CN1908021A - In situ polymerization one-dimensional electric high purity carbon/polyacrylonitrile composite polymer - Google Patents
In situ polymerization one-dimensional electric high purity carbon/polyacrylonitrile composite polymer Download PDFInfo
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- CN1908021A CN1908021A CN 200510088082 CN200510088082A CN1908021A CN 1908021 A CN1908021 A CN 1908021A CN 200510088082 CN200510088082 CN 200510088082 CN 200510088082 A CN200510088082 A CN 200510088082A CN 1908021 A CN1908021 A CN 1908021A
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Abstract
the invention discloses a preparing method of composite priority through CVD method, which comprises the following parts: 100 wt% acrylon, 1-25 wt% one-dimension conductive high-purity carbon, 0-15 wt% comonomer, 1-3 wt% initiator, 0-1 wt% disperser, 0-3 wt% molecular weight modifier and 150-900 wt% reacting dielectric. One-dimension conductive high-purity carbon is dispersed in the acrylon to polymerize on the one-dimension conductive high-purity carbon, which removes non-reacted acrylon, comonomer and initiator.
Description
Technical field
The present invention relates to a kind of composition polymer, particularly relate to a kind of preparation method of composite precursor, be mainly used in and adopt chemical vapour deposition (Chemical Vapor Dposition is called for short CVD) legal system to be equipped with continuous fibre carbon core.Therefore this composition polymer has improved the consistency of one-dimensional electric high purity carbon and polyacrylonitrile because its surface has identical composition with the body polyacrylonitrile, helps homodisperse and the dispersive stability of one-dimensional electric high purity carbon in polyacrylonitrile solution.With the carbon core of this composite precursor preparation, be especially suitable for use as the basic core of CVD method continuous carbonization silicon (silicon carbide is called for short SiC) fiber.
Background technology
It is to adopt the conduction continuous monofilament as core (or being called the deposition carrier) that the CVD legal system is equipped with the SiC fiber, make core at the tubular reactor uniform motion, and apply voltage at two ends and carry out resistive heating (or radio frequency heating), core is heated to certain temperature, the silane of will vaporizing simultaneously is (as CH
3SiCl
3, CH
3HSiCl
2Deng) mix back importing reactor with hydrogen, make it at scorching hot surface cracking of core silk and formation of deposits SiC layer.The domestic and international core of reporting has two kinds at present, thin tungsten filament (the about 12.5 μ m of diameter are called tungsten core SiC fiber) or major diameter mesophase pitch-based carbon fibers (the about 33 μ m of diameter are called carbon core SiC fiber).The advantage of tungsten is resistivity low (about 0.06 μ Ω m), so the tungsten core diameter can be very little.The shortcoming of tungsten is density height (about 19g/cm
3), the also higher (3.4g/cm of the SiC fibre density that obtains
3).Tungsten generates brittle middle layer (as WC etc.) with SiC reaction under hot conditions in addition, cause final CVD method SiC fiber degradation (look into the celebrating virtue, Liu Lang, the wing is brave, Zhu Xingming. Chinese patent, publication number: CN 1103904A; Lindley M.W., Jones B.F..Nature, 1975,255:474-475).The advantage of mesophase pitch (mesophase pitch) based carbon core is low (the about 2.1g/cm of density
3), also lower (the about 3.0g/cm of the SiC fibre density that obtains
3).And at high temperature, carbon does not react with SiC, so the use temperature of carbon core SiC fiber is higher than tungsten core SiC fiber.The shortcoming of mesophase pitch carbon core is a raw material modulation process complexity, the spinning temperature height, and precursor fragility is big, continuous spinning and preoxidation technique difficulty are big, and carbon core intensity lower (700MPa～900MPa) (Edie D.D..Carbon, 1998,36 (4): 345-362; Shilin Lu, Clara Blanco, Brian Rand.Carbon, 2002,40:2109-2116; Charles A.L., Lucille A.G., Charles E.B., Richard E.T..J.Amer.Ceram.Soc., 1999,82 (2): 407-413).With the tungsten core relatively, mesophase pitch carbon core resistivity higher (2～8 μ Ω m), therefore in order to reach identical heats, the carbon core diameter is more much bigger than tungsten core diameter.
In the small diameter high performance carbon fiber, PAN-based carbon fiber accounts for 85%, and asphalt base carbon fiber accounts for 15%, and major cause is a PAN-based carbon fiber manufacturing technology maturation, and fibre property height and production cost are low.Do not adopt the report of PAN-based carbon fiber but have as yet at present as CVD method SiC fiber core.This is because the mesophase pitch-based carbon fibers ratio is easier to greying, form the graphite crystal of high-crystallinity, fabricating low-defect-density, so resistivity is lower.By contrast, PAN-based carbon fiber forms random lamellar graphite after handling through high temperature graphitization, and degree of crystallinity is relatively poor, thereby resistivity higher (about 14 μ Ω m).In order to reach the same resistance of mesophase pitch based carbon core, just need to strengthen the diameter of polyacrylonitrile-based carbon core fiber, thereby cause the diameter of final SiC fiber excessive, can't reel in the production process, can not continuous production.
Using PAN-based carbon fiber is to improve electric conductivity as the key of CVD method SiC fiber core, and the relevant report of this respect is not arranged at present as yet.Improving the effective means of electric conductivity is the material that adds other high conductivity, but the material that requires to be added possesses following performance: chemical reaction at high temperature and does not take place in (1) between the carbon fiber, otherwise will cause change in resistance; (2) at high temperature, and chemical reaction not taking place between the SiC, otherwise will reduce the performance of SiC fiber; (3) approaching with the thermal expansivity of carbon fiber, otherwise will produce large interface stress and reduce the performance of SiC fiber.
The preparation method of polymer matrix composite mainly contains completion method, situ aggregation method and sol-gel processing.Completion method is meant directly fills reinforcement materials in organic polymer.This method technology is simple, easy handling, and under solution, emulsion or molten state, can carry out.Therefore, the preparation method of the polymer matrix composite of bibliographical information mostly adopts this method.But this method also exists toughener to be difficult to homodisperse, to cause shortcomings such as final composite property difference with basal body interface bonding force difference.And situ aggregation method is that toughener is dispersed in polymer monomer or the performed polymer, and the trigger monomer in-situ polymerization generates the composition polymer that is dispersed with carbon nanotube under certain condition then.Because the polymer monomer molecule is little, viscosity is low, helps improving the dispersing property of toughener and combines situation with the interface of matrix.The collosol and gel rule is mainly used in preparation organic-inorganic nano composite material.The report that strengthens asphalt base carbon fiber and PAN-based carbon fiber with carbon nanotube of external report also all is to adopt completion method (R.Andrews, D.Jacques, A.M.Rao, T.Rantell, and F.Derbyshire.Nanotubecomposite carbon fibers, Applied Physics Letters, 1999,75 (9): 1329-1331; [8] T.Cho, Y.S.Lee, R.Rao, A.M.Rao, D.D.Edie, A.A.Ogale.Structure of carbon fiber obtain from nanotube-reinforcedmesophase pitch, Carbon, 2003,41:1419-1424), and also there is not in-situ polymerization to prepare the report of polyacrylonitrile-radical composition polymer.
Summary of the invention
The object of the present invention is to provide the method for a kind of in-situ polymerization one-dimensional electric high purity carbon and polyacrylonitrile.
The composition of the said one-dimensional electric high purity carbon/polyacrylonitrile composite polymer of the present invention and be by the content of mass fraction: the mass fraction of vinyl cyanide is 100 parts in reaction system, 1～25 part of one-dimensional electric high purity carbon, comonomer 0～15,1～3 part of initiator, 0～1 part of dispersion agent, 0～3 part of molecular weight regulator, 150～900 parts of reaction mediums.
Described one-dimensional electric high purity carbon is meant that carbon content is greater than 95% The Fiber Shape Carbon Material, can be carbon nanotube (axially resistivity is about 0.4 μ Ω m), gas-phase growth of carbon fibre (axially resistivity is about 1.3 μ Ω m) or graphite whisker (axially resistivity is about 0.7 μ Ω m).The spinning smoothly in order not stop up spinning jet, the diameter that requires one-dimensional electric high purity carbon is 0.005～10 μ m, is preferably 0.01～1 μ m; Length is 0.1～50 μ m, is preferably 1～20 μ m; Length-to-diameter ratio (L/D) is greater than 5.Described one-dimensional electric high purity carbon can be multi-walled carbon nano-tubes, gas-phase growth of carbon fibre or graphite whisker.Described in-situ polymerization can be solution polymerization, or precipitation polymerization.Comonomer is a vinyl monomer, comprises vinylformic acid, methyl acrylate, methyl methacrylate, methylene-succinic acid, acrylamide, ethyl propenoate or their mixture etc.; Initiator can be Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO), or redox initiator, as hydrogen peroxide and xitix, Ammonium Persulfate 98.5 and sodium bisulfite etc.; Dispersion agent can be polyvinyl alcohol, sodium laurylsulfonate etc.; Molecular weight regulator can be Virahol, thiocarbamide etc.; Reaction medium can be a water, the mixing solutions of organic solvent or organic solvent and water.
The preparation method of the said in-situ polymerization one-dimensional electric high purity carbon/polyacrylonitrile composite polymer of the present invention the steps include:
(1) with one-dimensional electric high purity carbon homodisperse in mixing solutionss such as vinyl cyanide, comonomer, initiator, dispersion agent, molecular weight regulator and reaction medium;
(2) under agitation make monomer in-situ polymerizations on one-dimensional electric high purity carbon such as vinyl cyanide, comonomer, initiator, dispersion agent, molecular weight regulator and reaction medium;
(3) remove unreacted vinyl cyanide, comonomer, initiator etc. completely, promptly obtain the in-situ polymerization one-dimensional electric high purity carbon/polyacrylonitrile composite polymer.
In step (1), with one-dimensional electric high purity carbon homodisperse in mixing solutionss such as vinyl cyanide, comonomer, initiator, dispersion agent, molecular weight regulator and reaction medium, with the coacervate that disperses one-dimensional electric high purity carbon to form.
In step (2), said polymerization process can adopt solution polymerization, also can adopt precipitation polymerization.Solution polymerization can dimethyl sulfoxide (DMSO), carry out in dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.Precipitation polymerization can be the aqueous phase precipitation polymerization, also can be the mixed solvent precipitation polymerization of water and dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.Polymeric reaction temperature is 50～72 ℃, and the reaction times is 1.5～48h.Through after the polymerization, the surface of one-dimensional electric high purity carbon coated by polyacrylonitrile or the polyacrylonitrile molecule in its surface growth, form the in-situ polymerization one-dimensional electric high purity carbon/polyacrylonitrile composite polymer.
In step (3), remove unreacted vinyl cyanide, comonomer, initiator etc. completely, can adopt to vacuumize or the method for underpressure distillation, also can adopt the method for washing, as washings such as water, ethanol, acetone.The product that adopts solution polymerization process to obtain can be directly used in spinning behind the unreacted monomer and realizes continuous production through removing, but that wherein unreacted monomer, initiator etc. are not easy to remove is clean, and the gained fibre property is relatively poor; And the product that obtains with precipitation polymerization process, need through washing, oven dry, dissolving could spinning again, technical process is longer, but unreacted monomer, initiator, dispersion agent etc. clean easily, remove in only, the concentration of spinning solution can be regulated as required, and the gained fibre property is good.Also the composition polymer that can obtain with in-situ polymerization prepares conjugated fibre with the composite solution that polyacrylonitrile is mixed with required composition and performance again as parent.
If one-dimensional electric high purity carbon length not in above-mentioned scope, can adopt ball-milling technology to reduce length.In spinning process, one-dimensional electric high purity carbon extrude with drawing process in therefore be subjected to the effect of shearing force and, will form the conductive channel of high conductivity along the precursor axial orientation, thereby the electric conductivity of raising PAN-based carbon fiber.In addition, therefore height-oriented one dimension high conductivity carbon can also improve the intensity of PAN-based carbon fiber because itself tensile strength and Young's modulus are higher than PAN-based carbon fiber far away, improves the processing performance of CVD.
The present invention with one dimension high conductivity carbon as adding material, for the chemical Vapor deposition process continuous fibre provides a kind of have spinning properties and dispersing property is good, The Nomenclature Composition and Structure of Complexes can be regulated composite precursor with the composite carbon core.Replace mesophase pitch with this composite precursor, easy control of process conditions not only, and can reduce environmental pollution, reduce cost, realize Sustainable development.With the carbon core of this composite precursor preparation have that processing performance is good, intensity is high, conductivity and diameter can control.Carbon core with the preparation of this presoma substitutes the tungsten core, can reduce cost and the density of SiC fiber, overcomes the shortcoming that tungsten at high temperature causes fibre property to descend with the SiC reaction; Carbon core with the preparation of this presoma substitutes the mesophase pitch based carbon core, can overcome mesophase pitch based carbon core raw material modulation difficulty, melt-spinning poor continuity, the pre-oxidation process technical difficulty is big, cost is high shortcoming.The preparation technology of the add-on by regulating one-dimensional electric high purity carbon, the synthesis condition of composition polymer and carbon core fibre can obtain that resistivity is controlled, the fiber of controllable diameter, and the core of different diameter is provided for CVD method fiber.This composition polymer also can be used for preparing other specialty fibers goods such as carbon fiber reinforce plastic, continuous pyrolysis carbon except being suitable for preparing the core of CVD method continuous fibre.
Description of drawings
Fig. 1 is an one-dimensional electric high purity carbon/polyacrylonitrile composite polymer preparation flow block diagram.
Embodiment
Embodiment 1: (mean diameter 0.015 μ m, mean length 10 μ m) use ultrasonic dispersing 4h in the mixing solutions of 95 parts of vinyl cyanide, 4 parts of methyl acrylates, 1 part of methylene-succinic acid and 300 parts of dimethyl sulfoxide (DMSO) with 5 parts of carbon nanotubes, and carbon nanotube is uniformly dispersed.These mixtures are transferred in the reactor; under nitrogen protection, stir (rotating speed 560r/min) 20min, add 2 parts of Diisopropyl azodicarboxylates, after the dissolving fully reactor is warmed up to 65 ℃ as initiator with the motor machine agitator; and isothermal reaction 24h, obtain black composition polymer solution.Reaction product is transferred to vacuum distillation apparatus, is to remove unreacted vinyl cyanide and methacrylate monomer completely under 50 ℃ under reduced pressure in vacuum tightness for the 150mmHg temperature.Be warmed up to 60 ℃ and enter swan neck through deaeration, after filtering and carry out wet-spinning then.Spinning technology parameter is that pump is for amount 0.15ml/min, single hole spinning nozzle, aperture 0.20mm.Precipitation bath one bath composition is 60% dimethyl sulphoxide aqueous solution, 10 ℃ of temperature, stretch ratio 0.8; Two baths are dimethyl sulphoxide aqueous solutions of 10%, 50 ℃ of temperature, stretch ratio 2; Three baths are stretching water-baths, 95 ℃ of temperature, stretch ratio 3; Four baths are washing water-baths, 25 ℃ of temperature, stretch ratio 1.05.Then enter dry air densification district, temperature is 200 ℃, and stretch ratio 1.05 then directly is wound on the bobbins, and winding speed is 25 meters/minute, the about 44 μ m of gained conjugated fibre diameter.
Embodiment 2～9: its preparation method is similar to Example 1, but reaction conditions is as shown in table 1.
The spinning properties of table 1 embodiment 2～9 solution polymerization conditions and composition polymer
| Form | Monomer ratio | Carbon nanotube | Reaction medium | Initiator | Molecular weight regulator | Temperature of reaction (℃) | Reaction times (h) | The product spinning properties |
| Embodiment 2 | AN 100 | SWNT 5 | DMF 150 | AIBN 3 | 0 | 60 | 48 | Difference |
| Embodiment 3 | AN 100，MA 15 | MWNT 1 | DMAc 900 | BPO 1 | IPA 3 | 72 | 36 | Good |
| Embodiment 4 | AN 100， MAA 3 | VGCF 5 | DMF 550 | AIBN | Thiocarbamide 1 | 64 | 24 | Good |
| Embodiment 5 | AN 100， MMA 5 | CW 8 | DMSO | AIBN 1.5 | Thiocarbamide 1.5 | 62 | 36 | Good |
| Embodiment 6 | AN 100，AM 3 | MWNT 20 | DMSO 300 | AIBN 2 | Thiocarbamide 2 | 66 | 36 | Relatively poor |
| Embodiment 7 | AN 100，IA 1 | SWNT 15 | DMSO 300 | BPO 1.5 | Thiocarbamide 1 | 66 | 24 | Relatively poor |
| Embodiment 8 | AN 100，EA 8 | MWNT 10 | DMF 500 | BPO 2 | Thiocarbamide 2 | 64 | 48 | Good |
| Embodiment 9 | AN 100，MA 6，IA 1 | VGCF 5 | DMSO 400 | AIBN 1.5 | IPA 1 | 62 | 48 | Good |
Annotate: the mass fraction in the table in each digitized representation reaction system, the material of each symbology is as follows:
The AN-vinyl cyanide, MA-methyl acrylate, MAA-vinylformic acid, the MMA-methyl methacrylate, AM-acrylamide, IA-methylene-succinic acid, the EA-ethyl propenoate, SWNT-Single Walled Carbon Nanotube, MWNT-multi-walled carbon nano-tubes, the VGCF-gas-phase growth of carbon fibre, CW-graphite whisker, DMF-dimethyl formamide, the inferior phenol of DMSO-dimethyl methyl, DMAc-N,N-DIMETHYLACETAMIDE, AIBN-Diisopropyl azodicarboxylate, the BPO-dibenzoyl peroxide, the IPA-Virahol
Embodiment 10: in reactor with electronic stirring (rotating speed 600r/min) with 1 part of sodium laurylsulfonate, 2 parts of hydrogen peroxide and 1 part of dissolution of ascorbic acid are in 300 parts of water.In 95 parts of vinyl cyanide, 4 parts of methyl methacrylates, 1 part of acrylic acid mixing solutions, add 5 parts of gas-phase growth of carbon fibre (mean diameter 0.150 μ m, mean length 10 μ m), also continue to stir 10min with pouring these mixtures into reactor behind the ultrasonic dispersing 4h.The temperature of reactor is risen to 50 ℃ and keep constant, make monomer reaction 8h such as vinyl cyanide, obtain black precipitate.With sedimentation and filtration, successively use 1000 parts of cold water, hot water (about 70 ℃), ethanol respectively to wash 2 times, wash 20min at every turn, put into 60 ℃ of dry 24h of vacuum drying oven behind the suction filtration, obtain gas-phase growth of carbon fibre/polyacrylonitrile composite polymer.18 parts of exsiccant gas-phase growth of carbon fibre/polyacrylonitrile composite polymers dissolved in 82 parts of dimethyl sulfoxide (DMSO) be mixed with spinning solution, be warmed up to 80 ℃ after deaeration, filtration enter swan neck and carry out wet-spinning.Spinning condition such as embodiment 1, the about 37 μ m of gained conjugated fibre diameter.
Embodiment 11: with embodiment 10, different is to change 2 parts of hydrogen peroxide and 1 part of xitix into 2 parts of Ammonium Persulfate 98.5s and 1 part of sodium bisulfite.The about 37 μ m of diameter of last gained conjugated fibre.
Embodiment 12: 150 parts of water and 150 parts of dimethyl sulfoxide (DMSO) are mixed with electric mixer (rotating speed 600r/min) in reactor.The PVA that adds 8 part 5% in reactor continues to stir 10min.With 5 parts of graphite whiskers (mean diameter 0.5 μ m, mean length 6 μ m), 95 parts of vinyl cyanide, 4 parts of ethyl propenoates, 1 part of methylene-succinic acid, 2 parts of Virahols with ultrasonic dispersing 4h after, adds 1 part of dibenzoyl peroxide and dissolves and mix.These mixtures are joined stir 10min in the reactor, temperature is raised to 54 ℃ and keep constant, obtain the black powder precipitation behind the reaction times 6h.Filter the back successively with 1000 parts of cold water, hot water (about 70 ℃), washing with acetone 2 times.Put into 60 ℃ of dry 24h of vacuum drying oven behind the suction filtration, obtain in-situ polymerization graphite whisker/polyacrylonitrile composite polymer.25 parts of exsiccant composition polymers with 75 parts of dmso solutions, are made into concentration and are 25% composition polymer solution, be warmed up to 80 ℃, enter swan neck through deaeration, after filtering and carry out dry-wet spinning.Spinning condition such as embodiment 1, gained conjugated fibre diameter are 44 μ m.
Embodiment 13～18: its preparation method is similar to Example 12, but reaction conditions is as shown in table 2.
The spinning properties of table 2 embodiment 13～18 precipitation polymerization reaction conditionss and composition polymer
| Form | Monomer ratio | Carbon nanotube | Reaction medium | Initiator | Molecular weight regulator | Dispersion agent (the 5%PVA aqueous solution) | Temperature of reaction (℃) | Reaction times (h) | The product spinning properties |
| Embodiment 2 | AN 100 | SWNT 5 | DMF 90，H 2O 210 | AIBN 3 | 0 | 0 | 60 | 1.5 | Good |
| Embodiment 3 | AN 100，MA 15 | MWNT 1 | DMAc 30， H 2O 270 | BPO 1 | IPA 3 | 5 parts | 64 | 4 | Good |
| Embodiment 4 | AN 100， MAA 3 | VGCF 5 | DMF 150， H 2O 150 | AIBN | IPA 2 | 25 parts | 64 | 6 | Good |
| Embodiment 5 | AN 100， MMA 5，IA 1 | CW 8 | DMSO120， H 2O 180 | AIBN 1.5 | IPA 1 | 80 parts | 62 | 5 | Good |
| Embodiment 6 | AN 100， AM 3 | MWNT 10 | DMSO 210， H 2O 90 | AIBN 2 | 0 | 20 parts | 66 | 6 | Relatively poor |
| Embodiment 7 | AN 100，EA 8，IA 1 | SWNT 8 | DMSO 240， H 2O 60 | BPO 1.5 | 0 | 0 | 66 | 8 | Difference |
Annotate: the meaning such as the table 1 of the numbers and symbols representative in the table.
As can be seen from the above embodiments, the present invention realizes the in-situ polymerization of one-dimensional electric high purity carbon and polyacrylonitrile, one-dimensional electric high purity carbon is coated by polyacrylonitrile, or polyacrylonitrile is grown on one-dimensional electric high purity carbon, obtain the one-dimensional electric high purity carbon/polyacrylonitrile composite polymer that surface and body polyacrylonitrile have same composition, to improve one-dimensional electric high purity carbon dispersed uniform and dispersive stability in polyacrylonitrile solution, thereby the conductivity of PAN-based carbon fiber favorable manufacturability energy and mechanical property and one-dimensional electric high purity carbon excellence is combined, the composite precursor of excellent performance is provided with the carbon core for the CVD continuous fibre.The composition of composite precursor provided by the invention, structure and performance can be controlled by the add-on of one-dimensional electric high purity carbon and the polymerizing condition of composition polymer.Prepare CVD continuous fibre carbon core with composite precursor provided by the invention, have that technological operation is good, advantage such as high specific strength, high conductivity, high-temperature behavior are good, can satisfy of the different requirements of all size (as 42 μ m, 33 μ m, 22 μ m etc.) carbon core to composite precursor.
Claims (10)
1, one-dimensional electric high purity carbon/polyacrylonitrile composite polymer, it is characterized in that its composition and by the content of mass fraction be: the mass fraction of vinyl cyanide is 100 parts in reaction system, 1～25 part of one-dimensional electric high purity carbon, comonomer 0～15,1～3 part of initiator, 0～1 part of dispersion agent, 0～3 part of molecular weight regulator, 150～900 parts of reaction mediums.
2, one-dimensional electric high purity carbon/polyacrylonitrile composite polymer as claimed in claim 1 is characterized in that one-dimensional electric high purity carbon is meant that carbon content greater than 95% The Fiber Shape Carbon Material, is selected from carbon nanotube, gas-phase growth of carbon fibre or graphite whisker.
3, one-dimensional electric high purity carbon/polyacrylonitrile composite polymer as claimed in claim 1, the diameter that it is characterized in that one-dimensional electric high purity carbon are 0.005～10 μ m, preferred 0.01～1 μ m; Length is 0.1～50 μ m, preferred 1～20 μ m; Length-to-diameter ratio is greater than 5.
4, as claim 1 or 3 described one-dimensional electric high purity carbon/polyacrylonitrile composite polymers, the diameter that it is characterized in that one-dimensional electric high purity carbon is 0.01～1 μ m; Length is 1～20 μ m; Length-to-diameter ratio is greater than 5.
5, one-dimensional electric high purity carbon/polyacrylonitrile composite polymer as claimed in claim 1, it is characterized in that comonomer is a vinyl monomer, be selected from least a in vinylformic acid, methyl acrylate, methyl methacrylate, methylene-succinic acid, acrylamide, the ethyl propenoate; Initiator is selected from Diisopropyl azodicarboxylate, dibenzoyl peroxide, or redox initiator, and redox initiator is selected from hydrogen peroxide and xitix, Ammonium Persulfate 98.5 and sodium bisulfite; Dispersion agent is selected from polyvinyl alcohol, sodium laurylsulfonate; Molecular weight regulator is selected from Virahol, thiocarbamide; Reaction medium is selected from water, the mixing solutions of organic solvent or organic solvent and water.
6, the preparation method of one-dimensional electric high purity carbon/polyacrylonitrile composite polymer as claimed in claim 1 is characterized in that the steps include:
(1) with one-dimensional electric high purity carbon homodisperse in vinyl cyanide, comonomer, initiator, dispersion agent, molecular weight regulator and reaction medium mixing solutions;
(2) under agitation make vinyl cyanide, comonomer, initiator, dispersion agent, molecular weight regulator and reaction medium monomer in-situ polymerization on one-dimensional electric high purity carbon;
(3) remove unreacted vinyl cyanide, comonomer, initiator completely, promptly obtain the in-situ polymerization one-dimensional electric high purity carbon/polyacrylonitrile composite polymer.
7, the preparation method of one-dimensional electric high purity carbon/polyacrylonitrile composite polymer as claimed in claim 6, it is characterized in that in step (2), said polymerization process is selected from solution polymerization process, or precipitation polymerization method, solution polymerization process carries out in dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE; Precipitation polymerization method is in the aqueous phase precipitation polymerization, or at the mixed solvent precipitation polymerization of water and dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, polymeric reaction temperature is 50～72 ℃, and the reaction times is 1.5～48h.
8, the preparation method of one-dimensional electric high purity carbon/polyacrylonitrile composite polymer as claimed in claim 6 is characterized in that in step (2), polymeric reaction temperature is 50～72 ℃, and the reaction times is 1.5～48h.
9, the preparation method of one-dimensional electric high purity carbon/polyacrylonitrile composite polymer as claimed in claim 6 is characterized in that in-situ polymerization is selected from solution polymerization, or precipitation polymerization in step (2).
10, the preparation method of one-dimensional electric high purity carbon/polyacrylonitrile composite polymer as claimed in claim 6, it is characterized in that in step (3), vinyl cyanide, comonomer, initiator are selected vacuumizing method for use completely to remove unreacted, distillation under vacuum, or washing method, washing method is selected from water, ethanol, washing with acetone.
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| CN102464848A (en) * | 2010-11-09 | 2012-05-23 | 财团法人工业技术研究院 | Composite material of polyacrylonitrile-based copolymer and carbon nanotubes, carbon fiber and preparation method of carbon fiber |
| CN102464848B (en) * | 2010-11-09 | 2014-05-28 | 财团法人工业技术研究院 | Composite material of polyacrylonitrile-based copolymer and carbon nanotubes, carbon fiber and preparation method of carbon fiber |
| CN102002772A (en) * | 2010-12-06 | 2011-04-06 | 中原工学院 | Method for preparing polyacrylonitrile bamboo charcoal composite fiber by in-situ polymerization |
| CN102002772B (en) * | 2010-12-06 | 2012-09-05 | 中原工学院 | Method for preparing polyacrylonitrile bamboo charcoal composite fiber by in-situ polymerization |
| US8865106B2 (en) | 2011-12-26 | 2014-10-21 | Industrial Technology Research Institute | Composite raw material, carbon fiber material and method for forming the same |
| CN106575750A (en) * | 2014-08-07 | 2017-04-19 | 罗伯特·博世有限公司 | A sulfur-pan composite, a method for preparing said composite, and an electrode and a lithium-sulfur battery comprising said composite |
| CN104630923A (en) * | 2015-01-26 | 2015-05-20 | 中复神鹰碳纤维有限责任公司 | Method for preparing carbon nano tube modified polyacrylonitrile fibers with solution in-situ polymerization technology |
| CN106935854A (en) * | 2015-12-31 | 2017-07-07 | 中国人民解放军63971部队 | A kind of carbon material for lithium battery and preparation method thereof |
| CN108912577A (en) * | 2018-07-11 | 2018-11-30 | 桐城市新瑞建筑工程有限公司 | A kind of shielding new material and preparation method thereof |
| CN111945274A (en) * | 2020-08-13 | 2020-11-17 | 黎扬程 | Antibacterial and antistatic functional fabric and preparation method thereof |
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