CN113480756B - Preparation method and application of cellulose nanocrystalline spiral self-assembly body and glycerol composite film - Google Patents
Preparation method and application of cellulose nanocrystalline spiral self-assembly body and glycerol composite film Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a cellulose nanocrystal spiral self-assembly and a glycerol composite film, and can obtain a cellulose nanocrystal suspension with high stability and a cellulose nanocrystal-glycerol composite film with chiral nematic liquid crystal properties. The method sequentially hydrolyzes, dilutes, stands, centrifuges, dialyzes and concentrates the cellulose raw material to obtain the cellulose nanocrystal suspension with the Zate potential of about-50 mV and high stability. The cellulose nanocrystalline-glycerol film can be prepared by mixing the suspension with glycerol. The invention provides a method for adjusting the initial color of a film through different glycerol contents, so that the film can better exert the function of a humidity-sensitive detection material. In addition, the application of the composite membrane to the detection of the concentration response of the hydrochloric acid gas is also provided.
Description
Technical Field
The invention relates to the field of preparation of cellulose nanocrystals, in particular to a preparation method of a composite film of the cellulose nanocrystals and glycerol.
Background
Cellulose is the most abundant natural polymer in nature, has the advantages of no toxicity, low price, biocompatibility, biodegradability and the like, and is a sustainable natural high polymer material widely researched at present. The cellulose nanocrystal can be prepared by adopting a method of acidolysis of cellulose, and is a renewable nano material with high crystallinity. When the cellulose nanocrystal is prepared by using sulfuric acid hydrolysis, sulfate groups can be introduced to the surface of the cellulose nanocrystal to generate electrostatic repulsion, so that the cellulose nanocrystal suspension can be self-assembled to form chiral nematic liquid crystal with a helical structure at a certain concentration, and the structure can be fixed in the cellulose nanocrystal helical assembly after drying. The cellulose nanocrystalline spiral assembly has special optical properties such as selective reflection, circular dichroism and optical rotation, and has wide application prospect in the fields of anti-counterfeiting identification, biosensing, optical information storage, liquid crystal display and the like. Therefore, the preparation method of the cellulose nanocrystalline spiral assembly has important theoretical and application values.
In Chinese patent with publication number CN108314803A, cellulose nanocrystal and glycerol are compounded to form a film, and a composite material with humidity response is prepared. However, the humidity-sensitive response material prepared by using the cellulose nanocrystals does not relate to the adjustment of the initial color of the film, and the invention can change the reflection wavelength of the material by adjusting and controlling the pitch of the cellulose nanocrystals, thereby preparing the film with the required initial color.
Disclosure of Invention
The invention aims to provide a simple preparation method of a cellulose nanocrystal-glycerol composite film and a method for adjusting the reflection wavelength of the cellulose nanocrystal-glycerol composite film, so that the humidity detection effect of the cellulose nanocrystal-glycerol composite film as a humidity sensitive material is better exerted, and the invention also provides application of the cellulose nanocrystal-glycerol composite film in concentration response detection of hydrochloric acid gas.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a cellulose nanocrystal-glycerol composite film comprises the following steps:
(1) Adding cellulose into sulfuric acid, uniformly stirring, and carrying out hydrolysis reaction to prepare a cellulose nanocrystalline suspension;
(2) Sequentially diluting, standing, centrifuging, dialyzing and concentrating the cellulose nanocrystalline suspension to obtain chiral nematic cellulose nanocrystalline suspension;
(3) And adding glycerol into the chiral nematic cellulose nanocrystalline suspension, stirring for 12 hours, and forming a film to obtain the cellulose nanocrystalline-glycerol film.
Preferably, the temperature of the hydrolysis reaction is 45 ℃;
the time of the hydrolysis reaction is 95-105 min.
Preferably, the acid-to-substance ratio is 1g and 17.5ml, and the sulfuric acid concentration is 64wt%.
Preferably, the endpoint pH value of the dialysis is 6.8-7.2;
the end point mass concentration of the concentration is 1.8-2.7%.
The invention provides a method for adjusting the reflection wavelength of a cellulose nanocrystal-glycerol film, which comprises the steps of adding glycerol into a cellulose nanocrystal suspension, carrying out ultrasonic treatment, and stirring for 12 hours to form a film; the cellulose nanocrystal-glycerol film has different reflection wavelengths according to the amount of the added glycerol.
The cellulose nanocrystal-glycerol film prepared by the method is used as a humidity-sensitive indicating material capable of regulating and controlling the initial color of the film.
The cellulose nanocrystalline-glycerol film prepared by the invention is used for detecting hydrochloric acid gas.
The invention has the advantages that:
1) The cellulose nanocrystal suspension prepared under the condition has uniform size, the length is about 200-400nm, and the width is about 25-40nm. And the Zate potential is about-50 mV, and the stability is high.
2) The invention provides a method for adjusting the reflection wavelength of a chiral nematic cellulose nanocrystal-glycerol composite film, which can adjust the reflection wavelength of the chiral nematic cellulose nanocrystal-glycerol composite film according to requirements so as to better exert the function of a humidity-sensitive detection material.
3) The chiral nematic cellulose nanocrystalline-glycerol composite film provided by the invention can be applied to humidity detection as a humidity sensitive indicating material. The test results of the embodiment show that the chiral nematic cellulose nanocrystalline-glycerol composite film provided by the invention has different responses to light in hydrochloric acid gas atmosphere with different concentrations, can display different colors, has reversible stimulus response performance, and has wide prospects in hydrochloric acid gas detection.
Drawings
FIG. 1 is a photograph of an acidolysis solution and a cellulose nanocrystal helix assembly at different acidolysis reaction times.
FIG. 2 is a UV-Vis spectrum of the cellulose nanocrystal helix assembly for different acidolysis reaction times.
FIG. 3 is a TEM image of cellulose nanocrystals prepared under the reaction conditions of the present invention.
Fig. 4 is a process diagram of cellulose nanocrystal self-assembly.
FIG. 5 is a POM diagram of a cellulose nanocrystalline helix assembly prepared under the reaction conditions of the present invention.
Fig. 6 is a diagram showing that the cellulose nanocrystal-glycerol composite film gradually undergoes red shift in color with changes in humidity.
Fig. 7 is a hydrochloric acid gas stimulation response diagram of cellulose nanocrystal-glycerol with different glycerol addition amounts.
Detailed description of the invention
The invention provides a cellulose nanocrystalline suspension with high stability and a preparation method of a cellulose nanocrystalline spiral assembly with chiral nematic liquid crystal property.
The invention is further illustrated with reference to the following figures and examples without thereby restricting the invention to the described embodiments.
1. Diluting 98% concentrated sulfuric acid with deionized water to prepare 64% sulfuric acid: 440ml of deionized water is poured into a 1000ml beaker, then the beaker is placed in an ice water bath, 450ml of 98% concentrated sulfuric acid is slowly added, and the solution is stirred by a glass rod while being added in the adding process, so that the solution is prevented from being overheated. And finally, storing the prepared sulfuric acid with the concentration of 64% for later use.
2. 350ml of sulfuric acid with the concentration of 64% is measured by a measuring cylinder and poured into a beaker, the beaker is placed on a magnetic stirrer for stirring, and then 20g of microcrystalline cellulose is weighed and slowly added into the sulfuric acid for uniform stirring.
3. Pouring the uniformly stirred mixed solution of sulfuric acid and microcrystalline cellulose into a 500ml round-bottom flask, uniformly stirring in a constant-temperature water bath to gradually carry out acidolysis on the microcrystalline cellulose by the sulfuric acid to obtain cellulose nanocrystals until the yellowing reaction of the solution is finished, then adding 5 times of deionized water to terminate the acidolysis reaction, and standing for precipitation. The acidolysis reaction conditions such as the reaction time and the reaction temperature are shown in table 1.
TABLE 1 preparation conditions of cellulose nanocrystal suspensions
4. And after standing for 24 hours, pouring out supernatant, centrifuging the cellulose nanocrystal suspension at the lower layer, and washing the cellulose nanocrystal suspension for several times by using deionized water, wherein the centrifugal speed is 9000r/min, and the time is 6min.
5. Putting the cellulose nanocrystalline obtained after centrifugation into a dialysis bag with the molecular weight of 8000-14000 for dialysis for 2-3 days until the cellulose nanocrystalline is neutral.
6. And measuring the solid content of the prepared cellulose nanocrystalline suspension by a vacuum freeze drying method, and then adding deionized water for dilution to prepare the cellulose nanocrystalline suspension with the mass fraction of 2.3 wt%.
7. Glycerol of different masses was added to a CNC suspension with a mass fraction of 2.3wt%, the addition amounts and ratios are as shown in table 2. Stirring for 12h to mix thoroughly, pouring 3ml of the mixture into a disposable plastic culture dish with the diameter of 3.5cm, standing for self-assembly, and preparing the glycerol/CNC composite membrane.
TABLE 2 color of the solution after acid hydrolysis at different times and temperatures
Table 3 shows the color of the solution after acidolysis at different reaction times and temperatures. When the reaction temperature is 40 ℃, the microcrystalline cellulose is gradually acidolyzed into cellulose nanocrystals along with the gradual increase of the acidolysis time, and the solution gradually changes from white to bright yellow; when the reaction temperature is 45 ℃, the acidolysis reaction speed is accelerated along with the increase of the reaction temperature, and the color of the solution is gradually changed from yellow to dark brown in the process of acidolysis time from 1h to 3 h; when the reaction temperature is 50 ℃, the acidolysis reaction becomes very rapid, the color of the reaction solution becomes dark yellow when the acidolysis time is 1h, and the color of the reaction solution is black when the reaction time reaches 3h, which indicates that the carbonization phenomenon has occurred when the acidolysis time is too long.
TABLE 3 State and color of cellulose nanocrystal suspensions at different times and temperatures
Table 4 shows the state and color of the cellulose nanocrystal suspensions prepared at different reaction times and temperatures. When the temperature is 40 ℃, the cellulose nanocrystalline suspension prepared for 1 hour, 1.5 hours and 2 hours can generate a layering phenomenon, which shows that the reaction temperature is too low, the acidolysis reaction activity is low, the reaction is insufficient, the prepared cellulose nanocrystalline has larger granularity, the content of sulfate groups on the surface is less, so that the suspension is unstable, the layering phenomenon is caused, and the light blue cellulose nanocrystalline suspension can not be obtained when the reaction time is 2.5 hours and 3 hours. When the reaction temperature is 45 ℃, the prepared cellulose nanocrystalline suspension does not generate a layering phenomenon, the dispersibility is good, and the color of the suspension is light blue at 1.5 h. When the reaction temperature is 50 ℃, the color of the prepared cellulose nanocrystal suspension is gradually changed from blue-white to yellow and brown, the time for the light blue suspension to appear in the middle is too short, and the yield of the cellulose nanocrystal is low, which indicates that the carbonization phenomenon already occurs when the reaction temperature is too high at 50 ℃. In summary, when the reaction temperature is too low, the acidolysis reaction is insufficient and a bluish cellulose nanocrystal suspension cannot be obtained, and when the reaction temperature is too high, the acidolysis reaction is excessive and the bluish cellulose nanocrystal suspension appears in a short time and at a low yield, so the optimum reaction temperature for the preparation of cellulose nanocrystals by the acidolysis of cellulose with sulfuric acid is about 45 ℃.
Table 4 Zeta potential of different batches of cellulose nanocrystal suspensions prepared under the reaction conditions of the present invention
Photographs of the acidolysis solution and the cellulose nanocrystal helical assembly prepared at a reaction temperature of 45 ℃ for 60min, 90min, 100min, 110min, 120min and 150min, respectively, as shown in fig. 1. As can be seen from the figure, the color of the reaction solution gradually changed from yellow to dark brown as the acidolysis reaction time increased, and the colors corresponding to 60min, 90min, 100min, 110min, 120min and 150min were yellow, light brown, dark brown, brown and dark brown, respectively. From 60min to 100min, gradually carrying out acidolysis by sulfuric acid to remove an amorphous region of cellulose along with the increase of reaction time, and obtaining the cellulose nanocrystal with higher crystallinity. In the acidolysis process, the number of sulfate groups on the surface of the cellulose nanocrystal is gradually increased, the negative charge on the surface is increased, the electrostatic repulsion force borne by the cellulose nanocrystal during self-assembly is increased, the pitch of the obtained cellulose nanocrystal spiral assembly is increased, and the increase of the pitch causes the structural color of the cellulose nanocrystal spiral assembly to be red-shifted from yellow. When the acidolysis reaction time is from 110min to 150min, along with the continuous acidolysis reaction, after the sulfuric acid has performed acidolysis on the amorphous region of the cellulose, the acidolysis crystalline region is further performed, so that the particle size of the cellulose nanocrystal is rapidly reduced, the pitch of the cellulose nanocrystal spiral assembly is reduced, the structural color is blue-shifted, and the acidolysis reaction is excessive.
The uv-vis spectroscopy test was performed on the cellulose nanocrystal spiral assemblies at different reaction times, and the results are shown in fig. 2. It can be seen from the figure that from 60min to 100min, the reflection wavelength of the cellulose nanocrystal spiral assembly shifts from 450nm to 760nm, and a red shift occurs. According to the formula lambda = nPsin theta, the reflection wavelength is in a proportional relation with the pitch P, the reflection wavelength is red-shifted, which indicates that the pitch of the cellulose nanocrystal spiral assembly is increased, and when the reaction time is continuously increased, the reflection wavelength of the cellulose nanocrystal spiral assembly is blue-shifted, which indicates that the pitch of the cellulose nanocrystal spiral assembly is reduced and is consistent with the change trend of the structural color of the cellulose nanocrystal spiral assembly. When the acidolysis reaction time is 120min to 150min, the reflection wavelength moves from 400nm to 500nm again, and the red shift occurs, which is mainly because on one hand, along with the continuous acidolysis reaction, the sulfate group on the surface of the cellulose nanocrystal is increased, the negative charge amount is increased, so that the screw pitch of the cellulose nanocrystal spiral assembly is increased, and on the other hand, the particle size of the cellulose nanocrystal is reduced due to excessive acidolysis, so that the screw pitch of the cellulose nanocrystal spiral assembly is reduced. Finally, the influence of the amount of the negative charges on the screw pitch is larger than the influence of the cellulose nanocrystal particle size on the screw pitch, so that the screw pitch of the cellulose nanocrystal spiral assembly is increased in a small range after the acidolysis reaction is excessive. In summary, when the reaction time is 100min, the cellulose nanocrystal helix assembly having the maximum reflection wavelength can be obtained, and it can be confirmed that the optimum reaction time is 100min.
The cellulose nanocrystal suspension prepared by sulfuric acid hydrolysis is diluted with deionized water to a concentration of about one thousandth, and then characterized by a transmission electron microscope, as shown in fig. 3. As can be seen from the figure 3a, the cellulose nanocrystals prepared by sulfuric acid hydrolysis have uniform sizes and are tapered long rods. Further analysis from FIG. 3b shows that the cellulose nanocrystals prepared according to the present invention have a length of about 200-400nm and a width of between 25-40nm.
Table 5 shows the Zeta potential of cellulose nanocrystal suspensions prepared from different batches under the same acidolysis conditions. As can be seen from the table, the Zeta potentials of the prepared cellulose nanocrystal suspensions of 8 batches are basically consistent and are all around-50 mV. The surface of the cellulose nanocrystal prepared by sulfuric acid hydrolysis is provided with sulfate groups, so that the cellulose nanocrystal is negatively charged, and the potential is a negative value. The potential is an important index for judging the stability of the suspension, when the absolute value of the potential of the suspension is 30mV, the suspension can exist stably, while the absolute value of the potential of the cellulose nanocrystal prepared by the invention is 50mV which is far higher than the value required by the stability of the suspension, thereby showing that the cellulose nanocrystal suspension prepared by the invention can exist very stably.
TABLE 5 Zeta potential of cellulose nanocrystalline suspensions prepared in different batches under the same acidolysis conditions
The results of adding glycerol in the amounts of 0mg, 9mg, 15mg, 21mg, 30mg and 45mg to 3ml of CNC suspension, stirring for 12 hours, and then performing self-assembly to obtain the cellulose nanocrystal-glycerol composite film are shown in fig. 4, and the colors corresponding to the composite films in the amounts of 0mg, 9mg, 15mg, 21mg, 30mg and 45mg of glycerol are light blue, dark blue, light brown, brown and dark brown, respectively. It can be seen from the figure that the structural color of the cellulose nanocrystal spiral assembly changes after different contents of glycerol are added. When no glycerol is added, the structural color of the cellulose nanocrystal spiral assembly is light blue, the structural color gradually shifts to red along with the addition of the glycerol, and when the addition amount of the glycerol is 45mg, the structural color of the cellulose nanocrystal-glycerol composite film shifts to dark brown. The addition of glycerol can adjust the structural color of the cellulose nanocrystalline spiral assembly, and the structural color is red-shifted with the increase of the addition amount. The ultraviolet-visible spectrum test results of the cellulose nanocrystal-glycerol thin films with different glycerol addition amounts are shown in fig. 5, when the glycerol addition amount is 0mg, the reflection wavelength of the cellulose nanocrystal spiral assembly is 340nm, and the reflection wavelength of the cellulose nanocrystal-glycerol composite thin film gradually shifts in red along with the continuous increase of the glycerol addition amount. The variation trend of the reflection wavelength is consistent with the variation trend of the structural color. It is thus possible to adjust the reflection wavelength of the CNC screw assembly by adding glycerol, and the reflection wavelength gradually red-shifts as the amount of addition increases.
As shown in fig. 6, when the cellulose nanocrystal-glycerol composite film with the glycerol addition amount of 3mg is placed under the condition that the relative humidity is 40%, the composite film initially presents blue, the structural color of the composite film gradually generates red shift as the relative humidity is gradually increased from 40% to 90%, the colors of the composite film at the relative humidity of 40%, 50%, 60%, 70% and 80% are respectively blue, green, light yellow, yellow and red, and when the relative humidity is 90%, the reflection wavelength of the composite film is beyond the visible light range, and the structural color is close to colorless. In addition, with the gradual reduction of the relative humidity, the composite film can gradually perform blue shift to restore the original color, and when the environmental humidity changes, the chromaticity is reversible.
Further, the hydrochloric acid gas stimulus response performance was performed for the cellulose nanocrystal-glycerin with different amounts of glycerin added, as shown in fig. 7. The composite films with the glycerol addition amounts of 15mg, 30mg and 45mg are placed in a closed space filled with hydrochloric acid gas, and the composite films can be seen by naked eyes, and the structural color of the cellulose nanocrystal-glycerol composite film is red shifted until the structural color is red along with the increase of the placing time. When hydrochloric acid gas is removed, and the cellulose nanocrystal-glycerol composite film is dried, the composite film can be restored to the original color from red. The cellulose nanocrystal-glycerol composite membrane has reversible stimulus responsiveness to hydrochloric acid gas, can be repeated for many times, and has good reversibility. Therefore, the glycerol/CNC composite membrane has good reversible stimulation responsiveness to hydrochloric acid gas.
From the above embodiments, it can be known that the chiral nematic cellulose nanocrystal-glycerol composite film prepared by the method provided by the present invention can be applied to a humidity sensitive indicating material, and the reflection wavelength of the chiral nematic cellulose nanocrystal-glycerol composite film can be adjusted as required, so that the function of the humidity sensitive indicating material can be better exerted; the preparation method provided by the invention has the advantages of easily available raw materials and simple operation, and the prepared cellulose nanocrystal suspension has good stability. In addition, the invention also provides application of the cellulose nanocrystal-glycerol composite film in detecting the concentration response of hydrochloric acid gas.
Claims (1)
1. The application of the cellulose nanocrystal-glycerol composite film is characterized in that the cellulose nanocrystal-glycerol composite film is used for detecting hydrochloric acid gas, 15mg, 30mg and 45mg of glycerol are respectively added into 3ml of CNC suspension, the cellulose nanocrystal-glycerol composite film is obtained through self-assembly, the cellulose nanocrystal-glycerol composite film is placed in a closed space filled with hydrochloric acid gas, the cellulose nanocrystal-glycerol composite film can be seen by naked eyes, the structural color of the cellulose nanocrystal-glycerol composite film is subjected to red shift until the cellulose nanocrystal-glycerol composite film becomes red along with the increase of the placing time, and when the hydrochloric acid gas is removed, the composite film is dried and then returns to the original color from the red;
the preparation method of the cellulose nanocrystal-glycerol composite film comprises the following steps:
(1) Adding cellulose into sulfuric acid, uniformly stirring, and carrying out hydrolysis reaction to prepare a cellulose nanocrystalline suspension; the hydrolysis reaction temperature is 45 ℃; the hydrolysis reaction time is 100 min; the acid mass ratio is 1g, and the sulfuric acid concentration is 64wt percent; the obtained cellulose nanocrystal has the length of 200-400nm and the width of 25-40 nm; and the Zeta potential is about-50 mV;
(2) Sequentially diluting, standing, centrifuging, dialyzing and concentrating the cellulose nanocrystalline suspension to obtain chiral nematic cellulose nanocrystalline suspension;
(3) And adding glycerol into the chiral nematic cellulose nanocrystalline suspension, and stirring to form a film to obtain the cellulose nanocrystalline-glycerol film.
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| CN103172886A (en) * | 2013-03-14 | 2013-06-26 | 南京林业大学 | Method for quickly preparing colorful nanocrystalline cellulose film |
| WO2017113275A1 (en) * | 2015-12-31 | 2017-07-06 | 宁波艾特米克锂电科技有限公司 | Composite nanofiber membrane for electrochemical element, preparation method and energy storage device |
| CN108314803A (en) * | 2018-02-06 | 2018-07-24 | 东北林业大学 | A kind of chiral nematic Cellulose nanocrystal body-glycerine laminated film and its preparation method and application |
| CN112661993A (en) * | 2020-12-24 | 2021-04-16 | 南京信息工程大学 | CNC/polyol composite film and preparation method thereof |
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| CN103172886A (en) * | 2013-03-14 | 2013-06-26 | 南京林业大学 | Method for quickly preparing colorful nanocrystalline cellulose film |
| WO2017113275A1 (en) * | 2015-12-31 | 2017-07-06 | 宁波艾特米克锂电科技有限公司 | Composite nanofiber membrane for electrochemical element, preparation method and energy storage device |
| CN108314803A (en) * | 2018-02-06 | 2018-07-24 | 东北林业大学 | A kind of chiral nematic Cellulose nanocrystal body-glycerine laminated film and its preparation method and application |
| CN112661993A (en) * | 2020-12-24 | 2021-04-16 | 南京信息工程大学 | CNC/polyol composite film and preparation method thereof |
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