CN110667129A - Carbon nano tube-polyphosphazene composite material and preparation method thereof - Google Patents
Carbon nano tube-polyphosphazene composite material and preparation method thereof Download PDFInfo
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- CN110667129A CN110667129A CN201910849593.1A CN201910849593A CN110667129A CN 110667129 A CN110667129 A CN 110667129A CN 201910849593 A CN201910849593 A CN 201910849593A CN 110667129 A CN110667129 A CN 110667129A
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- 229920002627 poly(phosphazenes) Polymers 0.000 title claims abstract description 155
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 79
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 79
- 239000000835 fiber Substances 0.000 claims description 40
- 239000002238 carbon nanotube film Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000005096 rolling process Methods 0.000 claims description 16
- 238000003490 calendering Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
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- 238000001125 extrusion Methods 0.000 claims description 7
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- -1 cyclic phosphazene small molecule Chemical class 0.000 claims description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000012298 atmosphere Substances 0.000 description 2
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 239000002048 multi walled nanotube Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
- B29C66/114—Single butt joints
- B29C66/1142—Single butt to butt joints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/43—Joining a relatively small portion of the surface of said articles
- B29C66/432—Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms
- B29C66/4322—Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms by joining a single sheet to itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/45—Joining of substantially the whole surface of the articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/18—Polymers of nitriles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
- B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
- B29K2105/167—Nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention relates to the field of composite materials, and particularly discloses a preparation method of a carbon nanotube-polyphosphazene composite material, which comprises the following steps: the carbon nanotubes are composited with polyphosphazenes. Compounding the carbon nano tube with the polyphosphazene, because the carbon nano tube has better temperature resistance, and the heat conductivity is very excellent, under the high temperature environment, the polyphosphazene can isolate a large amount of heat as a heat insulating material, and a small amount of heat transferred into the polyphosphazene can be directly led out by the carbon nano tube, so that the overall temperature resistance and heat insulation performance of the carbon nano tube-polyphosphazene composite material are greatly improved, the carbon nano tube can still continuously keep in keeping off heat even after the polyphosphazene fails at high temperature, and the defect of high temperature resistance of the polyphosphazene is overcome.
Description
Technical Field
The embodiment of the invention relates to the field of composite materials, in particular to a carbon nanotube-polyphosphazene composite material and a preparation method thereof.
Background
Polyphosphazenes are organic and inorganic polymer materials formed by alternately connecting single bonds and double bonds of phosphorus and nitrogen atoms, and the phosphorus and nitrogen atoms with rich main chains endow the materials with excellent phosphorus and nitrogen flame retardant properties. In addition, due to their low thermal conductivity, low ablation rate, low or no smoke during combustion, they can be used as thermal insulation layers, either alone or in combination with other materials, for example as described in U.S. patent publication No. 5024860: a rocket heat insulating layer with low smoke generation is prepared from polyphosphazene and other materials. However, the thermal decomposition temperatures are not very high, about two to three hundred degrees, in terms of the thermal stability of polyphosphazenes, e.g. phenoxypolyphosphazenes in N2The initial decomposition temperature in the atmosphere is 280 ℃, and the temperature of the polyphosphazene containing the nitro group can reach about 353 ℃, so that the high-temperature resistance of the polyphosphazene is not very high in general.
In view of the foregoing, there is a need to provide a composite material with good thermal stability and flame retardant and thermal insulation properties.
Disclosure of Invention
The embodiment of the invention aims to provide a carbon nanotube-polyphosphazene composite material and a preparation method thereof, and the composite material with good thermal stability, flame retardance and heat insulation performance is prepared.
In order to solve the above technical problems, an embodiment of the first aspect of the present invention provides a method for preparing a carbon nanotube-polyphosphazene composite material, including the following steps:
the carbon nanotubes are composited with polyphosphazenes.
The embodiment of the second aspect of the invention also provides a carbon nano tube-polyphosphazene composite material prepared by the method.
In addition, the preparation method of the carbon nanotube-polyphosphazene composite material can also have the following additional technical characteristics:
according to one embodiment of the present invention, the carbon nanotube is a carbon nanotube film or a carbon nanotube powder; the polyphosphazene is a polyphosphazene film, and the carbon nano tube and the polyphosphazene are compounded together by a rolling method or an extrusion method.
According to one embodiment of the present invention, the method for preparing the carbon nanotube film comprises the following steps:
heating, mixing and rolling the carbon nanotube fiber and the adhesive resin;
the preparation method of the polyphosphazene film comprises the following steps:
the polyphosphazene solution and the binding resin are heated, kneaded and rolled.
According to one embodiment of the present invention, the opposite sides of the composite material are bent toward each other, and then the opposite edges are bonded to form the tubular carbon nanotube-polyphosphazene composite material.
According to one embodiment of the invention, the carbon nanotubes are carbon nanotube solution, the polyphosphazene is polyphosphazene solution, and the release agent, the polyphosphazene solution and the carbon nanotube solution are sequentially coated on the outer surface of the cylindrical mold, and the cylindrical mold is dried and then released.
According to one embodiment of the invention, the carbon nanotubes are carbon nanotube fibers; the polyphosphazene is a polyphosphazene solution, carbon nanotube fibers are soaked in the polyphosphazene solution, the solvent is volatilized to coat the polyphosphazene on the surfaces of the carbon nanotube fibers, and then the polyphosphazene-coated carbon nanotube fibers are woven into fiber cloth.
According to one embodiment of the invention, the carbon nanotubes are carbon nanotube fibers; and the polyphosphazene is a polyphosphazene solution, carbon nanotube fibers are woven into fiber cloth, the fiber cloth is soaked in the polyphosphazene solution, and the solvent is volatilized to obtain the polyphosphazene-coated carbon nanotube fiber cloth.
According to one embodiment of the invention, the polyphosphazene is selected from one or more of linear polydichlorophosphazene, linear polyphosphazene, cyclic phosphazene small molecule derivatives and cyclic clustered phosphazene. Preferably, the polyphosphazene is selected from linear polydichlorophosphazenes, cyclic phosphazene small molecule derivatives, cyclic clustered phosphazenes.
According to one embodiment of the invention, the polyphosphazene is prepared by solution polymerization or melt polymerization. Preferably, the polyphosphazene is prepared by a solution polymerization method.
According to one embodiment of the invention, the carbon nanotubes are prepared by arc, laser ablation or chemical vapor deposition. Preferably, the carbon nanotubes are prepared by an arc method.
According to one embodiment of the invention, the binder resin is selected from phosphazenes or epoxy resins. Preferably, the adhesive resin is selected from epoxy resins.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
1. the carbon nano-tube is a good heat conduction material or an additive of the heat conduction material, the heat conductivity of a single-walled carbon nano-tube at room temperature is higher than 6000W/(m.K), and the heat conductivity of a single multi-walled carbon nano-tube at room temperature is also higher than 3000W/(m.K). In terms of heat resistance, the thermal stability of the carbon nanotube is better than that of polyphosphazene, the phenomenon of thermal weight loss begins to occur only at about 503 ℃ in an air atmosphere, and the carbon nanotube can even bear the high temperature of more than 1727 ℃ in a vacuum or inert gas environment. Compounding the carbon nano tube with the polyphosphazene, because the carbon nano tube has better temperature resistance, and the heat conductivity is very excellent, under the high temperature environment, the polyphosphazene can isolate a large amount of heat as a heat insulating material, and a small amount of heat transferred into the polyphosphazene can be directly led out by the carbon nano tube, so that the overall temperature resistance and heat insulation performance of the carbon nano tube-polyphosphazene composite material are greatly improved, the carbon nano tube can still continuously keep in keeping off heat even after the polyphosphazene fails at high temperature, and the defect of high temperature resistance of the polyphosphazene is overcome.
Drawings
One or more embodiments are illustrated by way of example in the accompanying drawings, which correspond to the figures in which like reference numerals refer to similar elements and which are not to scale unless otherwise specified.
FIG. 1 is a cross-sectional view of a carbon nanotube-polyphosphazene composite in example 1 of the present invention;
FIG. 2 is a cross-sectional view of a carbon nanotube-polyphosphazene composite in example 2 of the present invention;
FIG. 3 is a cross-sectional view of a carbon nanotube-polyphosphazene composite in example 3 of the present invention;
FIG. 4 is a cross-sectional view of a carbon nanotube-polyphosphazene composite in example 4 of the present invention;
FIG. 5 is a cross-sectional view of a carbon nanotube-polyphosphazene composite in example 5 of the present invention;
FIG. 6 is a cross-sectional view of a carbon nanotube fiber coated with polyphosphazene in example 7 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it will be appreciated by those of ordinary skill in the art that in various embodiments of the invention, numerous technical details are set forth in order to provide a better understanding of the present application. However, the technical solution claimed in the present application can be implemented without these technical details and various changes and modifications based on the following embodiments.
The embodiment of the first aspect of the invention provides a preparation method of a carbon nanotube-polyphosphazene composite material, which comprises the following steps:
the carbon nanotubes are composited with polyphosphazenes.
It is worth mentioning that the polyphosphazene plays a role in flame retardance and heat insulation, the carbon nano tube is used as a good heat conductor, and the carbon nano tube is a heat conduction layer in the composite material, so that the prepared carbon nano tube-polyphosphazene composite material has excellent heat insulation performance.
The polyphosphazene of the present invention has the general formula:
it is noted that R1、R2Different or same substituent groups are adopted, and n is more than or equal to 3. When R is1、R2When Cl, the polyphosphazene may be a linear polydichlorophosphazene, when R is1、R2When the phosphonitrile is a monofunctional nucleophilic reagent, the polyphosphazene can react with linear polydichlorophosphazene to obtain linear polyphosphazene; when R is1、R2When the phosphonitrile is a monofunctional nucleophilic reagent, the polyphosphazene can react with hexachlorocyclotriphosphazene to obtain a cyclic phosphazene micromolecule derivative; when R is1、R2When at least one is a polyfunctional nucleophile, the polyphosphazene can react with hexachlorocyclotriphosphazene to form a cycloclustered phosphazene.
It is worth mentioning that the polyphosphazene can be prepared by solution polymerization or melt polymerization, and specifically, when the polyphosphazene is linear polydichlorophosphazene, the preparation method is as follows:
dissolving hexachlorocyclotriphosphazene in high-boiling-point chloride solvent, using fuming sulfuric acid as catalyst and ultrapure water as synergistic catalyst, under the protection of inert gas, heating to 200-215 deg.C, and reacting for 3-10 hr. And after the reaction is finished, pouring the reaction mixed solution into n-heptane, separating out the product linear polydichlorophosphazene, and washing with n-heptane for several times to obtain pure linear polydichlorophosphazene.
The solvent used is 1,2, 4-trichlorobenzene or chloronaphthalene. Dissolving the polydichlorophosphazene, dripping appropriate nucleophilic stituent reagent to react for 1-48h at the temperature of room temperature to 100 ℃, and then precipitating, washing and drying the product by using a precipitator.
When the polyphosphazene is a cyclic phosphazene small molecule derivative, the preparation method comprises the following steps:
dissolving hexachlorocyclotriphosphazene in proper solvent such as dehydrated tetrahydrofuran or pyridine, dripping excessive nucleophilic substitution reagent with single functionality to react at room temperature to 100 ℃ for 1-48h, and precipitating, washing and drying the product by using a precipitator.
When the polyphosphazene is a ring cluster phosphazene, the preparation method comprises the following steps:
dissolving hexachlorocyclotriphosphazene in proper solvent such as dehydrated tetrahydrofuran or pyridine, dripping excessive nucleophilic substitution reagent with multiple functionality degree into the solvent to react for 1 to 48 hours at the temperature of room temperature to 100 ℃, and then precipitating, washing and drying the product by using a precipitator.
In addition, the carbon nanotubes can be prepared by conventional preparation methods, for example, arc method, laser ablation method, chemical vapor deposition method, or the like.
The following will further illustrate the preparation method of the carbon nanotube-polyphosphazene composite material in the present application with reference to specific examples.
Example 1
The embodiment relates to a preparation method of a carbon nanotube-polyphosphazene composite material, which specifically comprises the following steps:
the carbon nano tube is a carbon nano tube film; polyphosphazene is a polyphosphazene film, the polyphosphazene can be linear polydichlorophosphazene, a layer of carbon nano tube film 1 is compounded on a layer of polyphosphazene film 2 in a manner suitable for large-scale industrial production such as a calendaring method or an extrusion method, and specifically, the carbon nano tube film 1 and the polyphosphazene film 2 are respectively refined by a roller mill for 2-3 times before compounding so as to be preheated and uniformly gelled; the polyphosphazene refined by the calender passes through the calender to obtain an initial polyphosphazene film, then the carbon nano tubes refined by the calender with the same volume are added on the polyphosphazene film, and the mixture is repeatedly refined by the calender for 2-3 times, so that the structure of the obtained carbon nano tube-polyphosphazene composite material is shown in figure 1.
The preparation method of the carbon nanotube film comprises the following steps: heating carbon nanotube fibers and bonding resin, uniformly stirring at a high speed, then feeding into an internal mixer, uniformly mixing, then passing through a rolling wheel machine, and then calendering by a calender; specifically, E51 epoxy resin with the mass fraction of 10% is added into carbon nanotube fiber, the mixture is heated and stirred uniformly at 60 ℃, then the mixture is mixed in an internal mixer and refined by a rolling mill for 2-3 times to preheat and gel uniformly, and the carbon nanotube refined by a calender is repeatedly calendered by the calender for 2-3 times to obtain a carbon nanotube film product.
Further, the preparation method of the polyphosphazene film comprises the following steps:
and heating the polyphosphazene solution and the bonding resin, uniformly stirring at a high speed, then feeding the mixture into an internal mixer, uniformly mixing, then passing through a rolling machine, and finally calendering by a calender. Wherein the adhesive resin may be selected from epoxy resins.
Example 2
The embodiment relates to a preparation method of a carbon nanotube-polyphosphazene composite material, which specifically comprises the following steps:
the carbon nano tube is a carbon nano tube film; polyphosphazene is a polyphosphazene film, polyphosphazene can be cyclic cluster phosphazene, a layer of carbon nanotube film 1 is respectively compounded on the upper surface and the lower surface of a layer of polyphosphazene film 2 by a calendering method or an extrusion method, and the structure of the obtained carbon nanotube-polyphosphazene composite material is shown in figure 2.
The preparation method of the carbon nanotube film comprises the following steps: heating carbon nanotube fibers and bonding resin, uniformly stirring at a high speed, then feeding into an internal mixer, uniformly mixing, then passing through a rolling wheel machine, and then calendering by a calender;
further, the preparation method of the polyphosphazene film comprises the following steps:
and heating the polyphosphazene solution and the bonding resin, uniformly stirring at a high speed, then feeding the mixture into an internal mixer, uniformly mixing, then passing through a rolling machine, and finally calendering by a calender. Wherein the adhesive resin may be selected from epoxy resins.
Example 3
The embodiment relates to a preparation method of a carbon nanotube-polyphosphazene composite material, which specifically comprises the following steps:
the carbon nano tube is a carbon nano tube film; polyphosphazene is a polyphosphazene film, polyphosphazene can be a ring cluster phosphazene, a layer of polyphosphazene film 2 is respectively compounded on the upper surface and the lower surface of a layer of carbon nanotube film 1 by a calendering method or an extrusion method, and the structure of the obtained carbon nanotube-polyphosphazene composite material is shown in figure 3.
The preparation method of the carbon nanotube film comprises the following steps: heating carbon nanotube fibers and bonding resin, uniformly stirring at a high speed, then feeding into an internal mixer, uniformly mixing, then passing through a rolling wheel machine, and then calendering by a calender;
further, the preparation method of the polyphosphazene film comprises the following steps:
and heating the polyphosphazene solution and the bonding resin, uniformly stirring at a high speed, then feeding the mixture into an internal mixer, uniformly mixing, then passing through a rolling machine, and finally calendering by a calender. Wherein the adhesive resin may be selected from epoxy resins.
Example 4
The embodiment relates to a preparation method of a carbon nanotube-polyphosphazene composite material, which specifically comprises the following steps:
the carbon nano tube is a carbon nano tube film; polyphosphazene is a polyphosphazene film, the polyphosphazene can be linear polydichlorophosphazene, a layer of carbon nanotube film 1 is compounded on a layer of polyphosphazene film 2 through a rolling method or an extrusion method, two opposite sides of the compounded composite material are bent towards the direction close to each other, and then two opposite edges of the compounded composite material are bonded to form the tubular carbon nanotube-polyphosphazene composite material shown in the figure 4.
The preparation method of the carbon nanotube film comprises the following steps: heating carbon nanotube fibers and bonding resin, uniformly stirring at a high speed, then feeding into an internal mixer, uniformly mixing, then passing through a rolling wheel machine, and then calendering by a calender;
further, the preparation method of the polyphosphazene film comprises the following steps:
and heating the polyphosphazene solution and the bonding resin, uniformly stirring at a high speed, then feeding the mixture into an internal mixer, uniformly mixing, then passing through a rolling machine, and finally calendering by a calender. Wherein the adhesive resin may be selected from epoxy resins.
Example 5
The embodiment relates to a preparation method of a carbon nanotube-polyphosphazene composite material, which specifically comprises the following steps:
the carbon nano tube is a carbon nano tube film; polyphosphazene is a polyphosphazene film, the polyphosphazene can be linear polydichlorophosphazene, a layer of polyphosphazene film 2 is compounded on a layer of carbon nanotube film 1 through a rolling method or an extrusion method, two opposite sides of the compounded composite material are bent towards the direction close to each other, and then two opposite edges of the compounded composite material are bonded to form the tubular carbon nanotube-polyphosphazene composite material shown in fig. 5.
The preparation method of the carbon nanotube film comprises the following steps: heating carbon nanotube fibers and bonding resin, uniformly stirring at a high speed, then feeding into an internal mixer, uniformly mixing, then passing through a rolling wheel machine, and then calendering by a calender;
further, the preparation method of the polyphosphazene film comprises the following steps:
and heating the polyphosphazene solution and the bonding resin, uniformly stirring at a high speed, then feeding the mixture into an internal mixer, uniformly mixing, then passing through a rolling machine, and finally calendering by a calender. Wherein the adhesive resin may be selected from epoxy resins.
Example 6
The embodiment relates to a preparation method of a carbon nanotube-polyphosphazene composite material, which specifically comprises the following steps:
the carbon nano tube is carbon nano tube solution, the polyphosphazene is polyphosphazene solution, the release agent, the polyphosphazene solution and the carbon nano tube solution are sequentially coated on the outer surface of the cylindrical mold, and the mold is taken out after drying, so that the tubular carbon nano tube-polyphosphazene composite material shown in the figure 4 or 5 is formed.
Example 7
The embodiment relates to a preparation method of a carbon nanotube-polyphosphazene composite material, which specifically comprises the following steps:
the carbon nano tube is carbon nano tube fiber; polyphosphazene is a polyphosphazene solution, carbon nanotube fibers are soaked in the polyphosphazene solution, the solvent is volatilized to coat the polyphosphazene on the surfaces of the carbon nanotube fibers, so that the polyphosphazene 2-coated carbon nanotube fibers 3 shown in fig. 6 are formed, and then the polyphosphazene-coated carbon nanotube fibers are woven into fiber cloth.
The polyphosphazene-coated carbon nanotube fiber shown in fig. 6 can also be formed by weaving carbon nanotube fibers into a fiber cloth, immersing the fiber cloth in a polyphosphazene solution, and volatilizing the solvent to obtain the polyphosphazene-coated carbon nanotube fiber cloth.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific embodiments for practicing the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
Claims (11)
1. A preparation method of a carbon nanotube-polyphosphazene composite material is characterized by comprising the following steps:
the carbon nanotubes are composited with polyphosphazenes.
2. The production method according to claim 1, wherein the carbon nanotube is a carbon nanotube film or a carbon nanotube powder; the polyphosphazene is a polyphosphazene film, and the carbon nano tube and the polyphosphazene are compounded together by a calendering method or an extrusion method.
3. The method of claim 2, wherein the method of manufacturing the carbon nanotube film comprises the steps of:
heating, mixing and rolling the carbon nanotube fiber and the adhesive resin;
the preparation method of the polyphosphazene film comprises the following steps:
the polyphosphazene solution and the binding resin are heated, kneaded and rolled.
4. The production method according to claim 2,
and bending the two opposite sides of the compounded composite material towards the direction close to each other, and then bonding the two opposite edges of the compounded composite material to form the tubular carbon nanotube-polyphosphazene composite material.
5. The method according to claim 1, wherein the carbon nanotubes are a carbon nanotube solution, the polyphosphazene is a polyphosphazene solution, and the release agent, the polyphosphazene solution and the carbon nanotube solution are sequentially coated on the outer surface of the cylindrical mold, and the cylindrical mold is dried and then released.
6. The production method according to claim 1, wherein the carbon nanotube is a carbon nanotube fiber; the polyphosphazene is a polyphosphazene solution, carbon nanotube fibers are soaked in the polyphosphazene solution, the solvent is volatilized to coat the polyphosphazene on the surfaces of the carbon nanotube fibers, and then the polyphosphazene-coated carbon nanotube fibers are woven into fiber cloth.
7. The production method according to claim 1, wherein the carbon nanotube is a carbon nanotube fiber; and the polyphosphazene is a polyphosphazene solution, carbon nanotube fibers are woven into fiber cloth, the fiber cloth is soaked in the polyphosphazene solution, and the solvent is volatilized to obtain the polyphosphazene-coated carbon nanotube fiber cloth.
8. The preparation method of claim 1, wherein the polyphosphazene is selected from one or more of linear polydichlorophosphazene, linear polyphosphazene, cyclic phosphazene small molecule derivatives and cyclic clustered phosphazene.
9. The method of claim 1, wherein the polyphosphazene is prepared by solution polymerization or melt polymerization.
10. The method according to any one of claims 1 to 9, wherein the carbon nanotubes are produced by arc, laser ablation or chemical vapor deposition.
11. A carbon nanotube-polyphosphazene composite material obtainable by the method of any of claims 1 to 10.
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