CN104726967A - Polyamide acid/polyacrylonitrile-based carbon fiber and preparation method thereof - Google Patents
Polyamide acid/polyacrylonitrile-based carbon fiber and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polyamide acid/polyacrylonitrile-based carbon fiber and a preparation method thereof, and belongs to the technical field of carbon fibers. The method comprises the following steps: firstly, preparing PAA/PAN primary blending fibers from a PAA/PAN blended solution by adopting a wet spinning method; heating the PAA/PAN fibers at an air atmosphere at 200-280 DEG C to cyclically transform PAA into polyimide (PI) and PAN to realize pre-oxidation so as to obtain PI/pre-oxidized PAN blended yarns; and treating at high temperature in the protection of inert gas to prepare the carbon fibers. The method is short in production cycle, the prepared carbon fibers have the advantages of high compactness, high coefficients of electric and thermal conductivities and small thermal expansion coefficient, and a novel source is provided to exploration of carbon fiber raw materials.
Description
Technical field
The present invention relates to a kind of method of new precursor power carbon fiber, be specifically related to a kind of polyamic acid/polyacrylonitrile-based carbon fibre and preparation method thereof, belong to Carbon Fiber Technology field.
Background technology
Carbon fiber is a kind of high specific strength, high ratio modulus, high temperature resistant, anticorrosive, creep-resistant property is good, conduction, heat conduction and the little elite clone of thermal coefficient of expansion, it is widely used in the high-end fields such as space flight and aviation, automobile, high-grade sports equipment, particularly the development of Aero-Space cause is to the demand of high-performance carbon fibre, become the outstanding person in important strategic materials and field of new, its research level also becomes one of important symbol representing a national new material and Aero-Space career development level.But because the raw material of preparation of industrialization carbon fiber are less, constrain the development of carbon fiber, need constantly to explore the raw-material new source of carbon fiber.
Polyacrylonitrile (PAN) base carbon fibre refers to PAN precursor for raw material, through the fiber obtained by oxidative stabilization, carbonization, graphitization and post processing.Because its phosphorus content has an architectural feature of the Ppolynuclear aromatic of similar controlled micro crystallization more than 90%, it is made to become a kind of good heat resistance, quality is light, tensile strength is high and Young's modulus is high high-performance fiber.Whole world carbon fiber 80% from PAN system, and 20% from pitch and other artificial silks.PAN precursor is mainly used in high-strength carbon fiber and produces, and high modulus carbon fiber is then raw material with asphaltic base.
Polyimides (PI) is a kind of aromatic heterocyclic polymer, has excellent heat resistance, chemical stability, dielectric properties and high strength, its product development starts from the sixties, subsequently, is widely used in multiple field such as electronics, Aero-Space as high-performance polymer.In recent years, along with industrialization and the cost degradation of the various dianhydride of synthesis PI, diamine monomer, and the progress of PI synthesis and process technology, the research of PI and product development process are accelerated greatly, and Application Areas is constantly widened.
A large amount of nitrogenous five-ring heterocycles, phenyl ring etc. are had in PI main chain, its phosphorus content is made to reach 70%, virtue heterocycle produces grips effect altogether, the orientation effect of fiber adds polyimides has good heat-resistant stability easily to form complete graphite-structure after carbonized graphite, and these structural factors determine that it is that high-performance carbon fibre raw material are selected very well.Simultaneously based on PAN and PI presoma (polyamic acid-PAA) at cosolvent (DMSO, DMF etc.) in good compatibility, PAA/PAN blend solution is adopted to be that spinning solution carries out spinning, in to the heat treatment process of fiber, complete the cyclisation of PAA and the pre-oxidation of PAN, obtain PI/ pre-oxidation PAN blended fiber.This blended fiber, in carbonisation, utilizes PAN to have successional feature to carbon fiber evolution process macromolecular chain structure, makes up the embrittlement caused due to PI molecular chain rupture.
Carbon fiber has excellent performance, but the raw material due to preparation of industrialization carbon fiber only have polyacrylonitrile, pitch and cellulose, constrain the development of carbon fiber, therefore explore the raw-material new source of carbon fiber and receive increasing concern, the invention provides a kind of manufacture method of polyimides/polyacrylonitrile-based carbon fibre based on this.
Summary of the invention
Little based on carbon fiber raw material, industrializedly can only have polyacrylonitrile, pitch and cellulose iii kind at present, constrain the development of carbon fiber, newly originating to widen carbon fiber raw material, having prepared polyamic acid/polyacrylonitrile-based carbon fibre.
Another object of the present invention is to provide a kind of internal structure and all complete novel carbon fiber of external structure and preparation method.The invention provides the preparation method of above-mentioned polyamic acid/polyacrylonitrile-based carbon fibre.
A preparation method for polyamic acid/polyacrylonitrile-based carbon fibre, is characterized in that, needs to carry out according to following steps:
A. with dianhydride and diamine monomer for Material synthesis PAA solution, then the PAN solution that will configure, proportionally adds in PAA solution and obtains blend solution, and application wet spinning technology is prepared PAA/PAN and to be come into being blended fiber;
B. nascent blended fiber steps A obtained is placed in temperature programming baking oven, in air atmosphere, heat-treats in the mode of continuous warming, obtains PI/ pre-oxidized PAN fibers;
C. PI/ pre-oxidized PAN fibers is wrapped on graphite cake, then graphite cake is placed in two panels carbon film centre and puts into vacuum tube furnace, in vacuum tube furnace, pass into high-purity N
2, setting heating schedule, carries out carbonization treatment, obtains carbon fiber.
Wherein, PAA solution in steps A, can be obtained through polycondensation reaction by a kind of dianhydride and a kind of diamines, as with 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), p-phenylenediamine (PPD) (PDA) obtains PAA solution for raw material polycondensation, or obtained by a kind of dianhydride and several diamines copolycondensation, as with 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD) (PDA) obtains PAA solution for raw material copolycondensation.
In steps A in PAA/PAN blend solution wet spinning technology, coagulating bath can be one or both the mixed solution in water, ethanol, also can be water or ethanol and N, the mixture of wherein one or more such as dinethylformamide, DMA (DMAc), dimethyl sulfoxide (DMSO) (DMSO).Preferred dianhydride monomer is 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), pyromellitic acid anhydride (PMDA) and 3, one or more in 3 ', 4,4 '-two methyl phenyl ethers anisole tetracarboxylic dianhydride (ODPA); Diamine monomer is 4, the one in 4 '-diaminodiphenyl ether (ODA) and p-phenylenediamine (PPD) (PDA) or two kinds.
In steps A, in PAA/PAN blend solution, PAN accounts for the preferred 10%-50% of mass percentage of PAA/PAN.The solvent preparing blended liquid in steps A is dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide, N, any one in N-dimethylacetylamide (DMAc), 1-METHYLPYRROLIDONE (NMP), DMF (DMF).
Wet spinning process in steps A: co-blended spinning liquid bubble removing under vacuum, and then at N
2pressure under to extrude from spinning head and enter coagulating bath and water-bath successively, obtain nascent blended fiber.
In steps A, PAA/PAN blend solution wet spinning process water-eliminating method is the hot stove crossing 80 DEG C, 80 DEG C, 100 DEG C, 150 DEG C four gradient temperatures successively.
In step B, nascent blended fiber to be placed in temperature programming baking oven, in air atmosphere, concrete mode so that the mode of continuous warming is heat-treated: nascent blended fiber is applied certain drafting force and be wrapped on carbon paper and put into temperature programming baking oven, the speed heated up is 2-5 DEG C/min, intensification initial sum final temperature is respectively 200 DEG C and 280 DEG C in the mode of continuous warming, heat treatment 40-60min, obtains PI/ pre-oxidation PAN blended fiber.
Being wrapped on graphite cake by PI/ pre-oxidized PAN fibers in step C is to apply certain drafting force.
The setting of carburizing temperature in step C, heating rate is 2-10 DEG C/min, and final carburizing temperature is 1000-1500 DEG C, and temperature retention time is 10-60min at the final temperature.
High-purity N in step C
2flow velocity be greater than 200ml/min, to take away the gas of the non-carbon that the cracking in high temperature cabonization process of PAA/PAN blended fiber is deviate from, high-purity N
2purity is greater than 99.9%.
Carbon fiber tool prepared by this method has the following advantages:
1, PI after PAA cyclisation has the feature of abundant fragrant heterocycle structure, various altered chemical structure and high carbon content, to make by oneself, the PAA of structure-controllable, with PAN be auxiliary blended fiber for matrix, both have complementary advantages, prepare carbon fiber, widen the raw material sources of high-performance carbon fibre.
2, carbon fiber prepared by this method all has very high carbon yield under different heating rate and temperature retention time.
3, carbon fiber prepared by this method has good compactness, inside and outside structural regularity.
4, this method can obtain the higher carbon fiber of carbon content at a lower temperature, with short production cycle, and output is large, low to the requirement of equipment in the whole process of preparation, saves preparation cost.
5, the carbon fiber that the present invention obtains has high fine and close, the advantage that high connductivity, heat conduction and thermal coefficient of expansion are little, and the present invention simultaneously also provides a kind of new source for exploring carbon fiber raw material.
Accompanying drawing explanation
Fig. 1 is the Electronic Speculum figure of embodiment 1 polyamic acid/polyacrylonitrile-based carbon fibre;
Wherein a, c and b, d are respectively the section of polyamic acid/polyacrylonitrile-based carbon fibre and surface scan Electronic Speculum figure, a and b multiplication factor is 2000, c and d multiplication factor is 6000;
Fig. 2 is the Electronic Speculum figure of embodiment 7 polyamic acids/polyacrylonitrile-based carbon fibre;
Wherein a, b are respectively section and the surface scan Electronic Speculum figure of polyamic acid/polyacrylonitrile-based carbon fibre, and multiplication factor is 6000;
Fig. 3 is the Raman collection of illustrative plates of embodiment 1-5 gained polyamic acid/polyacrylonitrile-based carbon fibre.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Need to illustrate that polyamic acid in following embodiment steps A/polyacrylonitrile blended solution wet spinning water-eliminating method was 80,80, the hot stove of 100,150 4 gradient temperatures.
Embodiment 1:
A: with 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD) (PDA) is Material synthesis polyamic acid (PAA) solution, again the PAN solution configured being mixed in PAA solution by accounting for PAA/PAN blend solution mass fraction 30%, obtaining nascent blended fiber by wet spinning.
B: nascent blended fiber steps A obtained is placed in temperature programming baking oven and applies certain drawing-off, in the mode of continuous warming from 200 DEG C of process to 280 DEG C, obtains PI/ pre-oxidized PAN fibers.
C: PI/ pre-oxidized PAN fibers is wrapped on graphite cake with certain drafting force, vacuum tube furnace is put into after graphite cake being placed in two panels carbon film centre again, high-purity N 2 is passed in vacuum tube furnace, with the heating rate of 10 DEG C/min, be warming up to 1200 DEG C, under 1200 DEG C of conditions, be incubated 60min again, treat that it naturally cools to room temperature and namely obtains polyamic acid/polyacrylonitrile-based carbon fibre.
In Fig. 1, a, c are the sectional drawing of carbon fiber prepared by this method, can find out that incision position does not totally extract the brittle fracture that this embodies carbon fiber in a figure; C figure is sectional enlarged drawing, and the carbon fiber even compact prepared of this method, does not have pore space structure, the compactness of the complete and final carbon fiber structural of PAN pre-oxidation is described as seen from the figure; B, d figure is the exterior view of carbon fiber, and in figure, fiber surface is more smooth and defect is less.
Embodiment 2:
A: with 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD) (PDA) is Material synthesis polyamic acid (PAA) solution, again the PAN solution configured being mixed in PAA solution by accounting for PAA/PAN blend solution mass fraction 10%, obtaining nascent blended fiber by wet spinning.
B: nascent blended fiber steps A obtained is placed in temperature programming baking oven and applies certain drawing-off, in the mode of continuous warming from 200 DEG C of process to 280 DEG C, obtains PI/ pre-oxidized PAN fibers.
C: PI/ pre-oxidized PAN fibers is wrapped on graphite cake with certain drafting force, vacuum tube furnace is put into after graphite cake being placed in two panels carbon film centre again, high-purity N 2 is passed in vacuum tube furnace, with the heating rate of 10 DEG C/min, be warming up to 1200 DEG C, under 1200 DEG C of conditions, be incubated 60min again, treat that it naturally cools to room temperature and namely obtains polyamic acid/polyacrylonitrile-based carbon fibre.
Embodiment 3:
A: with 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD) (PDA) is Material synthesis polyamic acid (PAA) solution, again the PAN solution configured being mixed in PAA solution by accounting for PAA/PAN blend solution mass fraction 20%, obtaining nascent blended fiber by wet spinning.
B: nascent blended fiber steps A obtained is placed in temperature programming baking oven and applies certain drawing-off, in the mode of continuous warming from 200 DEG C of process to 280 DEG C, obtains PI/ pre-oxidized PAN fibers.
C: PI/ pre-oxidized PAN fibers is wrapped on graphite cake with certain drafting force, vacuum tube furnace is put into after graphite cake being placed in two panels carbon film centre again, high-purity N 2 is passed in vacuum tube furnace, with the heating rate of 10 DEG C/min, be warming up to 1200 DEG C, under 1200 DEG C of conditions, be incubated 60min again, treat that it naturally cools to room temperature and namely obtains polyamic acid/polyacrylonitrile-based carbon fibre.
Embodiment 4:
A: with 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD) (PDA) is Material synthesis polyamic acid (PAA) solution, again the PAN solution configured being mixed in PAA solution by accounting for PAA/PAN blend solution mass fraction 40%, obtaining nascent blended fiber by wet spinning.
B: nascent blended fiber steps A obtained is placed in temperature programming baking oven and applies certain drawing-off, in the mode of continuous warming from 200 DEG C of process to 280 DEG C, obtains PI/ pre-oxidized PAN fibers.
C: PI/ pre-oxidized PAN fibers is wrapped on graphite cake with certain drafting force, vacuum tube furnace is put into after graphite cake being placed in two panels carbon film centre again, high-purity N 2 is passed in vacuum tube furnace, with the heating rate of 10 DEG C/min, be warming up to 1200 DEG C, under 1200 DEG C of conditions, be incubated 60min again, treat that it naturally cools to room temperature and namely obtains polyamic acid/polyacrylonitrile-based carbon fibre.
Embodiment 5:
A: with 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD) (PDA) is Material synthesis polyamic acid (PAA) solution, again the PAN solution configured being mixed in PAA solution by accounting for PAA/PAN blend solution mass fraction 50%, obtaining nascent blended fiber by wet spinning.
B: nascent blended fiber steps A obtained is placed in temperature programming baking oven and applies certain drawing-off, in the mode of continuous warming from 200 DEG C of process to 280 DEG C, obtains PI/ pre-oxidized PAN fibers.
C: PI/ pre-oxidized PAN fibers is wrapped on graphite cake with certain drafting force, vacuum tube furnace is put into after graphite cake being placed in two panels carbon film centre again, high-purity N 2 is passed in vacuum tube furnace, with the heating rate of 10 DEG C/min, be warming up to 1200 DEG C, under 1200 DEG C of conditions, be incubated 60min again, treat that it naturally cools to room temperature and namely obtains polyamic acid/polyacrylonitrile-based carbon fibre.
Fig. 3 is shown in by the Raman collection of illustrative plates of embodiment 1-5 gained polyamic acid/polyacrylonitrile-based carbon fibre.What obtain at 1630cm-1 place in Raman collection of illustrative plates is G peak, and the half-peak breadth narrower carbon fiber and graphite degree showing that this method obtains in G peak is higher, and C planar alignment is more regular.
Embodiment 6:
A: with 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD) (PDA) is Material synthesis polyamic acid (PAA) solution, again the PAN solution configured being mixed in PAA solution by accounting for PAA/PAN blend solution mass fraction 30%, obtaining nascent blended fiber by wet spinning.
B: nascent blended fiber steps A obtained is placed in temperature programming baking oven and applies certain drawing-off, in the mode of continuous warming from 200 DEG C of process to 280 DEG C, obtains PI/ pre-oxidized PAN fibers.
C: PI/ pre-oxidized PAN fibers is wrapped on graphite cake with certain drafting force, vacuum tube furnace is put into after graphite cake being placed in two panels carbon film centre again, high-purity N 2 is passed in vacuum tube furnace, with the heating rate of 2 DEG C/min, be warming up to 1500 DEG C, under 1500 DEG C of conditions, be incubated 60min again, treat that it naturally cools to room temperature and namely obtains polyamic acid/polyacrylonitrile-based carbon fibre.
Embodiment 7:
A: with 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD) (PDA) is Material synthesis polyamic acid (PAA) solution, again the PAN solution configured being mixed in PAA solution by accounting for PAA/PAN blend solution mass fraction 30%, obtaining nascent blended fiber by wet spinning.
B: nascent blended fiber steps A obtained is placed in temperature programming baking oven and applies certain drawing-off, in the mode of continuous warming from 200 DEG C of process to 280 DEG C, obtains PI/ pre-oxidized PAN fibers.
C: PI/ pre-oxidized PAN fibers is wrapped on graphite cake with certain drafting force, vacuum tube furnace is put into after graphite cake being placed in two panels carbon film centre again, high-purity N 2 is passed in vacuum tube furnace, with the heating rate of 10 DEG C/min, be warming up to 1400 DEG C, under 1400 DEG C of conditions, be incubated 20min again, treat that it naturally cools to room temperature and namely obtains polyamic acid/polyacrylonitrile-based carbon fibre.
In Fig. 2, a, b are sectional drawing and the exterior view of carbon fiber prepared by this method, and a figure is sectional drawing, and the carbon fiber even compact prepared by the known this method of figure a, does not have pore space structure, the compactness of the complete and final carbon fiber structural of PAN pre-oxidation is described; B figure is the exterior view of carbon fiber, and in figure, fiber surface is more smooth and defect is less.
Table 1: each constituent content of polyamic acid/polyacrylonitrile-based carbon fibre under different Carbonization Conditions
| N[％] | C[％] | H[％] | O[％] | |
| Embodiment 1 | 0.63 | 96.6 | 0.225 | 0.176 |
| Embodiment 2 | 0.48 | 96.05 | 0.298 | 0.173 |
| Embodiment 3 | 0.683 | 97.14 | 0.206 | 0.149 |
| Embodiment 4 | 0.924 | 95.74 | 0.159 | 0.149 |
| Embodiment 5 | 1.97 | 94.92 | 0.158 | 0.18 |
| Embodiment 6 | 1.965 | 95.09 | 0.242 | 2.703 |
| Embodiment 7 | 1.905 | 94.61 | 0.189 | 3.296 |
Claims (9)
1. a preparation method for polyamic acid/polyacrylonitrile-based carbon fibre, is characterized in that, needs to carry out according to following steps:
A. with dianhydride and diamine monomer for Material synthesis PAA solution, then the PAN solution that will configure, proportionally adds in PAA solution and obtains blend solution, and application wet spinning technology is prepared PAA/PAN and to be come into being blended fiber;
B. nascent blended fiber steps A obtained is placed in temperature programming baking oven, in air atmosphere, heat-treats in the mode of continuous warming, obtains PI/ pre-oxidized PAN fibers;
C. PI/ pre-oxidized PAN fibers is wrapped on graphite cake, then graphite cake is placed in two panels carbon film centre and puts into vacuum tube furnace, in vacuum tube furnace, pass into high-purity N
2, setting heating schedule, carries out carbonization treatment, obtains carbon fiber.
2. according to the method for claim 1, it is characterized in that, in steps A, dianhydride monomer is 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), pyromellitic acid anhydride (PMDA) and 3, one or more in 3 ', 4,4 '-two methyl phenyl ethers anisole tetracarboxylic dianhydride (ODPA); Diamine monomer is 4, the one in 4 '-diaminodiphenyl ether (ODA) and p-phenylenediamine (PPD) (PDA) or two kinds.
3. according to the method for claim 1, it is characterized in that, in steps A, in PAA/PAN blend solution, PAN accounts for the preferred 10%-50% of mass percentage of PAA/PAN; The solvent preparing blended liquid is dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide, N, any one in N-dimethylacetylamide (DMAc), 1-METHYLPYRROLIDONE (NMP), DMF (DMF).
4. according to the method for claim 1, it is characterized in that, wet spinning process in steps A: co-blended spinning liquid bubble removing under vacuum, and then at N
2pressure under to extrude from spinning head and enter coagulating bath and water-bath successively, obtain nascent blended fiber.
5. according to the method for claim 4, it is characterized in that, in steps A, PAA/PAN blend solution wet spinning process water-eliminating method is the hot stove crossing 80 DEG C, 80 DEG C, 150 DEG C, 80 DEG C four gradient temperatures successively.
6. according to the method for claim 1, it is characterized in that, the concrete mode of step B: nascent blended fiber is applied certain drafting force and be wrapped on carbon paper and put into temperature programming baking oven, the speed heated up is 2-5 DEG C/min, intensification initial sum final temperature is respectively 200 DEG C and 280 DEG C in the mode of continuous warming, heat treatment 40-60min, obtains PI/ pre-oxidation PAN blended fiber.
7. according to the method for claim 1, it is characterized in that, the setting of carburizing temperature in step C, heating rate is 2-10 DEG C/min, and final carburizing temperature is 1000-1500 DEG C, and temperature retention time is 10-60min at the final temperature.
8. according to the method for claim 1, it is characterized in that, high-purity N in step C
2flow velocity be greater than 200ml/min, to take away the gas of the non-carbon that the cracking in high temperature cabonization process of PAA/PAN blended fiber is deviate from.
9. according to polyamic acid/polyacrylonitrile-based carbon fibre that any one method of claim 1-8 obtains.
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