CN115819848A - 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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Abstract
The invention discloses a multifunctional nano-cellulose composite solution and a preparation method and application thereof. Firstly, plant or industrial pulp fiber such as needle-leaved wood, broad-leaved wood, straw or bamboo is taken as a raw material, modified fiber is prepared by modification means such as peroxy acid oxidation treatment, TEMPO oxidation treatment, enzymolysis treatment and the like, functional components are mixed in the fibrillation process of the modified fiber, and uniform and stable composite solution is directly obtained. The traditional functional nano-cellulose composite solution needs to prepare nano-cellulose first and then mix with functional components to realize dispersion. According to the preparation method of the functionalized nano-cellulose composite solution, in the processing process, micro-nano and dispersion of functional components are synchronously carried out, and 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 preparation of functional composite solutions, and particularly relates to a multifunctional nano-cellulose composite solution and a preparation method and application thereof.
Background
With the rapid development of science and technology and the increasing demand of people for high-quality life, the demand of functional products with high additional price is also increasing. However, nanocellulose, which is the most widely available natural renewable material in nature, is increasingly a research hotspot due to its good dispersibility, biocompatibility, plasticity and excellent mechanical properties, and nanocellulose-based composites are widely used in various fields such as agriculture, electronics, beauty cosmetics, food, medical treatment and the like.
Aiming at the defects of single component and deficient functionality of the nano-cellulose, blending and adding other functional components become the most mainstream means, such as introducing functional molecules and functional particles, such as carbon nanotubes, graphene and the like. In order to realize the dispersion of the functional components and the nano-cellulose particles on the micro-nano scale, the functional components are subjected to micro-nano treatment in a liquid phase, particularly an aqueous solution, and then are mixed with the nano-cellulose dispersion liquid. The method has the advantages of multiple operation steps, high energy consumption, poor compatibility of certain functional components and the nano-cellulose, non-uniform mixing of the composite solution caused by flocculation, sedimentation in the storage process and the like, thereby greatly limiting the application of the composite solution.
Disclosure of Invention
The invention aims to provide a multifunctional nano-cellulose composite solution and a preparation method and application thereof aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a multifunctional nanocellulose composite solution, which comprises the following steps:
(1) Preparing modified fibers: carrying out peroxy acid oxidation treatment on the plant fibers to obtain modified fibers;
obtaining modified fiber from industrial pulp fiber through TEMPO oxidation treatment or enzymolysis treatment;
(2) Preparing a multifunctional nano-cellulose composite solution: mixing the modified fiber obtained 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 diatomate, glycerol, essential oil, nile red, rhodamine B, carbon nano tube, 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 components is 1:0.01 to 20.
Further, in the step (1), the modified fiber obtained by the oxidation treatment of the plant fiber by the peroxyacid specifically comprises the following substeps:
a1 Adding 1 part by mass of plant fiber into 30-50 parts by mass of 4-6 wt% of peroxy acid solution, adding 20wt% of sodium hydroxide solution to adjust the pH value to 4-6, reacting at 85 ℃ for 1-3 h, and filtering to obtain a filtrate;
a2 Repeating the operation of the step a 1) until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction 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, thus obtaining the modified fiber.
Further, in the step (1), the modified fiber obtained by the industrial pulp fiber through the TEMPO oxidation treatment is specifically: dispersing 1 part by mass of industrial paper 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 for 6-72 hours at 40-60 ℃, filtering and washing the pH of a reactant to 6.5-7.5 by using deionized water after the reaction is finished, and obtaining modified fiber;
the mass ratio of the industrial pulp fiber to the effective chlorine content in TEMPO, sodium chlorate and sodium hypochlorite is respectively 1.
Further, in the step (1), the modified fiber obtained by the industrial pulp fiber through enzymolysis treatment specifically comprises: dispersing 1 part by mass of industrial paper pulp fibers 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 virens, reacting at 48-52 ℃ for 48-72 h, taking out a reactant, and filtering and washing the reactant with deionized water until the pH value is 6.5-7.5 to obtain the modified fibers.
Further, modified fibers obtained by the plant fibers through the oxidation treatment of the peroxy acid are subjected to TEMPO oxidation treatment or enzymolysis treatment, and specifically the modified fibers are obtained by the following steps: dispersing 1 part by mass of the modified fiber in 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 content of available chlorine in TEMPO, sodium chlorate and sodium hypochlorite is respectively 1;
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 virens, reacting for 48-72 h at 48-52 ℃, taking out the reactant, and filtering and washing the reactant by deionized water to 6.5-7.5.
Further, the fibrillation apparatus is a high-pressure homogenizer, a grinder or a mechanical stirrer.
Further, the peroxy acid is peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxymonophosphoric acid, or peroxydiphosphonic acid.
In a second aspect, the present invention provides a multifunctional nanocellulose composite solution.
In a third aspect, the present invention provides a use of a multifunctional nanocellulose composite solution as a coating.
In a fourth aspect, the invention provides an application of the multifunctional nano-cellulose composite solution as an antistatic material, an electromagnetic shielding packaging material, a photo-thermal material or a fluorescent material.
The invention has the beneficial effects that: the modified paper pulp fiber is mixed with 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 a mechanical shearing process, namely the nanocellulose assists in dispersing the functional particles and the functional particles assist in separating the nanocellulose fibrils; meanwhile, the nanocellulose and the functional molecules can be mixed in different proportions of 0.01-20wt% 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 diagram showing the multifunctional nano-cellulose composite solution prepared in example 2 as an antistatic coating;
FIG. 2 is a diagram showing a composite membrane prepared from the multifunctional nano-cellulose composite solution prepared in example 3;
fig. 3 is a transmission electron microscope photograph of carbon black particles and a multifunctional nanocellulose composite solution prepared in example 5, wherein fig. 3a is a transmission electron microscope photograph of carbon black particles, and fig. 3b is a transmission electron microscope photograph of a multifunctional nanocellulose composite solution prepared in example 5;
fig. 4 is a transmission electron microscope photograph of bulk multi-layered molybdenum disulfide and the multifunctional nanocellulose composite solution prepared in example 6, wherein fig. 4a is a transmission electron microscope photograph of bulk multi-layered molybdenum disulfide, and fig. 4b is a transmission electron microscope photograph of the multifunctional nanocellulose composite solution prepared in example 6;
FIG. 5 is a diagram showing a composite membrane prepared from the multifunctional nano-cellulose composite solution prepared in example 6;
fig. 6 is a transmission electron microscope photograph of bulk multi-layer graphene and the multifunctional nanocellulose composite solution prepared in example 7, wherein fig. 6a is a transmission electron microscope photograph of bulk multi-layer graphene, and fig. 6b is a transmission electron microscope photograph of the multifunctional nanocellulose composite solution prepared in example 7;
FIG. 7 is a diagram showing a composite membrane prepared from the multifunctional nano-cellulose composite solution prepared in example 7;
FIG. 8 is a diagram showing a composite membrane prepared from the multifunctional nano-cellulose composite solution prepared in example 8;
fig. 9 is a diagram showing a composite membrane prepared from the multifunctional nanocellulose composite solution prepared in example 9.
Detailed Description
For purposes of promoting an understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description of the embodiments taken in conjunction with the accompanying drawings, it being understood that the specific embodiments described herein are illustrative of the invention and are not intended to be exhaustive. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative 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, if not otherwise indicated, are commercially available.
It should be noted that the high-pressure homogenizer, grinder or juicer of the present invention is used as a fiberizing apparatus; the functional components are beta-glucan, carboxymethyl cellulose, chitosan, hemicellulose, sodium diatomate, glycerol, essential oil, nile red, rhodamine B, carbon nano tube, clay, graphene, titanium dioxide, molybdenum disulfide, tungsten trioxide, calcium carbonate or carbon black; the peroxy acid is peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxymonophosphate or peroxydiphosphate.
Example 1
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
dispersing 10g of industrial pulp fiber in 1L of 0.1mol/L phosphoric acid-sodium acetate buffer solution, sequentially adding 0.1594g of TEMPO, 5g of sodium chlorate and 0.5g of sodium hypochlorite, uniformly mixing, reacting for 72 hours at 40 ℃, filtering and washing the reactant with deionized water until the pH value is 6.5 after the reaction is finished, and obtaining the modified fiber.
(2) Preparing a multifunctional nano cellulose composite solution:
and (2) 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 20 times to the total volume of 750mL to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nano-cellulose composite solution prepared in example 1 has a cellulose concentration of 0.6wt%, and β -glucan is uniformly dispersed in the multifunctional nano-cellulose composite solution. Compared with the composite solution prepared by the blending method, the multifunctional nano-cellulose composite solution prepared in the embodiment 1 can be kept stable and uniformly dispersed in one month.
The multifunctional nano-cellulose composite solution prepared in the embodiment 1 is used as a medical moisture-keeping dressing:
the multifunctional nano-cellulose composite solution prepared in the embodiment 1 is directly used as a medical moisturizing dressing; the wound healing potential of the multifunctional nano-cellulose composite solution is tested by taking the incision surface induced in vitro by a male diabetic mouse as a treatment object and is used as an experimental group, and the composite solution prepared by a blending method is used as a treatment group; compared with the experimental group and the treatment group, the multifunctional nano-cellulose composite solution prepared in the example 1 shows the capability of promoting wound healing more rapidly, and shows that the multifunctional nano-cellulose composite solution prepared by the method provided by the invention has application potential in the field of medical moisturizing dressings.
Example 2
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
the plant fiber used in this example was white pine;
peroxy acid oxidation treatment:
a1 40g of white pine is added to 1.2L of a 4wt% peroxy acid solution, 20wt% sodium hydroxide solution is added to adjust the pH to 4, the reaction is carried out at 85 ℃ for 3h, and the filtrate is obtained by filtration;
a2 Repeating the operation of the step a 1) for 3 times until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction to obtain a reactant; and filtering and washing the reactant by deionized water until the pH value of the filtrate is 6.5 to obtain the modified fiber.
(2) Preparing a multifunctional nano cellulose composite solution:
and (2) dispersing 3g of the modified fiber prepared in the step (1) and 0.03g of carbon black particles into 3500mL of water, mixing, transferring the carbon black particles to a high-pressure homogenizer for 5 times of high-speed stirring to obtain the multifunctional nano-cellulose composite solution, wherein the size of the carbon black particles is 30-45 nm.
The multifunctional nano-cellulose composite solution prepared in the embodiment 2 has a cellulose concentration of 0.09wt%, and carbon black particles are processed into small particles with uniform sizes under the synergistic effect of cellulose, the small particles are uniformly dispersed and adsorbed on the surface of nano-cellulose, and the diameter of the small particles is 8-15 nm. The multifunctional nano-cellulose composite solution prepared in the embodiment 2 can keep stable within 6 months; the size of the carbon black particles in the composite solution prepared by 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 in the composite solution are obviously settled in about half a month.
The multifunctional nano-cellulose composite solution prepared in example 2 is applied as an antistatic coating:
the multifunctional nanocellulose composite solution prepared in example 2 was uniformly sprayed onto the surface of the PET film by a spray coater to form a dense thin film to obtain an antistatic coating, as shown in fig. 1, the conductivity of the obtained antistatic coating was 0.01S/cm. The composite solution prepared by the blending method cannot realize the preparation of a uniform functional coating because the carbon black is not uniformly dispersed, and the obtained coating has no conductivity.
Example 3
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
dispersing 0.4g of industrial pulp fiber into 40mL of 0.2mol/l acetic acid-sodium acetate buffer solution, adding 0.2g of trichoderma virens, reacting for 72h at 48 ℃, taking out a reactant, and filtering and washing the reactant with deionized water to adjust the pH value to 6.5 to obtain the modified fiber.
(2) Preparing a multifunctional nano-cellulose composite solution:
and (2) mixing 3g of the modified fiber prepared in the step (1) with 6g of carbon particles, transferring the carbon particles with the size of 1-5 um to a mechanical stirrer for stirring, and adding deionized water for 30 times until the total volume is 750mL to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nano-cellulose composite solution prepared in example 3 has a cellulose concentration of 0.4wt%, and carbon black particles are processed into small particles with uniform size and size less than 10nm under the synergistic effect of cellulose, and the small particles are uniformly dispersed and adsorbed on the surface of nano-cellulose. The multifunctional nano-cellulose composite solution prepared in the embodiment 3 can keep stable within 6 months; the size of the carbon black particles in the composite solution prepared by 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 in the composite solution are obviously settled in about half a month.
The composite film prepared from the multifunctional nano-cellulose composite solution prepared in the embodiment 3 is applied as an 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 disperser at 10000rpm, transferred to 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. 2. The conductivity of the composite film prepared from the multifunctional nano-cellulose composite solution prepared in the embodiment 3 is 25 +/-4S/cm, and the composite film can be used as an antistatic or electromagnetic shielding packaging material.
The composite solution prepared by the blending method cannot prepare a composite film with excellent performance due to uneven dispersion of the carbon black, and the prepared composite film has poor conductivity which is about 0.02 +/-0.006S/cm. And the mechanical strength of the composite membrane prepared by using the multifunctional nano-cellulose composite solution prepared in example 3 is superior to that of the composite membrane prepared by using the composite solution prepared by the blending method, and comparative data of the two are shown in table 1. The mechanical strength includes tensile strength and elastic modulus.
Table 1: mechanical strength comparison table
Example 4
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
the plant fiber used in this example was bamboo;
(1.1) Peroxyacid Oxidation treatment:
a1 50g of bamboo was put into a 2L beaker, a 6wt% peracetic acid solution of 2.5L was added, followed by addition of 20wt% sodium hydroxide solution to adjust pH to 6, reaction at 85 ℃ for 1h, and filtration to give a filtrate;
a2 Repeating the operation of the step a 1) again until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction to obtain a reactant; in the embodiment, the operation of the step a 1) is repeated for 3 times, and the filtered substance reaches fibrosis and the color is changed into pure white; filtering and washing reactants by using deionized water until the pH value of a filtrate is 7.5 to obtain modified fibers subjected to peroxyacid oxidation treatment;
(1.2) adopting enzymolysis treatment: dispersing 1g of the modified fiber subjected to peroxyacid oxidation treatment prepared in the step (1.1) in 100mL of 0.2mol/l acetic acid-sodium acetate buffer solution, adding 0.01g of trichoderma virens, reacting at 52 ℃ for 48h, taking out the reactant, and filtering and washing the reactant with deionized water until the pH value is 7.5 to obtain the modified fiber.
The modified fiber obtained by firstly carrying out peroxyacid oxidation treatment and then carrying out enzymolysis treatment has higher length-diameter ratio, and the surface of the modified fiber is provided with a small amount of charges, so that the modified fiber is beneficial to the stability and the mechanical performance of film formation of modified cellulose.
(2) Preparing a multifunctional nano cellulose composite solution:
mixing the modified fiber obtained in the step (1) of 3g with 15 g carbon black particles, wherein the size of the carbon black particles is 30-45nm, transferring the carbon black particles to a grinding machine, and adding deionized water 10 times to the total volume of 300 mL to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nano-cellulose composite solution prepared in example 4 has a cellulose concentration of 1wt%, and 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 nano-cellulose. The multifunctional nano-cellulose composite solution prepared in example 4 can be stable within half a month without obvious sedimentation. The size of the carbon black particles in the composite solution prepared by 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 in the composite solution are obviously settled in about half a month.
Example 4 application of a composite film prepared from the multifunctional nanocellulose composite solution prepared in example 4 as an antistatic material or an electromagnetic shielding packaging material:
dispersing 0.4g of the multifunctional nano-cellulose composite solution prepared in the example 4 into 500mL of water, dispersing for 2 minutes by an Ultraturrax dispersion machine under the condition of 10000rpm, transferring into a vacuum funnel with the diameter of 10cm for filtering, and drying the filtrate for 6 minutes at 95 ℃ in a vacuum pressure paper drying machine to obtain the composite membrane. The conductivity of the composite film prepared by using the multifunctional nano-cellulose composite solution prepared in the example 4 is 55 +/-1.2S/cm, and the composite film can be used as an antistatic or electromagnetic shielding packaging material.
The composite solution prepared by the blending method cannot prepare a composite film with excellent performance due to uneven dispersion of the carbon black, and the prepared composite film has poor conductivity of about 0.01 +/-0.002S/cm. And the mechanical strength of the composite membrane prepared by using the multifunctional nano-cellulose composite solution prepared in example 4 is superior to that of the composite membrane prepared by using the composite solution prepared by the blending method, and comparative data of the two are shown in table 2.
Table 2: mechanical strength comparison table
Example 5
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
the plant fiber used in this example is reed;
(1.1) Peroxyacid Oxidation treatment:
a1 80g of reed was put into a 5L beaker, 3.2L of a 5wt% peracetic acid solution was added, followed by addition of a 20wt% sodium hydroxide solution to adjust the pH to 5, reaction was carried out at 85 ℃ for 2 hours, and filtration was carried out to obtain a filtrate;
a2 Repeating the operation of the step a 1) again until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction to obtain a reactant; in the embodiment, the operation of the step a 1) is repeated for 3 times, and the filtered substance reaches fibrosis and the color is changed into pure white; filtering and washing the reactant by deionized water until the pH value of the filtrate is 7.0 to obtain modified fiber subjected to peroxyacid oxidation treatment;
(1.2) TEMPO Oxidation treatment: and (2) dispersing 20g of the modified fiber subjected to 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 for 8h at 60 ℃, filtering and washing the reactant with deionized water until the pH value is 7.5 after the reaction is finished, and thus obtaining the modified fiber.
The modified fiber obtained by firstly carrying out peroxy acid oxidation treatment and then carrying out TEMPO oxidation treatment has higher length-diameter ratio and is beneficial to the mechanical performance of film formation.
(2) Preparing a multifunctional nano cellulose composite solution:
and (2) 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, transferring the carbon black particles to a mechanical stirrer for stirring as shown in figure 3a, and adding deionized water for 35 times until the total volume is 750mL to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nanocellulose composite solution prepared in example 5 had a cellulose concentration of 0.4wt%, and carbon black particles were processed into small particles of uniform size under the synergistic effect of cellulose to be uniformly dispersed and adsorbed on the surface of nanocellulose, as shown in fig. 3 b. The multifunctional nano-cellulose composite solution prepared in the example 5 can be kept stable within 6 months; the size of the carbon black particles in the composite solution prepared by 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 in the composite solution are obviously settled in about half a month.
The composite film prepared from the multifunctional nano-cellulose composite solution prepared in the embodiment 5 is applied as an antistatic or electromagnetic shielding packaging material:
dispersing 0.35g of the multifunctional nano-cellulose composite solution prepared in the example 5 into 500mL of water, dispersing for 2 minutes by an Ultraturrax dispersion machine under the condition of 10000rpm, transferring into a vacuum funnel with the diameter of 10cm for filtration, and drying the filtrate for 6min at 95 ℃ in a vacuum pressure paper drying machine to obtain the composite membrane. The conductivity of the composite film prepared by using the multifunctional nano-cellulose 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.
The composite solution prepared by the blending method cannot prepare a composite film with excellent performance due to uneven dispersion of the carbon black, and the prepared composite film has poor conductivity of about 0.05 +/-0.005S/cm. And the mechanical strength of the composite membrane prepared by using the multifunctional nano-cellulose composite solution prepared in example 5 is superior to that of the composite membrane prepared by using the composite solution prepared by the blending method, and the comparative data of the two are shown in table 3.
Table 3: mechanical strength comparison table
Example 6
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
the plant fiber used in this example was straw;
(1.1) Peroxyacid Oxidation treatment:
a1 50g of straw was added to 1.75L of a 4.5wt% solution of peroxyacetic acid, followed by addition of a 20wt% solution of sodium hydroxide to adjust the pH to 4.5, reaction was carried out at 85 ℃ for 1.5 hours, and filtration was carried out to obtain a filtrate;
a2 Repeating the operation of the step a 1) again until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction to obtain a reactant; in the embodiment, the operation of the step a 1) is repeated for 3 times, and the filtered substance reaches fibrosis and the color is changed into pure white; filtering and washing reactants by using deionized water until the pH value of a filtrate is 6.5 to obtain modified fibers subjected to peroxyacid oxidation treatment;
(1.2) TEMPO Oxidation treatment: and (2) dispersing 10g of the modified fiber subjected to 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 for 48h at 50 ℃, filtering and washing the reactant with deionized water until the pH value is 7.0 after the reaction is finished, and thus obtaining the modified fiber.
The modified fiber obtained by firstly carrying out peroxy acid oxidation treatment and then carrying out TEMPO oxidation treatment has higher length-diameter ratio and is beneficial to the mechanical performance of film formation.
(2) Preparing a multifunctional nano-cellulose composite solution:
mixing 3g of the modified fiber prepared in the step (1) with 45g of blocky multilayer molybdenum disulfide, wherein the diameter of the blocky multilayer molybdenum disulfide is 3-8 mu m, as shown in a figure 4 a; and transferring to a mechanical stirrer for stirring, and adding deionized water for 25 times until the total volume is 750mL to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nano-cellulose composite solution prepared in example 6 has a cellulose concentration of 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 the nano-cellulose, and the diameter of the small particles is 350-2000 nm, as shown in fig. 4 b. The multifunctional nano-cellulose composite solution prepared in example 6 can be kept stable within half a month without obvious sedimentation.
Example 6 application of a composite film prepared from the multifunctional nanocellulose composite solution prepared in example 6 as a photo-thermal material:
dispersing 0.5g of the multifunctional nano-cellulose composite solution prepared in the embodiment 6 into 700mL of water, dispersing for 2 minutes by an Ultraturrax dispersion machine under the condition of 10000rpm, transferring into a vacuum funnel with the diameter of 10cm for filtering, drying the filtrate for 6 minutes at 95 ℃ in a vacuum pressure paper drying machine to prepare 60g/m 2 The composite membrane of (2), as shown in FIG. 5. The composite film prepared from the multifunctional nano-cellulose composite solution prepared in the embodiment 6 has a photo-thermal effect, the surface temperature of 3s can be raised to 90 ℃ under the irradiation of a near-infrared light source, the composite film has the photo-thermal effect, and the composite film can be used as a photo-thermal material.
The composite membrane prepared from the composite solution prepared by the blending method does not have photo-thermal characteristics because the molybdenum disulfide is still in a blocky multi-layer state, is not stripped and has poor dispersion effect; and the mechanical strength of the composite membrane prepared by using the multifunctional nano-cellulose composite solution prepared in example 6 is superior to that of the composite membrane prepared by using the composite solution prepared by the blending method, and comparative data of the two are shown in table 4.
Table 4: mechanical strength comparison table
Example 7
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
the plant fiber used in the embodiment is straw;
(1.1) Peroxyacid Oxidation treatment:
a1 30g of straw was added to 3L of a 5.5wt% peracetic acid solution, followed by addition of a 20wt% sodium hydroxide solution to adjust the pH to 5.5, reaction was carried out at 85 ℃ for 2.5 hours, and filtration was carried out to obtain a filtrate;
a2 Repeating the operation of the step a 1) again until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction to obtain a reactant; in the embodiment, the operation of the step a 1) is repeated for 3 times, and the filtered substance reaches fibrosis and the color is changed into pure white; filtering and washing reactants by using deionized water until the pH value of a filtrate is 7.5 to obtain modified fibers subjected to peroxyacid oxidation treatment;
(1.2) TEMPO Oxidation treatment: and (2) dispersing 10g of the modified fiber subjected to 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 with deionized water until the pH value is 7.0 to obtain the modified fiber.
(2) Preparing a multifunctional nano cellulose composite solution:
mixing 3g of the modified paper fiber prepared in the step (1) with 3g of blocky multi-layer graphene, wherein the diameter of the blocky multi-layer graphene is 1-8 mu m, and is shown in a figure 6 a; and transferring to a mechanical stirrer for stirring, and adding deionized water for 25 times until the total volume is 750mL to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nano-cellulose composite solution prepared in example 7 has a cellulose concentration of 0.4wt%, and bulk 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, and have a diameter of 200-800 nm, as shown in fig. 6 b. The multifunctional nanocellulose composite solution prepared in example 7 can be kept stable within half a month without significant sedimentation.
The composite film prepared from the multifunctional nanocellulose composite solution prepared in example 7 is applied as an 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 to 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 nano-cellulose 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 graphene in the composite solution prepared by the blending method is still in a blocky multi-layer state, so that the graphene is not peeled off and has poor dispersion effect, and the prepared composite membrane has poor conductivity of about 0.5 +/-0.2S/cm. And the mechanical strength of the composite membrane prepared by using the multifunctional nanocellulose composite solution prepared in example 7 is superior to that of the composite membrane prepared by using the composite solution prepared by the blending method, and comparative data of the two are shown in table 5.
Table 5: mechanical strength comparison table
Example 8
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
the plant fiber used in this example was beetroot;
(1.1) Peroxyacid Oxidation treatment:
a1 60g of beetroot are added to 6L of a 5% by weight solution of peroxyacetic acid, followed by addition of a 20% by weight solution of sodium hydroxide to adjust the pH to 5, reacted at 85 ℃ for 1.5h and filtered to give a filtrate;
a2 Repeating the operation of the step a 1) again until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction to obtain a reactant; in the embodiment, the operation of the step a 1) is repeated for 3 times, and the filtered substance reaches fibrosis and the color is changed into pure white; filtering and washing reactants by using deionized water until the pH value of a filtrate is 7.0 to obtain modified fibers subjected to peroxyacid oxidation treatment;
(1.2) TEMPO Oxidation treatment: and (2) dispersing 10g of the modified fiber subjected to 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 for 12h at 50 ℃, filtering and washing the reactant with deionized water until the pH value is 7.5 after the reaction is finished, and thus obtaining the modified fiber.
(2) Preparing a multifunctional nano-cellulose composite solution:
and (2) mixing 3g of the modified fiber prepared in the step (1) with 0.1g of rhodamine B, transferring the mixture to a mechanical stirrer for stirring, and adding deionized water for 25 times until the total volume is 600mL to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nanocellulose composite solution prepared in example 8 has a cellulose concentration of 0.5wt%, and rhodamine B is uniformly adsorbed on the surface of the nanocellulose.
The composite membrane prepared from the multifunctional nanocellulose composite solution prepared in example 8 is applied as a fluorescent material:
0.5g of the multifunctional nanocellulose composite solution prepared in example 8 was dispersed in 600mL of water, dispersed for 2min at 10000rpm by an Ultraturrax disperser, filtered by being transferred to a vacuum funnel with a diameter of 10cm, 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 membrane prepared by using the multifunctional nano-cellulose composite solution prepared in example 8 has fluorescence properties, and can be used as a fluorescent material.
Example 9
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
the vegetable fiber used in this example was potato;
(1.1) Peroxyacid Oxidation treatment:
a1 20g of potatoes were put into 2L of a 4wt% peracetic acid solution, followed by addition of a 20wt% sodium hydroxide solution to adjust the pH to 4.6, reaction at 85 ℃ for 1.5 hours, and filtration to obtain a filtrate;
a2 Repeating the operation of the step a 1) again until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction to obtain a reactant; in the embodiment, the operation of the step a 1) is repeated for 3 times, and the filtered substance reaches fibrosis and the color is changed into pure white; filtering and washing reactants by using deionized water until the pH value of a filtrate is 7.0 to obtain modified fibers subjected to peroxyacid oxidation treatment;
(1.2) TEMPO oxidation treatment: and (2) dispersing 20g of the modified fiber subjected to 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 with deionized water until the pH value is 7.0 to obtain the modified fiber.
(2) Preparing a multifunctional nano-cellulose composite solution:
and (2) 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 for 30 times until the total volume is 500mL to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nanocellulose composite solution prepared in example 9 had a cellulose concentration of 0.6wt%, and nile red was uniformly adsorbed on the nanocellulose surface. The multifunctional nanocellulose composite solution prepared in example 9 can be stable within half a month without significant sedimentation.
The application of the composite membrane prepared from the multifunctional nano-cellulose composite solution prepared in the embodiment 9 as a fluorescent material:
0.35g of the multifunctional nanocellulose composite solution prepared in example 9 was dispersed in 500mL of water, dispersed for 2min at 10000rpm by an Ultraturrax disperser, filtered by being transferred to a vacuum funnel with a diameter of 10cm, 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 membrane prepared by using the multifunctional nano-cellulose composite solution prepared in example 9 has fluorescent properties, and the composite membrane can be used as a fluorescent material.
Example 10
A preparation process of the multifunctional nano-cellulose composite solution comprises the following steps:
(1) Preparing modified fibers:
the plant fiber used in this example was white pine;
(1.1) Peroxyacid Oxidation treatment:
a1 10g of white pine was put into 1L of a 4.5wt% peracetic acid solution, followed by addition of 20wt% sodium hydroxide solution to adjust pH to 5, reaction at 85 ℃ for 2 hours, and filtration to give a filtrate;
a2 Repeating the operation of the step a 1) again until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction to obtain a reactant; in the embodiment, the operation of the step a 1) is repeated for 3 times, and the filtered substance reaches fibrosis and the color is changed into pure white; filtering and washing reactants by using deionized water until the pH value of a filtrate is 7.0 to obtain modified fibers subjected to peroxyacid oxidation treatment;
(1.2) TEMPO Oxidation treatment: and (2) dispersing 20g of modified fiber subjected to 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 with deionized water until the pH value is 7.0 to obtain the modified fiber.
(2) Preparing a multifunctional nano cellulose composite solution:
and (2) mixing 3g of the modified fiber prepared in the step (1) with 60g of zinc sulfide, transferring to a grinding machine, and adding deionized water for 30 times until the total volume is 750mL to obtain the multifunctional nano-cellulose composite solution.
The multifunctional nanocellulose composite solution prepared in example 10 had a cellulose concentration of 0.4wt%, and zinc sulfide was uniformly dispersed in the composite solution. The multifunctional nanocellulose composite solution prepared in example 10 can be stable within half a month without significant sedimentation.
The composite film prepared from the multifunctional nanocellulose composite solution prepared in example 10 is applied as an electroluminescent material: dispersing 0.35g of the multifunctional nano-cellulose composite solution prepared in the embodiment 10 into 500mL of water, dispersing for 2min by an Ultraturrax dispersing machine under the condition of 10000rpm, transferring into a vacuum funnel with the diameter of 10cm for filtering, and drying the filtrate for 6min at 95 ℃ in a vacuum pressure paper drying machine to obtain the composite membrane. The composite film prepared from the multifunctional nano-cellulose composite solution prepared in the embodiment 10 can emit light after being connected with transparent electrodes on two sides and pressurized, and the composite film can be used as an electroluminescent material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the multifunctional nano-cellulose composite solution is characterized by comprising the following steps:
(1) Preparing modified fibers: carrying out peroxy acid oxidation treatment on the plant fibers to obtain modified fibers;
obtaining modified fiber from industrial pulp fiber through TEMPO oxidation treatment or enzymolysis treatment;
(2) Preparing a multifunctional nano-cellulose composite solution: mixing the modified fiber obtained 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 diatomate, glycerol, essential oil, nile red, rhodamine B, carbon nano tube, 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 components is 1:0.01 to 20.
2. The method for preparing the multifunctional nanocellulose composite solution as claimed in claim 1, wherein in step (1), the modified fiber obtained by the oxidation treatment of the plant fiber by the peroxyacid specifically comprises the following substeps:
a1 Adding 1 part by mass of plant fiber into 30-50 parts by mass of 4-6 wt% of peroxy acid solution, adding 20wt% of sodium hydroxide solution to adjust the pH value to 4-6, reacting at 85 ℃ for 1-3 h, and filtering to obtain a filtrate;
a2 Repeating the operation of the step a 1) until the filtrate reaches fibrosis and the color is changed into pure white, and finishing the reaction 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, thus obtaining the modified fiber.
3. The method for preparing the multifunctional nanocellulose composite solution according to claim 1, wherein in step (1), the modified fiber obtained by the industrial pulp fiber through TEMPO oxidation treatment is specifically: dispersing 1 part by mass of industrial paper 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 for 6-72 hours at 40-60 ℃, filtering and washing the pH of a reactant to 6.5-7.5 by using deionized water after the reaction is finished, and obtaining modified fiber;
the mass ratio of the industrial pulp fiber to the effective chlorine content in TEMPO, sodium chlorate and sodium hypochlorite is respectively 1.
4. The method for preparing the multifunctional nanocellulose composite solution according to claim 1, wherein in step (1), the modified fibers obtained by the industrial pulp fibers through enzymolysis are specifically: dispersing 1 part by mass of industrial paper 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 virens, reacting for 48-72 h at 48-52 ℃, taking out a reactant, and filtering and washing the reactant with deionized water until the pH value is 6.5-7.5 to obtain the modified fiber.
5. The method for preparing the multifunctional nanocellulose composite solution according to claim 2, wherein modified fibers obtained by oxidation treatment of plant fibers by peroxyacid are subjected to TEMPO oxidation treatment or enzymolysis treatment, specifically: dispersing 1 part by mass of the modified fiber in 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 content of available chlorine in TEMPO, sodium chlorate and sodium hypochlorite is respectively 1;
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 virens, reacting for 48-72 h at 48-52 ℃, taking out the reactant, and filtering and washing the reactant by deionized water to 6.5-7.5.
6. The method of claim 1, wherein the fibrillation apparatus is a high-pressure homogenizer, a grinder, or a mechanical mixer.
7. The method of claim 2, wherein said peroxyacid is peroxyformic acid, peroxyacetic acid, peroxypropionic acid, peroxymonophosphoric acid, or peroxydiphosphonic acid.
8. A multifunctional nanocellulose composite solution prepared by the method of any one of claims 1 to 7.
9. The multifunctional nanocellulose composite solution of claim 8 applied as a coating.
10. The use of the composite film prepared from the multifunctional nanocellulose composite solution according to claim 8 as an antistatic material, an electromagnetic shielding packaging material, a photo-thermal material or a fluorescent material.
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