CN107675294A - A kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors - Google Patents

A kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors Download PDF

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Publication number
CN107675294A
CN107675294A CN201710997204.0A CN201710997204A CN107675294A CN 107675294 A CN107675294 A CN 107675294A CN 201710997204 A CN201710997204 A CN 201710997204A CN 107675294 A CN107675294 A CN 107675294A
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pan
carbon fibre
nano material
nitrile
preparation
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余木火
乔蒙蒙
孔海娟
丁小马
吴瑶
余许多
林江滨
张路伟
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Shanghai Hua Yu New Material Science And Technology Ltd
Donghua University
National Dong Hwa University
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Shanghai Hua Yu New Material Science And Technology Ltd
Donghua University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention relates to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors, this method includes the synthesis of finely dispersed PAN solution, the synthesis of nano material RPP nitrile PAN carbon fibre precursors；The nano material RPP nitrile PAN carbon fibre precursors being prepared are in supercritical CO2Aromatic ring reaction occurs under state.The method of the present invention is simple to operate, environmental protection, and the reaction time is short；The nano material RPP nitrile PAN carbon fibre precursors being prepared carry out aromatic ring reaction, can obtain the fiber of high intensity and high-modulus, a kind of new technology and method are provided for the preparation of high-performance carbon fibre.

Description

A kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors
Technical field
The invention belongs to fibre modification field, more particularly to a kind of nano material RPP nitrile PAN carbon fibre precursors Preparation method.
Background technology
Polyacrylonitrile-based carbon fibre is a kind of new material of excellent in mechanical performance, have high intensity, high-modulus, low-density, The excellent properties such as high temperature resistant, corrosion-resistant, rub resistance, conduction, the small, damping of the coefficient of expansion, be Aero-Space, national defense and military industry not The engineering material that can lack, meanwhile, with the development of carbon fiber technique, it is in sports goods, communications and transportation, medicine equipment and soil The civil areas such as Wood construction also extensive application.
Polyacrylonitrile (Polyacrylonitrile--PAN) fiber is the important presoma for preparing high-performance carbon fibre, its Performance largely affects the performance of carbon fiber, but PAN precursor pre-oxidation techniques play a very important role, right The influence of PAN base carbon fibres is most important.The intensity of PAN precursor is very low, therefore causes PAN that pre- oxygen occurs with fibre modification is crossed Change, the PAN of pre-oxidation is cyclized, and its fibre structure turns into trapezoidal-structure so that the intensity increase of fiber.Traditional PAN changes Property method be catalytic cyclization, here it is will add certain catalyst so that this cyclization process program increase, in addition, not having The presence of tension force also causes PAN fiber to be difficult to have good crystallization.
Supercritical CO2There is fluid asepsis environment-protecting, density to be bordering on liquid, and viscosity is bordering on gas, diffusion coefficient height, dissolves and ooze , important use be present in fields such as medicine extraction, foaming, sewage disposals in the advantages that ability is big thoroughly.Utilize supercritical CO2Fluid skill It is a kind of method that new development is got up that art, which carries out polymer modification,.
CNT is as a kind of monodimension nanometer material, the cylindric material being mainly made up of the carbon atom of hexagonal arrangement Material, as a kind of existence form of new carbon.
Chinese patent publication discloses a kind of Application No.：CN201110218710.8, entitled one kind polyacrylonitrile The patent application of the chemical modification method of base carbon fiber protofilament, the method are poly- to impregnate by configuring certain density hydrogen peroxide Dralon, follow-up pre-oxidation is then carried out again, although having carried out cyclization before pre-oxidation, be cyclized Cheng Zhonghui releases substantial amounts of heat, and this problem is not solved, and skin-core structure can be caused not improved.
Chinese patent publication discloses a kind of Application No.：CN201110274739.8, a kind of entitled polyacrylonitrile-radical The patent application of the method for precursor pre-oxidation, the distribution in the method preoxidation process for temperature range carry out multistage stretching, Orientation and fibre strength can be improved, but the method operates the speed of hell to pay, and the bad control of temperature, cooling and heating Also can have an impact to result.
Chinese patent publication also discloses a kind of Application No.：CN201310419414.3, a kind of entitled aramid fiber Stretching orientation improves the patent application of the method for mechanical property in supercritical fluid, and its major programme is that aramid fiber faces super Apply tension force in boundary's carbon dioxide, swelling reaction occurs in supercritical carbon dioxide for aramid fiber first, makes under tension Molecular chain orientation degree improves, and so as to improve the mechanical property of aramid fiber, the method environmental protection, simple, feasibility is good.
Supercritical fluid technique and PAN fiber are modified to the technology combined in the prior art and report seldom, supercritical fluid Lot of advantages such as：Asepsis environment-protecting, density are bordering on liquid, and viscosity is bordering on that gas, diffusion coefficient are high, solution pervasion ability is big etc. all Have great advantage to its application in terms of fibre modification, but there is no so far and fiber and CNT are incorporated in shooting flow Aromatic ring report in body, CNT is added to be undoubtedly a useful supplement to treatment with supercritical fluid technology, it is fine to improving Dimension performance has very great help.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of nano material RPP nitrile PAN carbon fibre precursors Preparation method, this method is simple to operate, environmental protection, and the reaction time is short；The nano material RPP nitrile PAN carbon being prepared is fine Precursor is tieed up in supercritical CO2Under the conditions of aromatic ring reaction occurs, reach the modification of fiber.
A kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors of the present invention, is comprised the following steps that：
(1) by the dissolving of polyacrylonitrile (PAN) carbon fibre precursor in a solvent, stirring, finely dispersed PAN solution is obtained, its The ratio of middle polyacrylonitrile (PAN) carbon fibre precursor and solvent is 50g:15mL-100g:15mL；
(2) CNT is added in step (1) in finely dispersed PAN solution, ultrasound, stirring, obtains spinning solution, Then carry out spinning, wire drawing, heat treatment obtains nano material RPP nitrile PAN carbon fibre precursors, wherein CNT with PAN mass ratio is 1:2000-1:6000.
Polyacrylonitrile (PAN) carbon fibre precursor is that carbon fiber T1000, T800, T300 or diameter are less than in the step (1) Precursor corresponding to 100 nanometers.
Solvent is DMSO in the step (1).
The temperature of stirring is 140-280 DEG C in the step (1), and the speed of stirring is 20r/min-400r/min.
CNT is multi-walled carbon nanotube, single armed CNT or both arms CNT in the step (2).
Spinning is dry-jet wet spinning in the step (2), and the concentration of dope of dry-jet wet spinning is 11%-14%.
The stretching ratio of heat treatment is 2-50 times in the step (2).
Nano material RPP nitrile PAN carbon fibre precursors carry out aromatic ring reaction, specific steps in the step (2) It is as follows：Nano material RPP nitrile PAN carbon fibre precursors to be put and reacted in a kettle, reaction temperature is 140-220 DEG C, Reaction pressure is 8-18Mpa, first excludes air in course of reaction, is re-filled with CO2, closed container inner space is in overcritical CO2State, pressure release at a slow speed, that is, obtain modified PAN.
The reaction time is 2-120min.
The pressure release at a slow speed refers to slowly open air outlet valve, container inner pressure is reduced to normal pressure with very little speed, let out at a slow speed The pressure time is 2-4min.
The temperature is to ensure CO2An important indicator in Supercritical Conditions, only temperature are more than 80 DEG C, match somebody with somebody Unification constant-pressure could realize CO2In Supercritical Conditions, temperature has important shadow to aromatic ring reaction in addition Ring.
The nano material RPP nitrile PAN carbon fibre precursors that the present invention is prepared carry out aromatic ring reaction, due to CNT and supercritical CO2The presence of fluid, ensure that it is aromatic ring during heat rapid dispersion, take fiber molecule chain Xiang Du, crystallinity increase, crystal grain also become big, and crystallization tends to be complete, is advantageous to the raising of fibre strength and modulus.
Beneficial effect
The method of the present invention is simple to operate, environmental protection, and the reaction time is short；The nano material RPP nitrile being prepared PAN carbon fibre precursors carry out aromatic ring reaction, can obtain the fiber of high intensity and high-modulus, are the preparation of high-performance carbon fibre A kind of new technology and method are provided.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Embodiment 1
(1) 85g PAN (13K, T800) powder is dissolved in 15ml DMSO solvents, for 140 DEG C and stirred in whipping temp Speed is mixed to make PAN be completely dispersed uniformly under the conditions of 40r/min, obtains finely dispersed PAN solution.
(2) 0.0152g multi-walled carbon nanotubes are added in the finely dispersed PAN solution obtained in step (1), in ultrasound It is ultrasonic in ripple, spinning solution is uniformly mixing to obtain, carries out dry-jet wet spinning, concentration of dope 12.8wt%, wire drawing, at heat Reason, stretching ratio 50, obtains nano material RPP nitrile PAN carbon fibre precursors.
(3) the nano material RPP nitrile PAN carbon fibre precursors obtained in step (2) are placed in reactor, first Air is excluded, then pours CO2, reactor inner space is in supercritical CO2State, it is 10Mpa conditions in 140 DEG C and pressure Under, after reacting 90min, pressure release at a slow speed, time 4min, that is, obtain modified PAN.
(4) by FT-IR spectrograms, by formulaThe cyclisation rate that PAN is calculated reaches 33%；Schemed by DSC, by formula degree of cyclization(wherein Δ H0It is PAN precursor in N2In thermal discharge, Δ H1 It is the PAN after processing in N2In thermal discharge) be calculated PAN degree of cyclization be 34%.
Embodiment 2
(1) 85g PAN (13K, T800) powder is dissolved in 15ml DMSO solvents, whipping temp be 160 DEG C and Stir speed (S.S.) makes PAN be completely dispersed uniformly under the conditions of being 40r/min, obtains finely dispersed PAN solution.
(2) 0.0152g multi-walled carbon nanotubes are added in the finely dispersed PAN solution obtained in step (1), in ultrasound It is ultrasonic in ripple, spinning solution is uniformly mixing to obtain, carries out dry-jet wet spinning, concentration of dope 12.8wt%, wire drawing, at heat Reason, stretching ratio 50, obtains nano material RPP nitrile PAN carbon fibre precursors.
(3) the nano material RPP nitrile PAN carbon fibre precursors obtained in step (2) are placed in reactor, first Air is excluded, then pours CO2, reactor inner space is in supercritical CO2State, it is 10Mpa conditions in 160 DEG C and pressure Under, after reacting 90min, pressure release at a slow speed, time 4min, that is, obtain modified PAN.
(4) by FT-IR spectrograms, by formulaThe cyclisation rate that PAN is calculated reaches 46%；Schemed by DSC, by formula degree of cyclization(wherein Δ H0It is PAN precursor in N2In thermal discharge, Δ H1 It is the PAN after processing in N2In thermal discharge) be calculated PAN degree of cyclization be 49%.
Embodiment 3
(1) 85g PAN (13K, T800) powder is dissolved in 15ml DMSO solvents, for 180 DEG C and stirred in whipping temp Speed is mixed to make PAN be completely dispersed uniformly under the conditions of 40r/min, obtains finely dispersed PAN solution.
(2) 0.0152g multi-walled carbon nanotubes are added in the finely dispersed PAN solution obtained in step (1), in ultrasound It is ultrasonic in ripple, spinning solution is uniformly mixing to obtain, carries out dry-jet wet spinning, concentration of dope 12.8wt%, wire drawing, at heat Reason, stretching ratio 50, obtains nano material RPP nitrile PAN carbon fibre precursors.
(3) the nano material RPP nitrile PAN carbon fibre precursors obtained in step (2) are placed in reactor, first Air is excluded, then pours CO2, reactor inner space is in supercritical CO2State, it is 10Mpa conditions in 180 DEG C and pressure Under, after reacting 90min, pressure release at a slow speed, time 4min, that is, obtain modified PAN.
(4) by FT-IR spectrograms, by formulaThe cyclisation rate that PAN is calculated reaches 57%；Schemed by DSC, by formula degree of cyclization(wherein Δ H0It is PAN precursor in N2In thermal discharge, Δ H1 It is the PAN after processing in N2In thermal discharge) be calculated PAN degree of cyclization be 58%.
Embodiment 4
(1) 85g PAN (13K, T800) powder is dissolved in 15ml DMSO solvents, for 200 DEG C and stirred in whipping temp Speed is mixed to make PAN be completely dispersed uniformly under the conditions of 40r/min, obtains finely dispersed PAN solution.
(2) 0.0152g multi-walled carbon nanotubes are added in the finely dispersed PAN solution obtained in step (1), in ultrasound It is ultrasonic in ripple, spinning solution is uniformly mixing to obtain, carries out dry-jet wet spinning, concentration of dope 12.8wt%, wire drawing, at heat Reason, stretching ratio 50, obtains nano material RPP nitrile PAN carbon fibre precursors.
(3) the nano material RPP nitrile PAN carbon fibre precursors obtained in step (2) are placed in reactor, first Air is excluded, then pours CO2, reactor inner space is in supercritical CO2State, it is 10Mpa conditions in 200 DEG C and pressure Under, after reacting 90min, pressure release at a slow speed, time 4min, that is, obtain modified PAN.
(4) by FT-IR spectrograms, by formulaThe cyclisation rate that PAN is calculated reaches 78%；Schemed by DSC, by formula degree of cyclization(wherein Δ H0It is PAN precursor in N2In thermal discharge, Δ H1 It is the PAN after processing in N2In thermal discharge) be calculated PAN degree of cyclization be 83%.
Embodiment 5
(1) 85g PAN (13K, T800) powder is dissolved in 15ml DMSO solvents, for 220 DEG C and stirred in whipping temp Speed is mixed to make PAN be completely dispersed uniformly under the conditions of 40r/min, obtains finely dispersed PAN solution.
(2) 0.0152g multi-walled carbon nanotubes are added in the finely dispersed PAN solution obtained in step (1), in ultrasound It is ultrasonic in ripple, spinning solution is uniformly mixing to obtain, carries out dry-jet wet spinning, concentration of dope 12.8wt%, wire drawing, at heat Reason, stretching ratio 50, obtains nano material RPP nitrile PAN carbon fibre precursors.
(3) the nano material RPP nitrile PAN carbon fibre precursors obtained in step (2) are placed in reactor, first Air is excluded, then pours CO2, reactor inner space is in supercritical CO2State, it is 10Mpa conditions in 220 DEG C and pressure Under, after reacting 90min, pressure release at a slow speed, time 4min, that is, obtain modified PAN.
(4) by FT-IR spectrograms, by formulaThe cyclisation rate that PAN is calculated reaches 89%；Schemed by DSC, by formula degree of cyclization(wherein Δ H0It is PAN precursor in N2In thermal discharge, Δ H1 It is the PAN after processing in N2In thermal discharge) be calculated PAN degree of cyclization be 93%.
Embodiment 6
(1) 85g PAN (13K, T800) powder is dissolved in 15ml DMSO solvents, for 180 DEG C and stirred in whipping temp Speed is mixed to make PAN be completely dispersed uniformly under the conditions of 40r/min, obtains finely dispersed PAN solution.
(2) 0.0152g single-walled carbon nanotubes are added in the finely dispersed PAN solution obtained in step (1), in ultrasound It is ultrasonic in ripple, spinning solution is uniformly mixing to obtain, carries out dry-jet wet spinning, concentration of dope 12.8wt%, wire drawing, at heat Reason, stretching ratio 50, obtains nano material RPP nitrile PAN carbon fibre precursors.
(3) the nano material RPP nitrile PAN carbon fibre precursors obtained in step (2) are placed in reactor, first Air is excluded, then pours CO2, reactor inner space is in supercritical CO2State, it is 10Mpa conditions in 180 DEG C and pressure Under, after reacting 90min, pressure release at a slow speed, time 4min, that is, obtain modified PAN.
(4) by FT-IR spectrograms, by formulaThe cyclisation rate that PAN is calculated reaches 65%；Schemed by DSC, by formula degree of cyclization(wherein Δ H0It is PAN precursor in N2In thermal discharge, Δ H1 It is the PAN after processing in N2In thermal discharge) be calculated PAN degree of cyclization be 68%.
Embodiment 7
(1) 85g PAN (13K, T800) powder is dissolved in 15ml DMSO solvents, for 200 DEG C and stirred in whipping temp Speed is mixed to make PAN be completely dispersed uniformly under the conditions of 40r/min, obtains finely dispersed PAN solution.
(2) 0.0152g single-walled carbon nanotubes are added in the finely dispersed PAN solution obtained in step (1), in ultrasound It is ultrasonic in ripple, spinning solution is uniformly mixing to obtain, carries out dry-jet wet spinning, concentration of dope 12.8wt%, wire drawing, at heat Reason, stretching ratio 50, obtains nano material RPP nitrile PAN carbon fibre precursors.
(3) the nano material RPP nitrile PAN carbon fibre precursors obtained in step (2) are placed in reactor, first Air is excluded, then pours CO2, reactor inner space is in supercritical CO2State, it is 10Mpa conditions in 200 DEG C and pressure Under, after reacting 90min, pressure release at a slow speed, time 4min, that is, obtain modified PAN.
(4) by FT-IR spectrograms, by formulaThe cyclisation rate that PAN is calculated reaches 80%；Schemed by DSC, by formula degree of cyclization(wherein Δ H0It is PAN precursor in N2In thermal discharge, Δ H1 It is the PAN after processing in N2In thermal discharge) be calculated PAN degree of cyclization be 85%.
Embodiment 8
(1) 85g PAN (13K, T800) powder is dissolved in 15ml DMSO solvents, for 220 DEG C and stirred in whipping temp Speed is mixed to make PAN be completely dispersed uniformly under 40r/min, obtains finely dispersed PAN solution.
(2) 0.0152g single-walled carbon nanotubes are added in the finely dispersed PAN solution obtained in step (1), in ultrasound It is ultrasonic in ripple, spinning solution is uniformly mixing to obtain, carries out dry-jet wet spinning, concentration of dope 12.8wt%, wire drawing, at heat Reason, stretching ratio 50, obtains nano material RPP nitrile PAN carbon fibre precursors.
(3) the nano material RPP nitrile PAN carbon fibre precursors obtained in step (2) are placed in reactor, first Air is excluded, then pours CO2, reactor inner space is in supercritical CO2State, it is 10Mpa conditions in 220 DEG C and pressure Under, after reacting 90min, pressure release at a slow speed, time 4min, that is, obtain modified PAN.
(4) by FT-IR spectrograms, by formulaThe cyclisation rate that PAN is calculated reaches 92%；Schemed by DSC, by formula degree of cyclization(wherein Δ H0It is PAN precursor in N2In thermal discharge, Δ H1 It is the PAN after processing in N2In thermal discharge) be calculated PAN degree of cyclization be 93%.

Claims (10)

1. a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors, is comprised the following steps that：
(1) by the dissolving of polyacrylonitrile (PAN) carbon fibre precursor in a solvent, stirring, finely dispersed PAN solution is obtained, wherein poly- The ratio of acrylonitrile PAN carbon fibre precursors and solvent is 50g:15mL-100g:15mL；
(2) CNT is added in step (1) in finely dispersed PAN solution, ultrasound, stirring, obtains spinning solution, then Spinning is carried out, wire drawing, heat treatment, obtains nano material RPP nitrile PAN carbon fibre precursors, wherein CNT and PAN Mass ratio be 1:2000-1:6000.
2. according to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors described in claim 1, it is special Sign is that polyacrylonitrile (PAN) carbon fibre precursor is precursor corresponding to carbon fiber T1000, T800 or T300 in the step (1).
3. according to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors described in claim 1, it is special Sign is that solvent is DMSO in the step (1).
4. according to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors described in claim 1, it is special Sign is that the temperature of stirring is 140-280 DEG C in the step (1), and the speed of stirring is 20r/min-400r/min.
5. according to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors described in claim 1, it is special Sign is that CNT is multi-walled carbon nanotube, single armed CNT or both arms CNT in the step (2).
6. according to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors described in claim 1, it is special Sign is that spinning is dry-jet wet spinning in the step (2), and the concentration of dope of dry-jet wet spinning is 11%-14%.
7. according to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors described in claim 1, it is special Sign is that the stretching ratio of heat treatment is 2-50 times in the step (2).
8. according to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors described in claim 1, it is special Sign is that the nano material RPP nitrile PAN carbon fibre precursors in the step (2) carry out aromatic ring reaction, specific step It is rapid as follows：Nano material RPP nitrile PAN carbon fibre precursors are put and reacted in a kettle, reaction temperature 140-220 DEG C, reaction pressure 8-18Mpa, air is first excluded in course of reaction, is re-filled with CO2, reactor inner space is in super and face Boundary CO2State, pressure release at a slow speed, that is, obtain modified PAN.
9. according to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors described in claim 8, it is special Sign is that the reaction time is 2-120min.
10. according to a kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors described in claim 8, its It is characterised by, the pressure release at a slow speed refers to slowly open air outlet valve, container inner pressure is reduced to normal pressure with very little speed, lets out at a slow speed The pressure time is 2-4min.
CN201710997204.0A 2017-10-20 2017-10-20 A kind of preparation method of nano material RPP nitrile PAN carbon fibre precursors Pending CN107675294A (en)

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