CN105200566B - A kind of method that high-strength high-modules carbon fibre is prepared using precursor stretching technique - Google Patents
A kind of method that high-strength high-modules carbon fibre is prepared using precursor stretching technique Download PDFInfo
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- CN105200566B CN105200566B CN201510687523.2A CN201510687523A CN105200566B CN 105200566 B CN105200566 B CN 105200566B CN 201510687523 A CN201510687523 A CN 201510687523A CN 105200566 B CN105200566 B CN 105200566B
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Abstract
The present invention relates to a kind of method that high strength high modulus carbon fiber is produced using precursor stretching technique, this method includes spinning solution preparation and wet spinning, as-spun fibre solidification are drawn into the steps such as protofilament, fiber preoxidation and carbonization with steam drafting processing, precursor.The present invention can efficiently reduce fiber again in precursor preparation process the defects of microstructure, and compared with not applying this process of fiber, pre-oxidation is further improved with fiber-wall-element model degree, and carbonized fiber mechanical property significantly improves；Because fiber stretches again more than glass transition temperature so that fibre number reduces, and specific surface area increases in high-temperature process, is effectively improved heat treatment efficiency；Handled by present invention process, it will be apparent that improve fiber quality.
Description
【Technical field】
The invention belongs to high-performance fiber processing technique field.More particularly it relates to a kind of stretched using precursor
The method that technology prepares high-strength high-modules carbon fibre.
【Background technology】
High-strength and high-modulus amount carbon fiber is the special fibre as made from polyacrylonitrile organic fiber by carbonization treatment, and it has
The excellent specific properties such as high specific strength, specific modulus, electric conductivity, thermal coefficient of expansion be low and anticorrosive.Utilize its flexible, anisotropy feature
By braiding, the fields such as military affairs, civilian industry are widely used in frequently as composite material reinforcement body material.
Carbon fiber preparation technology is complicated, and tedious process, apparatus and process require high, and high-quality polyacrylonitrile fibre is to prepare height
By force, the premise of high-modules carbon fibre, the quality of its quality will directly influence final fiber quality.Polyacrylonitrile fibre generally use
Wet spinning and dry-wet spinning technology, residual solvent is removed by multistage drafting and then with substantial amounts of washing, by oiling, doing
The processes such as scorching sizing obtain protofilament, then are handled by 200~350 DEG C of fiber thermostabilizations, then pre-oxidized fibers are divided
Do not handle to obtain final high-performance carbon fibre by 600~900 DEG C of low-temperature carbonizations and 1200~1400 DEG C of high temperature cabonizations.In order to carry
High microsteping hot property, preoxidation time etc. is reduced, generally use fibre modification, improve the methods of heat treatment heating rate.For example,
CN104313717A is related under high drafting, reduces fiber internal stress, increases fiber-wall-element model degree and then improves fiber heat endurance.
CN 101235568A and CN 02247164 all refers to boron salt and is modified protofilament, increases fiber preoxidation effect, realizes and improves
Fiber a certain kind effect.
Above patent application needs to carry out larger change to existing equipment, and equipment processing is cumbersome, or improves fiber again
The mechanical property that fiber will be had a strong impact on during other inorganic elements, then high temperature cabonization, property are introduced while heat endurance
Counter subtract can not be increased.
Currently, in the process of high-temperature process polyacrylonitrile fibril fiber, focus mostly in pre-oxidation gradient, preoxidation time,
The research of the technique such as low high temperature carburizing temperature and draft ratio, but tend to omit physical extension protofilament raising fiber
The method of performance.
The present inventor compensate for the heat treatment step of protofilament, on the basis of prior art is summarized, by a large amount of real
Research and analysis is tested, completes the present invention.
【The content of the invention】
[technical problems to be solved]
It is an object of the invention to provide a kind of method that high-strength high-modules carbon fibre is produced using precursor stretching technique.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of production method with high-strength polypropylene nitrile fiber.
The step of this method, is as follows：
A, spinning solution preparation and wet spinning
It is 3 × 10 by weight average molecular weight5Polyacrylonitrile polymer above is dissolved in dimethyl sulfoxide solvent, obtains one kind
Solution, allow described solution to be placed under 3.0~4.0kPa of pressure to remove the monomer wherein contained and the bubble of entrainment, then make
Filtered with candle wick formula filter, obtain the viscosity in temperature 60 C be 500~1600 pools, solids content be by weight 16
~20% spinning solution；Then,
Allow described spinning solution by aperture be 0.05~0.08mm, draw ratio no more than 1.5 spinneret carry out wet method
Spinning, obtain a kind of as-spun fibre；
B, as-spun fibre solidification is handled with steam drafting
Allowing the as-spun fibre that is obtained in step A, 35~45% dimethyl are sub- by weight by 48~52 DEG C of temperature, concentration
Coagulating bath of the sulfone in pure water handles 1.5~3.0min, solidifies the as-spun fibre, at the same keep drawing of fiber rate for-
8%；Then allow solidification as-spun fibre by godet by 32~38 DEG C of temperature, concentration by weight 35~45% diformazan
Coagulating bath of the base sulfoxide in pure water handles 1.0~2.0min, while it is 0% to keep drawing of fiber rate；Again by temperature 22~
28 DEG C, concentration by weight 5~10% coagulating bath of the dimethyl sulfoxide (DMSO) in pure water handle 0.5~1.0min, keep simultaneously
Drawing of fiber rate is 5%, then obtains a kind of coagulated fibre；Then,
Using hi-precision roller draw roll by described coagulated fibre in the water-bath of 75~85 DEG C of temperature pre-stretching 1.2~
1.8 times, then the washing water washing of 40~60 DEG C of temperature in use, is finally placed in aminosiloxane emulsion and handles, obtain one kind
Oil fiber；Then
Allow the described fiber that oils that densification is dried at 160~180 DEG C of temperature, then existed by hot bellows
Hot wire-CVD processing is carried out at 100~110 DEG C of temperature, obtains a kind of dry heat treatment fiber；This dry heat treatment fiber is steamed again
The processing of vapour HTHP high drafting, then dries, obtains a kind of polyacrylonitrile fibril fiber；
C, precursor is drawn into protofilament；
Allow polyacrylonitrile fibril fiber that step B obtains in hot-blast heater in 150~160 DEG C of temperature and the bar of air
Stretch processing is carried out under part, obtains a kind of stretching protofilament；
D, fiber preoxidation and carbonization；
The stretching protofilament that step C is obtained is allowed to carry out thermostabilization processing at 200~300 DEG C of temperature, then in nitrogen
Handled under conditions of 600~800 DEG C of gas atmosphere and temperature by low temperature carbonization furnace, then in ultrapure nitrogen atmosphere and temperature
Handled under conditions of 1200~1400 DEG C by high temperature carbonization furnace, so obtain described carbon fiber.
A preferred embodiment of the invention, in step, described spinning solution contain by weight 95% with
Upper polyacrylonitrile and 0.5~5.0% unsaturated carboxylic acid comonomer.
According to another preferred embodiment of the present invention, in step, the hole count of the spinneret is 1000~3000
It is individual.
According to another preferred embodiment of the present invention, in stepb, the coagulated fibre of washing contains by weight
Below 5ppm metal ion and 0.005~0.02% residual solvent.
According to another preferred embodiment of the present invention, in stepb, described coagulated fibre is after washing in amino
0.5~1.0min is handled in silicone emulsion.
According to another preferred embodiment of the present invention, in stepb, the compacting by drying processing of the fiber that oils
Time is 30~60s, and hot wire-CVD processing time is 10~20 seconds.
According to another preferred embodiment of the present invention, in stepb, the processing of steam HTHP high drafting is satisfied
It is 0.5~-0.01MPa with water vapour pressure, draft ratio is 1.2~2.5 times.
According to another preferred embodiment of the present invention, in step C, polyacrylonitrile fibril fiber stretch processing time
4~6 minutes, stretching ratio was 2~5 times.
According to the present invention another preferred embodiment, in step D, at described stretching protofilament thermostabilization
It is 50~60 minutes to manage the time.
According to another preferred embodiment of the present invention, it is in step D, described stretching precursor is in thermostabilization
0.5~1.5min is handled after processing in low temperature carbonization furnace；0.2~1.0min is handled in high temperature carbonization furnace.
The present invention is described in more detail below.
The present invention relates to a kind of precursor stretching technique to realize high-strength high-modules carbon fibre method.
Larger for existing carbon fiber degraded performance, CV values, the present invention redraws technique using a kind of precursor, can be effective
Fiber microscopic damage is reduced, final carbon fiber strength, modulus and production efficiency is improved, realizes the life of high-strength and high-modulus amount carbon fiber
Production.
The inventive method can allow its fiber to be orientated again more than the second glass transition temperature so that fibre crystallinity
Improve, can further reduce fiber micropore and fiber number.The inventive method can make fiber more efficient in process is pre-oxidized
Ground carries out thermostabilization processing.This method is easily implemented, technique is simple, it is only necessary to 2 meters or so of hot-blast stove is set up before pre-oxidation furnace,
Without largely being reequiped to existing equipment or public work.The inventive method enables to fibre number to reduce, and speed improves,
So that the time shortens in whole carbon fiber production process, energy consumption is reduced, it is adapted to high-performance polyacrylonitrile-based carbon fiber work
Industry metaplasia is produced.
According to the present invention, spinning solution is allowed by wet method (or wet-dry change) spinning, enters multistage coagulating bath and real through godet
Primary drawing-off is applied, dissolvent residual rate meets the requirements in fiber after washing step, after oiling and being heat-treated with compacting by drying, with
Afterwards after high temperature and high pressure steam drawing-off, dry, polyacrylonitrile fibril fiber is made.Under hot blast effect, fiber is carried out again
Stretching, then by thermostabilization and low and high temperature carbonization treatment.Stretching protofilament can effectively reduce fiber fibre again
Degree, the degree of orientation, crystallinity are improved, improve fiber preoxidation and carbonization efficiency, reduce fiber microscopic damage；Effectively raise poly-
The mechanical property of acrylonitrile protofilament.
The step of this method, is as follows：
A, spinning solution preparation and wet spinning
It is 3 × 10 by weight average molecular weight5Polyacrylonitrile polymer above is dissolved in dimethyl sulfoxide solvent, obtains one kind
Solution, allow described solution to be placed under 3.0~4.0kPa of pressure to remove the monomer wherein contained and the bubble of entrainment, then make
Filtered with candle wick formula filter, obtain the viscosity in temperature 60 C be 500~1600 pools, solids content be by weight 16
~20% spinning solution；Then,
Allow described spinning solution by aperture be 0.05~0.08mm, draw ratio no more than 1.5 spinneret carry out wet method
Spinning, obtain a kind of as-spun fibre；
Polyacrylonitrile is obtained by monomers acrylonitrile through Raolical polymerizable, and it is fine mainly for the production of polyacrylonitrile
Dimension, polyacrylonitrile fibre intensity is not high, and wearability and fatigue resistance are also poor.
The weight average molecular weight that the present invention uses is 3 × 105Polyacrylonitrile polymer above is current market sales of
Product, such as by Beijing Chemical Co., Ltd., the happy Industrial Co., Ltd.s of Shanghai Jin Jin, Shenyang chemical reagent factory, Shandong Shandong stone
The product that Hua Qitai petrochemical industries Co., Ltd is sold with trade name acrylonitrile.
In the polyacryl-nitrile spinning fluid that the present invention uses, the content of polyacrylonitrile is by weight more than 95%, insatiable hunger
Content with carboxylic acid comonomers is by weight 0.5~5.0%.
In the present invention, in the monomer and bubble in removing the solution, if the pressure is less than 3.0kPa, take off
Demonomerization and bubble DeGrain；If the pressure is higher than 4.0kPa, its effect is also bad；Therefore, described pressure
Be for 3.0~4.0kPa it is suitable, preferably 3.2~3.8；More preferably 3.4~3.6kPa.
In this step, spinning solution clarification, the degree of bubble-free should be reached by removing monomer and bubble, therefore can be adopted
Removing monomer and bubble effect are detected with visual method.
Removing monomer is filtered again with bubble.The candle wick formula filter that the present invention uses is a kind of candle for spinning-drawing machine
Core filter, its filter screen are three-layer metal filter structure, are protected including internal layer supporting network, middle level screen pack and outer layer
Net.The candle wick formula filter that the present invention uses is current market sales of product, such as limited by Shanghai profit haze filter plant
Company with trade name RH-ZS candle filters, Shanghai Si Lv environmental protection equipments Co., Ltd with trade name think filter SL-ACF filters,
The product that Shanghai Jia Yu filter plants Co., Ltd is sold with trade name ZL series candle formulas hermetic filtering machine.The candle that the present invention uses
Core type filter operation is carried out in the way of illustrating in product description.The filtrate (spinning solution) being filtrated to get is carried out
Viscosity and solid content measuring.
The viscosity of spinning solution is with trade name according to capillary tube method use by Shanghai Di Bai experimental facilities Co., Ltd
What the instrument of D01002-022 Ubbelohde viscometers sale determined under the conditions of 25 DEG C ± 0.05 DEG C.
In the present invention, if the spinning solution is less than 500 pools in the viscosity of temperature 60 C, spinning solution easily occurs " disconnected
Stream " phenomenon；, can the increase of spinning solution die swell effect if the viscosity of spinning solution is more than 1600 pools；Therefore, spinning solution is viscous
It is suitable, preferably 680~1400 pools to spend for 500~1600 pools, more preferably 800~1200 pool.
The solids content of the spinning solution is also inappropriate when exceeding this scope, because solids content is crossed senior general and caused
Polymer viscosity increase, is also easy to produce physical crosslinking, pipeline pressure is excessive in spinning process, causes equipment damage.
If the viscosity or solids content of the spinning solution exceed its scope, addition solvent DMSO is generally respectively adopted
Its viscosity and solids content regulation are reached described scope by the method for dilution.
The hole count for the spinneret that the present invention uses is 1000~3000.Described spinneret is to plate tantalum material system with high rigidity
Into.
B, as-spun fibre solidification is handled with steam drafting
Allowing the as-spun fibre that is obtained in step A, 35~45% dimethyl are sub- by weight by 48~52 DEG C of temperature, concentration
Coagulating bath of the sulfone in pure water handles 1.5~3.0min, solidifies the as-spun fibre, at the same keep drawing of fiber rate for-
8%；Then allow solidification as-spun fibre by godet by 32~38 DEG C of temperature, concentration by weight 35~45% diformazan
Coagulating bath of the base sulfoxide in pure water handles 1.0~2.0min, while it is 0% to keep drawing of fiber rate；Again by temperature 22~
28 DEG C, concentration by weight 5~10% coagulating bath of the dimethyl sulfoxide (DMSO) in pure water handle 0.5~1.0min, keep simultaneously
Drawing of fiber rate is 5%, then obtains a kind of coagulated fibre；Then,
In the present invention, described solidification is it should be understood that " phase in version " that polymer occurs in spinning process, i.e., first
Transformation of the raw fiber from liquid to solid-state.In order to reach slow, uniform, fine-denier purpose, present invention employs three sections of solidifications
Mode, first paragraph are with being solidified in 35~45% dimethyl sulfoxide (DMSO) coagulating baths in 48~52 DEG C of temperature；Second segment is in temperature
32~38 DEG C of degree in 35~45% dimethyl sulfoxide (DMSO) coagulating baths with being solidified；3rd section be 22~28 DEG C of temperature with 5~
Solidified in 10% dimethyl sulfoxide (DMSO) coagulating bath.It is of course also possible to realized just using more coagulation steps according to actual conditions
Raw fibre solidification.
Then, described coagulated fibre is pre-stretched in the water-bath of 75~85 DEG C of temperature using hi-precision roller draw roll
1.2~1.8 times, then with the washing water washing of 60~80 DEG C of temperature, finally it is placed in aminosiloxane emulsion and handles, obtain one
Plant the fiber that oils.
In the present invention, the purpose of pre-stretching is so that fiber-wall-element model, fine-denier, improves as-spun fibre mechanical property.
The hi-precision roller draw roll that the present invention uses is it should be understood that a kind of drive the roller of multiaxis to lead by servomotor
Stretch roller, the product e.g. sold by Zhengzhou Heng Tian heavy industrys company with trade name hi-precision roller draw roll.
In this step, described coagulated fibre needs to use water washing after pre-stretching, to remove the solvent of residual
With metal ion.Described residual solvent, which comes from, to be prepared solvent or as-spun fibre used in polyacrylonitrile polymer solution and coagulates
Gu when the solvent that uses, they mainly remain in the dimethyl sulfoxide (DMSO) that the coagulating bath that fiber surface do not remove or double diffusion go out.
Solvent residual amount should be controlled by weight 0.005~0.02%.If the quantity of solvent of residual can cause fiber more than 5ppm
More vacancies are fallen into carbonisation.
Metal ion content is below 5ppm by weight in the fiber with washing water washing.Described metal ion comes
From in monomer, polymeric kettle and pipeline, they are, for example, potassium, sodium, iron plasma.
The solvent residual amount and metal ion content all determine to obtain using conventional method.
The rinsing bowl used during with washing water washing should have sufficient length, so as to which fully washing removes residual solvent
With metal ion, reach its requirement.It is typically 8~12 meters to wash slot length.If the length of rinsing bowl exceedes this scope,
Can water washing effect unobvious or waste of resource.
Washing fiber, which is placed in aminosiloxane emulsion, carries out oiling treatment.Washing fiber is located in aminosiloxane emulsion
The effect of reason is to make its fiber reach abundant wetting, so that its fiber separates, does not assemble, be not adhered.
In stepb, described coagulated fibre handles 0.5~1.0min in aminosiloxane emulsion after washing.
Described aminosiloxane emulsion is current market sales of product, such as limited by the Shanghai spectrum biotechnology that shakes
The product that company of company is sold with trade name 70131-67-8.
Allow the described fiber that oils that densification is dried at 160~180 DEG C of temperature, then existed by hot bellows
Hot wire-CVD processing is carried out at 100~110 DEG C of temperature, obtains a kind of dry heat treatment fiber；This dry heat treatment fiber is steamed again
The processing of vapour HTHP high drafting, is then dried to obtain polyacrylonitrile fibril fiber.
In the present invention, compacting by drying processing in high temperature (160~180 DEG C of temperature) and bright and clean hot-rolling it should be understood that make
The micropore in the fiber is set further to reduce or disappear under.Compacting by drying processing time is 30~60s.Preferably 35
~55s, more preferably 40~50s.
Compacting by drying processing equipment is current market sales of product, such as by spinning smart industry electromechanical equipment machine in Beijing
The product that electric equipment Co., Ltd is sold with trade name RGWTSK-1R7TRS1.
In the present invention, the effect of hot wire-CVD processing is to reduce fiber due to internal stress caused by high draft.Hot wire-CVD
Processing is handled 10~20 seconds at 100~110 DEG C of temperature, obtains dry heat treatment fiber.Preferably, the temperature of hot wire-CVD processing
It it is 102~108 DEG C, the time is 12~18 seconds.It is highly preferred that the temperature of hot wire-CVD processing is 104~106 DEG C, the time is 14~
16 seconds.The degree of draft of hot wire-CVD processing is zero.
Hot wire-CVD processing equipment is current market sales of product, such as by Xi'an Fu Ruida Science and Technology Ltd.s with business
The product of name of an article FRD-O13 sale.
Described dry heat treatment fiber carries out the processing of steam HTHP high drafting again.
The effect of steam HTHP high drafting processing is further to make fiber crystallization and is orientated, and it is strong to improve fiber
Degree.The saturation vapor pressure of steam HTHP high drafting processing is 0.50~-0.01MPa, and draft ratio is 2~5 times.
Equipment used in the processing of steam HTHP high drafting is current market sales of product, such as must be installed with by Yangzhou is prosperous
The product that standby Manufacturing Co., Ltd is sold with trade name high temperature and high pressure steam drafting system.
Heat is dried under conditions of 102~108 DEG C of temperature and air through the fiber that steam HTHP high drafting is handled
Relaxation processes obtain polyacrylonitrile fibril fiber.Equipment used in drying hot wire-CVD processing is current market sales of production
Product, such as the product sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-O13.
C, precursor stretching protofilament；
Allow polyacrylonitrile fibril fiber that step B obtains in hot-blast heater in 150~160 DEG C of temperature and the bar of air
Stretch processing 4~6 minutes is carried out under part, stretching ratio is 1~1.7 times, obtains a kind of stretching protofilament；
The purpose of this stretch processing step is that reducing the excessive drawing-off of precursor causes fiber internal stress so that fiber enters one
Step heat orientation.
In the present invention, the hot-blast heater used is the homemade equipment of the present inventor, its structural representation such as institute of accompanying drawing 1
Show.For cold humid air after air heater 5, its temperature rises to 80~120 DEG C, after isothermal holding hot air duct 4, uniformly
Purged by hot-air mouth 3 to wire passage 2, so as to reach technological requirement.
D, fiber preoxidation and carbonization；
The stretching protofilament that step C is obtained is allowed to carry out thermostabilization processing at 200~300 DEG C of temperature, then in nitrogen
Handled under conditions of 600~800 DEG C of gas atmosphere and temperature by low temperature carbonization furnace, then in ultrapure nitrogen atmosphere and temperature
Handled under conditions of 1200~1400 DEG C by high temperature carbonization furnace, so obtain described carbon fiber.
The effect of thermostabilization processing is so that protofilament is transformed into heat-resisting trapezium structure by linear structure,
So that the heat treatment of higher temperature can be born.
Described stretching protofilament thermostabilization processing time is 50~60 minutes.
Equipment used in thermostabilization processing is, for example, with trade name FRD- by Xi'an Fu Ruida Science and Technology Ltd.s
The product of YYH13 sale.
The purpose that described stretching precursor is handled in low temperature carbonization furnace is further to improve heat-resisting trapezium structure so that
Fiber can at a higher temperature be heat-treated and not damage；The purpose handled in high temperature carbonization furnace is turning for graphite Turbostratic
Become, fibre strength increases substantially.
Described stretching precursor handles 0.5~1.5min after thermostabilization processing in low temperature carbonization furnace；In pyrocarbon
Change stove and handle 0.2~1.0min.
After thermostabilization processing, stretching protofilament is carrying out cryogenic carbon at 600~800 DEG C of temperature and nitrogen atmosphere
Change stove processing.In the present invention, nitrogen gas purity is the key for producing high-performance carbon fibre, and purity should be ultrapure rank, and oxygen content is small
In 5ppm, dew point is not higher than -72 DEG C.
The low temperature carbonization furnace that the present invention uses is, for example, with trade name FRD-LC13 by Xi'an Fu Ruida Science and Technology Ltd.s
The product of sale.
The high temperature carbonization furnace that the present invention uses is, for example, with trade name FRD-HC13 by Xi'an Fu Ruida Science and Technology Ltd.s
The product of sale.
According to GBT 3362-2005 method of testings, using by Instron companies with the type universal material testing of trade name 5966
It is 3.45 that the instrument of machine sale determines polyacrylonitrile fibre intensity prepared by the present invention under the conditions of rate of extension is 5cm/min
~4.42GPa, 260.66~291.00GPa of modulus.
Mechanics Performance Testing is carried out to the carbon fiber produced according to the inventive method, its test result is listed in Table 1 below.
Table 1：Different precursor final carbon fiber mechanical property under different stretch ratio
Note：* it is GPa to represent the data unit in the column.
The result of table 1 clearly demonstrates protofilament by appropriate pre-stretching, and same pre-oxidation, carbonization technique can make
Fibre strength is obtained to have been lifted.
In the market, popularization or utilization rate highest are toray T300 grade carbon fibers, using GBT 3362-
2005 standard methods determine, and its measurement result, which meets, has announced data, i.e., intensity is 3.5GPa, modulus 230GPa.It is same with this
When, determined using same method, the intensity highest of carbon fiber is produced according to the inventive method can reach 4.42GPa, modulus
291GPa。
As can be seen here, compared with prior art, the inventive method enables to carbon fiber strength to improve 1.26 times, modulus
Increase by 26.5%.
[beneficial effect]
The beneficial effects of the invention are as follows：
1st, the present invention can efficiently reduce fiber again in precursor preparation process the defects of microstructure, with not applying this work
Skill fiber is compared, and pre-oxidation is further improved with fiber-wall-element model degree, and carbonized fiber mechanical property significantly improves.
2nd, because fiber stretches again more than glass transition temperature so that fibre number reduces, and compares in high-temperature process
Surface area increases, and is effectively improved heat treatment efficiency；
3rd, handled by present invention process, it will be apparent that improve fiber quality, polyacrylonitrile-based carbon fibre intensity of the present invention
26% is improved, modulus increase by 26.5%.
【Brief description of the drawings】
Fig. 1 is the hot-blast heater structural representation that the present invention uses.
In figure：
1- bodies of heater；2- wire passages；3- hot-air mouths；4- hot air ducts；5- air heaters；6- airflow pipes.
【Embodiment】
The present invention is will be better understood that by following embodiments.
Embodiment 1：High strength high modulus carbon fiber is produced using the inventive method
The implementation steps of the embodiment are as follows：
A, spinning solution preparation and wet spinning
Weight average molecular weight using trade name PAN-P1 sale will be produced as 3 × 10 by Xibei Chemical Inst5The above is gathered
Acrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain it is a kind of containing 95.2% polyacrylonitrile and 1.0% by weight not
The solution of saturated carboxylic acid comonomer, described solution is allowed to be placed under pressure 3.2kPa to remove the monomer wherein contained and entrainment
Bubble, reach spinning solution clarification, the degree of bubble-free.Then use by Shanghai Run Lan filter plants Co., Ltd with trade name
The candle wick formula filter of RH-ZS candle filters sale is filtered, and is determined, obtained using the method described in specification
Spinning solution viscosity in temperature 60 C is 800 pools, solids content is by weight 16.0%；Then,
Described spinning solution is allowed by aperture to be 0.05mm, draw ratio is no more than the spray that the 1.5, hole count of spinneret is 1000
Filament plate carries out wet spinning, obtains a kind of as-spun fibre；
B, as-spun fibre solidification is handled with steam drafting
Allow the as-spun fibre obtained in step A by 48 DEG C of temperature, concentration by weight 38% dimethyl sulfoxide (DMSO) in pure water
In coagulating bath processing 2.0min, solidify the as-spun fibre, while it is -8% to keep drawing of fiber rate；Then solidification is allowed
As-spun fibre by godet by 34 DEG C of temperature, concentration by weight 38% dimethyl sulfoxide (DMSO) at coagulating bath in pure water
1.0min is managed, while it is 0% to keep drawing of fiber rate；Again by 26 DEG C of temperature, concentration by weight 5% dimethyl sulfoxide (DMSO) exist
Coagulating bath processing 0.5min in pure water, while it is 5% to keep drawing of fiber rate, then obtains a kind of coagulated fibre；Then,
Using by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. with the height of the trade name HTCT13 constant temperature coagulating basin equipment sold
Described coagulated fibre is pre-stretched 1.8 times by precision roller draft roller in the water-bath of 75 DEG C of temperature, is then 8 meters of water in length
The washing water washing of 50 DEG C of temperature in use removes residual solvent in washing trough, and solvent residual amount control is by weight 0.015%, gold
Category ion concentration is below 5ppm by weight.Finally it is placed in by company of Shanghai Pu Zhen bio tech ltd with trade name
0.6min is handled in the aminosiloxane emulsion of 70131-67-8 sale, one kind is obtained and oils fiber；Then
Sold using by Beijing Zhong Fangjingye electromechanical equipments mechanical ＆ electronic equipment corporation, Ltd with trade name RGWTSK-1R7TRS1
Equipment, allow the described fiber that oils that densification 40s is dried at 160 DEG C of temperature by compacting by drying hot-rolling,
Then use and carried out by Xi'an Fu Ruida Science and Technology Ltd.s with the hot bellows that trade name FRD-O13 is sold at 102 DEG C of temperature
Hot wire-CVD is handled 12 seconds, and the degree of draft of hot wire-CVD processing is zero, obtains a kind of dry heat treatment fiber；
This dry heat treatment fiber reuses to be steamed by Yangzhou Heng get Rong device fabrications Co., Ltd with trade name HTHP
The product of vapour drafting system sale carries out the processing of steam HTHP high drafting under saturation vapor pressure 0.50MPa, leads
It is 3 times to stretch multiplying power, then uses and is done by Xi'an Fu Ruida Science and Technology Ltd.s with the trade name FRD-O13 equipment sold
It is dry, obtain polyacrylonitrile fibril fiber；
C, precursor is drawn into protofilament；
Using the hot-blast heater of self-control design processing, relevant design is as illustrated, the polyacrylonitrile for allowing step B to obtain is former
Silk fiber carries out stretch processing 5.4 minutes in hot-blast heater under conditions of 156 DEG C of temperature and air, and stretching ratio is
1.1 times, obtain a kind of stretching protofilament；
D, fiber preoxidation and carbonization；
Equipment using being sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-YYH13, allow what step C was obtained
Stretch protofilament thermostabilization is carried out at 260 DEG C of temperature and handle 58 minutes, then use limited by Xi'an Fu Ruida science and technology
The low temperature carbonization furnace that company is sold with trade name FRD-LC13, by low under conditions of 700 DEG C of ultrapure nitrogen atmosphere and temperature
Warm carbide furnace carries out processing 0.5min, reuses the height sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-HC13
Warm carbide furnace, processing 0.2min is carried out by high temperature carbonization furnace under conditions of 1360 DEG C of ultrapure nitrogen atmosphere and temperature, so
Obtain described carbon fiber.
The method described to specifications determines strong using final carbon fiber under the conditions of carbonization technique of the invention and corresponding
Spend for 3.45~3.92GPa, 260.66~274.45GPa of modulus.
Embodiment 2：High strength high modulus carbon fiber is produced using the inventive method
The implementation steps of the embodiment are as follows：
A, spinning solution preparation and wet spinning
By by Beijing Chemical Co., Ltd. using the weight average molecular weight that trade name acrylonitrile is sold as 3 × 105Above poly- third
Alkene nitrile polymer is dissolved in dimethyl sulfoxide solvent, is obtained one kind and is contained 95.5% polyacrylonitrile and 0.5% insatiable hunger by weight
With the solution of carboxylic acid comonomers, described solution is allowed to be placed under pressure 3.8kPa to remove the monomer wherein contained and entrainment
Bubble, reach spinning solution clarification, the degree of bubble-free, then use and thought by Shanghai Si Lv environmental protection equipments Co., Ltd with trade name
The candle wick formula filter of filter SL-ACF filter sale is filtered, and is determined using the method described in specification, obtained spinning
Silk liquid viscosity in temperature 60 C is 1200 pools, solids content is by weight 18.2%；Then,
Described spinning solution is allowed by aperture to be 0.06mm, draw ratio is no more than the spray that the 1.5, hole count of spinneret is 2800
Filament plate carries out wet spinning, obtains a kind of as-spun fibre；
B, as-spun fibre solidification is handled with steam drafting
Allow the as-spun fibre obtained in step A by temperature 50 C, concentration by weight 35% dimethyl sulfoxide (DMSO) in pure water
In coagulating bath processing 1.5min, solidify the as-spun fibre, while it is -8% to keep drawing of fiber rate；Then solidification is allowed
As-spun fibre by godet by 36 DEG C of temperature, concentration by weight 35% dimethyl sulfoxide (DMSO) at coagulating bath in pure water
2.0min is managed, while it is 0% to keep drawing of fiber rate；Again by 28 DEG C of temperature, concentration by weight 8% dimethyl sulfoxide (DMSO) exist
Coagulating bath processing 1.0min in pure water, while it is 5% to keep drawing of fiber rate, then obtains a kind of coagulated fibre；Then,
Using by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. with the height of the trade name HTCT13 constant temperature coagulating basin equipment sold
Described coagulated fibre is pre-stretched 1.2 times by precision roller draft roller in the water-bath of 78 DEG C of temperature, is then 10 meters in length
The washing water washing of 40 DEG C of temperature in use removes residual solvent in rinsing bowl, and solvent residual amount is controlled by weight
0.005%, metal ion content is below 5ppm by weight.Finally it is placed in by company of Shanghai Pu Zhen bio tech ltd
To handle 0.6min in the aminosiloxane emulsion of trade name 70131-67-8 sale, obtain one kind and oil fiber；Then
Sold using by Beijing Zhong Fangjingye electromechanical equipments mechanical ＆ electronic equipment corporation, Ltd with trade name RGWTSK-1R7TRS1
Equipment, allow the described fiber that oils that densification 50s is dried at 170 DEG C of temperature by compacting by drying hot-rolling,
Then use and carried out by Xi'an Fu Ruida Science and Technology Ltd.s with the hot bellows that trade name FRD-O13 is sold at 108 DEG C of temperature
Hot wire-CVD is handled 18 seconds, and the degree of draft of hot wire-CVD processing is zero, obtains a kind of dry heat treatment fiber；
This dry heat treatment fiber reuses to be steamed by Yangzhou Heng get Rong device fabrications Co., Ltd with trade name HTHP
The product of vapour drafting system sale carries out the processing of steam HTHP high drafting under saturation vapor pressure 0.20MPa, leads
It is 4 times to stretch multiplying power, then uses and is done by Xi'an Fu Ruida Science and Technology Ltd.s with the trade name FRD-O13 equipment sold
It is dry, obtain polyacrylonitrile fibril fiber；
C, precursor is drawn into protofilament；
Using the hot-blast heater of self-control design processing, relevant design is as illustrated, the polyacrylonitrile for allowing step B to obtain is former
Silk fiber carries out stretch processing 4.0 minutes in hot-blast heater under conditions of 150 DEG C of temperature and air, and stretching ratio is
1.6 times, obtain a kind of stretching protofilament；
D, fiber preoxidation and carbonization；
Equipment using being sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-YYH13, allow what step C was obtained
Stretch protofilament thermostabilization is carried out at 200 DEG C of temperature and handle 50 minutes, then use limited by Xi'an Fu Ruida science and technology
The low temperature carbonization furnace that company is sold with trade name FRD-LC13, by low under conditions of 650 DEG C of ultrapure nitrogen atmosphere and temperature
Warm carbide furnace carries out processing 1.5min, reuses the height sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-HC13
Warm carbide furnace, processing 0.5min is carried out by high temperature carbonization furnace under conditions of 1320 DEG C of ultrapure nitrogen atmosphere and temperature, so
Obtain described carbon fiber.
The method described to specifications determines strong using final carbon fiber under the conditions of carbonization technique of the invention and corresponding
Spend for 3.52~3.97GPa, 266.18~275.83GPa of modulus.
Embodiment 3：High strength high modulus carbon fiber is produced using the inventive method
The implementation steps of the embodiment are as follows：
A, spinning solution preparation and wet spinning
By by the happy Industrial Co., Ltd.s of Shanghai Jin Jin using the weight average molecular weight that trade name acrylonitrile is sold as 3 × 105More than
Polyacrylonitrile polymer be dissolved in dimethyl sulfoxide solvent, obtain it is a kind of containing 95.8% polyacrylonitrile by weight with
The solution of 2.1% unsaturated carboxylic acid comonomer, described solution is allowed to be placed under pressure 3.0kPa to remove the list wherein contained
Body and the bubble of entrainment, reach spinning solution clarification, the degree of bubble-free, then use by Shanghai Jia Yu filter plants Co., Ltd
Filtered with the candle wick formula filter that trade name ZL series candle formulas hermetic filtering machine is sold, using the method described in specification
Measure, obtained spinning solution viscosity in temperature 60 C is 500 pools, solids content is by weight 20.0%；Then,
Described spinning solution is allowed by aperture to be 0.08mm, draw ratio is no more than the spray that the 1.5, hole count of spinneret is 3000
Filament plate carries out wet spinning, obtains a kind of as-spun fibre；
B, as-spun fibre solidification is handled with steam drafting
Allow the as-spun fibre obtained in step A by 52 DEG C of temperature, concentration by weight 38% dimethyl sulfoxide (DMSO) in pure water
In coagulating bath processing 3.0min, solidify the as-spun fibre, while it is -8% to keep drawing of fiber rate；Then solidification is allowed
As-spun fibre by godet by 32 DEG C of temperature, concentration by weight 38% dimethyl sulfoxide (DMSO) at coagulating bath in pure water
1.5min is managed, while it is 0% to keep drawing of fiber rate；Again by 22 DEG C of temperature, concentration by weight 10% dimethyl sulfoxide (DMSO)
Coagulating bath processing 0.6min in pure water, while it is 5% to keep drawing of fiber rate, then obtains a kind of coagulated fibre；Then,
Using by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. with the height of the trade name HTCT13 constant temperature coagulating basin equipment sold
Described coagulated fibre is pre-stretched 1.4 times by precision roller draft roller in the water-bath of 82 DEG C of temperature, is then 12 meters in length
The washing water washing of 48 DEG C of temperature in use removes residual solvent in rinsing bowl, solvent residual amount control by weight 0.008%,
Metal ion content is below 5ppm by weight.Finally it is placed in by company of Shanghai Pu Zhen bio tech ltd with trade name
0.6min is handled in the aminosiloxane emulsion of 70131-67-8 sale, one kind is obtained and oils fiber；Then
Sold using by Beijing Zhong Fangjingye electromechanical equipments mechanical ＆ electronic equipment corporation, Ltd with trade name RGWTSK-1R7TRS1
Equipment, allow the described fiber that oils that densification 30s is dried at 180 DEG C of temperature by compacting by drying hot-rolling,
Then use and carried out by Xi'an Fu Ruida Science and Technology Ltd.s with the hot bellows that trade name FRD-O13 is sold at 100 DEG C of temperature
Hot wire-CVD is handled 10 seconds, and the degree of draft of hot wire-CVD processing is zero, obtains a kind of dry heat treatment fiber；
This dry heat treatment fiber reuses to be steamed by Yangzhou Heng get Rong device fabrications Co., Ltd with trade name HTHP
The product of vapour drafting system sale carries out the processing of steam HTHP high drafting under saturation vapor pressure 0.10MPa, leads
It is 2 times to stretch multiplying power, then uses and is done by Xi'an Fu Ruida Science and Technology Ltd.s with the trade name FRD-O13 equipment sold
It is dry, obtain polyacrylonitrile fibril fiber；
C, precursor is drawn into protofilament；
Using the hot-blast heater of self-control design processing, relevant design is as illustrated, the polyacrylonitrile for allowing step B to obtain is former
Silk fiber carries out stretch processing 5.0 minutes in hot-blast heater under conditions of 152 DEG C of temperature and air, and stretching ratio is
1.4 times, obtain a kind of stretching protofilament；
D, fiber preoxidation and carbonization；
Equipment using being sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-YYH13, allow what step C was obtained
Stretch protofilament thermostabilization is carried out at 250 DEG C of temperature and handle 52 minutes, then use limited by Xi'an Fu Ruida science and technology
The low temperature carbonization furnace that company is sold with trade name FRD-LC13, by low under conditions of 600 DEG C of ultrapure nitrogen atmosphere and temperature
Warm carbide furnace carries out processing 0.8min, reuses the height sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-HC13
Warm carbide furnace, processing 1.0min is carried out by high temperature carbonization furnace under conditions of 1200 DEG C of ultrapure nitrogen atmosphere and temperature, so
Obtain described carbon fiber.
The method described to specifications determines strong using final carbon fiber under the conditions of carbonization technique of the invention and corresponding
Spend for 3.71~3.91GPa, 272.39~291.00GPa of modulus.
Embodiment 4：High strength high modulus carbon fiber is produced using the inventive method
The implementation steps of the embodiment are as follows：
A, spinning solution preparation and wet spinning
By by Shenyang chemical reagent factory using the weight average molecular weight that trade name acrylonitrile is sold as 3 × 105Polypropylene above
Nitrile polymer is dissolved in dimethyl sulfoxide solvent, is obtained a kind of unsaturated containing 95.1% polyacrylonitrile by weight and 4.5%
The solution of carboxylic acid comonomers, described solution is allowed to be placed under pressure 4.0kPa to remove the monomer wherein contained and the gas of entrainment
Bubble, reach spinning solution clarification, the degree of bubble-free, then use by Shanghai Jia Yu filter plants Co., Ltd with trade name ZL systems
The candle wick formula filter of row candle formula hermetic filtering machine sale is filtered, and is determined, obtained using the method described in specification
Spinning solution viscosity in temperature 60 C is 1600 pools, solids content is by weight 17.4%；Then,
Described spinning solution is allowed by aperture to be 0.05mm, draw ratio is no more than the spray that the 1.5, hole count of spinneret is 1600
Filament plate carries out wet spinning, obtains a kind of as-spun fibre；
B, as-spun fibre solidification is handled with steam drafting
Allow the as-spun fibre obtained in step A by 48 DEG C of temperature, concentration by weight 40% dimethyl sulfoxide (DMSO) in pure water
In coagulating bath processing 2.4min, solidify the as-spun fibre, while it is -8% to keep drawing of fiber rate；Then solidification is allowed
As-spun fibre by godet by 34 DEG C of temperature, concentration by weight 40% dimethyl sulfoxide (DMSO) at coagulating bath in pure water
1.4min is managed, while it is 0% to keep drawing of fiber rate；Again by 24 DEG C of temperature, concentration by weight 5% dimethyl sulfoxide (DMSO) exist
Coagulating bath processing 0.8min in pure water, while it is 5% to keep drawing of fiber rate, then obtains a kind of coagulated fibre；Then,
Using by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. with the height of the trade name HTCT13 constant temperature coagulating basin equipment sold
Described coagulated fibre is pre-stretched 1.6 times by precision roller draft roller in the water-bath of 85 DEG C of temperature, is then 8 meters of water in length
The washing water washing of 60 DEG C of temperature in use removes residual solvent in washing trough, and solvent residual amount control is by weight 0.015%, gold
Category ion concentration is below 5ppm by weight.Finally it is placed in by company of Shanghai Pu Zhen bio tech ltd with trade name
0.6min is handled in the aminosiloxane emulsion of 70131-67-8 sale, one kind is obtained and oils fiber；Then
Sold using by Beijing Zhong Fangjingye electromechanical equipments mechanical ＆ electronic equipment corporation, Ltd with trade name RGWTSK-1R7TRS1
Equipment, allow the described fiber that oils that densification 60s is dried at 160 DEG C of temperature by compacting by drying hot-rolling,
Then use and carried out by Xi'an Fu Ruida Science and Technology Ltd.s with the hot bellows that trade name FRD-O13 is sold at 110 DEG C of temperature
Hot wire-CVD is handled 20 seconds, and the degree of draft of hot wire-CVD processing is zero, obtains a kind of dry heat treatment fiber；
This dry heat treatment fiber reuses to be steamed by Yangzhou Heng get Rong device fabrications Co., Ltd with trade name HTHP
The product of vapour drafting system sale carries out the processing of steam HTHP high drafting in the case where saturation vapor pressure is 0.40MPa,
Draft ratio is 3 times, then uses and is done by Xi'an Fu Ruida Science and Technology Ltd.s with the trade name FRD-O13 equipment sold
It is dry, obtain polyacrylonitrile fibril fiber；
C, precursor is drawn into protofilament；
Using the hot-blast heater of self-control design processing, relevant design is as illustrated, the polyacrylonitrile for allowing step B to obtain is former
Silk fiber carries out stretch processing 6.0 minutes in hot-blast heater under conditions of 156 DEG C of temperature and air, and stretching ratio is
1.7 times, obtain a kind of stretching protofilament；
D, fiber preoxidation and carbonization；
Equipment using being sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-YYH13, allow what step C was obtained
Stretch protofilament and thermostabilization processing 54min is carried out at 300 DEG C of temperature, then use by the limited public affairs of Xi'an Fu Ruida science and technology
The low temperature carbonization furnace that department is sold with trade name FRD-LC13, pass through low temperature under conditions of 800 DEG C of ultrapure nitrogen atmosphere and temperature
Carbide furnace carries out processing 1.0min, reuses the high temperature sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-HC13
Carbide furnace, processing 0.6min is carried out by high temperature carbonization furnace under conditions of 1300 DEG C of ultrapure nitrogen atmosphere and temperature, such
To described carbon fiber.
The method described to specifications determines strong using final carbon fiber under the conditions of carbonization technique of the invention and corresponding
Spend for 3.93~4.42GPa, 270.32~287.56GPa of modulus.
Embodiment 5：High strength high modulus carbon fiber is produced using the inventive method
The implementation steps of the embodiment are as follows：
A, spinning solution preparation and wet spinning
By by Shandong Qilu Petrochemical Qi Tai petrochemical industries Co., Ltd using the weight average molecular weight that trade name acrylonitrile is sold as 3
×105Polyacrylonitrile polymer above is dissolved in dimethyl sulfoxide solvent, is obtained a kind of containing 95.7% poly- third by weight
The solution of alkene nitrile and 5.0% unsaturated carboxylic acid comonomer, allow described solution to be placed under pressure 3.4kPa and wherein contained with removing
Some monomers and the bubble of entrainment, reach spinning solution clarification, the degree of bubble-free, then use is had by Shanghai profit haze filter plant
The candle wick formula filter that limit company is sold with trade name RH-ZS candle filters is filtered, using the side described in specification
Method determines, and obtained spinning solution viscosity in temperature 60 C is 680 pools, solids content is by weight 16.8%；Then,
Described spinning solution is allowed by aperture to be 0.06mm, draw ratio is no more than the spray that the 1.5, hole count of spinneret is 2000
Filament plate carries out wet spinning, obtains a kind of as-spun fibre；
B, as-spun fibre solidification is handled with steam drafting
Allow the as-spun fibre obtained in step A by temperature 50 C, concentration by weight 45% dimethyl sulfoxide (DMSO) in pure water
In coagulating bath processing 2.8min, solidify the as-spun fibre, while it is -8% to keep drawing of fiber rate；Then solidification is allowed
As-spun fibre by godet by 36 DEG C of temperature, concentration by weight 45% dimethyl sulfoxide (DMSO) at coagulating bath in pure water
1.6min is managed, while it is 0% to keep drawing of fiber rate；Again by 26 DEG C of temperature, concentration by weight 8% dimethyl sulfoxide (DMSO) exist
Coagulating bath processing 0.5min in pure water, while it is 5% to keep drawing of fiber rate, then obtains a kind of coagulated fibre；Then,
Using by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. with the height of the trade name HTCT13 constant temperature coagulating basin equipment sold
Described coagulated fibre is pre-stretched 1.5 times by precision roller draft roller in the water-bath of 78 DEG C of temperature, is then 10 meters in length
The washing water washing of 56 DEG C of temperature in use removes residual solvent in rinsing bowl, and solvent residual amount is controlled by weight
0.02%, metal ion content is below 5ppm by weight.Finally it is placed in by company of Shanghai Pu Zhen bio tech ltd
To handle 0.6min in the aminosiloxane emulsion of trade name 70131-67-8 sale, obtain one kind and oil fiber；Then
Sold using by Beijing Zhong Fangjingye electromechanical equipments mechanical ＆ electronic equipment corporation, Ltd with trade name RGWTSK-1R7TRS1
Equipment, allow the described fiber that oils that densification 35s is dried at 170 DEG C of temperature by compacting by drying hot-rolling,
Then use and carried out by Xi'an Fu Ruida Science and Technology Ltd.s with the hot bellows that trade name FRD-O13 is sold at 104 DEG C of temperature
Hot wire-CVD is handled 14 seconds, and the degree of draft of hot wire-CVD processing is zero, obtains a kind of dry heat treatment fiber；
This dry heat treatment fiber reuses to be steamed by Yangzhou Heng get Rong device fabrications Co., Ltd with trade name HTHP
The product of vapour drafting system sale carries out the processing of steam HTHP high drafting in the case where saturation vapor pressure is 0.05MPa,
Draft ratio is 4 times, then uses and is done by Xi'an Fu Ruida Science and Technology Ltd.s with the trade name FRD-O13 equipment sold
It is dry, obtain polyacrylonitrile fibril fiber；
C, precursor is drawn into protofilament；
Using the hot-blast heater of self-control design processing, relevant design is as illustrated, the polyacrylonitrile for allowing step B to obtain is former
Silk fiber carries out stretch processing 4.6 minutes in hot-blast heater under conditions of 160 DEG C of temperature and air, and stretching ratio is
1.5 times, obtain a kind of stretching protofilament；
D, fiber preoxidation and carbonization；
Equipment using being sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-YYH13, allow what step C was obtained
Stretch protofilament and thermostabilization processing 60min is carried out at 240 DEG C of temperature, then use by the limited public affairs of Xi'an Fu Ruida science and technology
The low temperature carbonization furnace that department is sold with trade name FRD-LC13, pass through low temperature under conditions of 740 DEG C of ultrapure nitrogen atmosphere and temperature
Carbide furnace carries out processing 1.2min, reuses the high temperature sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-HC13
Carbide furnace, processing 0.8min is carried out by high temperature carbonization furnace under conditions of 1260 DEG C of ultrapure nitrogen atmosphere and temperature, such
To described carbon fiber.
The method described to specifications determines strong using final carbon fiber under the conditions of carbonization technique of the invention and corresponding
Spend for 3.55~3.97GPa, 271.70~284.11GPa of modulus.
Embodiment 6：High strength high modulus carbon fiber is produced using the inventive method
The implementation steps of the embodiment are as follows：
A, spinning solution preparation and wet spinning
Weight average molecular weight using trade name PAN-P1 sale will be produced as 3 × 10 by Xibei Chemical Inst5The above is gathered
Acrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain it is a kind of containing 95.4% polyacrylonitrile and 3.6% by weight not
The solution of saturated carboxylic acid comonomer, described solution is allowed to be placed under pressure 3.6kPa to remove the monomer wherein contained and entrainment
Bubble, reach spinning solution clarification, the degree of bubble-free, then use by Shanghai Run Lan filter plants Co., Ltd with trade name
The candle wick formula filter of RH-ZS candle filters sale is filtered, and is determined using the method described in specification, obtained spinning
Silk liquid viscosity in temperature 60 C is 1400 pools, solids content is by weight 18.0%；Then,
Described spinning solution is allowed by aperture to be 0.08mm, draw ratio is no more than the spray that the 1.5, hole count of spinneret is 2400
Filament plate carries out wet spinning, obtains a kind of as-spun fibre；
B, as-spun fibre solidification is handled with steam drafting
Allow the as-spun fibre obtained in step A by 52 DEG C of temperature, concentration by weight 40% dimethyl sulfoxide (DMSO) in pure water
In coagulating bath processing 1.8min, solidify the as-spun fibre, while it is -8% to keep drawing of fiber rate；Then solidification is allowed
As-spun fibre by godet by 38 DEG C of temperature, concentration by weight 40% dimethyl sulfoxide (DMSO) at coagulating bath in pure water
1.8min is managed, while it is 0% to keep drawing of fiber rate；Again by 28 DEG C of temperature, concentration by weight 10% dimethyl sulfoxide (DMSO)
Coagulating bath processing 0.8min in pure water, while it is 5% to keep drawing of fiber rate, then obtains a kind of coagulated fibre；Then,
Using by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. with the height of the trade name HTCT13 constant temperature coagulating basin equipment sold
Described coagulated fibre is pre-stretched 1.7 times by precision roller draft roller in the water-bath of 82 DEG C of temperature, is then 12 meters in length
The washing water washing of 50 DEG C of temperature in use removes residual solvent in rinsing bowl, solvent residual amount control by weight 0.008%,
Metal ion content is below 5ppm by weight.Finally it is placed in by company of Shanghai Pu Zhen bio tech ltd with trade name
0.6min is handled in the aminosiloxane emulsion of 70131-67-8 sale, one kind is obtained and oils fiber；Then
Sold using by Beijing Zhong Fangjingye electromechanical equipments mechanical ＆ electronic equipment corporation, Ltd with trade name RGWTSK-1R7TRS1
Equipment, allow the described fiber that oils that densification 55s is dried at 180 DEG C of temperature by compacting by drying hot-rolling,
Then use and carried out by Xi'an Fu Ruida Science and Technology Ltd.s with the hot bellows that trade name FRD-O13 is sold at 106 DEG C of temperature
Hot wire-CVD is handled 16 seconds, and the degree of draft of hot wire-CVD processing is zero, obtains a kind of dry heat treatment fiber；
This dry heat treatment fiber reuses to be steamed by Yangzhou Heng get Rong device fabrications Co., Ltd with trade name HTHP
The product of vapour drafting system sale carries out the processing of steam HTHP high drafting in the case where saturation vapor pressure is 0.01MPa,
Draft ratio is 5 times, then uses and is done by Xi'an Fu Ruida Science and Technology Ltd.s with the trade name FRD-O13 equipment sold
It is dry, obtain polyacrylonitrile fibril fiber；
C, precursor is drawn into protofilament；
Using the hot-blast heater of self-control design processing, relevant design is as illustrated, the polyacrylonitrile for allowing step B to obtain is former
Silk fiber carries out stretch processing 4.8 minutes in hot-blast heater under conditions of 158 DEG C of temperature and air, and stretching ratio is
1.6 times, obtain a kind of stretching protofilament；
D, fiber preoxidation and carbonization；
Equipment using being sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-YYH13, allow what step C was obtained
Stretch protofilament thermostabilization is carried out at 250 DEG C of temperature and handle 55 minutes, then use limited by Xi'an Fu Ruida science and technology
The low temperature carbonization furnace that company is sold with trade name FRD-LC13, by low under conditions of 780 DEG C of ultrapure nitrogen atmosphere and temperature
Warm carbide furnace carries out processing 1.4min, reuses the height sold by Xi'an Fu Ruida Science and Technology Ltd.s with trade name FRD-HC13
Warm carbide furnace, processing 0.9min is carried out by high temperature carbonization furnace under conditions of 1400 DEG C of ultrapure nitrogen atmosphere and temperature, so
Obtain described carbon fiber.
The method described to specifications determines strong using final carbon fiber under the conditions of carbonization technique of the invention and corresponding
Spend for 3.74~4.00GPa, 261.35~286.18GPa of modulus.
Claims (8)
- A kind of 1. method that high strength high modulus carbon fiber is produced using precursor stretching technique, it is characterised in that the step of this method It is as follows：A, spinning solution preparation and wet spinningIt is 3 × 10 by weight average molecular weight5Polyacrylonitrile polymer above is dissolved in dimethyl sulfoxide solvent, obtains a kind of solution, Described solution is allowed to be placed in remove the monomer wherein contained and the bubble of entrainment under 3.0~4.0kPa of pressure, then using candle Core type filter is filtered, obtain the viscosity in temperature 60 C be 500~1600 pools, solids content for by weight 16~ 20% spinning solution；Described spinning solution contains more than 95% polyacrylonitrile by weight and is total to 0.5~5.0% unsaturated carboxylic acid Polycondensation monomer；Then,Allow described spinning solution by aperture be 0.05~0.08mm, draw ratio no more than 1.5 spinneret carry out wet spinning, Obtain a kind of as-spun fibre；B, as-spun fibre solidification is handled with steam draftingAllowing the as-spun fibre obtained in step A, 35~45% dimethyl sulfoxide (DMSO)s exist by weight by 48~52 DEG C of temperature, concentration Coagulating bath in pure water handles 1.5~3.0min, solidifies the as-spun fibre, while it is -8% to keep drawing of fiber rate；Connect Allow solidification as-spun fibre by godet by 32~38 DEG C of temperature, concentration by weight 35~45% dimethyl sulfoxide (DMSO) Coagulating bath in pure water handles 1.0~2.0min, while it is 0% to keep drawing of fiber rate；Again by 22~28 DEG C of temperature, dense Degree by weight 5~10% coagulating bath of the dimethyl sulfoxide (DMSO) in pure water handle 0.5~1.0min, while keep drawing of fiber Rate is 5%, then obtains a kind of coagulated fibre；Then,Described coagulated fibre is pre-stretched 1.2~1.8 in the water-bath of 75~85 DEG C of temperature using hi-precision roller draw roll Times, then the washing water washing of 40~60 DEG C of temperature in use, is finally placed in aminosiloxane emulsion and handles, and obtains one kind and oils Fiber；ThenAllow the described fiber that oils that densification is dried at 160~180 DEG C of temperature, then by hot bellows in temperature Hot wire-CVD processing is carried out at 100~110 DEG C, obtains a kind of dry heat treatment fiber；This dry heat treatment fiber steams in saturation water again 0.5~-0.01MPa of atmospheric pressure is handled with carrying out steam HTHP high drafting under conditions of 1.2~2.5 times of draft ratio, Then it is dried to obtain polyacrylonitrile fibril fiber；C, precursor stretching protofilament；Allow polyacrylonitrile fibril fiber that step B obtains in hot-blast heater under conditions of 150~160 DEG C of temperature with air Stretch processing is carried out, obtains a kind of stretching protofilament；D, fiber preoxidation and carbonization；The stretching protofilament that step C is obtained is allowed to carry out thermostabilization processing at 200~300 DEG C of temperature, then in nitrogen gas Under atmosphere by temperature be 600~800 DEG C low temperature carbonization furnace handle, then under ultrapure nitrogen atmosphere by temperature be 1200~ 1400 DEG C of high temperature carbonization furnace processing, so obtains described carbon fiber.
- 2. production method according to claim 1, it is characterised in that in step, the hole count of the spinneret for 1000~ 3000.
- 3. according to the method for claim 1, it is characterised in that in stepb, the coagulated fibre of washing contains by weight Below 5ppm metal ion and 0.005~0.02% residual solvent.
- 4. according to the method for claim 1, it is characterised in that in stepb, described coagulated fibre is after washing in ammonia 0.5~1.0min is handled in radical siloxane emulsion.
- 5. according to the method for claim 1, it is characterised in that in stepb, at the compacting by drying of the fiber that oils It is 30~60s to manage the time, and hot wire-CVD processing time is 10~20 seconds.
- 6. according to the method for claim 1, it is characterised in that in stepb, the processing of steam HTHP high drafting Saturation vapor pressure is 0.5~-0.01MPa, and draft ratio is 1.2~2.5 times.
- 7. according to the method for claim 1, it is characterised in that in step D, described stretching protofilament thermostabilization Processing time is 50~60 minutes.
- 8. according to the method for claim 1, it is characterised in that in step D, described stretching precursor is at thermostabilization 0.5~1.5min is handled after reason in low temperature carbonization furnace；0.2~1.0min is handled in high temperature carbonization furnace.
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| CN109402791B (en) * | 2018-09-20 | 2021-02-05 | 北京化工大学 | High-strength high-modulus carbon fiber with regular surface cross-section structure and preparation method thereof |
| CN109440230B (en) * | 2018-11-09 | 2021-07-30 | 中国科学院山西煤炭化学研究所 | Preparation method of low-cost carbon fiber precursor fiber, pre-oxidized fiber or carbon fiber |
| CN109537106B (en) * | 2018-11-09 | 2021-05-18 | 中国科学院山西煤炭化学研究所 | Method for preparing precursor fiber, pre-oxidized fiber or carbon fiber of carbon fiber with special-shaped section by high-speed dry jet spinning |
| CN110129934A (en) * | 2019-05-21 | 2019-08-16 | 江西先材纳米纤维科技有限公司 | The preparation method and application of the continuous long yarns of electrospinning polyacrylonitrile nanofiber |
| CN112226829B (en) * | 2019-07-15 | 2022-04-05 | 中国石油化工股份有限公司 | Preparation method of high-strength polyacrylonitrile precursor |
| CN112226837B (en) * | 2019-07-15 | 2023-01-24 | 中国石油化工股份有限公司 | Polyacrylonitrile nascent fiber and preparation method thereof |
| CN112226851B (en) * | 2019-07-15 | 2023-01-24 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber |
| TWI832071B (en) * | 2021-07-19 | 2024-02-11 | 臺灣塑膠工業股份有限公司 | Manufacturing method for carbon fiber |
| CN113789607B (en) * | 2021-09-22 | 2023-07-07 | 辽宁兴汇碳材料科技有限公司 | Polyacrylonitrile-based fiber mat and preparation method and application thereof |
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