CN113943462A - Conductive polymer composite material and preparation method and application thereof - Google Patents
Conductive polymer composite material and preparation method and application thereof Download PDFInfo
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- CN113943462A CN113943462A CN202111329081.6A CN202111329081A CN113943462A CN 113943462 A CN113943462 A CN 113943462A CN 202111329081 A CN202111329081 A CN 202111329081A CN 113943462 A CN113943462 A CN 113943462A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to the technical field of conductive composite materials, in particular to a conductive polymer composite material and a preparation method and application thereof. The invention provides a preparation method of a conductive polymer composite material, which comprises the following steps: carrying out in-situ graft polymerization on a conductive high molecular polymer monomer on the surface of cellulose fiber to obtain two-dimensional organic conductive fiber; and mixing the two-dimensional organic conductive fiber, the inorganic conductive filler and the polymer resin, and molding to obtain the conductive polymer composite material. The preparation method provided by the invention provides a novel hybrid conductive network filling system suitable for melt processing and solution processing for different polymer matrixes, is suitable for development of conductive composite materials with low content of conductive filler, high conductivity and mechanical property, has strong universality, and is suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of conductive composite materials, in particular to a conductive polymer composite material and a preparation method and application thereof.
Background
Most polymer materials are excellent insulators, are easy to generate static electricity, and can cause adverse effects on electronic components, radio equipment and the like, so that the conductive composite materials prepared by adding conductive fillers into polymer matrixes are produced. The conductive composite material has huge application and development prospects in the fields of electromagnetic shielding, antistatic materials, electrode materials, conductor materials, sensors and display materials, and the main reasons are that the composite material has the advantages of low density, large conductive range, excellent processing performance, strong corrosion resistance, relatively low cost and the like. In recent years, with the development of science and technology and the expansion of application range, higher requirements are put forward on the performance and cost of conductive materials, and the development of new technology of conductive composite materials is more and more emphasized.
The carbon-based and metal-based conductors are mainly used as fillers to be compounded with a polymer matrix in the prior art, the content of the conductive fillers is generally increased in order to realize good conductivity, and the increase of the conductive fillers can cause the mechanical property of the composite material to be reduced and the density and the cost of the material to be increased. Therefore, it is a problem of research on how to adjust and control the conductive network of the composite system to achieve higher conductivity at a lower filler content, and the current research mainly focuses on the improvement of the conductive network by carbon-based/metal-based hybridization, powder/fiber (metal) -like filler hybridization, conductive polymer and conductive filler hybridization, and the like. The hybridization modes for the conductive polymer and the conductive filler mainly include: the conductive polymer is used as a matrix to be directly compounded with the inorganic conductive filler to prepare the high-performance conductive composite material, but the cost is higher, the forming mode is limited, so that the high-performance conductive composite material is difficult to apply on a large scale, and then the conductive polymer and the inorganic conductive particles are hybridized into the conductive filler and then are blended with resin to prepare the conductive plastic, wherein the hybridization mode can be used for preparing the conductive material by coating the conductive polymer on the surfaces of the inorganic conductive particles and then compounding the conductive polymer with the resin, or preparing the conductive polymer into fibers and blending the fibers with the inorganic conductive particles and the resin. However, the hybrid mode of the coating can improve the dispersion effect of the inorganic conductive particles, but the inorganic conductive particles are difficult to participate in the conductive tunnel, and the actual effect of the conductive filler is greatly weakened. The blending of the conductive polymer fiber, the inorganic conductive particles and the resin requires a complicated preparation process of the conductive polymer fiber, and the conductive polymer fiber may have a possibility that a conductive network cannot be formed in the process of extruding the inorganic conductive particles and the resin, so that the conductive polymer fiber is difficult to be applied to more universal large-scale manufacturing.
Disclosure of Invention
The invention aims to provide a conductive polymer composite material, a preparation method and application thereof, wherein the preparation method can form a dense conductive network and is suitable for large-scale production.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a conductive polymer composite material, which comprises the following steps:
carrying out in-situ graft polymerization on a conductive high molecular polymer monomer on the surface of cellulose fiber to obtain two-dimensional organic conductive fiber;
and mixing the two-dimensional organic conductive fiber, the inorganic conductive filler and the polymer resin, and molding to obtain the conductive polymer composite material.
Preferably, the cellulose fibers have a length of 1 μm to 1cm and a diameter of 5nm to 50 μm.
Preferably, the conductive high molecular polymer monomer comprises one or more of aniline monomer, pyrrole monomer and thiophene monomer.
Preferably, the grafting rate of the in-situ graft polymerization is 50-500%.
Preferably, the inorganic conductive filler comprises one or more of carbon black, graphite and metal powder.
Preferably, the mass ratio of the two-dimensional organic conductive fibers, the inorganic conductive filler and the polymer resin is (1-10): (5-30): (70-90).
Preferably, the molding is melt molding or solution molding.
Preferably, when the molding mode is melt molding, the melt-molded raw material further comprises an auxiliary agent;
the auxiliary agent comprises a lubricant, an antioxidant and a compatilizer;
the mass ratio of the lubricant to the antioxidant to the compatilizer is (0.5-1.5): (0.5-1.5): (1-5).
The invention also provides a conductive polymer composite material prepared by the preparation method in the technical scheme, which comprises polymer resin, and two-dimensional organic conductive fibers and inorganic conductive filler which are dispersed in the polymer resin;
the two-dimensional organic conductive fiber comprises cellulose fiber and a conductive high polymer grafted and polymerized on the surface of the cellulose fiber in situ;
conductive network paths are formed among the two-dimensional organic conductive fibers, among the inorganic conductive fillers and among the two-dimensional organic conductive fibers and the inorganic conductive fillers.
The invention also provides application of the conductive polymer composite material in the technical scheme in the fields of electromagnetic shielding materials, antistatic materials, electrode materials, conductor material sensors or display materials.
The invention provides a preparation method of a conductive polymer composite material, which comprises the following steps: carrying out in-situ graft polymerization on a conductive high molecular polymer monomer on the surface of cellulose fiber to obtain two-dimensional organic conductive fiber; and mixing the two-dimensional organic conductive fiber, the inorganic conductive filler and the polymer resin, and molding to obtain the conductive polymer composite material.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the invention enables the conductive high molecular polymer to stably coat the surface of the cellulose fiber through the action of the covalent bond, so that the conductive polymer has the functions of conducting electricity and improving the compatibility of the cellulose and the high molecular resin;
2) the cellulose fiber selected by the invention has large surface area and wide scale range, can form fiber with a multi-level structure, and the conductive polymer is favorable for forming a denser conductive network with the inorganic conductive filler after being coated;
3) the cellulose fiber has high strength, is coated and has increased compatibility with high polymer resin, is favorable for improving the mechanical property of the material, has good heat resistance and is difficult to melt, is easy to keep the original morphological structure in the processing process, and is favorable for repeated processing;
4) the introduction of the cellulose fiber and the formation of the conductive network can ensure that the conductive composite material has better conductive performance under the condition of smaller addition amount of the inorganic conductive filler, is beneficial to reducing the cost and reducing the material density, and is beneficial to obtaining the conductive composite material with high mechanical property and high conductive performance so as to meet the wider application requirements of the conductive composite material.
Drawings
Fig. 1 is a schematic diagram of a conductive network path structure of the conductive polymer composite material according to the present invention.
Detailed Description
The invention provides a preparation method of a conductive polymer composite material, which comprises the following steps:
carrying out in-situ graft polymerization on a conductive high molecular polymer monomer on the surface of cellulose fiber to obtain two-dimensional organic conductive fiber;
and mixing the two-dimensional organic conductive fiber, the inorganic conductive filler and the polymer resin, and molding to obtain the conductive polymer composite material.
In the present invention, the starting materials for the preparation are all commercially available products well known to those skilled in the art, unless otherwise specified.
The invention carries out in-situ graft polymerization on the conductive high molecular polymer monomer on the surface of the cellulose fiber to obtain the two-dimensional organic conductive fiber.
In the present invention, the length of the cellulose fiber is preferably 1 μm to 1cm, more preferably 300 μm to 2 mm; the diameter is preferably 5nm to 50 μm, more preferably 100 to 3000 nm.
In the present invention, the cellulose fiber is more preferably a cellulose fiber of a multilevel structure; the cellulose fibers of the multi-layered structure preferably include nanocellulose fibers and microfibril fibers. The mass ratio of the nano cellulose fibers to the micron cellulose fibers is preferably (0.01-0.2): 1, more preferably (0.05 to 0.1): 1. in the invention, the nano cellulose fiber is cellulose fiber with the diameter of nanometer level; the micron cellulose fiber is a cellulose fiber with the diameter of micron grade. In the invention, the length of the nano-cellulose is preferably 100-1000 μm, and more preferably 200-500 μm; the diameter is preferably 5 to 100nm, and more preferably 10 to 50 nm; the length of the micron cellulose is preferably 0.5-5 mm, and more preferably 1-3 mm; the diameter is preferably 5 to 50 μm, and more preferably 10 to 30 μm.
In the present invention, when the length and diameter of the cellulose fiber are out of the above ranges, the present invention preferably performs a pretreatment of the cellulose fiber, the pretreatment preferably including a shearing treatment or a strong mechanical treatment; the shearing treatment is preferably carried out by adopting a wall breaking machine, and the strong mechanical treatment is preferably carried out by adopting a high-pressure homogenizer; the process of shearing and strong mechanical treatment is not subject to any particular limitation, and is carried out by processes well known to those skilled in the art, and it is sufficient to ensure that cellulose fibers within the above-mentioned length and diameter ranges are obtained.
In the present invention, the grafting ratio of the in-situ graft polymerization is preferably 50 to 500%, and more preferably 100 to 300%.
In the invention, the conductive high molecular polymer monomer preferably comprises one or more of aniline monomer, pyrrole monomer and thiophene monomer; more preferably, aniline monomers, pyrrole monomers or thiophene monomers; when the conductive high molecular polymer monomer is more than two of the above specific substances, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion. The aniline monomer, pyrrole monomer or thiophene monomer is not limited in kind in the present invention, and may be polyaniline, polypyrrole or polythiophene known to those skilled in the art.
In the present invention, when the conductive high molecular polymer is polyaniline, the in-situ graft polymerization process preferably includes the following steps:
and mixing cellulose fibers, phosphoric acid, aniline and ammonium persulfate solution, and carrying out in-situ graft polymerization to obtain the two-dimensional organic conductive fiber.
In the present invention, the ratio of the amounts of phosphoric acid and aniline is preferably (0.5 to 4.0): 1, more preferably (1.0 to 3.0): 1, most preferably 2.0: 1.
in the invention, the mass ratio of the ammonium persulfate to the aniline in the ammonium persulfate solution is preferably (1-2): 1.
in the present invention, the mass ratio of the cellulose fibers to the aniline is preferably 1: (0.01 to 3.5), more preferably 1: (1-3.1).
In the present invention, the mixing is preferably performed by mixing phosphoric acid and aniline, then mixing with cellulose fibers, and finally dropping the ammonium persulfate solution. In the present invention, the dropping is preferably dropwise.
In the invention, the temperature of the in-situ graft polymerization is preferably 0-5 ℃, and the time is preferably 8 h. In the present invention, the in-situ graft polymerization is preferably performed under vacuum conditions.
After the in-situ graft polymerization is finished, the method also preferably comprises the step of carrying out post-treatment on the organic conductive fiber obtained by the in-situ graft polymerization, wherein the post-treatment preferably comprises the steps of cleaning and drying which are carried out in sequence; the cleaning preferably comprises a first cleaning and a second cleaning which are sequentially carried out; the first cleaning preferably comprises repeatedly washing with 0.01mol/L hydrochloric acid solution and acetone in sequence to remove unreacted organic substances and oligomers; the second cleaning is preferably 3 times rinsing with deionized water. In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 40 ℃, and the time is preferably 36 h.
When the conductive high molecular polymer is polypyrrole, the in-situ graft polymerization process preferably includes the following steps:
mixing cellulose fibers, a hydrochloric acid solution and ferric chloride to obtain a cellulose fiber mixed solution;
and mixing the cellulose fiber mixed solution with pyrrole, and carrying out in-situ graft polymerization to obtain the two-dimensional organic conductive fiber.
The invention mixes cellulose fiber, hydrochloric acid solution and ferric chloride to obtain cellulose fiber mixed solution.
In the present invention, the mixing is preferably performed by mixing the hydrochloric acid solution and ferric chloride and then mixing the mixture with the cellulose fibers. In the invention, the concentration of hydrochloric acid in the mixed solution obtained by mixing the hydrochloric acid solution and ferric chloride is preferably 0.5-2 mol/L, and more preferably 1.0-1.5 mol/L; the concentration of ferric chloride in the mixed solution obtained by mixing the hydrochloric acid solution and ferric chloride is preferably 0.1-0.5 mol/L, and more preferably 0.2-0.4 mol/L.
In the present invention, the mass ratio of the volume of the mixed solution obtained by mixing the hydrochloric acid solution and ferric chloride to the cellulose fiber is preferably (10 to 50) mL:1g of the total weight of the composition.
In the present invention, the mixing preferably comprises ultrasound and stirring sequentially; the frequency of the ultrasound and the rotational speed of the stirring are not limited in any way, and those known to those skilled in the art can be used. In the present invention, the time of the ultrasonic treatment is preferably 15min, and the time of the stirring is preferably 15 min.
After the cellulose fiber mixed solution is obtained, the cellulose fiber mixed solution and pyrrole are mixed for in-situ graft polymerization, and the two-dimensional organic conductive fiber is obtained.
In the present invention, the mass ratio of the pyrrole to the cellulose fiber in the cellulose fiber solution is preferably (0.01 to 3.5): 1, more preferably (0.1 to 0.5): 1.
the mixing process is not particularly limited, and may be performed by a method known to those skilled in the art.
In the invention, the temperature of the in-situ graft polymerization is preferably 4 ℃, and the time is preferably 30-300 min, more preferably 60-240 min, and most preferably 180 min.
After the in-situ graft polymerization is completed, the method also preferably comprises post-treatment, wherein the post-treatment preferably comprises dialysis, centrifugation and drying which are sequentially carried out; the dialysis process is preferably carried out for 48 hours in a 8000-14000 Da dialysis bag, and water is changed every 6-12 hours in the dialysis process. The centrifugation is preferably carried out 5 times by adopting deionized water to carry out centrifugation washing at the rotating speed of 10000 r/min. The drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 40 ℃, and the time is preferably 36 h.
When the conductive high molecular polymer is polythiophene, the in-situ graft polymerization process preferably includes the following steps:
mixing 3-methylthiophene, an organic solvent, ferric chloride and cellulose fibers, and carrying out in-situ graft polymerization to obtain the conductive polymer composite material.
In the present invention, the concentration of ferric chloride in the mixed solution obtained by the mixing is preferably 0.1 to 0.5mol/L, and more preferably 0.3 to 0.4 mol/L.
In the present invention, the organic solvent preferably comprises chloroform and/or acetonitrile, and when the organic solvent is chloroform and acetonitrile, the amount ratio of chloroform and acetonitrile is not particularly limited, and the organic solvent may be mixed at any amount ratio.
In the present invention, the mass ratio of the 3-methylthiophene to the cellulose fibers is preferably (0.01 to 2.5): 1, more preferably (0.1 to 0.5): 1.
in the present invention, the mass ratio of the volume of the mixed liquid obtained after the mixing to the cellulose fibers is preferably (10 to 100) mL:1 g.
In the invention, the temperature of the in-situ graft polymerization is preferably 5 ℃, and the time is preferably 2-24 h, and more preferably 8-12 h.
After the in-situ graft polymerization is completed, the method also preferably comprises post-treatment, wherein the post-treatment preferably comprises cleaning and drying which are sequentially carried out; the washing preferably employs isopropanol to remove ungrafted thiophene, polythiophene and ferric chloride. In the present invention, the drying temperature is preferably 60 ℃ and the drying time is preferably 20 min.
When the conductive high molecular polymer is two or more of polypyrrole, polyaniline and polythiophene, the in-situ graft polymerization process is preferably to graft the cellulose fibers in sequence according to the above process. For example, when the conductive high molecular polymer is polypyrrole and polyaniline, the in-situ graft polymerization process is preferably to graft polypyrrole and polyaniline in sequence. The process for grafting polypyrrole and polyaniline preferably refers to the process described in the above technical scheme.
After the two-dimensional organic conductive fiber is obtained, the two-dimensional organic conductive fiber, the inorganic conductive filler and the polymer resin are mixed and molded to obtain the conductive polymer composite material.
In the present invention, the inorganic conductive filler preferably includes one or more of carbon black, graphite, and metal powder; the metal powder preferably comprises one or more of aluminum powder, copper powder and silver powder; when the inorganic conductive filler is more than two of the specific choices, the proportion of the specific materials is not limited in any way, and the specific materials can be mixed according to any proportion. In the present invention, the particle size of the inorganic conductive filler is preferably 10nm to 10 μm, and more preferably 50nm to 1 μm.
In the invention, the polymer resin preferably comprises one or more of polypropylene (PP), Polyethylene (PE), Polyamide (PA), Polystyrene (PS) and ethylene-vinyl acetate copolymer (EVA); when the polymer resin is more than two of the above specific choices, the present invention does not have any special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion.
In the invention, the mass ratio of the two-dimensional organic conductive fiber, the inorganic conductive filler and the polymer resin is preferably (1-10): (5-30): (70-90), more preferably (2-8): (10-25): (75-85), most preferably (4-6): (15-20): (78-82).
The mixing process is not particularly limited, and may be performed by a method known to those skilled in the art.
In the present invention, the molding is preferably melt molding or solution molding.
In the invention, when the blending mode is melt molding, the melt-molded raw materials further preferably comprise an auxiliary agent; the mass ratio of the two-dimensional organic conductive fibers to the auxiliary agent is preferably (1-20) to 1, more preferably (2-5): 1.
in the present invention, the auxiliary agent preferably includes a lubricant, an antioxidant and a compatibilizer; the mass ratio of the lubricant to the antioxidant to the compatilizer is preferably (0.5-1.5): (0.5-1.5): (0.5 to 5), more preferably (0.8 to 1.2): (0.8-1.2): (2-4).
In the present invention, the lubricant preferably includes one or more of zinc stearate, stearate and polyethylene wax; when the lubricant is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances can be mixed according to any proportion. In the present invention, the antioxidant preferably comprises one or more of 2, 6-di-tert-butylphenol, phosphite ester and p-phenylenediamine, and when the antioxidant is more than two of the above specific choices, the present invention does not have any special limitation on the proportion of the above specific substances, and the specific substances can be mixed according to any proportion. In the present invention, the compatibilizer preferably comprises one or more of maleic anhydride grafted polypropylene, oxazoline grafted PS and ionomer, and when the compatibilizer is two or more of the above specific choices, the specific proportions of the above specific materials are not particularly limited, and the materials may be mixed at any proportions.
In the present invention, the melt molding preferably includes melt extrusion and hot press molding, which are sequentially performed.
In the invention, the melt extrusion temperature is preferably 160-220 ℃, and more preferably 190 ℃; the rotation speed is preferably 30-100 r/min, and more preferably 50 r/min.
In the invention, the hot-press forming temperature is preferably 150-210 ℃, and more preferably 190 ℃; the time is preferably 5 to 20min, and more preferably 10 min.
In the present invention, when the molding manner is solution molding, the mixing also preferably includes a solvent; the solvent preferably comprises one or more of n-heptane, toluene, xylene, tetrahydrofuran and dichloromethane; when the solvent is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances are mixed according to any proportion; when the polymer resin is PP, the solvent is preferably n-heptane; when the polymer resin is PE, the solvent is preferably xylene; when the polymer resin is PA, the solvent is preferably tetrahydrofuran; when the polymer resin is PS, the solvent is preferably dichloromethane; when the polymer resin is EVA, the solvent is preferably toluene.
In the present invention, the mass ratio of the polymer resin to the solvent is preferably (0.1 to 1): 10, more preferably (0.2 to 0.5): 10.
in the invention, the mixing is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 300-1500 r/min, and more preferably 1000 r/min; the time is preferably 0.2 to 1 hour, and more preferably 0.5 hour.
In the present invention, the solution forming preferably includes casting and forming which are performed sequentially. The casting and forming process of the present invention is not particularly limited, and may be performed according to a process known to those skilled in the art.
The invention also provides a conductive polymer composite material prepared by the preparation method in the technical scheme, which comprises polymer resin, and two-dimensional organic conductive fibers and inorganic conductive filler which are dispersed in the polymer resin;
the two-dimensional organic conductive fiber comprises cellulose fiber and a conductive high polymer grafted and polymerized on the surface of the cellulose fiber in situ;
conductive network paths are formed among the two-dimensional organic conductive fibers, among the inorganic conductive fillers and among the two-dimensional organic conductive fibers and the inorganic conductive fillers (as shown in fig. 1).
In the invention, the mass ratio of the two-dimensional organic conductive fiber, the inorganic conductive filler and the polymer resin is preferably (1-10): (5-30): (70-90), more preferably (2-8): (10-25): (75-85), most preferably (4-6): (15-20): (78-82).
The invention also provides application of the conductive polymer composite material in the technical scheme in the fields of electromagnetic shielding materials, antistatic materials, electrode materials, conductor material sensors or display materials. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The following will explain the conductive polymer composite material provided by the present invention, its preparation method and application in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 0.05mol of phosphoric acid and 0.05mol of aniline (4.65g), then mixing with 2.3g of cellulose fibers with the length of 5mm and the diameter of 20 mu m, finally dropwise adding 200mL of ammonium persulfate solution with the concentration of 0.5mol/L, carrying out in-situ graft polymerization for 8h under the vacuum condition and at the temperature of 5 ℃, and repeatedly washing by adopting 0.01mol/L hydrochloric acid solution and acetone in sequence to remove unreacted organic matters and oligomers; washing with deionized water for 3 times, and vacuum drying at 40 ℃ for 36h to obtain the two-dimensional organic conductive fiber (the grafting rate is 200%);
mixing 4g of the two-dimensional organic conductive fiber, 10g of carbon black conductive filler, 83g of polystyrene resin and 3g of auxiliary agent (comprising 1g of zinc stearate, 1g of antioxidant 2, 6-di-tert-butylphenol and 1g of oxazoline grafted PS), extruding, performing hot-press molding at the temperature of 190 ℃ and the rotating speed of 50r/min, wherein the temperature of the hot-press molding is 190 ℃ and the time is 10min, and thus obtaining the conductive polymer composite material.
Example 2
Shearing cellulose fibers by using a wall breaking machine, wherein the rotating speed of the shearing treatment is 20000r/min, the time is 10min, and the cellulose fibers with the length of 2mm and the diameter of 15 mu m are obtained;
mixing 0.05mol of phosphoric acid and 0.05mol of aniline (4.65g), then mixing with 1.5g of cellulose fibers with the length of 2mm and the diameter of 15 mu m, finally dropwise adding 200mL of ammonium persulfate solution with the concentration of 0.5mol/L, carrying out in-situ graft polymerization for 8h under vacuum condition and at 5 ℃, and repeatedly washing by adopting 0.01mol/L hydrochloric acid solution and acetone in sequence to remove unreacted organic matters and oligomers; washing with deionized water for 3 times, and vacuum drying at 40 ℃ for 36h to obtain the two-dimensional organic conductive fiber (the grafting rate is 300%);
and (2) mixing 3g of the two-dimensional organic conductive fiber, 10g of graphite conductive filler, 85g of polystyrene resin and 2g of auxiliary agent (comprising 0.5g of zinc stearate, 1g of 2, 6-di-tert-butylphenol and 0.5g of oxazoline grafted PS), then carrying out extrusion molding, wherein the melt extrusion temperature is 190 ℃, the rotating speed is 50r/min, and carrying out hot press molding, wherein the hot press molding temperature is 190 ℃ and the hot press molding time is 10min, thus obtaining the conductive polymer composite material.
Example 3
Carrying out strong mechanical treatment on cellulose fibers by using a high-pressure homogenizer to obtain the cellulose fibers with the length of 300 mu m and the diameter of 50 nm;
mixing 0.1mol of phosphoric acid and 0.05mol of aniline (4.65g), then mixing with 1.5g of cellulose fibers with the length of 300 mu m and the diameter of 50nm, finally dropwise adding 200mL of ammonium persulfate solution with the concentration of 0.5mol/L, carrying out in-situ graft polymerization for 8h under vacuum condition and at 5 ℃, and repeatedly washing by adopting 0.01mol/L hydrochloric acid solution and acetone in sequence to remove unreacted organic matters and oligomers; washing with deionized water for 3 times, and vacuum drying at 40 ℃ for 36h to obtain the two-dimensional organic conductive fiber (the grafting rate is 300%);
and (2) mixing 1g of the two-dimensional organic conductive fiber, 12g of carbon black conductive filler, 84g of polystyrene resin and 3g of auxiliary agent (comprising 1g of zinc stearate, 1g of 2, 6-di-tert-butylphenol and 1g of ionomer), then carrying out extrusion molding, wherein the temperature of melt extrusion is 190 ℃, the rotating speed is 50r/min, carrying out hot press molding, and the temperature of hot press molding is 190 ℃ and the time is 10min, thus obtaining the conductive polymer composite material.
Example 4
Carrying out strong mechanical treatment on cellulose fibers by using a high-pressure homogenizer to obtain the cellulose fibers with the length of 300 mu m and the diameter of 50 nm;
mixing 4.8g of 3-methylthiophene, 200mL of chloroform, 3.24g of ferric chloride and 2.3g of cellulose fibers, carrying out in-situ graft polymerization at the temperature of 5 ℃ for 12h, removing ungrafted thiophene, polythiophene and ferric chloride by using isopropanol, and drying at the temperature of 60 ℃ for 20min to obtain the two-dimensional organic conductive fiber (the grafting rate is 200%);
and (2) mixing 2g of the two-dimensional organic conductive fiber, 10g of copper powder conductive filler, 86g of polystyrene resin and 2g of auxiliary agent (comprising 0.5g of polyethylene wax, 1g of 2, 6-di-tert-butylphenol and 0.5g of oxazoline grafted PS), then carrying out extrusion molding, wherein the temperature of melt extrusion is 190 ℃, the rotating speed is 50r/min, and carrying out hot press molding, wherein the temperature of hot press molding is 190 ℃, and the time is 10min, thus obtaining the conductive polymer composite material.
Example 5
Carrying out strong mechanical treatment on cellulose fibers by using a high-pressure homogenizer to obtain the cellulose fibers with the length of 300 mu m and the diameter of 50 nm;
mixing 1g of cellulose fiber, 200mL of hydrochloric acid with the concentration of 2mol/L and 7.68g of ferric chloride to obtain a cellulose fiber mixed solution;
mixing the cellulose fiber mixed solution with 3.2g of pyrrole, performing ultrasonic treatment for 15min, stirring for 15min, performing in-situ graft polymerization at the temperature of 4 ℃ for 180min, dialyzing the reacted slurry in a dialysis bag of 8000Da for 48h, replacing water every 6h, centrifugally washing the dialyzed material for 5 times at the rotating speed of 10000r/min by using deionized water, and performing vacuum drying at 40 ℃ for 36h to obtain the two-dimensional organic conductive fiber (the grafting rate is 300%);
mixing 8.4g of polystyrene and 100mL of dichloromethane to obtain a polystyrene solution;
and stirring 0.4g of the two-dimensional organic conductive fiber, 1.2g of the carbon black conductive filler and 8.4g of the polystyrene solution for 0.5h under the condition of 1000r/min, mixing, pouring into a mold, and drying to obtain the conductive polymer composite material.
Example 6
Shearing cellulose fibers by using a wall breaking machine, wherein the rotating speed of the shearing treatment is 20000r/min, the time is 10min, and the cellulose fibers with the length of 2mm and the diameter of 15 mu m are obtained;
mixing 0.05mol of phosphoric acid and 0.05mol of aniline (4.65g), then mixing with 2.3g of cellulose fibers with the length of 2mm and the diameter of 15 mu m, finally dropwise adding 200mL of ammonium persulfate solution with the concentration of 0.5, carrying out in-situ graft polymerization for 8h under the vacuum condition and at the temperature of 5 ℃, and repeatedly washing by sequentially adopting 0.01mol/L hydrochloric acid solution and acetone to remove unreacted organic matters and oligomers; washing with deionized water for 3 times, and vacuum drying at 40 deg.C for 36 h;
mixing cellulose fibers grafted with polyaniline, 200mL of hydrochloric acid with the concentration of 2M and 7.68g of ferric chloride to obtain a mixed solution, then mixing the mixed solution of the cellulose fibers and 4.65g of pyrrole, performing ultrasonic treatment for 15min, stirring for 15min, and then performing in-situ graft polymerization, wherein the temperature of the in-situ graft polymerization is 4 ℃, the time is 180min, the reacted slurry is dialyzed in a dialysis bag with the temperature of 8000Da for 48h, water is replaced every 6h, and the dialyzed material is dried in vacuum at the temperature of 40 ℃ for 36h to obtain the two-dimensional organic conductive fibers (the grafting rate is 400%);
and (2) mixing 3g of the two-dimensional organic conductive fiber, 10g of graphite conductive filler, 85g of polystyrene resin and 2g of auxiliary agent (comprising 0.5g of zinc stearate, 0.5g of 2, 6-di-tert-butylphenol and 1g of oxazoline grafted PS), then carrying out extrusion molding, wherein the temperature of melt extrusion is 190 ℃, the rotating speed is 50r/min, and carrying out hot press molding, wherein the temperature of hot press molding is 190 ℃ and the time is 10min, thus obtaining the conductive polymer composite material.
Example 7
Mixing 1g of nano cellulose fiber with the length of 300 mu m and the diameter of 50nm, 10g of cellulose fiber with the length of 2mm and the diameter of 15 mu m with 200g of water, standing, and freeze-drying to obtain cellulose fiber with a multi-level structure;
mixing 0.05mol of phosphoric acid and 0.05mol of aniline (4.65g), then mixing with 2.3g of cellulose fibers of the hierarchical structure, finally dropwise adding 200mL of ammonium persulfate solution with the concentration of 0.5mol/L, carrying out in-situ graft polymerization for 8h under the vacuum condition and at the temperature of 5 ℃, and repeatedly washing by adopting 0.01mol/L hydrochloric acid solution and acetone in sequence to remove unreacted organic matters and oligomers; washing with deionized water for 3 times, and vacuum drying at 40 ℃ for 36h to obtain the two-dimensional organic conductive fiber (the grafting rate is 200%);
and mixing 3g of the two-dimensional organic conductive fiber, 10g of carbon black conductive filler, 84g of polystyrene resin and 3g of auxiliary agent (comprising 1g of zinc stearate, 1g of phosphite ester and 1g of oxazoline grafted PS), extruding, performing hot press molding at the temperature of 190 ℃ and the rotating speed of 50r/min, wherein the temperature of the hot press molding is 190 ℃ and the time is 10min, and thus obtaining the conductive polymer composite material.
Comparative example 1
Mixing 20g of carbon black conductive filler, 77g of polystyrene resin and 3g of auxiliary agent (comprising 1g of lubricant (polyethylene wax), 1g of antioxidant (2, 6-di-tert-butylphenol) and 1g of compatilizer (oxazoline grafted PS)), extruding, performing hot-press molding at the temperature of 190 ℃ and the rotation speed of 50r/min, wherein the temperature of the hot-press molding is 190 ℃ and the time is 10min, and obtaining the conductive polymer composite material.
Comparative example 2
Mixing 0.05mol of phosphoric acid and 0.05mol of aniline (4.65g), and dropwise adding 200mL of ammonium persulfate solution with the concentration of 0.5mol/L for polymerization to obtain polyaniline;
mixing 4g of polyaniline and 40g of solvent (the kind of the solvent is methyl pyrrolidone) to obtain a polyaniline solution;
coating 1.3g of cellulose fiber with the length of 5mm and the diameter of 20 mu m in the polyaniline solution to obtain two-dimensional organic conductive fiber (the grafting rate is 300%);
mixing 5g of the two-dimensional organic conductive fiber, 10g of carbon black conductive filler, 81g of polystyrene resin and 4g of an auxiliary agent (comprising 1g of a lubricant (the specific type is zinc stearate), 1g of an antioxidant (the specific type is 2, 6-di-tert-butylphenol) and 2g of a compatilizer (the specific type is oxazoline grafted PS)), extruding, performing hot-press molding at the temperature of 190 ℃ and the rotating speed of 50r/min, and performing hot-press molding at the temperature of 190 ℃ for 10min to obtain the conductive polymer composite material.
Comparative example 3
Mixing 5g of cellulose fiber with the length of 5mm and the diameter of 20 mu m, 10g of carbon black conductive filler, 81g of polystyrene resin and 4g of auxiliary agent (comprising 1g of lubricant (zinc stearate in specific type), 1g of antioxidant (2, 6-di-tert-butylphenol in specific type) and 1g of compatilizer (oxazoline grafted PS in specific type)), extruding, and performing hot press molding at the temperature of 190 ℃ and the rotating speed of 50r/min for 10min to obtain the conductive polymer composite material.
Test example
Testing the conductivity of the conductive polymer composite materials of examples 1-7 and comparative examples 1-3 according to the GB/T3048.3 standard;
the conductive polymer composites of examples 1 to 7 and comparative examples 1 to 3 were tested for tensile strength according to the GB/T1040 standard, and the test results are shown in Table 1:
TABLE 1 tensile Strength and surface resistance of the conductive Polymer composites of examples 1 to 7 and comparative examples 1 to 3
| Sample (I) | Tensile Strength (MPa) | Surface resistance (omega) |
| Example 1 | 42 | 5.7×101 |
| Example 2 | 46 | 2.4×101 |
| Example 3 | 51 | 0.9×101 |
| Example 4 | 48 | 1.1×101 |
| Example 5 | 55 | 0.6×101 |
| Example 6 | 33 | 4.5×101 |
| Example 7 | 38 | 2.7×101 |
| Comparative example 1 | 23 | 3.5×103 |
| Comparative example 2 | 28 | 2.1×102 |
| Comparative example3 | 26 | 4.5×105 |
As can be seen from table 1, after the conductive polymer of the cellulose fiber medium is prepared by the preparation method of the present invention, the tensile strength and the conductive capability of the conductive polymer are significantly enhanced, and particularly, after the diameter of the cellulose fiber reaches the nanometer level, the dispersion degree of the cellulose loaded with the conductive polymer in the matrix is higher, so that the probability of contact or adjacency between the cellulose fiber and the inorganic conductive filler is higher, and the conductive performance is significantly increased with less content of the inorganic conductive filler. And the cellulose fiber has excellent mechanical properties, after nanocrystallization and coating, the compatibility with a matrix is increased, the reinforcing effect can be fully exerted, and the tensile strength of the conductive composite material is obviously improved. Therefore, the preparation method provides a novel hybrid conductive network filling system suitable for melt processing and solution processing for different polymer matrixes, is suitable for developing conductive composite materials with low content of conductive filler, high conductivity and mechanical property, has strong universality and is suitable for large-scale popularization and application.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the conductive polymer composite material is characterized by comprising the following steps:
carrying out in-situ graft polymerization on a conductive high molecular polymer monomer on the surface of cellulose fiber to obtain two-dimensional organic conductive fiber;
and mixing the two-dimensional organic conductive fiber, the inorganic conductive filler and the polymer resin, and molding to obtain the conductive polymer composite material.
2. The method of claim 1, wherein the cellulose fibers have a length of 1 μm to 1cm and a diameter of 5nm to 50 μm.
3. The method according to claim 2, wherein the conductive polymer monomer comprises one or more of aniline monomer, pyrrole monomer, and thiophene monomer.
4. The method according to claim 1, wherein the graft ratio of the in-situ graft polymerization is 50 to 500%.
5. The method of claim 2, wherein the inorganic conductive filler comprises one or more of carbon black, graphite, and metal powder.
6. The preparation method according to claim 1, wherein the mass ratio of the two-dimensional organic conductive fiber, the inorganic conductive filler and the polymer resin is (1-10): (5-30): (70-90).
7. The method according to claim 1, wherein the molding is performed by melt molding or solution molding.
8. The production method according to claim 1, wherein when the molding is melt molding, the melt-molded raw material further comprises an auxiliary;
the auxiliary agent comprises a lubricant, an antioxidant and a compatilizer;
the mass ratio of the lubricant to the antioxidant to the compatilizer is (0.5-1.5): (0.5-1.5): (1-5).
9. The conductive polymer composite material prepared by the preparation method of any one of claims 1 to 8, which is characterized by comprising a polymer resin, and two-dimensional organic conductive fibers and inorganic conductive fillers dispersed in the polymer resin;
the two-dimensional organic conductive fiber comprises cellulose fiber and a conductive high polymer grafted and polymerized on the surface of the cellulose fiber in situ;
conductive network paths are formed among the two-dimensional organic conductive fibers, among the inorganic conductive fillers and among the two-dimensional organic conductive fibers and the inorganic conductive fillers.
10. Use of the conductive polymer composite of claim 9 in the field of electromagnetic shielding materials, antistatic materials, electrode materials, conductive material sensors or display materials.
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