CN113563615B - Preparation method of cellulose nanocrystal doped high-transmittance-haze cellulose membrane - Google Patents
Preparation method of cellulose nanocrystal doped high-transmittance-haze cellulose membrane Download PDFInfo
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- CN113563615B CN113563615B CN202110775244.7A CN202110775244A CN113563615B CN 113563615 B CN113563615 B CN 113563615B CN 202110775244 A CN202110775244 A CN 202110775244A CN 113563615 B CN113563615 B CN 113563615B
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Abstract
The invention discloses a preparation method of a cellulose nanocrystal doped high-transmittance haze cellulose membrane, which specifically comprises the following steps: step 1, preparing a cellulose nanocrystal suspension; and 2, preparing a haze film according to the product obtained in the step 1. The invention is prepared by physically compounding cellulose nanocrystalline with smaller size and grain diameter and bamboo pulp fiber. The cellulose membrane prepared by the invention has low toxicity, high haze and high light transmittance, has a certain softening effect on glare, and reduces the damage of strong light to human eyes, so that an observer can obtain better visual experience.
Description
Technical Field
The invention belongs to the technical field of biomass photoelectric nano materials, and relates to a preparation method of a cellulose nanocrystal doped high-transmittance haze cellulose membrane.
Background
The cellulose is a natural polymer with the largest reserve in the nature, and has the advantages of degradability, reproducibility, low pollution, wide distribution and the like. The cellulose nanofiber has the nano-structure characteristics that the diameter of a single fiber is 1-100 nm, the length can reach several micrometers, and the cellulose nanofiber has a large length-diameter ratio and a large specific surface area. When it is oxidized, the size distribution of the fiber becomes smaller, the overall size of the fiber becomes more regular, and by winding and twining, a film with smooth surface and certain haze can be easily woven.
As is well known, plain paper is generally a planar structure formed by stacking large-sized cellulose fibers, and because of the large size of the fibers, the fibers and the fiber stack form large gaps, and the formed paper is generally high in haze and is opaque. However, as an optical material, particularly for OLED substrates and solar cell substrates, the thin film requires not only high haze but also good light transmittance. The low light transmittance of the spectral transmission paper limits the application of the spectral transmission paper in the field of substrates.
Disclosure of Invention
The cellulose film prepared by the method has low toxicity, high haze and high light transmittance, has a certain softening effect on glare, and reduces the damage of strong light to human eyes, so that an observer can obtain better visual experience.
The technical scheme adopted by the invention is that the preparation method of the cellulose nanocrystal-doped high-transmittance haze cellulose membrane specifically comprises the following steps:
step 1, preparing a cellulose nanocrystal suspension;
and 2, preparing a haze film according to the product obtained in the step 1.
The invention is also characterized in that:
the specific process of the step 1 is as follows:
step 1.1, adding bamboo sawdust into a conical flask, and mixing the bamboo sawdust with a citrate buffer solution to obtain sawdust slurry with the concentration of 2-5%;
step 1.2, adding 5-20FPU/g cellulase solution into the wood chip slurry obtained in the step 1.1, then placing the conical flask in a constant-temperature water bath for reaction, and after the reaction is finished, immersing the conical flask into a sterilizing pot to inactivate cellulase;
step 1.3, adding distilled water into a conical flask for dilution to prepare a suspension;
and step 1.4, washing the suspension by using deionized water to remove residual cellulase in the suspension, and then carrying out ultrasonic dispersion on the suspension to prepare the cellulose nanocrystal suspension.
In the step 1.1, the pH value of the citrate is 3.8-5.8.
In the step 1.2, the treatment temperature of the conical flask in the constant-temperature water bath is 35-55 ℃, and the treatment time is 4-12 hours.
In the step 1.2, the time for enzyme inactivation treatment is 10-30 minutes.
In step 1.3, the suspension is obtained by centrifugation at 3500rpm for 10-20min at 25-50 ℃.
Step 1.4, the time of ultrasonic dispersion is 20-40 minutes.
The specific process of the step 2 is as follows:
step 2.1, taking three parts of bamboo pulp fibers, and carrying out ultrasonic treatment in 30-60ml of water for 30-60min to form cellulose dispersion liquid;
and 2.2, respectively adding 10ml, 20ml and 30ml of 2-4wt% cellulose nanocrystal suspension into the cellulose dispersion, stirring for 30-60min, then carrying out ultrasonic treatment for 30-60min to fully mix the cellulose nanocrystal suspension and the cellulose dispersion, and then carrying out reduced pressure volatilization for 12-20 h at 45-65 ℃ to form the high-haze and high-transmittance cellulose film.
The preparation method of the cellulose nanocrystal doped high-transmittance haze cellulose membrane has the beneficial effects that the cellulose nanocrystal doped high-transmittance haze cellulose membrane is prepared by physically compounding the cellulose nanocrystal with small size and particle size and bamboo pulp fibers. The cellulose membrane prepared by the invention has low toxicity, high haze and high light transmittance, has a certain softening effect on glare, and reduces the damage of strong light to human eyes, so that an observer can obtain better visual experience.
Drawings
FIG. 1 is a light transmittance line graph of a cellulose film obtained in example 1 of a method for preparing a cellulose nanocrystal-doped high light transmittance-haze cellulose film according to the present invention;
fig. 2 is a haze line diagram of the cellulose film obtained in example 1 of the method for preparing a cellulose nanocrystal-doped high light transmission-haze cellulose film according to the present invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
The preparation method of the cellulose nanocrystal doped high-transmittance haze cellulose membrane comprises the following steps:
step 1, preparing a cellulose nanocrystal suspension;
adding bamboo sawdust (5-20g) into conical flask, mixing with citrate buffer solution with pH of 3.8-5.8, adjusting slurry concentration to 2-4%, and adding cellulase solution 5-20 FPU/g. The conical flask is placed in a constant-temperature water bath, and stirring treatment is carried out at a set temperature of 35-55 ℃ for 4-12 hours. After the reaction is finished, the conical flask is immersed into an autoclave, and the enzyme is inactivated for 10-30 minutes. Further adding distilled water for dilution, centrifuging at 25-50 deg.C and 3500rpm for 10-20min to obtain suspension, washing with deionized water for several times to remove residual enzyme, and dispersing under the action of ultrasonic wave for 20-40min to obtain stable suspension. And then, centrifuging at the rotating speed of 5000-10000rpm at the temperature of 25-50 ℃ to prepare the cellulose nanocrystalline suspension, repeating the centrifugation and impurity removal for a plurality of times until the supernatant is light blue, namely the cellulose nanocrystalline suspension, and finally, regulating the mass concentration to quantitatively obtain 2-4wt% for later use.
And 2, preparing the haze film according to the product obtained in the step 1.
Taking three parts of bamboo pulp fiber (each part is 1-3g) and performing ultrasonic treatment in 30-60ml of water for 30-60min to form cellulose dispersion liquid; then, 10ml, 20ml and 30ml of 2-4wt% cellulose nanocrystal solution are respectively added into the cellulose dispersion liquid. Stirring for 30-60min, further performing ultrasonic treatment for 30-60min, mixing the nano-cellulose and the bamboo pulp fiber, and volatilizing at 45-65 ℃ under reduced pressure for 12-20 hours to form the high-haze and high-light-transmittance cellulose membrane.
Example 1
The preparation method of the cellulose nanocrystal doped high-transmittance haze cellulose membrane specifically comprises the following steps:
step 1, preparation of cellulose nanocrystals:
bamboo dust (10g) was added to an Erlenmeyer flask, mixed with a citrate buffer solution having a pH of 4.8, adjusted to a slurry concentration of 3%, and 10FPU/g cellulase solution was added. The Erlenmeyer flask was placed in a constant temperature water bath and stirred at a set temperature of 35 ℃ for 8 hours. After the reaction was completed, the Erlenmeyer flask was immersed in an autoclave and the enzyme was inactivated for 10 minutes. Further adding distilled water for dilution, centrifuging at 25 deg.C and 2500rpm for 15min to obtain suspension, washing with deionized water several times to remove residual enzyme, and dispersing under ultrasonic action for 30min to obtain stable suspension. And then, centrifuging at the rotation speed of 10000rpm at 25 ℃ to prepare the cellulose nanocrystal suspension, centrifuging and removing impurities repeatedly for several times until the supernatant is light blue, namely the cellulose nanocrystal suspension, and finally regulating the mass concentration to quantify 2% for later use.
Step 2, compounding the product obtained in the step 1 and bamboo pulp fibers to prepare the haze film:
taking three parts of bamboo pulp fiber (each part is 1g) and carrying out ultrasonic treatment in 60ml of water for 30min to form cellulose dispersion liquid; then 10ml, 20ml and 30ml of 3 wt% cellulose nanocrystal solution are respectively added into the cellulose dispersion liquid. The nano-cellulose and the bamboo pulp fiber are fully mixed by stirring for 30min and further ultrasonic treatment for 30min, and then are decompressed and volatilized for 12 hours at the temperature of 45 ℃ to form the high haze-high light-transmission cellulose membrane.
As shown in fig. 1, the high haze and high transmittance cellulose film prepared in example 1 of the present invention is not added with cellulose nanocrystals, and has a low transmittance of less than 20%. The light transmittance of the film is gradually increased along with the increase of the dosage of the cellulose nanocrystals. When the dosage of the bamboo pulp is 1g and the dosage of the cellulose nanocrystal is 30ml (2 wt%), the light transmittance can reach 88%. The reason is that the fine cellulose nanocrystals are filled in the gaps of the bamboo pulp cellulose and on the surface of the paper, thereby improving the light transmittance.
As shown in FIG. 2, the ordinary paper has no added cellulose nanocrystals, and the haze is good and reaches 100%. As the amount of cellulose nanocrystals increased, the film haze decreased slightly. When the amount of the bamboo pulp is 1g and the amount of the cellulose nanocrystal is 30ml (2 wt%), the haze is reduced but can still reach 92%. Therefore, the cellulose paper has excellent haze and light transmission characteristics compared to plain paper.
Example 2
The preparation method of the cellulose nanocrystal doped high-transmittance haze cellulose membrane comprises the following steps:
step 1, preparation of cellulose nanocrystals:
bamboo dust (5g) was added to an Erlenmeyer flask, mixed with a citrate buffer solution having a pH of 3.8, adjusted to a slurry concentration of 2%, and 5FPU/g cellulase solution was added. The Erlenmeyer flask was placed in a constant temperature water bath and treated with stirring at a set temperature of 45 ℃ for 4 hours. After the reaction was completed, the flask was immersed in an autoclave and the enzyme was inactivated for 20 minutes. Further adding distilled water for dilution, centrifuging at 30 deg.C for 10min at 1000rpm to obtain suspension, washing with deionized water several times to remove residual enzyme, and dispersing under ultrasound for 20min to obtain stable suspension. And then, centrifuging at the rotating speed of 5000rpm at 40 ℃ to prepare the cellulose nanocrystalline suspension, centrifuging and removing impurities repeatedly for several times until the supernatant is light blue, namely the cellulose nanocrystalline suspension, and finally regulating the mass concentration to quantify 3% for later use.
Step 2, compounding the product obtained in the step 1 and bamboo pulp fibers to prepare the haze film:
taking three parts of bamboo pulp fiber (2 g of each part) and carrying out ultrasonic treatment in 30ml of water for 45min to form cellulose dispersion liquid; then, 10ml, 20ml and 30ml of 2 wt% cellulose nanocrystal solution were added to the cellulose dispersion solution. The nano-cellulose and the bamboo pulp fiber are fully mixed by stirring for 45min and further ultrasonic processing for 45min, and then are decompressed and volatilized for 15 hours at 50 ℃ to form the high haze-high light-transmission cellulose membrane.
Example 3
The preparation method of the cellulose nanocrystal doped high-transmittance haze cellulose membrane comprises the following steps:
step 1, preparing cellulose nanocrystals:
bamboo dust (20g) was added to an erlenmeyer flask, mixed with a citrate buffer solution having a pH of 5.8, adjusted to a slurry concentration of 4%, and 20FPU/g cellulase solution was added. The Erlenmeyer flask was placed in a constant temperature water bath and stirred at a set temperature of 55 ℃ for 12 hours. After the reaction was completed, the flask was immersed in an autoclave and the enzyme was inactivated for 50 minutes. Further adding distilled water for dilution, centrifuging at 50 deg.C for 10min at 3500rpm to obtain suspension, washing with deionized water several times to remove residual enzyme, and dispersing under ultrasonic action for 40min to obtain stable suspension. And then, centrifuging at the rotating speed of 8000rpm at the temperature of 50 ℃ to prepare a cellulose nanocrystal suspension, repeatedly centrifuging and removing impurities for several times until the supernatant is light blue, namely the cellulose nanocrystal suspension, and finally, regulating the mass concentration to quantify 4% for later use.
Step 2, compounding the product obtained in the step 1 and bamboo pulp fibers to prepare the haze film: taking three parts of bamboo pulp fibers (each part is 3g) and carrying out ultrasonic treatment for 60min in 45ml of water to form cellulose dispersion liquid; then, 10ml, 20ml and 30ml of 4wt% cellulose nanocrystal solution were added to the cellulose dispersion solution. The nano-cellulose and the bamboo pulp fiber are fully mixed by stirring for 60min and further ultrasonic treatment for 60min, and then are decompressed and volatilized for 20 hours at 65 ℃, so that the high-haze and high-light-transmittance cellulose membrane is formed.
Claims (7)
1. The preparation method of the cellulose nanocrystal doped high-transmittance haze cellulose membrane is characterized by comprising the following steps: the method specifically comprises the following steps:
step 1, preparing a cellulose nanocrystal suspension;
the specific process of the step 1 comprises the following steps:
step 1.1, adding bamboo sawdust into a conical flask, and mixing the bamboo sawdust with a citrate buffer solution to obtain sawdust slurry with the concentration of 2-5%;
step 1.2, adding 5-20FPU/g cellulase solution into the wood chip slurry obtained in the step 1.1, then placing the conical flask in a constant-temperature water bath for reaction, and after the reaction is finished, immersing the conical flask into a sterilizing pot to inactivate cellulase;
step 1.3, adding distilled water into a conical flask for dilution to prepare a suspension;
step 1.4, washing the suspension by using deionized water to remove residual cellulase in the suspension, and then carrying out ultrasonic dispersion on the suspension to prepare a cellulose nanocrystalline suspension;
and 2, preparing the haze film according to the product obtained in the step 1.
2. The method for preparing the cellulose nanocrystal doped high transmittance-haze cellulose film according to claim 1, wherein the method comprises the following steps: in the step 1.1, the pH value of the citrate is 3.8-5.8.
3. The method for preparing the cellulose nanocrystal doped high transmittance-haze cellulose film according to claim 1, wherein the method comprises the following steps: in the step 1.2, the treatment temperature of the conical flask in the constant-temperature water bath is 35-55 ℃, and the treatment time is 4-12 hours.
4. The method for preparing the cellulose nanocrystal-doped high transmittance-haze cellulose film according to claim 1, wherein the method comprises the following steps: in the step 1.2, the time for enzyme inactivation treatment is 10-30 minutes.
5. The method for preparing the cellulose nanocrystal doped high transmittance-haze cellulose film according to claim 1, wherein the method comprises the following steps: in the step 1.3, the suspension is obtained by centrifugation at 3500rpm of 1000-50 ℃ for 10-20 min.
6. The method for preparing the cellulose nanocrystal-doped high transmittance-haze cellulose film according to claim 1, wherein the method comprises the following steps: the time of ultrasonic dispersion in the step 1.4 is 20-40 minutes.
7. The method for preparing the cellulose nanocrystal-doped high transmittance-haze cellulose film according to claim 1, wherein the method comprises the following steps: the specific process of the step 2 is as follows:
step 2.1, taking three parts of bamboo pulp fibers, and carrying out ultrasonic treatment in 30-60ml of water for 30-60min to form cellulose dispersion liquid;
step 2.2, respectively adding 10ml, 20ml and 30ml of 2-4wt% cellulose nanocrystalline suspension into the cellulose dispersion liquid, stirring for 30-60min, then performing ultrasonic treatment for 30-60min to fully mix the cellulose nanocrystalline suspension and the cellulose dispersion liquid, and then performing ultrasonic treatment at 45-65% o And C, volatilizing under reduced pressure for 12-20 hours to form the high-haze and high-transmittance cellulose film.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109400936A (en) * | 2018-09-26 | 2019-03-01 | 陕西科技大学 | A method of the photoelectricity mist degree of regulation modified nanometer cellulose film and ultraviolet filtering effect |
| CN109776870A (en) * | 2019-01-30 | 2019-05-21 | 陕西科技大学 | A kind of preparation method of the haze cellophane of nanocrystalline doping |
| CN110552253A (en) * | 2018-05-30 | 2019-12-10 | 华南理工大学 | high-folding-resistance, ultra-smooth and high-haze transparent holocellulose composite film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110552253A (en) * | 2018-05-30 | 2019-12-10 | 华南理工大学 | high-folding-resistance, ultra-smooth and high-haze transparent holocellulose composite film and preparation method thereof |
| CN109400936A (en) * | 2018-09-26 | 2019-03-01 | 陕西科技大学 | A method of the photoelectricity mist degree of regulation modified nanometer cellulose film and ultraviolet filtering effect |
| CN109776870A (en) * | 2019-01-30 | 2019-05-21 | 陕西科技大学 | A kind of preparation method of the haze cellophane of nanocrystalline doping |
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