CN109280997A - The high-strength high-modules carbon fibre and preparation method thereof of low degree of graphitization - Google Patents
The high-strength high-modules carbon fibre and preparation method thereof of low degree of graphitization Download PDFInfo
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- CN109280997A CN109280997A CN201811101975.8A CN201811101975A CN109280997A CN 109280997 A CN109280997 A CN 109280997A CN 201811101975 A CN201811101975 A CN 201811101975A CN 109280997 A CN109280997 A CN 109280997A
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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
- 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
Abstract
The invention discloses high-strength high-modules carbon fibre of low degree of graphitization and preparation method thereof, method includes: that acrylonitrile and itaconic acid or acrylonitrile and itaconic acid polymerize by (1) with methyl acrylate, obtains polymer spinning solution；(2) polymer spinning solution successively solidified, steam drafting, wash, oil, dry, superheated steam drawing-off and thermal finalization, obtaining polyacrylonitrile fibril；(3) polyacrylonitrile fibril pre-oxidized, be carbonized and graphitization processing, to obtain carbon fiber, wherein, in step (3), the temperature of the graphitization processing is 2000~2200 degrees Celsius, and the time is 3~5 minutes, drawing-off 6.0%~10.0%.More regular graphitization rearrangement structure can be obtained under relatively low graphitization temperature using this method reduces high-strength high-modules carbon fibre production cost to obtain high-strength high-modules carbon fibre.Specifically, 225~235g/km of line density (6K) of obtained carbon fiber, 435~447g/km (12K), volume density is 1.77~1.79g/cm3, tensile strength is 4.4~5.0GPa, and stretch modulus is 350~400GPa.
Description
Technical field
The invention belongs to carbon material preparation fields, specifically, the present invention relates to the high-strength and high-modulus carbon of low degree of graphitization
Fiber and preparation method thereof.
Background technique
In numerous kinds of high-performance carbon fibre, high-strength high-modulus fibre is only in the development technique of cosmic space due to it
Spy's application, occupys an important position.High-module high-strength carbon fiber has the characteristic of high ratio modulus, high specific strength, while having outstanding
The features such as it is good stability of the dimension, corrosion-resistant, fatigue behaviour is good, good anti-vibration, as a kind of ideal structural reinforcement material,
It is mainly used in the structural material of the external spaces aircraft such as satellite.
During the preparation process due to high-strength high-modules carbon fibre, the high temperature graphitization of at least 2000 degrees Celsius or more of experience is needed
Processing, degree of graphitization could obtain high-modulus characteristic after being continuously improved, therefore it is larger to consume energy in its production process, while by
In the inert gas seal of equipment the problems such as, leading to heating equipment, the service life is shorter at high temperature, affects production efficiency and product
Stability.
Summary of the invention
Technical problem to be solved by the invention is to provide the high-strength high-modules carbon fibres and its system of a kind of low degree of graphitization
Preparation Method can obtain more regular graphitization rearrangement structure using this method under relatively low graphitization temperature, thus
High-strength high-modules carbon fibre is obtained, high-strength high-modules carbon fibre production cost is reduced.Specifically, the line density of obtained carbon fiber
225~235g/km (6K), 435~447g/km (12K), volume density are 1.77~1.79g/cm3, tensile strength be 4.4~
5.0GPa, stretch modulus are 350~400GPa.
In one aspect of the invention, the invention proposes a kind of high-strength high-modules carbon fibres for preparing low degree of graphitization
Method.According to an embodiment of the invention, the described method includes: (1) is by acrylonitrile and itaconic acid or acrylonitrile and itaconic acid and third
E pioic acid methyl ester is polymerize, and polymer spinning solution is obtained；(2) polymer spinning solution is successively solidified, steam
Drawing-off is washed, is oiled, drying, superheated steam drawing-off and thermal finalization, obtains polyacrylonitrile fibril；(3) polyacrylonitrile is former
Silk is pre-oxidized, is carbonized and graphitization processing, to obtain carbon fiber, wherein in step (3), the graphitization processing
Temperature be 2000~2200 degrees Celsius, the time be 3~5 minutes, drawing-off 6.0%~10.0%.
Preferably, in step (1), the solid content of the polymer spinning solution is 20~25wt%.
Preferably, in step (1), the polymerization temperature is 55~65 degrees Celsius, and the time is 17~30 hours.
Preferably, in step (2), the process of setting uses three-level gradient freeze: the first solidification bath concentration for 65~
80wt%, temperature be 30~65 degrees Celsius, solidification drafting multiple be 0.5~1.0 times, the second gelation concentration be 35~
50wt%, temperature are 30~65 degrees Celsius, and it is 5~10wt% that third, which solidifies bath concentration, and temperature is 30~65 degrees Celsius.
Preferably, in step (2), the multiple of the steam drafting is 4.0~7.0.
Preferably, in step (2), the washing is washed using temperature gradient, and the washing temperature is 60~90 Celsius
Degree.
Preferably, in step (2), the oil concentration of the process that oils is 0.8~1.5wt%.
Preferably, in step (2), the drying process is dry using temperature gradient, and the temperature of the drying is 100~
150 degrees Celsius.
Preferably, in step (2), the temperature of the superheated steam is 120~160 degrees Celsius, 2.0~3.0 times of drawing-off.
Preferably, in step (2), the temperature of the thermal finalization is 140~180 degrees Celsius, and relaxation rate is 0~-10%.
Preferably, in step (3), the pre-oxidation carries out six warm area gradient increased temperatures, the pre- oxygen in air atmosphere
The temperature of change is 180~270 degrees Celsius, and the time is 35~70 minutes.
Preferably, in step (3), the carbonization includes high temperature cabonization and low-temperature carbonization, the temperature of the low-temperature carbonization
It is 350~800 degrees Celsius, the time is 2~6 minutes, and the temperature of the high temperature cabonization is 1200~1700 degrees Celsius, the time 3
~8 minutes.
In another aspect of the invention, the invention proposes a kind of carbon fibers.According to an embodiment of the invention, the carbon
Fiber, which is adopted, to be with the aforedescribed process prepared.
Compared with prior art, the present invention enables carbon fiber relatively by applying drawing-off in the graphitization stage
More regular graphitization rearrangement structure is obtained under low graphitization temperature, to obtain high-strength high-modules carbon fibre, is reduced high-strength
High-modules carbon fibre production cost.Specifically, 225~235g/km of line density (6K), the 435~447g/km of obtained carbon fiber
(12K), volume density are 1.77~1.79g/cm3, tensile strength is 4.4~5.0GPa, and stretch modulus is 350~400GPa.
Detailed description of the invention
Fig. 1 is the degree of graphitization datagram of carbon fiber obtained by the embodiment of the present application 1-5.
Specific embodiment
Below by the invention will be further described in conjunction with the embodiments, it is not limit that following embodiment, which is descriptive,
Qualitatively, this does not limit the scope of protection of the present invention.
The invention proposes a kind of methods of high-strength high-modules carbon fibre for preparing low degree of graphitization.Reality according to the present invention
Apply example, which comprises
S1: acrylonitrile and itaconic acid or acrylonitrile and itaconic acid are polymerize with methyl acrylate
In the step, with dimethyl sulfoxide (DMSO) for solvent, using azodiisobutyronitrile as initiator, by acrylonitrile and clothing
Health acid carries out dualistic polymerization or acrylonitrile and methyl acrylate and itaconic acid carries out terpolymerization, and it is molten to obtain polymer spinning
Liquid.Specifically, during being somebody's turn to do, using dimethyl sulfoxide as solvent, at 55~65 DEG C, with azodiisobutyronitrile at preferably 60 DEG C
(AIBN) (concentration is 0.2~0.3mol%) is that initiator carries out acrylonitrile, itaconic acid binary solution or acrylonitrile, acrylic acid first
Ester, itaconic acid ternary solution combined polymerization react 17~30 hours, preferably 25 hours, obtain polymer spinning solution, wherein third
The mass ratio of alkene nitrile, methyl acrylate and itaconic acid is (90~99.5): (0~7): (0.5~5).Then the case where stirring
Under, in 60~70 DEG C, preferably 65 DEG C, vacuum degree be greater than 0.095MPa under the conditions of remove polymer spinning solution in unreacted list
Body stops stirring after preferably 8 hours 7~9 hours, the standing and defoaming under 55~65 DEG C preferably 60 DEG C same vacuum conditions, most
The polymer spinning solution that solid content is 20~25wt% is obtained eventually.
S2: polymer spinning solution is successively solidified, steam drafting, washes, oil, drying, superheated steam drawing-off
And thermal finalization
In the step, polymer spinning solution obtained above is successively solidified, steam drafting, washes, oil, doing
Dry, superheated steam drawing-off and thermal finalization, obtain polyacrylonitrile fibril, wherein the process of setting is using three-level gradient freeze: the
One solidification bath concentration is 65~80wt%, and temperature is 30~65 degrees Celsius, and solidification drafting multiple is 0.5~1.0 times, the second solidification
Bath concentration is 35~50wt%, and temperature is 30~65 degrees Celsius, and it is 5~10wt% that third, which solidifies bath concentration, and temperature is 30~65
Degree Celsius.
Specifically, should during, using dimethyl sulfoxide (DMSO) aqueous solution as coagulating bath, by three-level gradient freeze at
Type, wherein the concentration of the first coagulating bath is 65~80wt%, and temperature is 30~65 DEG C, and preferably 45 DEG C, solidifying drafting multiple is
0.5~1.0 times, such as 0.5,0.6,0.7,0.8,0.9 and 1.0 times；The concentration of the second gelation is 35~50wt%, and temperature is
30~65 DEG C, preferably 35 DEG C；The concentration of third coagulating bath is 5~10wt%, and temperature is 30~65 DEG C, preferably 35 DEG C；Polymer
Spinning solution is changed into as-spun fibre, and then through steam drafting, (100 degrees Celsius of temperature, draw ratio is 4.0~7.0 times, for example
4.0,5.0,6.0 and 7.0), and wash and washed using temperature gradient, washing temperature is 60~90 DEG C；The finish for the process that oils
Concentration is 0.8~1.5wt%, and finish is amino modified silicone emulsion；Drying process is dry using temperature gradient, dry temperature
Degree is 100~150 degrees Celsius；The temperature of superheated steam is 120~160 degrees Celsius, 2.0~3.0 times of drawing-off；The temperature of thermal finalization
It is 140~180 degrees Celsius, relaxation rate is 0~-10%, finally obtains polyacrylonitrile fibril.
S3: polyacrylonitrile fibril is pre-oxidized, is carbonized and graphitization processing
In the step, above-mentioned polyacrylonitrile fibril is pre-oxidized, is carbonized and graphitization processing, carbon fiber is obtained.Tool
Body, pre-oxidation carries out gradient increased temperature in air atmosphere, and pre-oxidation carries out six warm area gradient increased temperatures, pre- oxygen in air atmosphere
The temperature of change is 180~270 degrees Celsius, and the time is 35~70 minutes, preferably 55 minutes；Carbonization includes high temperature cabonization and cryogenic carbon
Change, the temperature of low-temperature carbonization is 350~800 degrees Celsius, and the time is 2~6 minutes, and the temperature of high temperature cabonization is taken the photograph for 1200~1700
Family name's degree, time are 3~8 minutes；Graphited temperature be 2000~2200 degrees Celsius, the time be 3~5 minutes, drawing-off be 6.0~
10.0%.
Compared with prior art, the present invention enables carbon fiber relatively by applying drawing-off in the graphitization stage
More regular graphitization rearrangement structure is obtained under low graphitization temperature, to obtain high-strength high-modules carbon fibre, is reduced high-strength
High-modules carbon fibre production cost.Specifically, 225~235g/km of line density (6K), the 435~447g/km of obtained carbon fiber
(12K), volume density are 1.77~1.79g/cm3, tensile strength is 4.4~5.0GPa, and stretch modulus is 350~400GPa.
In another aspect of the invention, the invention proposes a kind of carbon fibers.According to an embodiment of the invention, the carbon fiber
Dimension is adopted to be prepared with the aforedescribed process.It as a result, can be in relatively low graphitization temperature by using the above method
It is lower to obtain more regular graphitization rearrangement structure, so that high-strength high-modules carbon fibre is obtained, the line density 225 of obtained carbon fiber
~235g/km (6K), 435~447g/km (12K), volume density are 1.77~1.79g/cm3, tensile strength be 4.4~
5.0GPa, stretch modulus are 350~400GPa.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
(1) using dimethyl sulfoxide as solvent, with azodiisobutyronitrile (AIBN), (concentration is at a temperature of 55 DEG C
Acrylonitrile, itaconic acid binary solution combined polymerization 0.3mol%) are carried out for initiator, reacts 25 hours, it is molten to obtain polymer spinning
Liquid, wherein acrylonitrile, itaconic acid mass ratio be 99.5:0.5.Then in the case of stirring, it is greater than in 65 DEG C, vacuum degree
Unreacted monomer in polymer spinning solution is removed under the conditions of 0.095MPa, stops stirring after 8 hours, it is same true at 65 DEG C
Standing and defoaming under empty condition finally obtains the polymer spinning solution that solid content is 20wt%；
(2) it using dimethyl sulfoxide (DMSO) aqueous solution as coagulating bath, is formed by three-level gradient freeze, wherein first is solidifying
Admittedly the concentration bathed is 65wt%, temperature is 50 DEG C, draw ratio 0.5；The concentration of the second gelation is 35wt%, temperature 35
℃；The concentration of third coagulating bath is 5wt%, and temperature is 30 DEG C；Polymer spinning solution is changed into as-spun fibre, then through steam
Drawing-off (draw ratio is 4.0 times), and wash and washed using temperature gradient, washing temperature is 90 DEG C；The finish for the process that oils is dense
Degree is 0.8wt%, and finish is amino modified silicone emulsion；Drying process is dry using temperature gradient, and dry temperature is 100
Degree Celsius；The temperature of superheated steam is 120 degrees Celsius, 2.0 times of drawing-off；The temperature of thermal finalization is 140 degrees Celsius, and relaxation rate is
0%, finally obtain polyacrylonitrile fibril.
(3) above-mentioned precursor is obtained into carbon fiber through pre-oxidation, carbonization and graphitization, wherein pre-oxidation treatment takes six temperature
Field gradient heating carries out in air atmosphere, pre-oxidizes 180 DEG C of initial temperature, pre-oxidizes 270 DEG C of final temperature, when pre-oxidizing total processing
Between 60 minutes；
Carbonization treatment includes two parts of low-temperature carbonization and high temperature cabonization, is all made of high pure nitrogen as protection gas, wherein
Low-temperature carbonization temperature is 350 DEG C, the residence time 6 minutes；High temperature cabonization temperature is 1200 DEG C, the residence time 3 minutes, graphited
Temperature is 2000 degrees Celsius, and the time is 3 minutes, drawing-off 6.0%.
Embodiment 2
(1) using dimethyl sulfoxide as solvent, with azodiisobutyronitrile (AIBN), (concentration is at a temperature of 65 DEG C
Acrylonitrile, itaconic acid binary solution combined polymerization 0.2mol%) are carried out for initiator, reacts 25 hours, it is molten to obtain polymer spinning
Liquid, wherein acrylonitrile, methyl acrylate, itaconic acid mass ratio be 95:4.5:0.5.Then in the case of stirring, in 65
DEG C, vacuum degree be greater than 0.095MPa under the conditions of remove polymer spinning solution in unreacted monomer, after 8 hours stop stirring,
The standing and defoaming under 65 DEG C of same vacuum conditions finally obtains the polymer spinning solution that solid content is 25wt%；
(2) it using dimethyl sulfoxide (DMSO) aqueous solution as coagulating bath, is formed by three-level gradient freeze, wherein first is solidifying
Admittedly the concentration bathed is 80wt%, temperature is 30 DEG C, draw ratio 0.6；The concentration of the second gelation is 60wt%, temperature 40
℃；The concentration of third coagulating bath is 10wt%, and temperature is 30 DEG C；Polymer spinning solution is changed into as-spun fibre, then through steaming
Vapour drawing-off (draw ratio is 7.0 times), and wash and washed using temperature gradient, washing temperature is 60 DEG C；The finish for the process that oils
Concentration is 1.5wt%, and finish is amino modified silicone emulsion；Drying process is dry using temperature gradient, and dry temperature is
150 degrees Celsius；The temperature of superheated steam is 160 degrees Celsius, 3.0 times of drawing-off；The temperature of thermal finalization is 180 degrees Celsius, relaxation rate
It is -10%, finally obtains polyacrylonitrile fibril.
(3) above-mentioned precursor is obtained into carbon fiber through pre-oxidation, carbonization and graphitization, wherein pre-oxidation treatment takes six temperature
Field gradient heating carries out in air atmosphere, pre-oxidizes 180 DEG C of initial temperature, pre-oxidizes 270 DEG C of final temperature, when pre-oxidizing total processing
Between 55 minutes；
Carbonization treatment includes two parts of low-temperature carbonization and high temperature cabonization, is all made of high pure nitrogen as protection gas, wherein
Low-temperature carbonization temperature is 800 DEG C, the residence time 2 minutes；High temperature cabonization temperature is 1700 DEG C, the residence time 8 minutes, graphited
Temperature is 2200 degrees Celsius, and the time is 4 minutes, drawing-off 7.0%.
Embodiment 3
(1) using dimethyl sulfoxide as solvent, third is carried out for initiator with azodiisobutyronitrile (AIBN) at a temperature of 60 DEG C
Alkene nitrile, itaconic acid binary solution combined polymerization react 25 hours, obtain polymer spinning solution, wherein acrylonitrile, acrylic acid first
Ester, itaconic acid mass ratio be 93:2:5.Then in the case of stirring, under the conditions of 60 DEG C, vacuum degree are greater than 0.095MPa
Unreacted monomer in polymer spinning solution is removed, stops stirring after 8 hours, is stood under 65 DEG C of same vacuum conditions de-
Bubble finally obtains the polymer spinning solution that solid content is 22wt%；
(2) it using dimethyl sulfoxide (DMSO) aqueous solution as coagulating bath, is formed by three-level gradient freeze, wherein first is solidifying
Admittedly the concentration bathed is 70wt%, temperature is 40 DEG C, draw ratio 0.7；The concentration of the second gelation is 40wt%, temperature 35
℃；The concentration of third coagulating bath is 7wt%, and temperature is 35 DEG C；Polymer spinning solution is changed into as-spun fibre, then through steam
Drawing-off (draw ratio is 6.0 times), and wash and washed using temperature gradient, washing temperature is 75 DEG C；The finish for the process that oils is dense
Degree is 1.2wt%, and finish is amino modified silicone emulsion；Drying process is dry using temperature gradient, and dry temperature is 130
Degree Celsius；The temperature of superheated steam is 130 degrees Celsius, 2.5 times of drawing-off；The temperature of thermal finalization be 150 degrees Celsius, relaxation rate be-
5%, finally obtain polyacrylonitrile fibril.
(3) above-mentioned precursor is obtained into carbon fiber through pre-oxidation, carbonization and graphitization, wherein pre-oxidation treatment takes six temperature
Field gradient heating carries out in air atmosphere, pre-oxidizes 180 DEG C of initial temperature, pre-oxidizes 270 DEG C of final temperature, when pre-oxidizing total processing
Between 70 minutes；
Carbonization treatment includes two parts of low-temperature carbonization and high temperature cabonization, is all made of high pure nitrogen as protection gas, wherein
Low-temperature carbonization temperature is 500 DEG C, the residence time 5 minutes；High temperature cabonization temperature is 1400 DEG C, the residence time 5 minutes, graphited
Temperature is 2100 degrees Celsius, and the time is 5 minutes, drawing-off 8.0%.
Embodiment 4
(1) using dimethyl sulfoxide as solvent, third is carried out for initiator with azodiisobutyronitrile (AIBN) at a temperature of 60 DEG C
Alkene nitrile, itaconic acid binary solution combined polymerization react 25 hours, obtain polymer spinning solution, wherein acrylonitrile, acrylic acid first
Ester, itaconic acid mass ratio be 93:2:5.Then in the case of stirring, under the conditions of 60 DEG C, vacuum degree are greater than 0.095MPa
Unreacted monomer in polymer spinning solution is removed, stops stirring after 8 hours, is stood under 65 DEG C of same vacuum conditions de-
Bubble finally obtains the polymer spinning solution that solid content is 22wt%；
(2) it using dimethyl sulfoxide (DMSO) aqueous solution as coagulating bath, is formed by three-level gradient freeze, wherein first is solidifying
Admittedly the concentration bathed is 70wt%, temperature is 40 DEG C, draw ratio 0.8；The concentration of the second gelation is 40wt%, temperature 35
℃；The concentration of third coagulating bath is 7wt%, and temperature is 35 DEG C；Polymer spinning solution is changed into as-spun fibre, then through steam
Drawing-off (draw ratio is 5.5 times), and wash and washed using temperature gradient, washing temperature is 75 DEG C；The finish for the process that oils is dense
Degree is 1.3wt%, and finish is amino modified silicone emulsion；Drying process is dry using temperature gradient, and dry temperature is 140
Degree Celsius；The temperature of superheated steam is 140 degrees Celsius, 2.7 times of drawing-off；The temperature of thermal finalization be 160 degrees Celsius, relaxation rate be-
3%, finally obtain polyacrylonitrile fibril.
(3) above-mentioned precursor is obtained into carbon fiber through pre-oxidation, carbonization and graphitization, wherein pre-oxidation treatment takes six temperature
Field gradient heating carries out in air atmosphere, pre-oxidizes 180 DEG C of initial temperature, pre-oxidizes 270 DEG C of final temperature, when pre-oxidizing total processing
Between 65 minutes；
Carbonization treatment includes two parts of low-temperature carbonization and high temperature cabonization, is all made of high pure nitrogen as protection gas, wherein
Low-temperature carbonization temperature is 600 DEG C, the residence time 5 minutes；High temperature cabonization temperature is 1500 DEG C, the residence time 5 minutes, graphited
Temperature is 2100 degrees Celsius, and the time is 3 minutes, drawing-off 9.0%.
Embodiment 5
(1) using dimethyl sulfoxide as solvent, third is carried out for initiator with azodiisobutyronitrile (AIBN) at a temperature of 60 DEG C
Alkene nitrile, itaconic acid binary solution combined polymerization react 25 hours, obtain polymer spinning solution, wherein acrylonitrile, acrylic acid first
Ester, itaconic acid mass ratio be 93:2:5.Then in the case of stirring, under the conditions of 60 DEG C, vacuum degree are greater than 0.095MPa
Unreacted monomer in polymer spinning solution is removed, stops stirring after 8 hours, is stood under 65 DEG C of same vacuum conditions de-
Bubble finally obtains the polymer spinning solution that solid content is 22wt%；
(2) it using dimethyl sulfoxide (DMSO) aqueous solution as coagulating bath, is formed by three-level gradient freeze, wherein first is solidifying
Admittedly the concentration bathed is 70wt%, temperature is 40 DEG C, draw ratio 1.0；The concentration of the second gelation is 40wt%, temperature 35
℃；The concentration of third coagulating bath is 7wt%, and temperature is 35 DEG C；Polymer spinning solution is changed into as-spun fibre, then through steam
Drawing-off (draw ratio is 6.0 times), and wash and washed using temperature gradient, washing temperature is 75 DEG C；The finish for the process that oils is dense
Degree is 1.4wt%, and finish is amino modified silicone emulsion；Drying process is dry using temperature gradient, and dry temperature is 140
Degree Celsius；The temperature of superheated steam is 150 degrees Celsius, 2.5 times of drawing-off；The temperature of thermal finalization be 170 degrees Celsius, relaxation rate be-
8%, finally obtain polyacrylonitrile fibril.
(3) above-mentioned precursor is obtained into carbon fiber through pre-oxidation, carbonization and graphitization, wherein pre-oxidation treatment takes six temperature
Field gradient heating carries out in air atmosphere, pre-oxidizes 180 DEG C of initial temperature, pre-oxidizes 270 DEG C of final temperature, when pre-oxidizing total processing
Between 70 minutes；
Carbonization treatment includes two parts of low-temperature carbonization and high temperature cabonization, is all made of high pure nitrogen as protection gas, wherein
Low-temperature carbonization temperature is 700 DEG C, the residence time 5 minutes；High temperature cabonization temperature is 1600 DEG C, the residence time 5 minutes, graphited
Temperature is 2100 degrees Celsius, and the time is 4 minutes, drawing-off 10.0%.
Carbon fiber and graphite degree obtained by embodiment 1-5 such as Fig. 1 (are characterized with the ratio at the peak D and the peak G in raman spectrum
The degree of graphitization of carbon fiber, R=ID/IG, R value is smaller, and degree of graphitization is higher) shown in, performance indicator is as shown in table 1.
Carbon fiber performance indicator obtained by 1 embodiment 1-5 of table
The above is only preferred embodiments of the invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as the protection scope that do not invent.
Claims (10)
1. a kind of method for the high-strength high-modules carbon fibre for preparing low degree of graphitization, wherein include:
(1) acrylonitrile and itaconic acid or acrylonitrile and itaconic acid are polymerize with methyl acrylate, it is molten obtains polymer spinning
Liquid；
(2) polymer spinning solution successively solidified, steam drafting, wash, oil, dry, superheated steam drawing-off
And thermal finalization, obtain polyacrylonitrile fibril；
(3) polyacrylonitrile fibril pre-oxidized, be carbonized and graphitization processing, to obtain carbon fiber,
Wherein, in step (3), the temperature of the graphitization processing is 2000~2200 degrees Celsius, and the time is 3~5 minutes, is led
Stretch 6.0%~10.0%.
2. the method for claim 1, wherein in step (1), the solid content of the polymer spinning solution is 20~
25wt%；
Optional, in step (1), the polymerization temperature is 55~65 degrees Celsius, and the time is 17~30 hours.
3. the process of setting is using three-level gradient freeze the method for claim 1, wherein in step (2): the
One solidification bath concentration is 65~80wt%, and temperature is 30~65 degrees Celsius, and solidification drafting multiple is 0.5~1.0 times,
The second gelation concentration is 35~50wt%, and temperature is 30~65 degrees Celsius,
It is 5~10wt% that third, which solidifies bath concentration, and temperature is 30~65 degrees Celsius.
4. the multiple of the steam drafting is 4.0~7.0 the method for claim 1, wherein in step (2)；
Optional, in step (2), the washing is washed using temperature gradient, and the washing temperature is 60~90 degrees Celsius.
5. the method for claim 1, wherein in step (2), the oil concentration of the process that oils is 0.8~
1.5wt%；
Optional, in step (2), the drying process is dry using temperature gradient, and the temperature of the drying is 100~150
Degree Celsius.
6. the temperature of the superheated steam is 120~160 Celsius the method for claim 1, wherein in step (2)
Degree, 2.0~3.0 times of drawing-off.
7. the temperature of the thermal finalization is 140~180 Celsius the method for claim 1, wherein in step (2)
Degree, relaxation rate are 0~-10%.
8. the pre-oxidation carries out six warm areas in air atmosphere the method for claim 1, wherein in step (3)
Gradient increased temperature, the temperature of the pre-oxidation are 180~270 degrees Celsius, and the time is 35~70 minutes.
9. the carbonization includes high temperature cabonization and low-temperature carbonization the method for claim 1, wherein in step (3),
The temperature of the low-temperature carbonization is 350~800 degrees Celsius, and the time is 2~6 minutes,
The temperature of the high temperature cabonization is 1200~1700 degrees Celsius, and the time is 3~8 minutes.
10. a kind of carbon fiber, wherein what the carbon fiber was prepared using method of any of claims 1-9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109881280A (en) * | 2019-02-18 | 2019-06-14 | 北京化工大学 | A kind of preparation method of polyacrylonitrile fibre, preparation method and its carbon fiber |
| CN110195272A (en) * | 2019-05-21 | 2019-09-03 | 湖南东映碳材料科技有限公司 | A kind of method that Mesophase Pitch Fiberss oil |
| CN113174657A (en) * | 2021-04-07 | 2021-07-27 | 山东大学 | Preparation method and application of graphene-doped carbon fiber |
| CN114687010A (en) * | 2022-04-18 | 2022-07-01 | 中国科学院宁波材料技术与工程研究所 | High-strength high-modulus high-elongation carbon fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220500A (en) * | 2004-02-09 | 2005-08-18 | Bussan Nanotech Research Institute Inc | Heat treatment apparatus for carbon fiber |
| CN102766989A (en) * | 2012-07-25 | 2012-11-07 | 北京化工大学 | Middle-modulus high-strength polyacrylonitrile-based carbon fiber, and preparation method thereof |
| CN104818546A (en) * | 2015-05-18 | 2015-08-05 | 威海拓展纤维有限公司 | Preparation method of high-strength high-modulus graphite fiber |
| CN105506785A (en) * | 2015-12-30 | 2016-04-20 | 北京化工大学 | Low-density high-strength high-modulus polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN108286090A (en) * | 2018-02-05 | 2018-07-17 | 北京化工大学 | A kind of preparation method of polyacrylonitrile-radical high-strength high-modules carbon fibre |
-
2018
- 2018-09-20 CN CN201811101975.8A patent/CN109280997A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220500A (en) * | 2004-02-09 | 2005-08-18 | Bussan Nanotech Research Institute Inc | Heat treatment apparatus for carbon fiber |
| CN102766989A (en) * | 2012-07-25 | 2012-11-07 | 北京化工大学 | Middle-modulus high-strength polyacrylonitrile-based carbon fiber, and preparation method thereof |
| CN104818546A (en) * | 2015-05-18 | 2015-08-05 | 威海拓展纤维有限公司 | Preparation method of high-strength high-modulus graphite fiber |
| CN105506785A (en) * | 2015-12-30 | 2016-04-20 | 北京化工大学 | Low-density high-strength high-modulus polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN108286090A (en) * | 2018-02-05 | 2018-07-17 | 北京化工大学 | A kind of preparation method of polyacrylonitrile-radical high-strength high-modules carbon fibre |
Non-Patent Citations (1)
| Title |
|---|
| 朱和国等: "《复合材料原理》", 31 July 2013, 国防工业出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109881280A (en) * | 2019-02-18 | 2019-06-14 | 北京化工大学 | A kind of preparation method of polyacrylonitrile fibre, preparation method and its carbon fiber |
| CN109881280B (en) * | 2019-02-18 | 2020-09-04 | 北京化工大学 | Polyacrylonitrile fiber, preparation method and preparation method of carbon fiber |
| CN110195272A (en) * | 2019-05-21 | 2019-09-03 | 湖南东映碳材料科技有限公司 | A kind of method that Mesophase Pitch Fiberss oil |
| CN110195272B (en) * | 2019-05-21 | 2021-06-08 | 湖南东映碳材料科技有限公司 | Method for oiling mesophase pitch fibers |
| CN113174657A (en) * | 2021-04-07 | 2021-07-27 | 山东大学 | Preparation method and application of graphene-doped carbon fiber |
| CN114687010A (en) * | 2022-04-18 | 2022-07-01 | 中国科学院宁波材料技术与工程研究所 | High-strength high-modulus high-elongation carbon fiber and preparation method thereof |
| CN114687010B (en) * | 2022-04-18 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | High-strength high-modulus high-elongation carbon fiber and preparation method thereof |
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