CN115819848B - Multifunctional nano-cellulose composite solution and preparation method and application thereof - Google Patents
Multifunctional nano-cellulose composite solution and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 32
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 30
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- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 6
- FYGDTMLNYKFZSV-URKRLVJHSA-N (2s,3r,4s,5s,6r)-2-[(2r,4r,5r,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5r,6s)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1[C@@H](CO)O[C@@H](OC2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-URKRLVJHSA-N 0.000 claims description 5
- 229920002498 Beta-glucan Polymers 0.000 claims description 5
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 claims description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 5
- 229940043267 rhodamine b Drugs 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005083 Zinc sulfide Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention discloses a multifunctional nano-cellulose composite solution and a preparation method and application thereof. Firstly, plant or industrial pulp fibers such as needle wood, broad-leaved wood, straw or bamboo are used as raw materials, modified fibers are prepared through modification means such as peroxy acid oxidation treatment, TEMPO oxidation treatment, enzymolysis treatment and the like, and functional components are mixed in the fibrillation process of the modified fibers, so that uniform and stable composite solution is directly obtained. The traditional functional nano cellulose composite solution needs to prepare nano cellulose firstly and then blend with functional components to realize dispersion. According to the preparation method of the functional nano cellulose composite solution, in the processing process, the micro-nanocrystallization and the dispersion of the functional components are synchronously carried out, and then the functional components are directly dispersed in the nano cellulose solution, so that the multifunctional composite solution with stable performance is prepared.
Description
Technical Field
The invention belongs to the technical field of functional composite solution preparation, and particularly relates to a multifunctional nano-cellulose composite solution, and a preparation method and application thereof.
Background
With the rapid development of technology and the increasing demand of people for high quality life, the demand of high-additional-price functional products is also increasing. The nanocellulose is taken as a natural renewable material with the most extensive natural sources, and by virtue of good dispersibility, biocompatibility, plasticity and excellent mechanical properties, the nanocellulose increasingly becomes a research hot spot, and the nanocellulose-based composite material is widely applied to various fields of agriculture, electronics, cosmetic, food, medical treatment and the like.
Aiming at the defects of single component and lack of functionality of the nanocellulose, blending and adding other functional components become the most mainstream means, such as introducing functional molecules, functional particles, such as carbon nanotubes, graphene and the like. In order to disperse the functional components and the nanocellulose particles on the micro-nano scale, the functional components are subjected to micro-nanocrystallization treatment in a liquid phase, particularly an aqueous solution, and then mixed with the nanocellulose dispersion liquid. The method has the advantages of multiple operation steps, high energy consumption, poor compatibility of certain functional components and nanocellulose, uneven mixing of the composite solution caused by flocculation, sedimentation in the storage process and the like, so that the application of the composite solution is limited to a great extent.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a multifunctional nano-cellulose composite solution and a preparation method and application thereof.
The aim of the invention is realized by the following technical scheme:
In a first aspect, the invention provides a method for preparing a multifunctional nanocellulose composite solution, comprising the following steps:
(1) Preparation of modified fibers: the plant fiber is oxidized by peroxy acid to obtain modified fiber;
The industrial pulp fiber is subjected to TEMPO oxidation treatment or enzymolysis treatment to obtain modified fiber;
(2) Preparation of multifunctional nanocellulose composite solution: mixing the modified fiber prepared in the step (1) with functional components, transferring to a fibrillation device, and stirring to obtain a multifunctional nano-cellulose composite solution; the functional components are beta-glucan, carboxymethyl cellulose, chitosan, hemicellulose, sodium diatomite, glycerol, essential oil, nile red, rhodamine B, carbon nano tubes, clay, graphene, titanium dioxide, molybdenum disulfide, tungsten trioxide, calcium carbonate, zinc sulfide or carbon black; the mass ratio of the modified fiber to the functional component is 1:0.01 to 20.
Further, in the step (1), the modified fiber obtained by the plant fiber through the peroxy acid oxidation treatment specifically comprises the following substeps:
a1 Adding 1 part by mass of plant fiber into 30-50 parts by mass of 4-6wt% peroxyacid solution, adding 20wt% of sodium hydroxide solution to adjust pH to 4-6, reacting for 1-3 h at 85 ℃, and filtering to obtain a filtrate;
a2 Repeating the operation of the step a 1) until the filtered material reaches fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; filtering and washing the reactant by deionized water until the pH value of the filtrate is 6.5-7.5, thus obtaining the modified fiber.
Further, in the step (1), the industrial pulp fiber is subjected to TEMPO oxidation treatment to obtain a modified fiber specifically comprising: dispersing 1 part by mass of industrial pulp fiber into 100 parts by mass of 0.1mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding TEMPO, sodium chlorate and sodium hypochlorite, uniformly mixing, reacting at 40-60 ℃ for 6-72 h, and filtering and washing a reactant by deionized water until the pH value of the reactant is 6.5-7.5 after the reaction is finished to obtain modified fiber;
the mass ratio of the industrial paper pulp fiber to the effective chlorine content in TEMPO, sodium chlorate and sodium hypochlorite is 1:0.01-0.02, 1:0.5-2 and 1:0.05-0.1 respectively.
Further, in the step (1), the modified fiber obtained by the enzymolysis treatment of the industrial pulp fiber is specifically: dispersing 1 part by mass of industrial pulp fiber into 100 parts by mass of 0.2mol/l acetic acid-sodium acetate buffer solution, adding 0.005-0.01 part by mass of trichoderma viride, reacting at 48-52 ℃ for 48-72 h, taking out reactants, filtering and washing the reactants with deionized water to pH 6.5-7.5, and obtaining the modified fiber.
Further, the modified fiber obtained by the plant fiber through the peroxy acid oxidation treatment is subjected to TEMPO oxidation treatment or enzymolysis treatment, and specifically comprises the following steps: dispersing 1 part by mass of the modified fiber into 100 parts by mass of 0.1mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding TEMPO, sodium chlorate and sodium hypochlorite, uniformly mixing, reacting at 40-60 ℃ for 6-72 h, and filtering and washing reactants to 6.5-7.5 by deionized water after the reaction is finished; the mass ratio of the modified fiber to the effective chlorine content in TEMPO, sodium chlorate and sodium hypochlorite is 1:0.01-0.02, 1:0.5-2 and 1:0.05-0.1 respectively;
or dispersing 1 part by mass of the modified fiber in 100 parts by mass of 0.2mol/l acetic acid-sodium acetate buffer solution, adding 0.005-0.01 part by mass of trichoderma viride, reacting at 48-52 ℃ for 48-72 h, taking out reactants, and filtering and washing the reactants to 6.5-7.5 by deionized water.
Further, the fibrillating device is a high pressure homogenizer, a grinder or a mechanical mixer.
Further, the peroxyacid is peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxymonophosphate or peroxydiphosphate.
In a second aspect, the present invention provides a multifunctional nanocellulose composite solution.
In a third aspect, the present invention provides the use of a multifunctional nanocellulose composite solution as a coating.
In a fourth aspect, the invention provides an application of a multifunctional nanocellulose composite solution as an antistatic material, an electromagnetic shielding packaging material, a photo-thermal material or a fluorescent material.
The beneficial effects of the invention are as follows: the modified pulp fiber is mixed with the functional molecules before fibrillation treatment, so that the functional molecules are more uniformly dispersed in the nano cellulose suspension; in addition, when the functional molecules are rigid functional particles, the nanocellulose and the functional particles can perform a synergistic effect in the mechanical shearing process, namely, the nanocellulose assists the functional particles to disperse, and the functional particles assist the nanocellulose fibrils to separate; meanwhile, the nanocellulose and the functional molecules can be mixed in different proportions between 0.01 and 20 weight percent of the functional molecules. The multifunctional nano-cellulose composite solution is uniformly and stably mixed, has a simple production process, and is suitable for large-scale production.
Drawings
FIG. 1 is a schematic representation of the multifunctional nanocellulose composite solution prepared in example 2 as an antistatic coating;
FIG. 2 is a display diagram of a composite membrane prepared from the multifunctional nanocellulose composite solution prepared in example 3;
FIG. 3 is a transmission electron microscope image of carbon black particles and the multifunctional nanocellulose composite solution prepared in example 5, wherein FIG. 3a is a transmission electron microscope image of carbon black particles and FIG. 3b is a transmission electron microscope image of the multifunctional nanocellulose composite solution prepared in example 5;
FIG. 4 is a transmission electron microscope image of a bulk multi-layer molybdenum disulfide and the multifunctional nanocellulose composite solution prepared in example 6, wherein FIG. 4a is a transmission electron microscope image of the bulk multi-layer molybdenum disulfide and FIG. 4b is a transmission electron microscope image of the multifunctional nanocellulose composite solution prepared in example 6;
FIG. 5 is a display of a composite membrane prepared from the multifunctional nanocellulose composite solution prepared in example 6;
fig. 6 is a transmission electron microscope image of a bulk multi-layered graphene and the multifunctional nanocellulose composite solution prepared in example 7, wherein fig. 6a is a transmission electron microscope image of the bulk multi-layered graphene, and fig. 6b is a transmission electron microscope image of the multifunctional nanocellulose composite solution prepared in example 7;
FIG. 7 is a display of a composite membrane prepared from the multifunctional nanocellulose composite solution prepared in example 7;
FIG. 8 is a display diagram of a composite membrane prepared from the multifunctional nanocellulose composite solution prepared in example 8;
fig. 9 is a display diagram of a composite membrane prepared from the multifunctional nanocellulose composite solution prepared in example 9.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples, it being understood that the specific examples described herein are for the purpose of illustrating the present invention only, and not all the examples. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are within the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, as described herein without any knowledge, are commercially available.
In the present invention, a high-pressure homogenizer, a grinder or a juicer is used as the fiberizing apparatus; the functional components are beta-glucan, carboxymethyl cellulose, chitosan, hemicellulose, sodium diatomite, glycerol, essential oil, nile red, rhodamine B, carbon nano tubes, clay, graphene, titanium dioxide, molybdenum disulfide, tungsten trioxide, calcium carbonate or carbon black; the peroxyacid is peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxymonophosphate or peroxydiphosphate.
Example 1
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
10g of industrial pulp fiber is dispersed in 1L of 0.1mol/L phosphoric acid-sodium acetate buffer solution, 0.1594g of TEMPO, 5g of sodium chlorate and 0.5g of sodium hypochlorite are sequentially added, the mixture is uniformly mixed and then reacted for 72 hours at 40 ℃, and after the reaction is finished, deionized water is used for filtering and washing the pH of the reactant to 6.5, so that the modified fiber is obtained.
(2) Preparation of multifunctional nanocellulose composite solution:
And (3) mixing 3g of the modified fiber prepared in the step (1) with 1.5g of beta-glucan, transferring to a mechanical stirrer for stirring, and adding deionized water to the total volume of 750mL for 20 times to obtain the multifunctional nano-cellulose composite solution.
The concentration of cellulose in the multifunctional nanocellulose composite solution prepared in example 1 is 0.6wt%, and beta-glucan is uniformly dispersed in the multifunctional nanocellulose composite solution. The multifunctional nanocellulose composite solution prepared in example 1 can remain stable and uniformly dispersed within one month compared with the composite solution prepared by the blending method.
Application of the multifunctional nanocellulose composite solution prepared in example 1 as a medical moisturizing dressing:
The multifunctional nanocellulose composite solution prepared in the embodiment 1 is directly used as a medical moisturizing dressing; taking the incision surface induced in vitro of a male diabetic mouse as a treatment object, testing the wound healing potential of the multifunctional nanocellulose composite solution and taking the wound healing potential as an experimental group, and taking the composite solution prepared by a blending method as a treatment group; compared with an experimental group and a treatment group, the multifunctional nano-cellulose composite solution prepared in the embodiment 1 has the capability of promoting wound healing more rapidly, and the multifunctional nano-cellulose composite solution prepared by the method provided by the invention has application potential in the field of medical moisturizing dressing.
Example 2
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
The plant fiber used in this example is white pine;
And (3) peroxy acid oxidation treatment:
a1 40g of white pine is added into 1.2L of 4wt percent peroxyacid solution, 20wt percent sodium hydroxide solution is added to adjust the pH to 4, the mixture is reacted for 3 hours at the temperature of 85 ℃, and the filtered product is obtained;
a2 Repeating the operation of the step a 1) for 3 times until the filtered matters reach fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; the reaction was filtered and washed with deionized water until the filtrate had a pH of 6.5 to give a modified fiber.
(2) Preparation of multifunctional nanocellulose composite solution:
3g of the modified fiber prepared in the step (1) and 0.03g of carbon black particles are dispersed into 3500mL of water and mixed, the size of the carbon black particles is 30-45nm, and the carbon black particles are transferred to a high-pressure homogenizer for 5 times of high-speed stirring, so that the multifunctional nano-cellulose composite solution is obtained.
The concentration of cellulose in the multifunctional nano-cellulose composite solution prepared in the example 2 is 0.09wt%, and the carbon black particles are processed into small particles with uniform size under the synergistic effect of cellulose, and the small particles are uniformly dispersed and adsorbed on the surface of the nano-cellulose, wherein the diameter of the small particles is 8-15 nm. The multifunctional nanocellulose composite solution prepared in example 2 can be kept stable within 6 months; the size of the carbon black particles in the composite solution prepared by adopting the blending method is still the original size, the size of the carbon black particles is not processed and reduced, the size is 1-5 um, and the carbon black particles of the composite solution are obviously settled in about half a month.
Application of the multifunctional nanocellulose composite solution prepared in example 2 as an antistatic coating:
The multifunctional nanocellulose composite solution prepared in the embodiment 2 is uniformly sprayed on the surface of a PET film through a spraying machine to form a layer of compact film to obtain an antistatic coating, and the conductivity of the antistatic coating is 0.01S/cm as shown in figure 1. The composite solution prepared by the blending method cannot realize the preparation of a uniform functional coating due to uneven carbon black dispersion, and the obtained coating has no conductivity.
Example 3
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
0.4g of industrial pulp fiber is dispersed in 40mL of 0.2mol/l acetic acid-sodium acetate buffer solution, 0.2g of trichoderma viride is added, the reaction is carried out for 72 hours at 48 ℃, the reactant is taken out, and the pH of the reactant is filtered and washed by deionized water to 6.5, so as to obtain the modified fiber.
(2) Preparation of multifunctional nanocellulose composite solution:
Mixing 3g of the modified fiber prepared in the step (1) with 6g of carbon particles, wherein the size of the carbon black particles is 1-5 um, transferring the carbon black particles to a mechanical stirrer for stirring, and adding deionized water to the total volume of 750mL for 30 times to obtain the multifunctional nano-cellulose composite solution.
The concentration of cellulose in the multifunctional nanocellulose composite solution prepared in example 3 is 0.4wt%, and carbon black particles are processed into small particles with uniform size and less than 10nm under the synergistic effect of cellulose, and the small particles are uniformly dispersed and adsorbed on the surface of nanocellulose. The multifunctional nanocellulose composite solution prepared in example 3 can be kept stable within 6 months; the size of the carbon black particles in the composite solution prepared by adopting the blending method is still the original size, the size of the carbon black particles is not processed and reduced, the size is 1-5 um, and the carbon black particles of the composite solution are obviously settled in about half a month.
Application of composite film prepared from multifunctional nanocellulose composite solution prepared in example 3 as antistatic or electromagnetic shielding packaging material:
0.35g of the multifunctional nanocellulose composite solution prepared in example 3 was dispersed in 500mL of water, dispersed for 2 minutes by an Ultraturrax dispersing machine at 10000rpm, transferred into a vacuum funnel with a diameter of 10cm for filtration, and the filtrate was dried at 95 ℃ for 6 minutes in a vacuum pressure paper dryer to prepare a composite membrane, as shown in FIG. 2. The conductivity of the composite film prepared by using the multifunctional nanocellulose composite solution prepared in example 3 is 25+/-4S/cm, and the composite film can be used as an antistatic or electromagnetic shielding packaging material.
And the composite solution prepared by the blending method cannot prepare the composite film with excellent performance due to uneven carbon black dispersion, and the prepared composite film has poor conductivity of about 0.02+/-0.006S/cm. And the mechanical strength of the composite film prepared by using the multifunctional nanocellulose composite solution prepared in example 3 is superior to that of the composite film prepared by using the composite solution prepared by the blending method, and the comparison data of the two are shown in table 1. The mechanical strength includes tensile strength and elastic modulus.
Table 1: mechanical strength comparison meter
Example 4
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
the plant fiber used in this example is bamboo;
(1.1) peroxoic acid oxidation treatment:
a1 Placing 50g of bamboo in a 2L beaker, adding 2.5L of 6wt% peracetic acid solution, then adding 20wt% sodium hydroxide solution to adjust the pH to 6, reacting for 1h at 85 ℃, and filtering to obtain a filtrate;
a2 Repeating the operation of the step a 1) until the filtered material reaches fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; in this example, the operation of step a 1) was repeated 3 times, the filtrate was fibrillated and the color became pure white; filtering and washing reactants by deionized water until the pH value of the filtrate is 7.5, and obtaining the modified fiber subjected to the peroxy acid oxidation treatment;
(1.2) enzymolysis treatment: dispersing 1g of the modified fiber subjected to the peroxyacid oxidation treatment prepared in the step (1.1) into 100mL of 0.2mol/l acetic acid-sodium acetate buffer solution, adding 0.01g of trichoderma viride, reacting at 52 ℃ for 48 hours, taking out the reactant, filtering and washing the reactant with deionized water to pH 7.5, and obtaining the modified fiber.
The modified fiber obtained by the peroxy acid oxidation treatment and the enzymolysis treatment has higher length-diameter ratio, and the surface of the modified fiber has a small amount of charges, so that the modified fiber is favorable for the stability of modified cellulose and the mechanical property of film formation.
(2) Preparation of multifunctional nanocellulose composite solution:
mixing 3g of the modified fiber prepared in the step (1) with 15g of carbon black particles, wherein the size of the carbon black particles is 30-45nm, transferring the carbon black particles to a grinder, and adding deionized water to the total volume of 300mL for 10 times to obtain the multifunctional nano-cellulose composite solution.
The concentration of cellulose in the multifunctional nano-cellulose composite solution prepared in example 4 is 1wt%, and carbon black particles are processed into small particles with uniform size under the synergistic effect of cellulose, uniformly dispersed and adsorbed on the surface of nano-cellulose. The multifunctional nano-cellulose composite solution prepared in the embodiment 4 can be kept stable within half a month without obvious sedimentation. The size of the carbon black particles in the composite solution prepared by adopting the blending method is still the original size, the size of the carbon black particles is not processed and reduced, the size is 1-5 um, and the carbon black particles of the composite solution are obviously settled in about half a month.
Application of composite film prepared from multifunctional nanocellulose composite solution prepared in example 4 as antistatic material or electromagnetic shielding packaging material:
Dispersing 0.4g of the multifunctional nanocellulose composite solution prepared in example 4 into 500mL of water, dispersing for 2 minutes by an Ultraturrax dispersing machine at 10000rpm, transferring into a vacuum funnel with the diameter of 10cm for filtering, and drying the filtrate in a vacuum pressure paper dryer at 95 ℃ for 6 minutes to prepare the composite membrane. The conductivity of the composite film prepared by using the multifunctional nanocellulose composite solution prepared in example 4 is 55+/-1.2S/cm, and the composite film can be used as an antistatic or electromagnetic shielding packaging material.
And the composite solution prepared by the blending method cannot prepare the composite film with excellent performance due to uneven carbon black dispersion, and the prepared composite film has poor conductivity of about 0.01+/-0.002S/cm. And the mechanical strength of the composite film prepared by using the multifunctional nanocellulose composite solution prepared in example 4 is superior to that of the composite film prepared by using the composite solution prepared by the blending method, and the comparison data of the two are shown in table 2.
Table 2: mechanical strength comparison meter
Example 5
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
The plant fiber used in the embodiment is reed;
(1.1) peroxoic acid oxidation treatment:
a1 80g reed is put into a 5L beaker, 3.2L of 5wt% peracetic acid solution is added, then 20wt% sodium hydroxide solution is added to adjust the pH to 5, the mixture is reacted for 2 hours at 85 ℃, and a filter material is obtained by filtration;
a2 Repeating the operation of the step a 1) until the filtered material reaches fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; in this example, the operation of step a 1) was repeated 3 times, the filtrate was fibrillated and the color became pure white; filtering and washing reactants by deionized water until the pH value of the filtrate is 7.0, and obtaining the modified fiber subjected to the peroxy acid oxidation treatment;
(1.2) TEMPO oxidation treatment: dispersing 20g of the modified fiber subjected to the peroxyacid oxidation treatment prepared in the step (1.1) in 2L of 0.1mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding 0.4g of TEMPO, 40g of sodium chlorate and 0.4g of sodium hypochlorite, uniformly mixing, reacting at 60 ℃ for 8 hours, and filtering and washing the reactant by deionized water until the pH value is 7.5 after the reaction is finished to obtain the modified fiber.
The modified fiber obtained by the peroxy acid oxidation treatment and the TEMPO oxidation treatment has higher length-diameter ratio and is favorable for the mechanical property of film formation.
(2) Preparation of multifunctional nanocellulose composite solution:
mixing 3g of the modified fiber prepared in the step (1) with 30g of carbon black particles, wherein the size of the carbon black particles is 1-5 um, as shown in figure 3a, transferring to a mechanical stirrer for stirring, and adding deionized water to the total volume of 750mL for 35 times to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nanocellulose composite solution prepared in example 5 has a cellulose concentration of 0.4wt%, and carbon black particles are processed into small particles with uniform size under the synergistic effect of cellulose, uniformly dispersed and adsorbed on the nanocellulose surface, as shown in fig. 3 b. The multifunctional nanocellulose composite solution prepared in example 5 can be kept stable within 6 months; the size of the carbon black particles in the composite solution prepared by adopting the blending method is still the original size, the size of the carbon black particles is not processed and reduced, the size is 1-5 um, and the carbon black particles of the composite solution are obviously settled in about half a month.
Application of composite film prepared from multifunctional nanocellulose composite solution prepared in example 5 as antistatic or electromagnetic shielding packaging material:
Dispersing 0.35g of the multifunctional nanocellulose composite solution prepared in example 5 into 500mL of water, dispersing for 2 minutes by an Ultraturrax dispersing machine at 10000rpm, transferring into a vacuum funnel with the diameter of 10cm for filtering, and drying the filtrate in a vacuum pressure paper dryer at 95 ℃ for 6 minutes to prepare the composite membrane. The conductivity of the composite film prepared by using the multifunctional nanocellulose composite solution prepared in example 5 is 15+/-5.5S/cm, and the composite film can be used as an antistatic or electromagnetic shielding packaging material.
And the composite solution prepared by the blending method cannot prepare the composite film with excellent performance due to uneven carbon black dispersion, and the prepared composite film has poor conductivity of about 0.05+/-0.005S/cm. And the mechanical strength of the composite film prepared by using the multifunctional nanocellulose composite solution prepared in example 5 is superior to that of the composite film prepared by using the composite solution prepared by the blending method, and the comparison data of the two are shown in table 3.
Table 3: mechanical strength comparison meter
Example 6
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
the plant fiber used in this example is straw;
(1.1) peroxoic acid oxidation treatment:
a1 50g of straw was added to 1.75L of a 4.5wt% peracetic acid solution, followed by addition of a 20wt% sodium hydroxide solution to adjust the pH to 4.5, reacted at 85℃for 1.5 hours, and filtered to give a filtrate;
a2 Repeating the operation of the step a 1) until the filtered material reaches fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; in this example, the operation of step a 1) was repeated 3 times, the filtrate was fibrillated and the color became pure white; filtering and washing reactants by deionized water until the pH value of the filtrate is 6.5, and obtaining the modified fiber subjected to the peroxy acid oxidation treatment;
(1.2) TEMPO oxidation treatment: dispersing 10g of the modified fiber subjected to the peroxyacid oxidation treatment prepared in the step (1.1) in 1L of 0.1mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding 0.1g of TEMPO, 10g of sodium chlorate and 0.8g of sodium hypochlorite, uniformly mixing, reacting at 50 ℃ for 48 hours, and filtering and washing the reactant to pH 7.0 by using deionized water after the reaction is finished to obtain the modified fiber.
The modified fiber obtained by the peroxy acid oxidation treatment and the TEMPO oxidation treatment has higher length-diameter ratio and is favorable for the mechanical property of film formation.
(2) Preparation of multifunctional nanocellulose composite solution:
mixing 3g of the modified fiber prepared in the step (1) with 45g of massive multi-layer molybdenum disulfide, wherein the diameter of the massive multi-layer molybdenum disulfide is 3-8 mu m, as shown in figure 4 a; transferring to a mechanical stirrer for stirring, and adding deionized water to the total volume of 750mL for 25 times to obtain the multifunctional nano-cellulose composite solution.
The concentration of cellulose in the multifunctional nano-cellulose composite solution prepared in example 6 is 0.4wt%, and the multi-layer molybdenum disulfide is processed into small particles with uniform size under the synergistic effect of cellulose, and the small particles are uniformly adsorbed on the surface of nano-cellulose, wherein the diameter of the small particles is 350-2000 nm, as shown in fig. 4 b. The multifunctional nano-cellulose composite solution prepared in the embodiment 6 can be kept stable within half a month without obvious sedimentation.
Application of composite film prepared from multifunctional nanocellulose composite solution prepared in example 6 as photo-thermal material:
0.5g of the multifunctional nanocellulose composite solution prepared in example 6 was dispersed in 700mL of water, dispersed for 2 minutes by an Ultraturrax dispersing machine at 10000rpm, transferred into a vacuum funnel with a diameter of 10cm for filtration, and the filtrate was dried for 6 minutes at 95 ℃ in a vacuum pressure paper dryer to prepare a 60g/m 2 composite membrane, as shown in FIG. 5. The composite film prepared by using the multifunctional nanocellulose composite solution prepared in the embodiment 6 has a photo-thermal effect, the surface temperature of 3s can be increased to 90 ℃ under the irradiation of a near infrared light source, the composite film has a photo-thermal effect, and the composite film can be used as a photo-thermal material.
The composite film prepared by the composite solution prepared by the blending method has the advantages that the molybdenum disulfide is still in a blocky multilayer state, is not stripped and has poor dispersion effect, and the composite film does not have photo-thermal characteristics; and the mechanical strength of the composite film prepared by using the multifunctional nanocellulose composite solution prepared in example 6 is superior to that of the composite film prepared by using the composite solution prepared by the blending method, and the comparison data of the two are shown in table 4.
Table 4: mechanical strength comparison meter
Example 7
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
the plant fiber used in the embodiment is straw;
(1.1) peroxoic acid oxidation treatment:
a1 30g of straw is added into 3L of 5.5wt% peracetic acid solution, then 20wt% sodium hydroxide solution is added to adjust the pH to 5.5, the mixture is reacted for 2.5 hours at 85 ℃, and the filtrate is obtained by filtration;
a2 Repeating the operation of the step a 1) until the filtered material reaches fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; in this example, the operation of step a 1) was repeated 3 times, the filtrate was fibrillated and the color became pure white; filtering and washing reactants by deionized water until the pH value of the filtrate is 7.5, and obtaining the modified fiber subjected to the peroxy acid oxidation treatment;
(1.2) TEMPO oxidation treatment: dispersing 10g of the modified fiber subjected to the peroxyacid oxidation treatment prepared in the step (1.1) in 1L of 0.1mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding 0.18g of TEMPO, 18g of sodium chlorate and 0.9g of sodium hypochlorite, uniformly mixing, reacting at 50 ℃ for 18h, and filtering and washing the reactant to pH 7.0 by using deionized water after the reaction is finished to obtain the modified fiber.
(2) Preparation of multifunctional nanocellulose composite solution:
Mixing 3g of the modified paper prepared in the step (1) with 3g of massive multi-layer graphene, wherein the diameter of the massive multi-layer graphene is 1-8 mu m, as shown in fig. 6 a; transferring to a mechanical stirrer for stirring, and adding deionized water to the total volume of 750mL for 25 times to obtain the multifunctional nano-cellulose composite solution.
The concentration of cellulose in the multifunctional nano-cellulose composite solution prepared in example 7 is 0.4wt%, and the massive multi-layer graphene is processed into small particles with uniform size under the synergistic effect of cellulose, and the small particles are uniformly adsorbed on the surface of nano-cellulose, wherein the diameter of the small particles is 200-800 nm, as shown in fig. 6 b. The multifunctional nano-cellulose composite solution prepared in the embodiment 7 can be kept stable within half a month without obvious sedimentation.
Application of composite film prepared from multifunctional nanocellulose composite solution prepared in example 7 as antistatic or electromagnetic shielding packaging material:
0.3g of the multifunctional nanocellulose composite solution prepared in example 7 was dispersed in 500mL of water, dispersed for 2 minutes by an Ultraturrax disperser at 10000rpm, transferred into a vacuum funnel with a diameter of 10cm for filtration, and the filtrate was dried in a vacuum pressure paper dryer at 95 ℃ for 6 minutes to prepare a composite membrane, as shown in fig. 7. The conductivity of the composite film prepared by using the multifunctional nanocellulose composite solution prepared in example 7 is 75+/-9S/cm, and the composite film can be used as an antistatic or electromagnetic shielding packaging material.
The composite solution prepared by the blending method is not stripped and has poor dispersion effect because the graphene is still in a blocky multilayer state, and the prepared composite film has poor conductivity of about 0.5+/-0.2S/cm. And the mechanical strength of the composite film prepared by using the multifunctional nanocellulose composite solution prepared in example 7 is superior to that of the composite film prepared by using the composite solution prepared by the blending method, and the comparison data of the two are shown in table 5.
Table 5: mechanical strength comparison meter
Example 8
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
The plant fiber used in this example is beet root;
(1.1) peroxoic acid oxidation treatment:
a1 60g of beet root is added into 6L of 5wt percent peracetic acid solution, then 20wt percent sodium hydroxide solution is added to adjust the pH to 5, the mixture is reacted for 1.5 hours at the temperature of 85 ℃, and the filtered product is obtained;
a2 Repeating the operation of the step a 1) until the filtered material reaches fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; in this example, the operation of step a 1) was repeated 3 times, the filtrate was fibrillated and the color became pure white; filtering and washing reactants by deionized water until the pH value of the filtrate is 7.0, and obtaining the modified fiber subjected to the peroxy acid oxidation treatment;
(1.2) TEMPO oxidation treatment: dispersing 10g of the modified fiber subjected to the peroxyacid oxidation treatment prepared in the step (1.1) in 1L of 0.1mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding 0.12g of TEMPO, 12g of sodium chlorate and 0.7g of sodium hypochlorite, uniformly mixing, reacting at 50 ℃ for 12 hours, and filtering and washing the reactant by deionized water until the pH value is 7.5 after the reaction is finished to obtain the modified fiber.
(2) Preparation of multifunctional nanocellulose composite solution:
mixing 3g of the modified fiber prepared in the step (1) with 0.1g of rhodamine B, transferring to a mechanical stirrer for stirring, and adding deionized water to the total volume of 600mL for 25 times to obtain the multifunctional nano-cellulose composite solution.
The concentration of cellulose in the multifunctional nano-cellulose composite solution prepared in the example 8 is 0.5wt%, and rhodamine B is uniformly adsorbed on the surface of the nano-cellulose.
Application of composite membrane prepared from multifunctional nanocellulose composite solution prepared in example 8 as fluorescent material:
0.5g of the multifunctional nanocellulose composite solution prepared in example 8 was dispersed in 600mL of water, dispersed for 2min by an Ultraturrax dispersing machine at 10000rpm, transferred into a vacuum funnel with a diameter of 10cm for filtration, and the filtrate was dried for 6min at 95 ℃ in a vacuum pressure paper dryer to prepare a composite membrane, as shown in FIG. 8. The composite film prepared by using the multifunctional nanocellulose composite solution prepared in the embodiment 8 has fluorescent property, and can be used as a fluorescent material.
Example 9
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
The plant fiber used in this example is potato;
(1.1) peroxoic acid oxidation treatment:
a1 20g of potato is put into 2L of 4wt% peracetic acid solution, then 20wt% sodium hydroxide solution is added to adjust the pH to 4.6, the reaction is carried out for 1.5 hours at 85 ℃, and the filtration is carried out to obtain a filtrate;
a2 Repeating the operation of the step a 1) until the filtered material reaches fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; in this example, the operation of step a 1) was repeated 3 times, the filtrate was fibrillated and the color became pure white; filtering and washing reactants by deionized water until the pH value of the filtrate is 7.0, and obtaining the modified fiber subjected to the peroxy acid oxidation treatment;
(1.2) TEMPO oxidation treatment: dispersing 20g of the modified fiber subjected to the peroxyacid oxidation treatment prepared in the step (1.1) in 2L of 0.1mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding 0.14g of TEMPO, 14g of sodium chlorate and 0.9g of sodium hypochlorite, uniformly mixing, reacting at 55 ℃ for 20h, and filtering and washing the reactant to pH 7.0 by using deionized water after the reaction is finished to obtain the modified fiber.
(2) Preparation of multifunctional nanocellulose composite solution:
Mixing 3g of the modified fiber prepared in the step (1) with 0.03g of nile red, transferring to a mechanical stirrer for stirring, and adding deionized water 30 times until the total volume reaches 500mL to obtain the multifunctional nanocellulose composite solution.
The concentration of cellulose in the multifunctional nanocellulose composite solution prepared in example 9 is 0.6wt%, and nile red is uniformly adsorbed on the surface of nanocellulose. The multifunctional nanocellulose composite solution prepared in example 9 can be kept stable within half a month without obvious sedimentation.
Application of composite membrane prepared from multifunctional nanocellulose composite solution prepared in example 9 as fluorescent material:
0.35g of the multifunctional nanocellulose composite solution prepared in example 9 was dispersed in 500mL of water, dispersed for 2min by an Ultraturrax dispersing machine at 10000rpm, transferred into a vacuum funnel with a diameter of 10cm for filtration, and the filtrate was dried for 6min at 95 ℃ in a vacuum pressure paper dryer to prepare a composite membrane, as shown in FIG. 9. The composite film prepared by using the multifunctional nanocellulose composite solution prepared in the embodiment 9 has fluorescent property, and can be used as a fluorescent material.
Example 10
The preparation process of the multifunctional nano cellulose composite solution comprises the following steps:
(1) Preparation of modified fibers:
The plant fiber used in this example is white pine;
(1.1) peroxoic acid oxidation treatment:
a1 10g of white pine is put into 1L of 4.5wt% peracetic acid solution, then 20wt% sodium hydroxide solution is added to adjust the pH to 5, the mixture is reacted for 2 hours at 85 ℃, and the filtered product is obtained;
a2 Repeating the operation of the step a 1) until the filtered material reaches fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; in this example, the operation of step a 1) was repeated 3 times, the filtrate was fibrillated and the color became pure white; filtering and washing reactants by deionized water until the pH value of the filtrate is 7.0, and obtaining the modified fiber subjected to the peroxy acid oxidation treatment;
(1.2) TEMPO oxidation treatment: dispersing 20g of the modified fiber subjected to the peroxyacid oxidation treatment prepared in the step (1.1) in 2L of 0.1mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding 0.16g of TEMPO, 17g of sodium chlorate and 0.8g of sodium hypochlorite, uniformly mixing, reacting at 55 ℃ for 24 hours, and filtering and washing the reactant to pH 7.0 by using deionized water after the reaction is finished to obtain the modified fiber.
(2) Preparation of multifunctional nanocellulose composite solution:
mixing 3g of the modified fiber prepared in the step (1) with 60g of zinc sulfide, transferring to a grinder, and adding deionized water to the total volume of 750mL for 30 times to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nanocellulose composite solution prepared in example 10 has a cellulose concentration of 0.4wt% and zinc sulfide is uniformly dispersed in the composite solution. The multifunctional nanocellulose composite solution prepared in example 10 can be kept stable within half a month without obvious sedimentation.
Application of composite film prepared from multifunctional nanocellulose composite solution prepared in example 10 as electroluminescent material: dispersing 0.35g of the multifunctional nanocellulose composite solution prepared in example 10 into 500mL of water, dispersing for 2min by an Ultraturrax dispersing machine under 10000rpm, transferring into a vacuum funnel with the diameter of 10cm for filtering, and drying the filtrate in a vacuum pressure paper dryer at 95 ℃ for 6min to prepare the composite membrane. The composite film prepared by using the multifunctional nanocellulose composite solution prepared in the embodiment 10 can emit light after being connected with transparent electrodes on two sides and pressurized, and can be used as an electroluminescent material.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather to enable any modification, equivalent replacement, improvement or the like to be made within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the multifunctional nanocellulose composite solution is characterized by comprising the following steps of: (1) preparation of modified fibers: the plant fiber is oxidized by peroxy acid to obtain modified fiber; the industrial pulp fiber is subjected to TEMPO oxidation treatment or Trichoderma viride enzymolysis treatment to obtain modified fiber; (2) preparation of multifunctional nanocellulose composite solution: mixing the modified fiber prepared in the step (1) with functional components, transferring to a fibrillation device, and stirring to obtain a multifunctional nano-cellulose composite solution; the functional components are beta-glucan, carboxymethyl cellulose, chitosan, hemicellulose, sodium diatomite, glycerol, essential oil, nile red, rhodamine B, carbon nano tubes, clay, graphene, titanium dioxide, molybdenum disulfide, tungsten trioxide, calcium carbonate, zinc sulfide or carbon black; the mass ratio of the modified fiber to the functional component is 1: 0.01-20; when the functional molecules are rigid functional particles, the nanocellulose and the functional particles can perform a synergistic effect in the mechanical shearing process, the nanocellulose assists in dispersing functional particles, and the functional particles assist in dispersing nanocellulose fibrils.
2. The method for preparing a multifunctional nanocellulose composite solution as claimed in claim 1, wherein in step (1), the plant fiber is modified fiber obtained by peroxidic acid oxidation treatment, specifically comprising the following substeps: a1 Adding 1 part by mass of plant fiber into 30-50 parts by mass of 4-6wt% peroxyacid solution, adding 20wt% sodium hydroxide solution to adjust pH to 4-6, reacting for 1-3 hours at 85 ℃, and filtering to obtain a filtrate; a2 Repeating the operation of the step a 1) until the filtered material reaches fibrosis and the color becomes pure white to finish the reaction, so as to obtain a reactant; and filtering and washing the reactant by deionized water until the pH value of the filtrate is 6.5-7.5, thereby obtaining the modified fiber.
3. The method for preparing a multifunctional nanocellulose composite solution as claimed in claim 1, wherein in step (1), the industrial pulp fiber is specifically modified fiber obtained by TEMPO oxidation treatment: dispersing 1 part by mass of industrial pulp fiber into 100 parts by mass of 0.1 mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding TEMPO, sodium chlorate and sodium hypochlorite, uniformly mixing, reacting for 6-72 h at 40-60 ℃, and filtering and washing the reactant with deionized water until the pH value of the reactant is 6.5-7.5 after the reaction is finished to obtain modified fiber: the mass ratio of the industrial pulp fiber to the effective chlorine content in TEMPO, sodium chlorate and sodium hypochlorite is 1:0.01-0.02, 1:0.5-2 and 1:0.05-0.1 respectively.
4. The method for preparing a multifunctional nanocellulose composite solution as claimed in claim 1, wherein in step (1), the modified fibers obtained by enzymolysis treatment of the industrial pulp fibers are specifically: dispersing 1 part by mass of industrial pulp fiber into 100 parts by mass of 0.2mol/l acetic acid-sodium acetate buffer solution, adding 0.005-0.01 part by mass of trichoderma viride, reacting at 48-52 ℃ for 48-72 h, taking out reactants, and filtering and washing the reactants with deionized water until the pH value of the reactants is 6.5-7.5, thus obtaining the modified fiber.
5. The method for preparing the multifunctional nanocellulose composite solution according to claim 2, wherein the modified fiber obtained by the plant fiber through the peroxyacid oxidation treatment is subjected to TEMPO oxidation treatment or enzymolysis treatment, specifically: dispersing 1 part by mass of the modified fiber into 100 parts by mass of 0.1 mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding TEMPO, sodium chlorate and sodium hypochlorite, uniformly mixing, reacting at 40-60 ℃ for 6-72 h, and filtering and washing reactants to 6.5-7.5 by deionized water after the reaction is finished; the mass ratio of the modified fiber to the effective chlorine content in TEMPO, sodium chlorate and sodium hypochlorite is 1:0.01-0.02, 1:0.5-2 and 1:0.05-0.1 respectively; or dispersing 1 part by mass of the modified fiber in 100 parts by mass of 0.2mol/l acetic acid-sodium acetate buffer solution, adding 0.005-0.01 part by mass of trichoderma viride, reacting at 48-52 ℃ for 48-72 h, taking out the reactant, and filtering and washing the reactant with deionized water to 6.5-7.5.
6. The method for preparing a multifunctional nanocellulose composite solution as claimed in claim 1 wherein said fibrillation device is a high pressure homogenizer, a grinder or a mechanical stirrer.
7. The method for preparing a multifunctional nanocellulose composite solution as claimed in claim 2 wherein said peroxyacid is peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxymonophosphate or peroxydiphosphate.
8. A multifunctional nanocellulose composite solution prepared by the method of any one of claims 1-7.
9. The multifunctional nanocellulose composite solution of claim 8 for application as a coating.
10. The use of a composite film prepared from the multifunctional nanocellulose composite solution as claimed in claim 8 as an antistatic material, an electromagnetic shielding packaging material, a photothermal material or a fluorescent material.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147355A (en) * | 2013-02-26 | 2013-06-12 | 中南林业科技大学 | Preparation method of biomass nano fiber conductive paper |
| CN105887235A (en) * | 2016-05-27 | 2016-08-24 | 东莞市联洲知识产权运营管理有限公司 | High-performance nano-crystalline cellulose/chitin composite fibers and preparing method thereof |
| CN106832426A (en) * | 2016-12-12 | 2017-06-13 | 山东圣泉新材料股份有限公司 | A kind of method for preparing nano-cellulose and gained nano-cellulose |
| CN109517863A (en) * | 2018-12-06 | 2019-03-26 | 武汉科丝力纤维制造有限公司 | A kind of preparation method of modified hydrophilic group nano cellulose crystal |
| CN109896522A (en) * | 2017-12-11 | 2019-06-18 | 山东省圣泉生物质石墨烯研究院 | A kind of graphene composite nano fiber element, preparation method and purposes |
| CN112500584A (en) * | 2020-12-18 | 2021-03-16 | 青岛科技大学 | Graphene/cellulose aqueous dispersion and preparation method thereof |
| CN113999322A (en) * | 2021-12-03 | 2022-02-01 | 青岛大学 | Low-energy-consumption preparation method of tempo oxidized cellulose with high carboxyl content |
| CN114068796A (en) * | 2021-11-15 | 2022-02-18 | 深圳大学 | Preparation method of composite thermoelectric material based on regenerated nano-cellulose |
-
2022
- 2022-11-28 CN CN202211506126.7A patent/CN115819848B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147355A (en) * | 2013-02-26 | 2013-06-12 | 中南林业科技大学 | Preparation method of biomass nano fiber conductive paper |
| CN105887235A (en) * | 2016-05-27 | 2016-08-24 | 东莞市联洲知识产权运营管理有限公司 | High-performance nano-crystalline cellulose/chitin composite fibers and preparing method thereof |
| CN106832426A (en) * | 2016-12-12 | 2017-06-13 | 山东圣泉新材料股份有限公司 | A kind of method for preparing nano-cellulose and gained nano-cellulose |
| CN109896522A (en) * | 2017-12-11 | 2019-06-18 | 山东省圣泉生物质石墨烯研究院 | A kind of graphene composite nano fiber element, preparation method and purposes |
| CN109517863A (en) * | 2018-12-06 | 2019-03-26 | 武汉科丝力纤维制造有限公司 | A kind of preparation method of modified hydrophilic group nano cellulose crystal |
| CN112500584A (en) * | 2020-12-18 | 2021-03-16 | 青岛科技大学 | Graphene/cellulose aqueous dispersion and preparation method thereof |
| CN114068796A (en) * | 2021-11-15 | 2022-02-18 | 深圳大学 | Preparation method of composite thermoelectric material based on regenerated nano-cellulose |
| CN113999322A (en) * | 2021-12-03 | 2022-02-01 | 青岛大学 | Low-energy-consumption preparation method of tempo oxidized cellulose with high carboxyl content |
Non-Patent Citations (3)
| Title |
|---|
| Eco-Friendly Cellulose Nanofibrils Designed by Nature: Effects from Preserving Native State;Xuan Yang等;ACS Nano;第14卷(第01期);第724–735页 * |
| Processing strategy for reduced energy demand of nanostructured CNF/clay composites with tailored interfaces;Yang X等;Carbohydrate Polymers;20230311;第312卷;第1-9页 * |
| 低氧化度石墨烯/纳米纤维素杂化材料的制备及应用;刘克;中国优秀硕士学位论文全文数据库工程科技Ⅰ辑;20220115(第01期);第B020-551页 * |
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