CN113912911A - Conductive polypyrrole/nano cellulose composite film material and preparation method thereof - Google Patents

Conductive polypyrrole/nano cellulose composite film material and preparation method thereof Download PDF

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CN113912911A
CN113912911A CN202111280944.5A CN202111280944A CN113912911A CN 113912911 A CN113912911 A CN 113912911A CN 202111280944 A CN202111280944 A CN 202111280944A CN 113912911 A CN113912911 A CN 113912911A
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cellulose
polypyrrole
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film material
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CN113912911B (en
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徐红
铁建飞
毛志平
张琳萍
钟毅
隋晓锋
冯雪凌
麻祎蒙
王碧佳
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Donghua University
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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Abstract

The invention relates to a preparation method of a conductive polypyrrole/nano-cellulose composite membrane material, which comprises the steps of uniformly mixing a solution containing pyrrole monomers and a nano-cellulose suspension to form a Pickering emulsion; adding a certain amount of Fe-containing into the Pickering emulsion3+The solution is subjected to a static interface diffusion reaction to obtain a polypyrrole/nano cellulose composite material suspension, and finally a composite membrane material is prepared; the Pickering emulsion takes nano-cellulose suspension as a continuous phase and takes solution containing pyrrole monomers as an internal phase. The prepared composite membrane material consists of polypyrrole and nano cellulose; the loading amount of polypyrrole in the composite film material is 26-35%, and the polypyrrole in the composite film material is nano-rodThe structure is uniformly deposited on the surface of the nano-cellulose and is tightly combined by hydrogen bonds; the conductivity of the composite film material is 4.1-5.2S/cm. The method of the invention can achieve uniform and continuous dispersion of the conductive polymer on the surface of the nano-cellulose in a short time, thereby obtaining the composite film material with high conductivity.

Description

Conductive polypyrrole/nano cellulose composite film material and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and relates to a conductive polypyrrole/nano cellulose composite film material and a preparation method thereof.
Background
The conductive polymers can be classified into intrinsic conductive polymers and composite conductive polymers according to the difference of structure, composition and preparation method. The intrinsic conductive polymer refers to the intrinsic conductive characteristic of the high molecular polymer, and common intrinsic conductive polymers mainly comprise polypyrrole, polyaniline, poly (3, 4-ethylenedioxythiophene) and the like; the polypyrrole has the advantages of high conductivity, no toxicity, easy film formation, reversible oxidation reduction and the like, so the polypyrrole has wide application prospects in the technical fields of electrochemistry, biology, microelectronics and the like. However, the composite conductive polymer is not conductive, and needs to be compounded with conductive filler to achieve the purpose of conductivity; common conductive fillers are carbon black, metal powder, and the like;
the cellulose is used as a natural polymer, has the characteristics of rich source, good biocompatibility, easy biodegradation and the like, and the rich hydroxyl on the surface of a cellulose molecular chain also provides good structural conditions for subsequent chemical modification and modification. Generally, nanocellulose refers to cellulose fibers with a particle size or width of 1 to 100nm, and common nanocellulose includes: cellulose nanocrystals, cellulose microwires, nanowires, and bacterial cellulose. The most remarkable characteristics are high crystallinity, high surface chemical activity, high nano-size structure, high mechanical strength and the like. In view of its excellent nano-size characteristics, nanocellulose has received a great deal of attention from researchers, and has been widely used in the fields of biomedicine, photoelectric devices, beauty care, catalyst carriers, supercapacitors, and the like.
The conductive polymer/cellulose composite material mainly embodies the dual characteristics of the conductive polymer and the cellulose. On one hand, the introduction of the conductive polymer effectively improves the added value of the cellulose and endows the cellulose with various characteristics such as conductivity, ion exchange performance, reversible redox capability and the like. The conductive polymer/cellulose composite material has wide conductive range, strong conductive capability comparable to metal, and can be used as an antistatic material even if the conductive capability is poor, so that novel cellulose-based composite materials such as conductive paper, conductive cloth and the like can be produced at the same time. Meanwhile, since the dopant in the conductive polymer has a reversible process of doping/dedoping, when some gas (such as NH) is used3、H2S, etc.) can cause a change in resistance upon contact with the conductive polymer, and various sensing materials can be prepared by utilizing this property. On the other hand, the cellulose has good processability, and the problem of poor processability of the conductive polymer is effectively solved by compounding the conductive polymer and the cellulose. In addition, cellulose has good degradability, and the performance is not influenced by the introduction of a small amount of conductive polymer. Therefore, the conductive polymer/cellulose composite membrane material is an rare green and environment-friendly product.
However, in the preparation process of the conductive polymer/cellulose composite membrane material, especially in the in-situ polymerization process of polypyrrole, the reaction speed is uncontrollable, and due to the characteristics of easy aggregation and easy sedimentation of polypyrrole, the polymerization rate is too fast, and large particles which are unevenly distributed and stacked are easily formed. The structure causes the problems that the structure is easy to fall off on the surface of a base material, the conductivity is uneven and the like, so that the application of the structure in the aspects of electric heating materials, sensing devices and the like is influenced.
Therefore, the design of the composite film material which can ensure that the polypyrrole is uniformly deposited and has high conductivity is of great significance.
Disclosure of Invention
In order to overcome the defects of the prior technical scheme, the invention provides a conductive polypyrrole/nano cellulose composite material and a preparation method thereof, and the preparation method specifically comprises the following steps: the method takes the nano-cellulose suspension which is abundant in natural source, green, cheap and commercialized as a raw material, and forms stable oil-in-water Pickering emulsion (the water phase of the nano-cellulose suspension is a continuous phase, and the oil phase of the cyclohexane solution is an internal phase) by the ultrasonic or homogenizing action of the nano-cellulose suspension and the cyclohexane solution containing pyrrole monomers under mild conditions; then adding a certain amount of Fe-containing solution into the continuous phase (water phase) at 0-4 DEG C3+After the solution is evenly mixed by oscillation, the solution is centrifugally washed and dispersed after a certain time of static emulsion interface diffusion reaction, and the polypyrrole/nano cellulose composite membrane material is obtained.
In order to achieve the purpose, the invention adopts the following scheme:
a method for preparing conductive polypyrrole/nano cellulose composite membrane material, mix solution containing pyrrole monomer and nano cellulose suspension evenly first to form pickering emulsion; adding a certain amount of Fe-containing into the Pickering emulsion3+The solution is subjected to a static interface diffusion reaction to obtain a polypyrrole/nano cellulose composite material suspension, and finally the polypyrrole/nano cellulose composite material suspension is subjected to suction filtration to form a composite membrane material; the Pickering emulsion takes a nano-cellulose suspension (water phase) as a continuous phase and a solution (oil phase) containing pyrrole monomers as an internal phase.
As a preferred technical scheme:
according to the preparation method of the conductive polypyrrole/nano cellulose composite membrane material, the static interface diffusion reaction time is 6-24 hours, and the temperature is 0-4 ℃. The static interface diffusion reaction time in the invention is short, and the high-efficiency and uniform deposition can be realized. The reaction temperature is controlled within the range of 0-4 ℃, so that the diffusion rate and the reaction rate of pyrrole monomers are reduced, and polypyrrole is more fully deposited on the surface of the nano-cellulose.
The preparation method of the conductive polypyrrole/nano cellulose composite membrane material comprises the following specific steps:
(1) adding a cyclohexane solution containing pyrrole monomers into the nano-cellulose suspension, uniformly mixing, and performing ultrasonic treatment or homogenization to obtain a nano-cellulose-cyclohexane oil-in-water Pickering emulsion;
the volume ratio of the nano-cellulose suspension to the cyclohexane solution containing the pyrrole monomer is 10: 1-1: 1;
the solid content of the nano-cellulose suspension is 0.5-2 wt%;
the concentration of pyrrole monomer in cyclohexane solution containing pyrrole monomer is 0.1-0.72M;
the parameter settings of the nano-cellulose suspension and the cyclohexane solution containing pyrrole monomer are used for controlling the reaction rate and the deposition density.
The cyclohexane is selected because the freezing point of the cyclohexane is 6.5 ℃, the cyclohexane is in a solid state at 0-5 ℃, water is in a liquid state, pyrrole monomers diffuse from a solid medium to a liquid water phase, the speed is slower, and the polymerization speed of pyrrole can be controlled, so that the reaction speed and diffusion can be controlled.
(2) Putting the Pickering emulsion obtained in the step (1) at 0-4 ℃, adding a certain amount of Fe-containing solution into the continuous phase of the Pickering solution after the temperature is balanced3+After the solution is evenly mixed by oscillation, the solution is centrifugally washed and dispersed after a certain time of static interface diffusion reaction, a polypyrrole/nano cellulose composite material suspension is obtained, and finally the composite membrane material is obtained by suction filtration.
According to the preparation method of the conductive polypyrrole/nano cellulose composite membrane material, the nano cellulose is more than one of cellulose nanocrystals, cellulose nanowires, cellulose microwires and bacterial cellulose.
The nano-cellulose is derived from more than one of wood pulp cellulose, cotton cellulose, bamboo cellulose, straw cellulose and carboxyl modified cellulose;
the diameter distribution of the cellulose nanocrystals is 3-20 nm, and the length distribution is 50-250 nm;
the cellulose nanowires have the diameter distribution of 1-200 nm and the length distribution of 50-700 nm;
the cellulose microwire has a diameter distribution of 20-200 nm and a length distribution of 1-30 μm;
the diameter distribution of the bacterial cellulose is 50-100 nm, and the length distribution is 20-100 mu m;
the nano-cellulose adopted by the invention can be used as an emulsion stabilizer, which shows that the method has wide applicability.
The preparation method of the conductive polypyrrole/nano cellulose composite membrane material has the ultrasonic or homogenizing temperature of 8-25 ℃; the ultrasonic treatment is carried out for 1-5 min under the condition of the power of an ultrasonic disperser of 800-1600W; homogenizing for 1-10 min at 8000-15000 rpm in a high speed homogenizer.
The ultrasonic treatment or homogenization is to disperse the aggregated polypyrrole to make the suspension uniform, so as to be prepared into a composite membrane material by subsequent suction filtration to ensure the stable conductivity of the composite membrane material.
The preparation method of the conductive polypyrrole/nano cellulose composite membrane material contains Fe3+The solution of (a) is more than one of ferric trichloride solution, 5-sulfosodium salicylate/ferric trichloride complex aqueous solution and p-toluenesulfonic acid/ferric trichloride complex aqueous solution.
Fe3+Is an oxidant, is dissolved in the water phase, and allows the oxidant to form a complex, pyrrole is transferred from the organic phase to the water phase, and the pyrrole diffused into the water phase meets Fe in the water solution3+When the length of the polypyrrole chain exceeds the solubility limit in water along with the polymerization reaction, the polypyrrole can be precipitated and separated out and deposited on the surface of the nano-cellulose. During the oxidative polymerization, the polypyrrole is doped while growing chains. The conjugated system of polypyrrole will be oxidized to form radical cation, i.e. polaron, and further oxidized to form bipolaron. The polaron and the bipolarator are mobile in the electric field, so that the polypyrrole has conductivity.
The preparation method of the conductive polypyrrole/nano cellulose composite membrane material contains Fe3+Fe in solution of3+Has a concentration of 0.1 to 0.72M and contains Fe3+The amount of the solution (b) added is the same as the volume of the cyclohexane solution containing the pyrrole monomer.
According to the preparation method of the conductive polypyrrole/nano cellulose composite membrane material, the temperature balance time is 2-6 h;
the shaking mixing is to maintain the Pickering emulsion and the Fe-containing emulsion3+The solution is mixed for 5-30 min at the temperature of 0-4 ℃;
in centrifugal washing, a washing solvent is ethanol or water, the centrifugal washing times are 4-6 times, the rotating speed of each centrifugation is 8000-15000 rpm, and the time of each centrifugation is 5-10 min;
after centrifugal washing, the centrifuged sediment was dispersed with water.
These parameters are set to reduce the production time and ensure the yield.
The invention also provides a composite membrane material prepared by the preparation method of the conductive polypyrrole/nano cellulose composite membrane material, which consists of polypyrrole and nano cellulose;
polypyrrole in the composite film material is uniformly deposited on the surface of the nano-cellulose in a nanorod structure (as can be seen from an SEM image of a product), and is tightly combined by hydrogen bonds;
the length of the nano-rods is within 100nm, and the diameter of the nano-rods is 20-30 nm; the loading amount of polypyrrole in the composite membrane material is 26-35%.
The composite membrane material prepared by the preparation method of the conductive polypyrrole/nano cellulose composite membrane material has the conductivity of 4.1-5.2S/cm.
The principle of the invention is as follows:
the preparation method of the conductive polypyrrole/nano cellulose composite membrane material provided by the invention is simple, and the reaction conditions are mild and controllable. At the temperature of 0-4 ℃, cyclohexane is in a condensed state, pyrrole monomers are driven by gravity to slowly diffuse into a liquid continuous phase (water phase), meanwhile, nanocellulose positioned on a Pickering emulsion interface is used as a carrier, and Fe in the continuous phase3+In-situ precipitation of pyrrole monomer under the oxidation ofDeposited on the surface of the nano-cellulose; in addition, under the action of the Pickering emulsion, on one hand, the interfacial contact area can be obviously improved, the polymerization rate of pyrrole is reduced, the aggregation degree of polypyrrole is reduced, and the order degree of polypyrrole is improved, so that a long conjugated structure is formed, and the conductivity is improved; on the other hand, the polymerization method improves the contact area of the pyrrole and the nano-cellulose, realizes the coating of the polypyrrole on the nano-cellulose, and improves the loading capacity, thereby improving the conductivity of the composite membrane. In addition, in the composite membrane material prepared by the invention, polypyrrole is in a nano rod-shaped structure, and has a longer conjugated structure, so that the conductivity is improved.
The conductive composite nano material belongs to a novel functional material with high added value, embodies the dual excellent characteristics of nano cellulose and conductive polymer, and can be widely applied to the fields of intelligent sensing, mechanical enhancement, photoinduced or electrogenerated heating materials and the like. In the preparation method, the reaction raw materials are green, environment-friendly and rich, the preparation process is simple, the operation is safe, and the method is expected to be widely used commercially.
Advantageous effects
(1) The preparation method of the conductive polypyrrole/nano cellulose composite film material can achieve uniform and continuous dispersion of the conductive polymer on the surface of the nano cellulose in a short time, so that the composite film material with high conductivity is obtained;
(2) according to the conductive polypyrrole/nano-cellulose composite membrane material, polypyrrole is uniformly dispersed on the surface of nano-cellulose in a nanorod structure, so that the conductivity of the composite membrane material can be greatly improved.
Drawings
FIG. 1 is a schematic view of a method for preparing a conductive polypyrrole/nanocellulose composite membrane material of the present invention;
FIG. 2 is an optical microscope photograph (scale bar 40 μm) of a Pickering emulsion of nanocellulose and a solution containing pyrrolic cyclohexane in example 2;
FIG. 3 is an optical microscope photograph (scale bar 40 μm) of a Pickering emulsion of nanocellulose and a solution containing pyrrolic cyclohexane in example 2 after optical standing for 7 days;
FIG. 4 shows a schematic view of a nano-meter of example 2Adding Fe-containing Pickering emulsion formed by rice cellulose and solution containing pyrrole cyclohexane3+Optical microscopy (scale bar 40 μm) of the solution;
FIG. 5 is a surface topography of the conductive polypyrrole/nanocellulose composite film material of example 2;
fig. 6 is an infrared spectrum of the conductive polypyrrole/nanocellulose composite membrane material (PPy @ CNF) in example 2.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The parameters of the nanocellulose in the invention are as follows:
species of Source Dimensional parameters
Cellulose nanocrystals Straw cellulose The diameter distribution of the cellulose nanocrystals is 3-20 nm, and the length distribution is 50-250 nm;
cellulose nanowires Wood pulp cellulose The cellulose nanowires have the diameter distribution of 1-200 nm and the length distribution of 50-700 nm;
cellulose microwire Cotton cellulose The cellulose microwire has a diameter distribution of 20-200 nm and a length distribution of 1-30 μm;
bacterial cellulose Wood pulp cellulose The diameter of the bacterial cellulose is 50-100 nm, and the length distribution is 20-100 mu m;
fe-containing in the present invention3+The parameters of the solution of (1) are as follows:
species of Source
Ferric chloride solution Chemical reagent of national drug group, Ltd, analytical purity
5-sulfosalicylic acid sodium/ferric trichloride complex aqueous solution Chemical reagent of national drug group, Ltd, analytical purity
P-toluenesulfonic acid/ferric trichloride complex aqueous solution Chemical reagent of national drug group, Ltd, analytical purity
Example 1
A preparation method of a conductive polypyrrole/nano cellulose composite membrane material comprises the following steps:
preparing raw materials:
a nanocellulose suspension with a solid content of 0.5 wt%; wherein the nanocellulose is cellulose nanocrystal;
a cyclohexane solution containing pyrrole monomers with the concentration of the pyrrole monomers being 0.1M;
containing Fe3+The solution of (a) is a solution of ferric chloride, wherein Fe3+The concentration of (A) is 0.1M;
the method comprises the following specific steps:
(1) adding a cyclohexane solution containing pyrrole monomers into the nano-cellulose suspension, uniformly mixing, and performing ultrasonic treatment to obtain a nano-cellulose-cyclohexane oil-in-water pickering emulsion;
wherein the volume ratio of the nano-cellulose suspension to the cyclohexane solution containing pyrrole monomer is 10: 1; the ultrasonic treatment is carried out for 1min under the power of an ultrasonic disperser of 800W; the ultrasonic temperature is 8 ℃;
the nanocellulose-cyclohexane oil-in-water Pickering emulsion takes a nanocellulose suspension as a continuous phase and a cyclohexane solution as an internal phase;
(2) putting the Pickering emulsion obtained in the step (1) at 0 ℃, adding Fe with the same volume as that of a cyclohexane solution containing pyrrole monomers into a Pickering solution continuous phase after the temperature is balanced3+The solution of (2) is shaken and mixed evenly (keeping the Pickering emulsion and Fe-containing3+The solution is mixed for 5min at the temperature of 1 ℃), and after a static interface diffusion reaction (the time is 6h and the temperature is 1 ℃) for a certain time, ethanol and water are adopted for centrifugal washing, the centrifugal washing frequency is 4 times (the first 2 times of ethanol washing and the later time of water washing), the rotating speed of each centrifugal washing is 8000rpm, and the time of each centrifugal washing is 5 min; after centrifugal washing, dispersing the centrifuged sediment by using water; obtaining polypyrrole/nano cellulose composite material suspension, and finally performing suction filtration to obtain a composite membrane material; wherein the temperature balance time is 2 h;
polypyrrole in the composite membrane material is uniformly dispersed on the surface of the nano-cellulose in a nano-rod-shaped structure and is tightly combined by a hydrogen bond; the length of the nano-rods is within 100nm, and the diameter of the nano-rods is 20-30 nm;
the loading amount of polypyrrole in the composite membrane material is 26%; the conductivity of the composite film material is 4.1S/cm.
Example 2
A method for preparing a conductive polypyrrole/nano cellulose composite membrane material (a schematic diagram of the principle is shown in figure 1) comprises the following steps:
preparing raw materials:
a nanocellulose suspension with a solid content of 0.7 wt%; wherein the nanocellulose is cellulose nanowires;
a cyclohexane solution containing pyrrole monomers with the concentration of the pyrrole monomers being 0.2M;
containing Fe3+The solution of (a) is a 5-sulfosalicylic acid sodium/ferric trichloride complex aqueous solution, wherein Fe3+The concentration of (A) is 0.2M;
the method comprises the following specific steps:
(1) adding a cyclohexane solution containing pyrrole monomers into the nano-cellulose suspension, uniformly mixing, and performing ultrasonic treatment to obtain a nano-cellulose-cyclohexane oil-in-water pickering emulsion;
wherein the volume ratio of the nano-cellulose suspension to the cyclohexane solution containing pyrrole monomer is 8: 1; the ultrasonic treatment is carried out for 2min under the power of an ultrasonic disperser of 1000W; the ultrasonic temperature is 12 ℃;
the nanocellulose-cyclohexane oil-in-water Pickering emulsion takes a nanocellulose suspension as a continuous phase and a cyclohexane solution as an internal phase; the optical micrograph of the pickering emulsion is shown in FIG. 2; as can be seen from fig. 2, the solution containing pyrrole and cyclohexane is coated by the nanocellulose in the form of micro-spheres, so that the contact area of pyrrole and nanocellulose is increased, and the load uniformity can be improved. And the optical micrograph of the pickering emulsion after being optically set for 7 days is shown in FIG. 3; as can be seen from fig. 3, the formed emulsion has excellent stability, providing basic conditions for the polymerization of pyrrole.
(2) Putting the Pickering emulsion obtained in the step (1) at 1 ℃, and after the temperature is balanced, adding the Pickering emulsion into a Pickering solution continuous phaseIn (1), Fe-containing solution with the same volume as the cyclohexane solution containing pyrrole monomer is added3+The solution of (2) is shaken and mixed evenly (keeping the Pickering emulsion and Fe-containing3+After mixing at a temperature of 1 ℃ for 10min (the optical microscope image of which is shown in FIG. 4; as can be seen from FIG. 4, FeCl is added3Emulsion is kept stable after the water solution, which shows feasibility of the method), after a certain time of static interface diffusion reaction (time is 6h, temperature is 1 ℃), ethanol and water are adopted for centrifugal washing, the centrifugal washing frequency is 4 times (ethanol washing is adopted for the first 3 times, water washing is adopted for the later time), the rotating speed of each centrifugation is 9000rpm, and the time of each centrifugation is 6 min; after centrifugal washing, dispersing the centrifuged sediment by using water; obtaining polypyrrole/nano cellulose composite material suspension, and finally performing suction filtration to obtain a composite membrane material; wherein the temperature balance time is 2 h;
the surface topography of the composite film material is shown in FIG. 5; as can be seen from fig. 5, the surface of the nanocellulose is completely covered by the polypyrrole, high conductivity is ensured, and the infrared spectrogram of the tested composite membrane material is shown in fig. 6, wherein CNF represents the cellulose nanowire, PPy @ CNF represents the composite membrane material; as can be seen in fig. 6, polypyrrole had been successfully deposited on the surface of the nanocellulose. As can be seen from FIGS. 5 to 6, polypyrrole in the composite membrane material is uniformly dispersed on the surface of the nanocellulose in a nanorod structure, and the polypyrrole and the nanocellulose are tightly combined through hydrogen bonds; the length of the nano-rods is within 100nm, and the diameter of the nano-rods is 20-30 nm; the loading amount of polypyrrole in the composite membrane material is 28%; the conductivity of the composite film material is 4.2S/cm.
Example 3
A preparation method of a conductive polypyrrole/nano cellulose composite membrane material comprises the following steps:
preparing raw materials:
a nanocellulose suspension with a solid content of 0.9 wt%; wherein the nano-cellulose is cellulose micron line;
a cyclohexane solution containing pyrrole monomers with the concentration of the pyrrole monomers being 0.3M;
containing Fe3+The solution of (a) is an aqueous solution of a p-toluenesulfonic acid/ferric trichloride complex, which isMiddle Fe3+The concentration of (A) is 0.3M;
the method comprises the following specific steps:
(1) adding a cyclohexane solution containing pyrrole monomers into the nano-cellulose suspension, uniformly mixing, and performing ultrasonic treatment to obtain a nano-cellulose-cyclohexane oil-in-water pickering emulsion;
wherein the volume ratio of the nano-cellulose suspension to the cyclohexane solution containing pyrrole monomer is 6: 1; the ultrasonic treatment is carried out for 3min under the condition of the ultrasonic disperser power of 1200W; the ultrasonic temperature is 16 ℃;
the nanocellulose-cyclohexane oil-in-water Pickering emulsion takes a nanocellulose suspension as a continuous phase and a cyclohexane solution as an internal phase;
(2) putting the Pickering emulsion obtained in the step (1) at 2 ℃, adding Fe with the same volume as that of a cyclohexane solution containing pyrrole monomers into a Pickering solution continuous phase after the temperature is balanced3+The solution of (2) is shaken and mixed evenly (keeping the Pickering emulsion and Fe-containing3+The solution is mixed for 15min at the temperature of 2 ℃), and after a certain time of static interface diffusion reaction (the time is 12h and the temperature is 2 ℃), ethanol and water are adopted for centrifugal washing, the centrifugal washing frequency is 4 times (the first 3 times of ethanol washing and the later time of water washing), the rotating speed of each centrifugal washing is 10000rpm, and the time of each centrifugal washing is 7 min; after centrifugal washing, dispersing the centrifuged sediment by using water; obtaining polypyrrole/nano cellulose composite material suspension, and finally performing suction filtration to obtain a composite membrane material; wherein the temperature balance time is 3 h;
polypyrrole in the composite membrane material is uniformly dispersed on the surface of the nano-cellulose in a nano-rod-shaped structure and is tightly combined by a hydrogen bond; the length of the nano-rods is within 100nm, and the diameter of the nano-rods is 20-30 nm;
the loading amount of polypyrrole in the composite membrane material is 30%; the conductivity of the composite film material is 4.5S/cm.
Example 4
A preparation method of a conductive polypyrrole/nano cellulose composite membrane material comprises the following steps:
preparing raw materials:
a nanocellulose suspension with a solid content of 1.2 wt%; wherein the nano-cellulose is bacterial cellulose;
a cyclohexane solution containing pyrrole monomers with the concentration of the pyrrole monomers being 0.4M;
containing Fe3+The solution of (a) is a solution of ferric chloride, wherein Fe3+The concentration of (A) is 0.4M;
the method comprises the following specific steps:
(1) adding a cyclohexane solution containing pyrrole monomers into the nano-cellulose suspension, uniformly mixing, and homogenizing to obtain a nano-cellulose-cyclohexane oil-in-water pickering emulsion;
wherein the volume ratio of the nano-cellulose suspension to the cyclohexane solution containing pyrrole monomer is 4: 1; homogenizing at 12000rpm for 9 min; the homogenization temperature is 20 ℃;
the nanocellulose-cyclohexane oil-in-water Pickering emulsion takes a nanocellulose suspension as a continuous phase and a cyclohexane solution as an internal phase;
(2) putting the Pickering emulsion obtained in the step (1) at 2 ℃, adding Fe with the same volume as that of a cyclohexane solution containing pyrrole monomers into a Pickering solution continuous phase after the temperature is balanced3+The solution of (2) is shaken and mixed evenly (keeping the Pickering emulsion and Fe-containing3+The solution is mixed for 20min at the temperature of 2 ℃), and after a certain time of static interface diffusion reaction (the time is 12h and the temperature is 2 ℃), ethanol and water are used for centrifugal washing for 6 times (the ethanol is used for washing for the first 3 times, and the water is used for washing for the later time), the rotating speed of each centrifugal washing is 15000rpm, and the time of each centrifugal washing is 8 min; after centrifugal washing, dispersing the centrifuged sediment by using water; obtaining polypyrrole/nano cellulose composite material suspension, and finally performing suction filtration to obtain a composite membrane material; wherein the temperature balance time is 3 h;
polypyrrole in the composite membrane material is uniformly dispersed on the surface of the nano-cellulose in a nano-rod-shaped structure and is tightly combined by a hydrogen bond; the length of the nano-rods is within 100nm, and the diameter of the nano-rods is 20-30 nm;
the loading amount of polypyrrole in the composite membrane material is 31 percent; the conductivity of the composite film material is 4.7S/cm.
Example 5
A preparation method of a conductive polypyrrole/nano cellulose composite membrane material comprises the following steps:
preparing raw materials:
a nanocellulose suspension with a solid content of 1.5 wt%; wherein the nanocellulose is cellulose nanowires;
a cyclohexane solution containing pyrrole monomers with the concentration of the pyrrole monomers being 0.54M;
containing Fe3+The solution of (a) is a 5-sulfosalicylic acid sodium/ferric trichloride complex aqueous solution, wherein Fe3+Is 0.54M;
the method comprises the following specific steps:
(1) adding a cyclohexane solution containing pyrrole monomers into the nano-cellulose suspension, uniformly mixing, and homogenizing to obtain a nano-cellulose-cyclohexane oil-in-water pickering emulsion;
wherein the volume ratio of the nano-cellulose suspension to the cyclohexane solution containing pyrrole monomer is 2: 1; homogenizing at 8000rpm for 10 min; the homogenization temperature is 25 ℃;
the nanocellulose-cyclohexane oil-in-water Pickering emulsion takes a nanocellulose suspension as a continuous phase and a cyclohexane solution as an internal phase;
(2) putting the Pickering emulsion obtained in the step (1) at 3 ℃, adding Fe with the same volume as that of a cyclohexane solution containing pyrrole monomers into a Pickering solution continuous phase after the temperature is balanced3+The solution of (2) is shaken and mixed evenly (keeping the Pickering emulsion and Fe-containing3+The solution is mixed for 30min at the temperature of 3 ℃), and after a certain time of static interface diffusion reaction (the time is 24h and the temperature is 3 ℃), ethanol and water are adopted for centrifugal washing, the centrifugal washing frequency is 5 times (the first 3 times of ethanol washing and the later times of water washing), the rotating speed of each centrifugal washing is 12000rpm, and the time of each centrifugal washing is 9 min; after centrifugal washing, dispersing the centrifuged sediment by using water; obtaining polypyrrole/nano cellulose composite material suspension, and finally performing suction filtration to obtain a composite membrane material; whereinThe temperature balance time is 6 hours;
polypyrrole in the composite membrane material is uniformly dispersed on the surface of the nano-cellulose in a nano-rod-shaped structure and is tightly combined by a hydrogen bond; the length of the nano-rods is within 100nm, and the diameter of the nano-rods is 20-30 nm;
the loading amount of polypyrrole in the composite membrane material is 33%; the conductivity of the composite film material is 5S/cm.
Example 6
A preparation method of a conductive polypyrrole/nano cellulose composite membrane material comprises the following steps:
preparing raw materials:
a nanocellulose suspension with a solid content of 2 wt%; wherein the nanocellulose is cellulose nanocrystal;
a cyclohexane solution containing pyrrole monomers with the concentration of the pyrrole monomers being 0.72M;
containing Fe3+The solution of (a) is a p-toluenesulfonic acid/ferric trichloride complex aqueous solution, wherein Fe3+The concentration of (A) is 0.72M;
the method comprises the following specific steps:
(1) adding a cyclohexane solution containing pyrrole monomers into the nano-cellulose suspension, uniformly mixing, and homogenizing to obtain a nano-cellulose-cyclohexane oil-in-water pickering emulsion;
wherein the volume ratio of the nano-cellulose suspension to the cyclohexane solution containing pyrrole monomer is 1: 1; homogenizing at 15000rpm for 10 min; the homogenization temperature is 25 ℃;
the nanocellulose-cyclohexane oil-in-water Pickering emulsion takes a nanocellulose suspension as a continuous phase and a cyclohexane solution as an internal phase;
(2) putting the Pickering emulsion obtained in the step (1) at 4 ℃, adding Fe with the same volume as that of a cyclohexane solution containing pyrrole monomers into a Pickering solution continuous phase after the temperature is balanced3+The solution of (2) is shaken and mixed evenly (keeping the Pickering emulsion and Fe-containing3+Mixing the solution at 4 deg.C for 30min), performing static interface diffusion reaction (for 24 hr, at 4 deg.C) for a certain time, adding ethanol and waterCarrying out centrifugal washing on water, wherein the centrifugal washing frequency is 4 times (the first 3 times of washing by using ethanol and the later time of washing by using water), the rotating speed of each time of centrifugation is 12000rpm, and the time of each time of centrifugation is 10 min; after centrifugal washing, dispersing the centrifuged sediment by using water; obtaining polypyrrole/nano cellulose composite material suspension, and finally performing suction filtration to obtain a composite membrane material; wherein the temperature balance time is 6 h;
polypyrrole in the composite membrane material is uniformly dispersed on the surface of the nano-cellulose in a nano-rod-shaped structure and is tightly combined by a hydrogen bond; the length of the nano-rods is within 100nm, and the diameter of the nano-rods is 20-30 nm;
the loading amount of polypyrrole in the composite membrane material is 35%; the conductivity of the composite film material is 5.2S/cm.

Claims (10)

1. A preparation method of a conductive polypyrrole/nano cellulose composite film material is characterized by comprising the following steps: uniformly mixing a solution containing pyrrole monomers with a nano cellulose suspension to form a Pickering emulsion; adding a certain amount of Fe-containing into the Pickering emulsion3+The solution is subjected to a static interface diffusion reaction to obtain a polypyrrole/nano cellulose composite material suspension; finally, preparing a composite membrane material from the polypyrrole/nano cellulose composite material suspension; the Pickering emulsion takes nano-cellulose suspension as a continuous phase and takes solution containing pyrrole monomers as an internal phase.
2. The preparation method of the conductive polypyrrole/nano cellulose composite film material according to claim 1, wherein the time of the static interfacial diffusion reaction is 6-24 h, and the temperature is 0-4 ℃.
3. The preparation method of the conductive polypyrrole/nano cellulose composite film material according to the claim 1 or 2, characterized by comprising the following steps:
(1) adding a cyclohexane solution containing pyrrole monomers into the nano-cellulose suspension, uniformly mixing, and performing ultrasonic treatment or homogenization to obtain a nano-cellulose-cyclohexane oil-in-water Pickering emulsion;
the volume ratio of the nano-cellulose suspension to the cyclohexane solution containing the pyrrole monomer is 10: 1-1: 1;
the solid content of the nano-cellulose suspension is 0.5-2 wt%;
the concentration of pyrrole monomer in cyclohexane solution containing pyrrole monomer is 0.1-0.72M;
(2) placing the nanocellulose-cyclohexane oil-in-water pickering emulsion in the step (1) at 0-4 ℃, adding a certain amount of Fe-containing solution into a continuous phase of the pickering solution after the temperature is balanced3+After the solution is evenly mixed by oscillation, the solution is centrifugally washed and dispersed after a certain time of static interface diffusion reaction, a polypyrrole/nano cellulose composite material suspension is obtained, and finally the composite membrane material is obtained by suction filtration.
4. The method for preparing a conductive polypyrrole/nanocellulose composite membrane material according to claim 3, wherein nanocellulose is more than one of cellulose nanocrystal, cellulose nanowire, cellulose microwire and bacterial cellulose.
5. The preparation method of the conductive polypyrrole/nano cellulose composite film material according to claim 3, wherein the ultrasonic or homogenizing temperature is 8-25 ℃; the ultrasonic treatment is carried out for 1-5 min under the condition of the power of an ultrasonic disperser of 800-1600W; homogenizing for 1-10 min at 8000-15000 rpm in a high speed homogenizer.
6. The preparation method of the conductive polypyrrole/nano-cellulose composite membrane material according to claim 3, characterized by comprising Fe3+The solution of (a) is more than one of ferric trichloride solution, 5-sulfosodium salicylate/ferric trichloride complex aqueous solution and p-toluenesulfonic acid/ferric trichloride complex aqueous solution.
7. The preparation method of the conductive polypyrrole/nano-cellulose composite membrane material according to claim 3, characterized by comprising Fe3+Fe in solution of3+Concentration of (2)0.1 to 0.72M, and Fe3+The amount of the solution (b) added is the same as the volume of the cyclohexane solution containing the pyrrole monomer.
8. The preparation method of the conductive polypyrrole/nano cellulose composite film material according to claim 3, wherein the temperature balance time is 2-6 h;
the shaking mixing is to maintain the Pickering emulsion and the Fe-containing emulsion3+The solution is mixed for 5-30 min at the temperature of 0-4 ℃;
in centrifugal washing, a washing solvent is ethanol or water, the centrifugal washing times are 4-6 times, the rotating speed of each centrifugation is 8000-15000 rpm, and the time of each centrifugation is 5-10 min;
after centrifugal washing, the centrifuged sediment was dispersed with water.
9. The composite film material prepared by the preparation method of the conductive polypyrrole/nano cellulose composite film material according to any one of claims 1 to 8, which is characterized in that: consists of polypyrrole and nano-cellulose; the loading amount of polypyrrole in the composite film material is 26-35%, and the polypyrrole in the composite film material is uniformly deposited on the surface of the nano-cellulose in a nanorod structure and is tightly combined by a hydrogen bond; wherein the length of the nano-rods is within 100nm, and the diameter of the nano-rods is 20-30 nm.
10. The composite film material prepared by the preparation method of the conductive polypyrrole/nano cellulose composite film material according to claim 9, wherein the conductivity of the composite film material is 4.1-5.2S/cm.
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