wherein the alkaline solution is a urea alkaline solution or a thiourea alkaline solution;
regenerating the cellulose-potassium titanate mixed solution in the solidification solution to obtain the cellulose-potassium titanate composite hydrogel, and drying.
A cellulose-potassium titanate composite film is prepared by applying the preparation method of the cellulose-potassium titanate composite film.
The cellulose-potassium titanate composite film is applied to the preparation of packaging materials or electrode materials of capacitors.
The embodiment of the invention provides a preparation method of a cellulose-potassium titanate composite film, which has the beneficial effects that: the method comprises the steps of mixing urea alkaline solution and potassium titanate, precooling to improve the solubility of mixed solution to cellulose to obtain cellulose-potassium titanate mixed solution, carrying out tape casting to obtain cellulose-potassium titanate composite gel, and drying to obtain the cellulose-potassium titanate composite membrane. The preparation method has the advantages of simple and easy operation, high process stability, no toxicity or pollution and low requirements on equipment. The invention also provides a cellulose-potassium titanate composite film which is prepared by the method, the tensile strength of the composite film is more than or equal to 106.5MPa, the composite film has good mechanical properties, and the composite film also has good light transmittance and biodegradability. The cellulose-potassium titanate composite film of the present invention can be applied to the production of a packaging material or an electrode material for capacitors, based on the above-mentioned advantages.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a photograph of a cellulose-potassium titanate composite film provided in example 1 of the present invention;
FIG. 2 is a photograph of a pure cellulose film provided in comparative example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the surface of a cellulose-potassium titanate composite film provided in example 1 of the present invention;
fig. 4 is a scanning electron microscope image of the surface of the pure cellulose film provided in comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The cellulose-potassium titanate composite film provided by the embodiment of the invention, the preparation method and the application thereof are specifically described below.
The preparation method of the cellulose-potassium titanate composite film provided by the embodiment of the invention comprises the following steps:
and S1, mixing the alkaline solution and potassium titanate, pre-cooling to obtain a mixed solution, and mixing the mixed solution and cellulose to obtain a cellulose-potassium titanate mixed solution.
It should be noted that cellulose cannot be melted and dissolved in a common solvent at normal temperature due to strong hydrogen bond interaction between cellulose molecules; in alkaline solution, urea and sodium hydroxide solvent micromolecules can form hydrogen bonds with cellulose, the hydrogen bonds are more stable at low temperature, and then the hydrogen bonds among cellulose molecules are destroyed, so that the cellulose is dissolved in the alkaline solution. Therefore, the invention adopts low temperature and mixes the potassium titanate and the cellulose in alkaline solution, which obviously increases the solubility of the cellulose.
In addition, the preparation method in the embodiment of the invention adopts the steps of mixing the alkaline solution and the potassium titanate as the solvent, pre-cooling the mixture, and mixing the mixture with the cellulose, so that the rapid dissolving process of the cellulose can be realized, and the mixing sequence cannot be reversed.
Cellulose is a natural polymer which is most abundant on the earth, and the cellulose has biodegradability and renewability, so that the research of the cellulose in the field of materials, particularly the field of packaging film materials and application of the cellulose has attracted attention increasingly. However, the mechanical properties of the cellulose film material need to be further improved. The potassium titanate has excellent heat insulation performance and wear resistance, high heat conductivity and infrared reflectivity, can be used as a matrix for rapid ion transmission, has the characteristics of extremely low heat conductivity coefficient at high temperature, lower price and the like, and has high application value and wide application field.
Specifically, the pre-cooling treatment process is to ensure that the temperature of the mixed solution is less than or equal to-12 ℃. The low-temperature precooling can ensure the cellulose to be fully dissolved, the precooling condition can be achieved by adopting a freezing chamber or a cold trap of a daily refrigerator, and the requirement on equipment is not high. Dissolving cellulose the cellulose raw material is placed in a pre-cooled solution and dissolved for 5-20min under mechanical stirring to realize full dissolution of the cellulose.
Specifically, the alkaline solution is a urea alkaline solution or a thiourea alkaline solution; in the alkaline solution, the mass fraction of the urea or thiourea is 6-15%, and the mass fraction of the alkali is 5-10%; wherein the alkali is NaOH or LiOH. H2And O. When the alkaline solution is prepared, only two substances are sequentially added into water and fully stirred. The proportion of raw materials in the alkaline solution affects the solubility of cellulose in the solution, and the cellulose can not be completely dissolved due to the fact that the content of urea is too low.
Specifically, the potassium titanate has a length of 5 to 60 μm and a diameter of 0.5 to 1.0. mu.m. The potassium titanate is common potassium titanate, and the adoption of the potassium titanate with the length-diameter ratio is beneficial to improving the uniform dispersion of the potassium titanate in the solution and exerting the performance of the potassium titanate.
Specifically, in the cellulose-potassium titanate mixed solution, the mass fraction of cellulose is 3 to 6%, and the mass fraction of potassium titanate is 0.05 to 1%. The content of potassium titanate is lower than 1 percent, so that the potassium titanate is not easy to agglomerate and settle; the proper cellulose concentration can enable the potassium titanate to be better dispersed in the cellulose solution, so that the structure of the obtained cellulose-potassium titanate composite membrane is more uniform.
Specifically, the mixing process of the alkaline solution and the potassium titanate is to mix the alkaline solution and the potassium titanate and stir for 0.1 to 1 hour, then carry out ultrasonic treatment for 5 to 30 minutes to obtain a solution, and then place the solution in a refrigerator for precooling. The raw materials cannot be fully mixed in a short time by single mechanical stirring, and the stirring effect is better while ultrasonic stirring under the allowable condition.
And S2, regenerating the cellulose-potassium titanate mixed solution in the solidification solution to obtain the cellulose-potassium titanate composite hydrogel, and drying.
The main function of the coagulation liquid is to reduce and destroy hydrogen bonds formed between alkali and urea molecules and cellulose, promote hydrogen bond bonding between cellulose molecules, coagulate cellulose out of the solution, and obtain cellulose-potassium titanate composite hydrogel. Drying the cellulose-potassium titanate composite hydrogel to form a cellulose-potassium titanate composite membrane, wherein the drying process is to fix four ends of the cellulose-potassium titanate composite gel on a glass plate by using an adhesive tape at room temperature for drying.
Specifically, the regeneration process in the solidification solution is to soak the cellulose-potassium titanate mixed solution in the solidification solution for 0.2 to 6 hours by adopting a tape casting method. The solidification time mainly influences the physical crosslinking degree of cellulose molecules in the composite hydrogel, so that the texture and brittleness of the hydrogel are influenced, and if the crosslinking time is too short, the crosslinking degree is low, and the hydrogel with regular appearance cannot be formed.
Specifically, the coagulation liquid is selected from any one of an ethanol solution, a sulfuric acid solution, and a sodium sulfate solution. The solidification liquid needs to be capable of completely immersing the cellulose-potassium titanate mixed liquid to effectively and fully exert the solidification function. The sulfuric acid solution may be a sulfuric acid solution with a mass fraction of about 10%, the sodium sulfate solution may be a sodium sulfate solution with a mass fraction of about 5%, and the ethanol solution may be an ethanol aqueous solution.
In other embodiments, the coagulating liquid may be a mixed solution of sulfuric acid and sodium sulfate.
Further, the cellulose-potassium titanate mixed solution is subjected to centrifugal separation before the cellulose-potassium titanate mixed solution is regenerated. The centrifugal separation process is to remove impurities caused by the addition of cellulose and bubbles generated in the stirring process, so that the obtained composite membrane product is purer. Specifically, the temperature of the centrifugal treatment is-5-5 ℃, and the centrifugal treatment process can be carried out for 10-20min at the rotating speed of 3000 r/min. The low-temperature centrifugation can ensure the fluidity of the cellulose-potassium titanate mixed solution, and is convenient to remove air bubbles in the cellulose-potassium titanate mixed solution, so that the obtained cellulose-potassium titanate composite gel has more uniform texture.
Preferably, before drying the cellulose-potassium titanate composite hydrogel, treating the cellulose-potassium titanate composite hydrogel with a plasticizer; the plasticizer is any one selected from glycerol, ethylene glycol and polyethylene glycol. The treatment of the plasticizer can obviously improve the plasticity of the material and is beneficial to expanding the application range of the cellulose-potassium titanate composite film.
Specifically, the plasticizer is used for processing, and the cellulose-potassium titanate composite hydrogel can be fully vibrated and soaked in the plasticizer solution, and then the soaked cellulose-potassium titanate composite hydrogel is dried at room temperature to obtain the cellulose-potassium titanate composite membrane. The instrument used for the oscillation is a constant-temperature oscillator for oscillation, the oscillation time is 6-24h, the temperature is 25 ℃, and the concentration of the plasticizer aqueous solution is 0.5-2%.
Further, before the cellulose-potassium titanate composite hydrogel is treated with the plasticizer, the cellulose-potassium titanate composite hydrogel is washed to be neutral by water, and the washing process mainly washes out residual urea, solidification liquid and the like on the hydrogel.
The embodiment of the invention also provides a cellulose-potassium titanate composite film, which is prepared by the preparation method of the cellulose-potassium titanate composite film, and the technology for preparing the high-strength cellulose-potassium titanate composite film by reinforcing cellulose with potassium titanate is not reported so far. The tensile strength of the composite membrane prepared in the embodiment of the invention is more than or equal to 106.5MPa, the composite membrane has good mechanical properties, and the composite membrane also has good biocompatibility and degradability.
The cellulose-potassium titanate-based composite film has good mechanical property, biocompatibility and degradability, and can be applied to packaging materials or electrode materials of capacitors.
In particular, the cellulose-potassium titanate-based composite film is used as a packaging material, such as an outer covering of flowers, a transparent window material for toys, etc., based on its excellent mechanical properties, flexibility, high light transmittance and a certain gas barrier property. The composite film can be used as an electrode material of a sodium ion capacitor because potassium titanate can be used as a matrix for rapid ion transmission.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a cellulose-potassium titanate composite membrane, which comprises the following steps:
first, 8.0g of LiOH. H was added2Dissolving O and 15.0g of urea in 71.9g of water to obtain 94.9g of LiOH-urea solution, adding 0.1g of potassium titanate with the length of 7 microns and the diameter of 0.7 microns into the LiOH-urea solution, mechanically stirring for 1h, further carrying out ultrasonic treatment for 10min, then placing the mixture in a refrigerator for precooling to-12.0 ℃, adding 5.0g of cellulose powder, and mechanically stirring for 10min to obtain the cellulose-potassium titanate mixed solution.
And centrifuging the cellulose-potassium titanate mixed solution at the temperature of minus 5 ℃ at the rotating speed of 3000r/min for 15min for defoaming, pouring the defoamed solution on a glass plate, controlling the thickness of a liquid layer to be 0.2mm, and slightly putting the glass plate with the liquid layer in an ethanol solution for soaking for 6h to obtain the cellulose-potassium titanate composite hydrogel.
Soaking and oscillating the obtained cellulose-potassium titanate composite gel in 1% glycerol aqueous solution by mass fraction, wherein the oscillation time is 12h, and then drying at room temperature to obtain the cellulose-potassium titanate composite membrane.
The embodiment also provides a cellulose-potassium titanate composite film which is prepared by applying the method.
Example 2
The embodiment provides a preparation method of a cellulose-potassium titanate composite membrane, which comprises the following steps:
first, 8.0g of LiOH. H was added2Dissolving O and 15.0g of urea in 71.9g of water to obtain 94.9g of LiOH-urea solution, adding 0.1g of potassium titanate with the length of 7 microns and the diameter of 0.7 microns into the LiOH-urea solution, mechanically stirring for 1h, further carrying out ultrasonic treatment for 10min, then placing the mixture in a refrigerator for precooling to-12.0 ℃, adding 5.0g of cellulose powder, and mechanically stirring for 10min to obtain the cellulose-potassium titanate mixed solution.
And centrifuging the cellulose-potassium titanate mixed solution at the temperature of minus 5 ℃ at the rotating speed of 3000r/min for 15min for defoaming, pouring the defoamed solution on a glass plate, controlling the thickness of a liquid layer to be 0.2mm, and slightly putting the glass plate with the liquid layer in an ethanol solution for soaking for 6h to obtain the cellulose-potassium titanate composite hydrogel.
And finally, drying the cellulose-potassium titanate composite hydrogel at room temperature to obtain the cellulose-potassium titanate composite membrane.
The embodiment also provides a cellulose-potassium titanate composite film which is prepared by applying the method.
Example 3
The embodiment provides a preparation method of a cellulose-potassium titanate composite membrane, which comprises the following steps:
first, 8.0g of LiOH. H was added2O and 15.0g of urea were dissolved in 71.95g of water to obtain 94.95g of a LiOH-urea solution, 0.05g of potassium titanate having a length of 7 μm and a diameter of 0.7 μm was added to the LiOH-urea solution, mechanically stirred for 1 hour, further subjected to ultrasonic treatment for 10 minutes, then placed in a refrigerator to be pre-cooled to-12.0 ℃, 5.0g of cellulose powder was added, and mechanically stirred for 10 minutes to obtain a cellulose-potassium titanate mixed solution.
And centrifuging the cellulose-potassium titanate mixed solution at the temperature of minus 5 ℃ at the rotating speed of 3000r/min for 15min for defoaming, pouring the defoamed solution on a glass plate, controlling the thickness of a liquid layer to be 0.2mm, and slightly putting the glass plate with the liquid layer in an ethanol solution for soaking for 6h to obtain the cellulose-potassium titanate composite hydrogel.
And finally, washing the cellulose-potassium titanate composite hydrogel to be neutral by using water, soaking and oscillating the cellulose-potassium titanate composite hydrogel by using a 1% ethylene glycol aqueous solution in a mass fraction manner, wherein the oscillation time is 12 hours, and drying the cellulose-potassium titanate composite hydrogel at room temperature to obtain the cellulose-potassium titanate composite membrane.
The embodiment also provides a cellulose-potassium titanate composite film which is prepared by applying the method.
Example 4
The embodiment provides a preparation method of a cellulose-potassium titanate composite membrane, which comprises the following steps:
first, 8.0g of LiOH. H was added2Dissolving O and 15.0g of urea in 71.8g of water to obtain 94.8g of LiOH-urea solution, adding 0.2g of potassium titanate with the length of 7 microns and the diameter of 0.7 microns into the LiOH-urea solution, mechanically stirring for 1h, further carrying out ultrasonic treatment for 10min, then placing the mixture in a refrigerator for precooling to-12.0 ℃, adding 5.0g of cellulose powder, and mechanically stirring for 10min to obtain the cellulose-potassium titanate mixed solution.
And centrifuging the cellulose-potassium titanate mixed solution at the temperature of minus 5 ℃ at the rotating speed of 3000r/min for 15min for defoaming, pouring the defoamed solution on a glass plate, controlling the thickness of a liquid layer to be 0.2mm, and slightly putting the glass plate with the liquid layer in an ethanol solution for soaking for 6h to obtain the cellulose-potassium titanate composite hydrogel.
And finally, washing the cellulose-potassium titanate composite hydrogel to be neutral by using water, soaking and oscillating the cellulose-potassium titanate composite hydrogel by using a polyethylene glycol aqueous solution with the mass fraction of 1%, wherein the oscillation time is 12h, and drying the cellulose-potassium titanate composite hydrogel at room temperature to obtain the cellulose-potassium titanate composite membrane.
The embodiment also provides a cellulose-potassium titanate composite film which is prepared by applying the method.
Example 5
The embodiment provides a preparation method of a cellulose-potassium titanate composite membrane, which comprises the following steps:
first, 7.0g of LiOH. H was added2Dissolving O and 13.0g of urea in 73.5g of water to obtain 93.5g of LiOH-urea solution, adding 1.0g of potassium titanate with the length of 5 mu m and the diameter of 0.5 mu m into the LiOH-urea solution, mechanically stirring for 0.5h, ultrasonically treating for 30min, placing the solution in a refrigerator for precooling to-13.0 ℃, adding 6.0g of cellulose powder, and mechanically stirring for 20min to obtain the cellulose-potassium titanate mixed solution.
And secondly, centrifuging the cellulose-potassium titanate mixed solution at 0 ℃ at a rotating speed of 3000r/min for 30min to defoam, pouring the defoamed solution on a glass plate, controlling the thickness of a liquid layer to be 0.2mm, and slightly putting the glass plate with the liquid layer in a 10% sulfuric acid aqueous solution for soaking for 0.2h to obtain the cellulose-potassium titanate composite hydrogel.
And finally, washing the cellulose-potassium titanate composite hydrogel to be neutral by using water, soaking and oscillating the cellulose-potassium titanate composite hydrogel by using a glycerol aqueous solution with the mass fraction of 2%, wherein the oscillation time is 6h, and drying the cellulose-potassium titanate composite hydrogel at room temperature to obtain the cellulose-potassium titanate composite membrane.
The embodiment also provides a cellulose-potassium titanate composite film which is prepared by applying the method.
Example 6
The embodiment provides a preparation method of a cellulose-potassium titanate composite membrane, which comprises the following steps:
firstly, 5.0g of NaOH and 10.0g of urea are dissolved in 80.5g of water to obtain 95.5g of NaOH-urea solution, 0.5g of potassium titanate with the length of 30 microns and the diameter of 0.8 microns is added into the NaOH-urea solution, mechanical stirring is carried out for 0.1h, ultrasonic treatment is carried out for 20min, then the solution is placed in a refrigerator to be pre-cooled to-13.5 ℃, 4.0g of cellulose powder is added, and mechanical stirring is carried out for 5min to obtain cellulose-potassium titanate mixed solution.
And secondly, centrifuging the cellulose-potassium titanate mixed solution at the temperature of 5 ℃ at the rotating speed of 3000r/min for 20min to defoam, pouring the defoamed solution on a glass plate, controlling the thickness of a liquid layer to be 0.2mm, and slightly putting the glass plate with the liquid layer in a 5% sodium sulfate solution to soak for 0.5h to obtain the cellulose-potassium titanate composite hydrogel.
And finally, washing the cellulose-potassium titanate composite hydrogel to be neutral by using water, soaking and oscillating the cellulose-potassium titanate composite hydrogel by using a glycerol aqueous solution with the mass fraction of 0.5%, wherein the oscillation time is 24h, and drying the cellulose-potassium titanate composite hydrogel at room temperature to obtain the cellulose-potassium titanate composite membrane.
The embodiment also provides a cellulose-potassium titanate composite film which is prepared by applying the method.
Example 7
The embodiment provides a preparation method of a cellulose-potassium titanate composite membrane, which comprises the following steps:
firstly, 10.0g of NaOH and 6.0g of urea are dissolved in 78.7g of water to obtain 94.7g of NaOH-urea solution, 0.3g of potassium titanate with the length of 60 mu m and the diameter of 1.0 mu m is added into the NaOH-urea solution, mechanical stirring is carried out for 0.5h, ultrasonic treatment is carried out for 30min, then the solution is placed in a refrigerator for pre-cooling to-13.7 ℃, 5.0g of cellulose powder is added, and mechanical stirring is carried out for 15min to obtain the cellulose-potassium titanate mixed solution.
And secondly, centrifuging the cellulose-potassium titanate mixed solution at the temperature of 3 ℃ at the rotating speed of 3000r/min for 20min to defoam, pouring the defoamed solution on a glass plate, controlling the thickness of a liquid layer to be 0.2mm, and slightly putting the glass plate with the liquid layer in a 5% sodium sulfate solution to soak for 6h to obtain the cellulose-potassium titanate composite hydrogel.
And finally, washing the cellulose-potassium titanate composite hydrogel to be neutral by using water, soaking and oscillating the cellulose-potassium titanate composite hydrogel by using a glycerol aqueous solution with the mass fraction of 1.0%, wherein the oscillation time is 18h, and drying the cellulose-potassium titanate composite hydrogel at room temperature to obtain the cellulose-potassium titanate composite membrane.
The embodiment also provides a cellulose-potassium titanate composite film which is prepared by applying the method.
Example 8
The embodiment provides a preparation method of a cellulose-potassium titanate composite membrane, which comprises the following steps:
firstly, 6.0g of NaOH and 11.0g of thiourea are dissolved in 79.6g of water to obtain 96.6g of NaOH-urea solution, 0.4g of potassium titanate with the length of 20 microns and the diameter of 0.6 microns is added into the NaOH-urea solution, mechanical stirring is carried out for 1h, ultrasonic treatment is carried out for 5min, then the NaOH-urea solution is placed in a refrigerator to be pre-cooled to-12.8 ℃, 3.0g of cellulose powder is added, and mechanical stirring is carried out for 15min to obtain cellulose-potassium titanate mixed solution.
And secondly, centrifuging the cellulose-potassium titanate mixed solution at 0 ℃ at a rotating speed of 3000r/min for 15min for defoaming, pouring the defoamed solution on a glass plate, controlling the thickness of a liquid layer to be 0.2mm, and slightly putting the glass plate with the liquid layer in a 10% sulfuric acid solution for soaking for 3h to obtain the cellulose-potassium titanate composite hydrogel.
And finally, washing the cellulose-potassium titanate composite hydrogel to be neutral by using water, soaking and oscillating the cellulose-potassium titanate composite hydrogel by using a glycerol aqueous solution with the mass fraction of 1.5%, wherein the oscillation time is 12h, and drying the cellulose-potassium titanate composite hydrogel at room temperature to obtain the cellulose-potassium titanate composite membrane.
The embodiment also provides a cellulose-potassium titanate composite film which is prepared by applying the method.
Comparative example
95.0g of LiOH. H was prepared2A mixed solution of O-urea, which consists of 8 wt% of LiOH & H2O and 15 wt% urea in water. And mechanically stirring the mixed solution for 1h, and performing ultrasonic treatment for 15min to obtain a mixed solution. Placing the mixed solution in a refrigerator for pre-cooling to-12.0 deg.C, adding 5.0g cellulose powder, and mechanically stirring for 10min to obtain cellulose solution.
And centrifuging the cellulose solution at the temperature of minus 5 ℃ at the rotating speed of 3000r/min for 15min for defoaming, pouring the defoamed solution on a glass plate, controlling the thickness of a liquid layer to be 0.2mm, and slightly soaking the glass plate with the liquid layer in an ethanol solution for 6h to obtain the cellulose gel.
Soaking the obtained cellulose-potassium titanate composite gel in 1% glycerol solution, shaking for 12h, and drying at room temperature to obtain cellulose membrane.
Test example 1
The tensile strength of the films prepared in examples 1 to 8 and comparative example was measured using a conventional tensile machine, and the results are shown in table 1.
TABLE 1 tensile Strength test results
As can be seen from Table 1, the tensile strength of the cellulose-potassium titanate composite membrane prepared by the method provided by the invention is basically over 115MPa, which is obviously higher than that of the cellulose membrane prepared in the comparative example. This is mainly due to: the existence of potassium titanate can bridge cracks of the cellulose matrix, and closed stress is applied to the surfaces of the cracks to prevent the cracks from expanding and play a role in strengthening and toughening. In addition, the plasticizer is not adopted for treatment in the embodiment 2, and the tensile strength of the material is obviously lower than that of other embodiments, so that the plasticizer adopted for treatment in the preparation method provided by the invention plays an important role in improving the mechanical property of the material.
Test example 2
The photographs of the films obtained in example 1 and comparative example are shown in fig. 1 and 2, and the surface structures of the films obtained in example 1 and comparative example are subjected to a scanning electron microscope test, and the test results are shown in fig. 3 and 4, respectively. As can be seen from FIGS. 3 and 4, the cellulose membrane has a flat surface, and the surface structure of the cellulose-potassium titanate composite membrane prepared by the method of the present invention is significantly different from that of the cellulose membrane, because the potassium titanate is uniformly distributed on the product obtained by the present invention, and the introduction of the potassium titanate effectively changes the original structure of the cellulose based on the strong hydrogen bonding effect of the cellulose and the potassium titanate.
In summary, according to the preparation method of the cellulose-potassium titanate composite film provided by the invention, the alkaline solution of urea or thiourea is mixed with potassium titanate crystals, the solubility of cellulose is improved through precooling treatment to obtain the cellulose-potassium titanate mixed solution, then the cellulose-potassium titanate composite gel is obtained through regeneration of a solidification solution through a tape casting method, and finally the composite film material is obtained through immersion in a glycerol aqueous solution and drying at room temperature. The preparation method has the advantages of simple and easy operation, high process stability, no toxicity or pollution and low requirements on equipment.
The invention also provides a high-strength cellulose-potassium titanate composite film which is prepared by the method, the tensile strength of the composite film is more than or equal to 106.5MPa, the composite film has good mechanical properties, and the composite film also has good light transmittance and biodegradability. Based on the performances, the cellulose-potassium titanate composite film obtained in the invention can be applied to the preparation process of packaging materials or electrode materials of sodium ion capacitors.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a cellulose-potassium titanate composite film is characterized by comprising the following steps:
mixing an alkaline solution and potassium titanate, then carrying out pre-cooling treatment to obtain a mixed solution, and mixing the mixed solution and cellulose to obtain a cellulose-potassium titanate mixed solution, wherein the alkaline solution is a urea alkaline solution or a thiourea alkaline solution;
soaking the cellulose-potassium titanate mixed solution in a solidification solution for 0.2-6h for regeneration to obtain cellulose-potassium titanate composite hydrogel, and drying;
in the alkaline solution, the mass fraction of the urea or thiourea is 6-15%, and the mass fraction of the alkali is 5-10%; wherein the alkali is NaOH or LiOH. H2O；
The coagulating liquid is selected from any one of an ethanol solution, a sulfuric acid solution and a sodium sulfate solution; in the cellulose-potassium titanate mixed solution, the mass fraction of the potassium titanate is 0.05 to 1%.
2. The method for producing a cellulose-potassium titanate composite film according to claim 1, wherein the cellulose-potassium titanate composite hydrogel is treated with a plasticizer before being dried;
the plasticizer is any one selected from glycerol, ethylene glycol and polyethylene glycol.
3. The method for producing a cellulose-potassium titanate composite film according to claim 2, wherein the cellulose-potassium titanate composite hydrogel is washed with water to neutrality before being treated with a plasticizer.
4. The method for producing a cellulose-potassium titanate composite film according to claim 1, wherein the cellulose-potassium titanate mixed solution is centrifuged before regenerating the cellulose-potassium titanate mixed solution.
5. The method of producing a cellulose-potassium titanate composite film according to claim 1, wherein the potassium titanate has a length of 5 to 60 μm and a diameter of 0.5 to 1.0 μm.
6. The method for producing the cellulose-potassium titanate composite film according to claim 5, wherein the mass fraction of the cellulose in the cellulose-potassium titanate mixed solution is 3 to 6%.
7. A cellulose-potassium titanate composite film characterized by being produced by the method for producing a cellulose-potassium titanate composite film according to any one of claims 1 to 6.
8. Use of the cellulose-potassium titanate composite film according to claim 7 for producing a packaging material or an electrode material for capacitors.
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| US4111866A (en) * | 1976-04-20 | 1978-09-05 | Agency Of Industrial Science And Technology | Method of making a chemical-resistant diaphragm thereof |
| CN101172164A (en) * | 2006-11-03 | 2008-05-07 | 中国科学院化学研究所 | Biopolymer nano tunica fibrosa material capable of being biological degraded and absorbed, preparing method and uses of the same |
| CN101555321A (en) * | 2008-04-09 | 2009-10-14 | 深圳市华亚数控机床有限公司 | Solvent composition and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4111866A (en) * | 1976-04-20 | 1978-09-05 | Agency Of Industrial Science And Technology | Method of making a chemical-resistant diaphragm thereof |
| CN101172164A (en) * | 2006-11-03 | 2008-05-07 | 中国科学院化学研究所 | Biopolymer nano tunica fibrosa material capable of being biological degraded and absorbed, preparing method and uses of the same |
| CN101555321A (en) * | 2008-04-09 | 2009-10-14 | 深圳市华亚数控机床有限公司 | Solvent composition and preparation method and application thereof |
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