CN105200566A - Method for preparing high-modulus carbon fiber by adopting precursor drawing technology - Google Patents
Method for preparing high-modulus carbon fiber by adopting precursor drawing technology Download PDFInfo
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- CN105200566A CN105200566A CN201510687523.2A CN201510687523A CN105200566A CN 105200566 A CN105200566 A CN 105200566A CN 201510687523 A CN201510687523 A CN 201510687523A CN 105200566 A CN105200566 A CN 105200566A
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Abstract
The invention relates to a method for producing a high-modulus carbon fiber by adopting a precursor drawing technology. The method comprises the following steps: preparing a spinning solution, carrying out the wet-method spinning, solidifying a nascent fiber, drawing in steam, stretching a precursor to precursor fiber, pre-oxidizing the fiber, and carbonizing the fiber. By adopting the method, the defect of a micro structure in the fiber precursor preparation process can be effectively reduced, compared with the process which does not utilize the process, the orientation degree of the pre-oxidized fiber is further improved, and the mechanical performance of the carbonized fiber is remarkably improved; since the fiber is re-stretched at a temperature above a vitrification temperature, the fiber fineness is reduced, the specific surface area is increased in the high-temperature treatment process, and the thermal treatment efficiency is effectively improved; by virtue of the process, the fiber quality is obviously improved.
Description
[technical field]
The invention belongs to high-performance fiber processing technique field.More specifically, the present invention relates to a kind of method adopting precursor stretching technique to prepare high-strength high-modules carbon fibre.
[background technology]
High-strength and high-modulus amount carbon fiber is by polyacrylonitrile organic fiber through the obtained special fibre of carbonization treatment, and it has the excellent specific properties such as high specific strength, specific modulus, electric conductivity, thermal coefficient of expansion are low and anticorrosive.Utilize its flexibility, anisotropy feature through braiding, Chang Zuowei composite material reinforcement body material is widely used in the field such as military affairs, civilian industry.
Carbon fiber complicated process of preparation, operation is loaded down with trivial details, apparatus and process requires high, and the polyacrylonitrile fibre of high-quality is that preparation is high-strength, the prerequisite of high-modules carbon fibre, and the quality of its quality will directly have influence on final fiber quality.Polyacrylonitrile fibre adopts wet spinning and dry-wet spinning technology usually, through multistage drafting, then remove residual solvent with a large amount of washings, the operations such as process oils, dry heat sizing obtain protofilament, again through the process of 200 ~ 350 DEG C of fiber thermostabilizations, then pre-oxidized fibers is obtained final high-performance carbon fibre respectively by 600 ~ 900 DEG C of low-temperature carbonizations and 1200 ~ 1400 DEG C of high temperature cabonization process.In order to improve fiber hot property, reduce preoxidation time etc., usually adopt fibre modification, improve the methods such as heat treatment heating rate.Such as, under CN104313717A relates to high drafting, reduce fiber internal stress, increase fiber-wall-element model degree and then improve fiber heat endurance.CN101235568A and CN02247164 all relates to boron salt modification protofilament, increases fiber preoxidation effect, realizes improving a certain effect of fiber.
Above patent application needs to carry out larger change to existing equipment, and equipment processing is loaded down with trivial details, or introduces other inorganic elements while improving fiber heat endurance again, then will have a strong impact on the mechanical property of fiber in high temperature cabonization process, and performance does not increase counter subtracting.
Current, in the operation of high-temperature process polyacrylonitrile fibril fiber, focus mostly in the research of pre-oxidation gradient, preoxidation time, low/technique such as high temperature cabonization temperature and draft ratio, but often easily omit the method that physical extension protofilament improves fibre property.
The present inventor compensate for the heat treatment step of protofilament, on the basis of summing up prior art, by lot of experiments and analysis, completes the present invention.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of method adopting precursor stretching technique to produce high-strength high-modules carbon fibre.
[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 the method is as follows:
The preparation of A, spinning solution and wet spinning
Be 3 × 10 by weight average molecular weight
5above polyacrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain a kind of solution, described solution is allowed to be placed under pressure 3.0 ~ 4.0kPa to remove the monomer wherein contained and the bubble carried secretly, then use candle wick formula filter to filter, obtain the spinning solution that the viscosity when temperature 60 C is 500 ~ 1600 pools, solids content is by weight 16 ~ 20%; Then,
Allow described spinning solution by aperture be 0.05 ~ 0.08mm, the draw ratio spinnerets that is no more than 1.5 carries out wet spinning, obtains a kind of as-spun fibre;
B, as-spun fibre solidify and steam drafting process
Allow the as-spun fibre obtained in steps A by temperature 48 ~ 52 DEG C, the concentration coagulating bath process 1.5 ~ 3.0min of 35 ~ 45% dimethyl sulfoxide (DMSO)s in pure water by weight, described as-spun fibre is solidified, keep drawing of fiber rate to be-8% simultaneously; Then allow the as-spun fibre that solidifies by godet roller by temperature 32 ~ 38 DEG C, concentration by weight 35 ~ 45% the coagulating bath process 1.0 ~ 2.0min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 0% simultaneously; Again by temperature 22 ~ 28 DEG C, concentration by weight 5 ~ 10% the coagulating bath process 0.5 ~ 1.0min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 5%, so obtain a kind of coagulated fibre simultaneously; Then,
Use hi-precision roller drawing roller by the predraft 1.2 ~ 1.8 times in the water-bath of temperature 75 ~ 85 DEG C of described coagulated fibre, then the washings washing of serviceability temperature 40 ~ 60 DEG C, is finally placed in aminosiloxane emulsion and processes, and obtains one and to oil fiber; Then
Allow the described fiber that oils carry out compacting by drying process at temperature 160 ~ 180 DEG C, then at temperature 100 ~ 110 DEG C, carry out hot wire-CVD process by hot bellows, obtain a kind of dry heat treatment fiber; This dry heat treatment fiber carries out the process of steam High Temperature High Pressure high drafting again, then dry, obtains a kind of polyacrylonitrile fibril fiber;
C, precursor are drawn into protofilament;
The polyacrylonitrile fibril fiber allowing step B obtain carries out stretch processing in hot-blast heater at temperature 150 ~ 160 DEG C with the condition of air, obtains a kind of stretching protofilament;
D, fiber preoxidation and carbonization;
The stretching protofilament allowing step C obtain carries out thermostabilization process at temperature 200 ~ 300 DEG C, then processed by low temperature carbonization furnace under the condition of nitrogen atmosphere and temperature 600 ~ 800 DEG C, processed by high temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 1200 ~ 1400 DEG C again, obtain described carbon fiber like this.
A preferred embodiment of the invention, in step, described spinning solution contains more than 95% polyacrylonitrile and 0.5 ~ 5.0% unsaturated carboxylic acid comonomer by weight.
According to another kind of preferred embodiment of the present invention, in step, the hole count of described spinnerets is 1000 ~ 3000.
According to another kind of preferred embodiment of the present invention, in stepb, the coagulated fibre of washing contains metal ion and 0.005 ~ 0.02% residual solvent of below 5ppm by weight.
According to another kind of preferred embodiment of the present invention, in stepb, described coagulated fibre processes 0.5 ~ 1.0min after washing in aminosiloxane emulsion.
According to another kind of preferred embodiment of the present invention, in stepb, described in oil compacting by drying processing time of fiber be 30 ~ 60s, the hot wire-CVD processing time is 10 ~ 20 seconds.
According to another kind of preferred embodiment of the present invention, in stepb, the saturation vapor pressure of steam High Temperature High Pressure high drafting process is 0.5 ~-0.01MPa, and draft ratio is 1.2 ~ 2.5 times.
According to another kind of preferred embodiment of the present invention, in step C, in 4 ~ 6 minutes polyacrylonitrile fibril tensile fiber processing times, stretching ratio is 2 ~ 5 times.
According to another kind of preferred embodiment of the present invention, in step D, the described stretching protofilament thermostabilization processing time is 50 ~ 60 minutes.
According to another kind of preferred embodiment of the present invention, be in step D, described stretching precursor processes 0.5 ~ 1.5min after thermostabilization process in low temperature carbonization furnace; At high temperature carbonization furnace process 0.2 ~ 1.0min.
In more detail the present invention will be described below.
The present invention relates to a kind of precursor stretching technique and realize high-strength high-modules carbon fibre method.
Comparatively large for existing carbon fiber degraded performance, CV value, the present invention utilizes a kind of precursor to redraw technique, can effectively reduce fiber microscopic damage, improve final carbon fiber strength, modulus and production efficiency, realize the production of high-strength and high-modulus amount carbon fiber.
The inventive method can allow its fiber carry out orientation again more than the second vitrification point, and fibre crystallinity is improved, and can reduce fiber micropore and fiber number further.The inventive method can make fiber more effectively carry out thermostabilization process in pre-oxidation operation.This method is easily implemented, technique simple, only need set up the hot-blast stove of about 2 meters before pre-oxidation furnace, without the need to reequiping in a large number existing equipment or public work.The inventive method can make fibre number reduce, and speed improves, thus time shorten, energy consumption in whole carbon fiber production process are reduced, and is applicable to high-performance polyacrylonitrile-based carbon fiber suitability for industrialized production.
According to the present invention, allow spinning solution by wet method (or wet-dry change) spinning, enter multistage coagulating bath through godet roller and implement elementary drawing-off, after washing step, in fiber, dissolvent residual rate meets the requirements, through oil and compacting by drying heat treatment after, subsequently after high temperature and high pressure steam drawing-off, dry, obtained polyacrylonitrile fibril fiber.Under hot blast effect, again carry out tensile fiber, then through thermostabilization and low and high temperature carbonization treatment.Stretching protofilament effectively can reduce fibre number again, improves the degree of orientation, degree of crystallinity, improves fiber preoxidation and carbonization efficiency, reduces fiber microscopic damage; Effectively raise the mechanical property of polyacrylonitrile fibril fiber.
The step of the method is as follows:
The preparation of A, spinning solution and wet spinning
Be 3 × 10 by weight average molecular weight
5above polyacrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain a kind of solution, described solution is allowed to be placed under pressure 3.0 ~ 4.0kPa to remove the monomer wherein contained and the bubble carried secretly, then use candle wick formula filter to filter, obtain the spinning solution that the viscosity when temperature 60 C is 500 ~ 1600 pools, solids content is by weight 16 ~ 20%; Then,
Allow described spinning solution by aperture be 0.05 ~ 0.08mm, the draw ratio spinnerets that is no more than 1.5 carries out wet spinning, obtains a kind of as-spun fibre;
Polyacrylonitrile is obtained through Raolical polymerizable by monomers acrylonitrile, and it is mainly for the production of polyacrylonitrile fibre, and polyacrylonitrile fibre intensity is not high, and ABRASION RESISTANCE and fatigue resistance are also poor.
The weight average molecular weight that the present invention uses is 3 × 10
5above polyacrylonitrile polymer is product sold in the market, such as by Beijing Chemical Co., Ltd., the happy Industrial Co., Ltd. of Shanghai Jin Jin, Shenyang chemical reagent factory, Shandong Qilu Petrochemical Qi Tai petrochemical industry Co., Ltd with trade name acrylonitrile product sold.
In the polyacryl-nitrile spinning fluid that the present invention uses, the content of polyacrylonitrile is by weight more than 95%, and the content of unsaturated carboxylic acid comonomer is by weight 0.5 ~ 5.0%.
In the present invention, when the monomer removed in described solution and bubble, if described pressure is lower than 3.0kPa, then remove monomer and bubble DeGrain; If described pressure is higher than 4.0kPa, then its effect is not good yet; Therefore, described pressure is 3.0 ~ 4.0kPa is suitable, is preferably 3.2 ~ 3.8; More preferably 3.4 ~ 3.6kPa.
In this step, remove monomer and bubble and should reach that spinning solution is clarified, bubble-free degree, visual method therefore can be adopted to detect and remove monomer and bubble effect.
Remove monomer and bubble filters again.The candle wick formula filter that the present invention uses is a kind of Candlewick filter for spinning machine, and its filter screen is three-layer metal filter structure, comprising internal layer supporting network, middle level screen pack and outer protecting wire net.The candle wick formula filter that the present invention uses is product sold in the market, such as, think filter SL-ACF filter, Shanghai Jia Yu filter plant Co., Ltd with trade name ZL series candle formula hermetic filtering machine product sold with trade name RH-ZS candle filter, Shanghai Si Lv environmental protection equipment Co., Ltd with trade name by Shanghai Run Lan filter plant Co., Ltd.The candle wick formula filter operation that the present invention uses is carried out according to the mode illustrated in product description.Filter the filtrate (spinning solution) obtained and carry out viscosity and solid content measuring.
The viscosity of spinning solution uses the instrument sold with trade name D01002-022 Ubbelohde viscometer by Shanghai Di Bai experimental facilities Co., Ltd to measure under 25 DEG C ± 0.05 DEG C condition according to capillary tube method.
In the present invention, if described spinning solution is less than 500 pools in the viscosity of temperature 60 C, then easily there is " cutout " phenomenon in spinning solution; If the viscosity of spinning solution is greater than 1600 pools, then can spinning solution die swell effect increase; Therefore, the viscosity of spinning solution is 500 ~ 1600 pools is suitable, preferably 680 ~ 1400 pools, more preferably 800 ~ 1200 pools.
The solids content of described spinning solution is also inappropriate when exceeding this scope, and cause polymer viscosity to increase because solids content crosses senior general, easily produce physical crosslinking, in spinning process, pipeline pressure is excessive, causes equipment damage.
If when the viscosity of described spinning solution or solids content exceed its scope, then usually adopt the method for adding solvent DMSO dilution its viscosity and solids content to be regulated respectively and reach described scope.
The hole count of the spinnerets that the present invention uses is 1000 ~ 3000.Described spinnerets high rigidity plating tantalum material is made.
B, as-spun fibre solidify and steam drafting process
Allow the as-spun fibre obtained in steps A by temperature 48 ~ 52 DEG C, the concentration coagulating bath process 1.5 ~ 3.0min of 35 ~ 45% dimethyl sulfoxide (DMSO)s in pure water by weight, described as-spun fibre is solidified, keep drawing of fiber rate to be-8% simultaneously; Then allow the as-spun fibre that solidifies by godet roller by temperature 32 ~ 38 DEG C, concentration by weight 35 ~ 45% the coagulating bath process 1.0 ~ 2.0min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 0% simultaneously; Again by temperature 22 ~ 28 DEG C, concentration by weight 5 ~ 10% the coagulating bath process 0.5 ~ 1.0min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 5%, so obtain a kind of coagulated fibre simultaneously; Then,
In the present invention, described solidifying should be appreciated that it is " phase in version " that polymer occurs in spinning process, namely as-spun fibre by liquid state to solid-state transformation.In order to reach the object at slow, even, thin dawn, present invention employs three sections of solidification modes, first paragraph solidifies in temperature 48 ~ 52 DEG C with 35 ~ 45% dimethyl sulfoxide (DMSO) coagulating baths; Second segment solidifies in temperature 32 ~ 38 DEG C with 35 ~ 45% dimethyl sulfoxide (DMSO) coagulating baths; 3rd section is solidify in temperature 22 ~ 28 DEG C with 5 ~ 10% dimethyl sulfoxide (DMSO) coagulating baths.Certainly, also more coagulation step can be adopted to realize as-spun fibre according to actual conditions to solidify.
Then, use hi-precision roller drawing roller by the predraft 1.2 ~ 1.8 times in the water-bath of temperature 75 ~ 85 DEG C of described coagulated fibre, then wash with the washings of temperature 60 ~ 80 DEG C, be finally placed in aminosiloxane emulsion and process, obtain one and to oil fiber.
In the present invention, the object of predraft is to make fiber-wall-element model, the thin dawn, improves as-spun fibre mechanical property.
The hi-precision roller drawing roller that the present invention uses should be appreciated that it is a kind of roller draft roller by driven by servomotor multiaxis, such as, be with trade name hi-precision roller drawing roller product sold by Zhengzhou Heng Tian heavy industry company.
In this step, described coagulated fibre needs to make to wash with water after predraft, to remove residual solvent and metal ion.Described residual solvent comes from the solvent prepared and use when solvent that polyacrylonitrile polymer solution uses or as-spun fibre solidify, and they mainly remain in coagulating bath that fiber surface do not remove or the dimethyl sulfoxide (DMSO) that double diffusion goes out.Solvent residual amount should control by weight 0.005 ~ 0.02%.If residual quantity of solvent can cause many vacancies in fibers carbonization process to fall into more than 5ppm.
In the fiber washed with washings, metal ion content is below 5ppm by weight.Described metal ion comes from monomer, polymeric kettle and pipeline, and they are such as potassium, sodium, iron plasma.
Described solvent residual amount and metal ion content all adopt conventional method to measure and obtain.
The rinsing bowl used when washing with washings should have sufficient length, fully can wash removing residual solvent and metal ion, reaches its requirement.Rinsing bowl length normally 8 ~ 12 meters.If the length of rinsing bowl exceedes this scope, then can water washing effect not obvious or waste resource.
Washing the fibre is placed in aminosiloxane emulsion and carries out oiling treatment.The effect that washing the fibre processes in aminosiloxane emulsion is to make its fiber reach fully wetting, thus makes its fiber separately, does not assemble, is not adhered.
In stepb, described coagulated fibre processes 0.5 ~ 1.0min after washing in aminosiloxane emulsion.
Described aminosiloxane emulsion is product sold in the market, such as by company of Pu Zhen bio tech ltd, Shanghai with trade name 70131-67-8 product sold.
Allow the described fiber that oils carry out compacting by drying process at temperature 160 ~ 180 DEG C, then at temperature 100 ~ 110 DEG C, carry out hot wire-CVD process by hot bellows, obtain a kind of dry heat treatment fiber; This dry heat treatment fiber carries out the process of steam High Temperature High Pressure high drafting again, and then drying obtains polyacrylonitrile fibril fiber.
In the present invention, compacting by drying process should be appreciated that it is under high temperature (temperature 160 ~ 180 DEG C) with bright and clean hot-rolling effect, the micropore in described fiber reduced further or disappear.The compacting by drying processing time is 30 ~ 60s.Preferably 35 ~ 55s, more preferably 40 ~ 50s.
Compacting by drying treatment facility is product sold in the market, such as by Beijing Zhong Fangjingye electromechanical equipment mechanical & electronic equipment corporation, Ltd with trade name RGWTSK-1R7TRS1 product sold.
In the present invention, the effect of hot wire-CVD process is the internal stress that minimizing fiber causes due to high draft.Hot wire-CVD process processes 10 ~ 20 seconds at temperature 100 ~ 110 DEG C, obtains dry heat treatment fiber.Preferably, the temperature of hot wire-CVD process is 102 ~ 108 DEG C, and the time is 12 ~ 18 seconds.More preferably, the temperature of hot wire-CVD process is 104 ~ 106 DEG C, and the time is 14 ~ 16 seconds.The degree of draft of hot wire-CVD process is zero.
Hot wire-CVD treatment facility is product sold in the market, such as by Xi'an Fu Ruida Science and Technology Ltd. with trade name FRD-O13 product sold.
Described dry heat treatment fiber carries out the process of steam High Temperature High Pressure high drafting again.
The effect of steam High Temperature High Pressure high drafting process is to make fiber crystallization and orientation further, improves fibre strength.The saturation vapor pressure of steam High Temperature High Pressure high drafting process is 0.50 ~-0.01MPa, and draft ratio is 2 ~ 5 times.The equipment that the process of steam High Temperature High Pressure high drafting uses is product sold in the market, such as by Yangzhou Heng get Rong device fabrication Co., Ltd with trade name high temperature and high pressure steam drafting system product sold.
Fiber dry heat relaxation processes at temperature 102 ~ 108 DEG C with the condition of air through the process of steam High Temperature High Pressure high drafting obtains polyacrylonitrile fibril fiber.The equipment that dry heat relaxation processes uses is product sold in the market, such as by Xi'an Fu Ruida Science and Technology Ltd. with trade name FRD-O13 product sold.
C, precursor stretching protofilament;
The polyacrylonitrile fibril fiber allowing step B obtain carries out stretch processing 4 ~ 6 minutes in hot-blast heater at temperature 150 ~ 160 DEG C with the condition of air, and stretching ratio is 1 ~ 1.7 times, obtains a kind of stretching protofilament;
The object of this stretch processing step is that reducing the excessive drawing-off of precursor causes fiber internal stress, makes the further hot orientation of fiber.
In the present invention, the hot-blast heater of use is the homemade equipment of the present inventor, and its structural representation as shown in Figure 1.Cold humid air is after air heater 5, and its temperature rises to 80 ~ 120 DEG C, after isothermal holding hot air duct 4, is purged to wire passage 2 uniformly, thus reach technological requirement by hot-air mouth 3.
D, fiber preoxidation and carbonization;
The stretching protofilament allowing step C obtain carries out thermostabilization process at temperature 200 ~ 300 DEG C, then processed by low temperature carbonization furnace under the condition of nitrogen atmosphere and temperature 600 ~ 800 DEG C, processed by high temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 1200 ~ 1400 DEG C again, obtain described carbon fiber like this.
The effect of described thermostabilization process is to make protofilament be transformed into heat-resisting trapezium structure by linear structure, to such an extent as to can bear the heat treatment of higher temperature.
The described stretching protofilament thermostabilization processing time is 50 ~ 60 minutes.
The equipment that thermostabilization process uses is such as with trade name FRD-YYH13 product sold by Xi'an Fu Ruida Science and Technology Ltd..
The object that described stretching precursor processes in low temperature carbonization furnace is to improve heat-resisting trapezium structure further, and fiber can not damaged at a higher temperature in heat treatment; The object processed in high temperature carbonization furnace is the transformation of graphite Turbostratic, and fibre strength increases substantially.
Described stretching precursor processes 0.5 ~ 1.5min after thermostabilization process in low temperature carbonization furnace; At high temperature carbonization furnace process 0.2 ~ 1.0min.
After thermostabilization process, stretching protofilament is carrying out low temperature carbonization furnace process at temperature 600 ~ 800 DEG C with nitrogen atmosphere.In the present invention, nitrogen gas purity is the key of producing high-performance carbon fibre, and purity should be ultrapure rank, and oxygen content is less than 5ppm, and dew point is not higher than-72 DEG C.
The low temperature carbonization furnace that the present invention uses is such as with trade name FRD-LC13 product sold by Xi'an Fu Ruida Science and Technology Ltd..
The high temperature carbonization furnace that the present invention uses is such as with trade name FRD-HC13 product sold by Xi'an Fu Ruida Science and Technology Ltd..
According to GBT3362-2005 method of testing, use and under rate of extension is for 5cm/min condition, determine polyacrylonitrile fibre intensity prepared by the present invention for 3.45 ~ 4.42GPa by Instron company with the instrument that trade name 5966 type universal testing machine is sold, modulus 260.66 ~ 291.00GPa.
Carried out Mechanics Performance Testing to the carbon fiber produced according to the inventive method, its test result is listed in table 1.
Table 1: different precursor is final carbon fiber mechanical property under different stretch ratio
Note: * represents that the data unit in this hurdle is GPa.
The result of table 1 clearly illustrates that protofilament is through suitable predraft, and same pre-oxidation, carbonization technique can make fibre strength promote to some extent.
Universal or utilization rate in the market the highest be toray T300 grade carbon fiber, adopt GBT3362-2005 standard method to measure, its measurement result meets publish data, and namely intensity is 3.5GPa, and modulus is 230GPa.Meanwhile, adopt the mensuration that uses the same method, 4.42GPa can be reached, modulus 291GPa according to the intensity of the inventive method production carbon fiber is the highest.
As can be seen here, compared with prior art, the inventive method can make carbon fiber strength improve 1.26 times, and modulus increases by 26.5%.
[beneficial effect]
The invention has the beneficial effects as follows:
1, the present invention can reduce the fiber defect of microstructure in precursor preparation process more effectively, and does not apply compared with this process of fiber, and pre-oxidation fiber-wall-element model degree improves further, and carbonized fiber mechanical property significantly improves.
2, because fiber again stretches more than vitrification point, fibre number is reduced, in high-temperature process, specific area increases, and effectively improves heat treatment efficiency;
3, through present invention process process, significantly improve fiber quality, polyacrylonitrile-based carbon fibre intensity of the present invention improves 26%, and modulus increases by 26.5%.
[accompanying drawing explanation]
Fig. 1 is the hot-blast heater structural representation that the present invention uses.
In figure:
1-body of heater; 2-wire passage; 3-hot-air mouth; 4-hot air duct; 5-air heater; 6-airflow pipe.
[detailed description of the invention]
The present invention can be understood better by following embodiment.
Embodiment 1: adopt the inventive method to produce high strength high modulus carbon fiber
The implementation step of this embodiment is as follows:
The preparation of A, spinning solution and wet spinning
To be produced by Xibei Chemical Inst with the weight average molecular weight of trade name PAN-P1 sale as 3 × 10
5above polyacrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain a kind of solution containing 95.2% polyacrylonitrile and 1.0% unsaturated carboxylic acid comonomer by weight, allow described solution be placed under pressure 3.2kPa to remove the monomer wherein contained and the bubble carried secretly, reach spinning solution clarification, bubble-free degree.Then use by Shanghai Run Lan filter plant Co., Ltd with trade name RH-ZS candle filter sell candle wick formula filter filter, adopt in description the method described to measure, the spinning solution obtained viscosity when temperature 60 C is 800 pools, solids content is by weight 16.0%; Then,
Allow described spinning solution carry out wet spinning by the spinnerets that aperture is 0.05mm, draw ratio is no more than 1.5, the hole count of spinnerets is 1000, obtain a kind of as-spun fibre;
B, as-spun fibre solidify and steam drafting process
Allow the as-spun fibre obtained in steps A by temperature 48 DEG C, the concentration coagulating bath process 2.0min of 38% dimethyl sulfoxide (DMSO) in pure water by weight, described as-spun fibre is solidified, keep drawing of fiber rate to be-8% simultaneously; Then allow the as-spun fibre that solidifies by godet roller by temperature 34 DEG C, concentration by weight 38% the coagulating bath process 1.0min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 0% simultaneously; Again by temperature 26 DEG C, concentration by weight 5% the coagulating bath process 0.5min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 5%, so obtain a kind of coagulated fibre simultaneously; Then,
Use the hi-precision roller drawing roller of the constant temperature coagulating basin equipment sold with trade name HTCT13 by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. by the predraft 1.8 times in the water-bath of temperature 75 DEG C of described coagulated fibre, then residual solvent is removed in the washings washing being serviceability temperature 50 DEG C in 8 meters of rinsing bowls in length, solvent residual amount controls by weight 0.015%, and metal ion content is below 5ppm by weight.Finally be placed in the aminosiloxane emulsion sold with trade name 70131-67-8 by company of Pu Zhen bio tech ltd, Shanghai and process 0.6min, obtain one and to oil fiber; Then
Use the equipment sold with trade name RGWTSK-1R7TRS1 by Beijing Zhong Fangjingye electromechanical equipment mechanical & electronic equipment corporation, Ltd, the described fiber that oils is allowed at temperature 160 DEG C, to carry out compacting by drying process 40s by compacting by drying hot-rolling, then the hot bellows sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. is used to carry out hot wire-CVD process 12 seconds at temperature 102 DEG C, the degree of draft of hot wire-CVD process is zero, obtains a kind of dry heat treatment fiber;
This dry heat treatment fiber re-uses and under saturation vapor pressure 0.50MPa, carries out the process of steam High Temperature High Pressure high drafting by Yangzhou Heng get Rong device fabrication Co., Ltd with trade name high temperature and high pressure steam drafting system product sold, draft ratio is 3 times, then use the equipment sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. to carry out drying, obtain polyacrylonitrile fibril fiber;
C, precursor are drawn into protofilament;
Use the hot-blast heater of self-control design processing, relevant design as shown in the figure, the polyacrylonitrile fibril fiber allowing step B obtain carries out stretch processing 5.4 minutes in hot-blast heater at temperature 156 DEG C with the condition of air, and stretching ratio is 1.1 times, obtains a kind of stretching protofilament;
D, fiber preoxidation and carbonization;
Use the equipment sold with trade name FRD-YYH13 by Xi'an Fu Ruida Science and Technology Ltd., the stretching protofilament allowing step C obtain carries out thermostabilization process 58 minutes at temperature 260 DEG C, then the low temperature carbonization furnace sold with trade name FRD-LC13 by Xi'an Fu Ruida Science and Technology Ltd. is used, process 0.5min is carried out by low temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 700 DEG C, re-use the high temperature carbonization furnace sold with trade name FRD-HC13 by Xi'an Fu Ruida Science and Technology Ltd., process 0.2min is carried out by high temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 1360 DEG C, obtain described carbon fiber like this.
Under the method described to specifications determines and uses the present invention and corresponding carbonization technique condition, final carbon fiber strength is 3.45 ~ 3.92GPa, modulus 260.66 ~ 274.45GPa.
Embodiment 2: adopt the inventive method to produce high strength high modulus carbon fiber
The implementation step of this embodiment is as follows:
The preparation of A, spinning solution and wet spinning
By the weight average molecular weight of being sold with trade name acrylonitrile by Beijing Chemical Co., Ltd. for 3 × 10
5above polyacrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain a kind of solution containing 95.5% polyacrylonitrile and 0.5% unsaturated carboxylic acid comonomer by weight, described solution is allowed to be placed under pressure 3.8kPa to remove the monomer wherein contained and the bubble carried secretly, reach spinning solution clarification, bubble-free degree, then the candle wick formula filter thinking the sale of filter SL-ACF filter with trade name by Shanghai Si Lv environmental protection equipment Co., Ltd is used to filter, the method described in description is adopted to measure, the spinning solution obtained viscosity when temperature 60 C is 1200 pools, solids content is by weight 18.2%, then,
Allow described spinning solution carry out wet spinning by the spinnerets that aperture is 0.06mm, draw ratio is no more than 1.5, the hole count of spinnerets is 2800, obtain a kind of as-spun fibre;
B, as-spun fibre solidify and steam drafting process
Allow the as-spun fibre obtained in steps A by temperature 50 C, the concentration coagulating bath process 1.5min of 35% dimethyl sulfoxide (DMSO) in pure water by weight, described as-spun fibre is solidified, keep drawing of fiber rate to be-8% simultaneously; Then allow the as-spun fibre that solidifies by godet roller by temperature 36 DEG C, concentration by weight 35% the coagulating bath process 2.0min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 0% simultaneously; Again by temperature 28 DEG C, concentration by weight 8% the coagulating bath process 1.0min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 5%, so obtain a kind of coagulated fibre simultaneously; Then,
Use the hi-precision roller drawing roller of the constant temperature coagulating basin equipment sold with trade name HTCT13 by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. by the predraft 1.2 times in the water-bath of temperature 78 DEG C of described coagulated fibre, then length be in 10 meters of rinsing bowls serviceability temperature 40 DEG C washings washing remove residual solvent, solvent residual amount controls by weight 0.005%, and metal ion content is below 5ppm by weight.Finally be placed in the aminosiloxane emulsion sold with trade name 70131-67-8 by company of Pu Zhen bio tech ltd, Shanghai and process 0.6min, obtain one and to oil fiber; Then
Use the equipment sold with trade name RGWTSK-1R7TRS1 by Beijing Zhong Fangjingye electromechanical equipment mechanical & electronic equipment corporation, Ltd, the described fiber that oils is allowed at temperature 170 DEG C, to carry out compacting by drying process 50s by compacting by drying hot-rolling, then the hot bellows sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. is used to carry out hot wire-CVD process 18 seconds at temperature 108 DEG C, the degree of draft of hot wire-CVD process is zero, obtains a kind of dry heat treatment fiber;
This dry heat treatment fiber re-uses and under saturation vapor pressure 0.20MPa, carries out the process of steam High Temperature High Pressure high drafting by Yangzhou Heng get Rong device fabrication Co., Ltd with trade name high temperature and high pressure steam drafting system product sold, draft ratio is 4 times, then use the equipment sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. to carry out drying, obtain polyacrylonitrile fibril fiber;
C, precursor are drawn into protofilament;
Use the hot-blast heater of self-control design processing, relevant design as shown in the figure, the polyacrylonitrile fibril fiber allowing step B obtain carries out stretch processing 4.0 minutes in hot-blast heater at temperature 150 DEG C with the condition of air, and stretching ratio is 1.6 times, obtains a kind of stretching protofilament;
D, fiber preoxidation and carbonization;
Use the equipment sold with trade name FRD-YYH13 by Xi'an Fu Ruida Science and Technology Ltd., the stretching protofilament allowing step C obtain carries out thermostabilization process 50 minutes at temperature 200 DEG C, then the low temperature carbonization furnace sold with trade name FRD-LC13 by Xi'an Fu Ruida Science and Technology Ltd. is used, process 1.5min is carried out by low temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 650 DEG C, re-use the high temperature carbonization furnace sold with trade name FRD-HC13 by Xi'an Fu Ruida Science and Technology Ltd., process 0.5min is carried out by high temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 1320 DEG C, obtain described carbon fiber like this.
Under the method described to specifications determines and uses the present invention and corresponding carbonization technique condition, final carbon fiber strength is 3.52 ~ 3.97GPa, modulus 266.18 ~ 275.83GPa.
Embodiment 3: adopt the inventive method to produce high strength high modulus carbon fiber
The implementation step of this embodiment is as follows:
The preparation of A, spinning solution and wet spinning
By the weight average molecular weight of being sold with trade name acrylonitrile by the happy Industrial Co., Ltd. of Shanghai Jin Jin for 3 × 10
5above polyacrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain a kind of solution containing 95.8% polyacrylonitrile and 2.1% unsaturated carboxylic acid comonomer by weight, described solution is allowed to be placed under pressure 3.0kPa to remove the monomer wherein contained and the bubble carried secretly, reach spinning solution clarification, bubble-free degree, then the candle wick formula filter sold with trade name ZL series candle formula hermetic filtering machine by Shanghai Jia Yu filter plant Co., Ltd is used to filter, the method described in description is adopted to measure, the spinning solution obtained viscosity when temperature 60 C is 500 pools, solids content is by weight 20.0%, then,
Allow described spinning solution carry out wet spinning by the spinnerets that aperture is 0.08mm, draw ratio is no more than 1.5, the hole count of spinnerets is 3000, obtain a kind of as-spun fibre;
B, as-spun fibre solidify and steam drafting process
Allow the as-spun fibre obtained in steps A by temperature 52 DEG C, the concentration coagulating bath process 3.0min of 38% dimethyl sulfoxide (DMSO) in pure water by weight, described as-spun fibre is solidified, keep drawing of fiber rate to be-8% simultaneously; Then allow the as-spun fibre that solidifies by godet roller by temperature 32 DEG C, concentration by weight 38% the coagulating bath process 1.5min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 0% simultaneously; Again by temperature 22 DEG C, concentration by weight 10% the coagulating bath process 0.6min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 5%, so obtain a kind of coagulated fibre simultaneously; Then,
Use the hi-precision roller drawing roller of the constant temperature coagulating basin equipment sold with trade name HTCT13 by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. by the predraft 1.4 times in the water-bath of temperature 82 DEG C of described coagulated fibre, then residual solvent is removed in the washings washing being serviceability temperature 48 DEG C in 12 meters of rinsing bowls in length, solvent residual amount controls by weight 0.008%, and metal ion content is below 5ppm by weight.Finally be placed in the aminosiloxane emulsion sold with trade name 70131-67-8 by company of Pu Zhen bio tech ltd, Shanghai and process 0.6min, obtain one and to oil fiber; Then
Use the equipment sold with trade name RGWTSK-1R7TRS1 by Beijing Zhong Fangjingye electromechanical equipment mechanical & electronic equipment corporation, Ltd, the described fiber that oils is allowed at temperature 180 DEG C, to carry out compacting by drying process 30s by compacting by drying hot-rolling, then the hot bellows sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. is used to carry out hot wire-CVD process 10 seconds at temperature 100 DEG C, the degree of draft of hot wire-CVD process is zero, obtains a kind of dry heat treatment fiber;
This dry heat treatment fiber re-uses and under saturation vapor pressure 0.10MPa, carries out the process of steam High Temperature High Pressure high drafting by Yangzhou Heng get Rong device fabrication Co., Ltd with trade name high temperature and high pressure steam drafting system product sold, draft ratio is 2 times, then use the equipment sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. to carry out drying, obtain polyacrylonitrile fibril fiber;
C, precursor are drawn into protofilament;
Use the hot-blast heater of self-control design processing, relevant design as shown in the figure, the polyacrylonitrile fibril fiber allowing step B obtain carries out stretch processing 5.0 minutes in hot-blast heater at temperature 152 DEG C with the condition of air, and stretching ratio is 1.4 times, obtains a kind of stretching protofilament;
D, fiber preoxidation and carbonization;
Use the equipment sold with trade name FRD-YYH13 by Xi'an Fu Ruida Science and Technology Ltd., the stretching protofilament allowing step C obtain carries out thermostabilization process 52 minutes at temperature 250 DEG C, then the low temperature carbonization furnace sold with trade name FRD-LC13 by Xi'an Fu Ruida Science and Technology Ltd. is used, process 0.8min is carried out by low temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 600 DEG C, re-use the high temperature carbonization furnace sold with trade name FRD-HC13 by Xi'an Fu Ruida Science and Technology Ltd., process 1.0min is carried out by high temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 1200 DEG C, obtain described carbon fiber like this.
Under the method described to specifications determines and uses the present invention and corresponding carbonization technique condition, final carbon fiber strength is 3.71 ~ 3.91GPa, modulus 272.39 ~ 291.00GPa.
Embodiment 4: adopt the inventive method to produce high strength high modulus carbon fiber
The implementation step of this embodiment is as follows:
The preparation of A, spinning solution and wet spinning
By the weight average molecular weight of being sold with trade name acrylonitrile by Shenyang chemical reagent factory for 3 × 10
5above polyacrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain a kind of solution containing 95.1% polyacrylonitrile and 4.5% unsaturated carboxylic acid comonomer by weight, described solution is allowed to be placed under pressure 4.0kPa to remove the monomer wherein contained and the bubble carried secretly, reach spinning solution clarification, bubble-free degree, then the candle wick formula filter sold with trade name ZL series candle formula hermetic filtering machine by Shanghai Jia Yu filter plant Co., Ltd is used to filter, the method described in description is adopted to measure, the spinning solution obtained viscosity when temperature 60 C is 1600 pools, solids content is by weight 17.4%, then,
Allow described spinning solution carry out wet spinning by the spinnerets that aperture is 0.05mm, draw ratio is no more than 1.5, the hole count of spinnerets is 1600, obtain a kind of as-spun fibre;
B, as-spun fibre solidify and steam drafting process
Allow the as-spun fibre obtained in steps A by temperature 48 DEG C, the concentration coagulating bath process 2.4min of 40% dimethyl sulfoxide (DMSO) in pure water by weight, described as-spun fibre is solidified, keep drawing of fiber rate to be-8% simultaneously; Then allow the as-spun fibre that solidifies by godet roller by temperature 34 DEG C, concentration by weight 40% the coagulating bath process 1.4min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 0% simultaneously; Again by temperature 24 DEG C, concentration by weight 5% the coagulating bath process 0.8min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 5%, so obtain a kind of coagulated fibre simultaneously; Then,
Use the hi-precision roller drawing roller of the constant temperature coagulating basin equipment sold with trade name HTCT13 by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. by the predraft 1.6 times in the water-bath of temperature 85 DEG C of described coagulated fibre, then residual solvent is removed in the washings washing being serviceability temperature 60 DEG C in 8 meters of rinsing bowls in length, solvent residual amount controls by weight 0.015%, and metal ion content is below 5ppm by weight.Finally be placed in the aminosiloxane emulsion sold with trade name 70131-67-8 by company of Pu Zhen bio tech ltd, Shanghai and process 0.6min, obtain one and to oil fiber; Then
Use the equipment sold with trade name RGWTSK-1R7TRS1 by Beijing Zhong Fangjingye electromechanical equipment mechanical & electronic equipment corporation, Ltd, the described fiber that oils is allowed at temperature 160 DEG C, to carry out compacting by drying process 60s by compacting by drying hot-rolling, then the hot bellows sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. is used to carry out hot wire-CVD process 20 seconds at temperature 110 DEG C, the degree of draft of hot wire-CVD process is zero, obtains a kind of dry heat treatment fiber;
This dry heat treatment fiber re-uses and under saturation vapor pressure is 0.40MPa, carries out the process of steam High Temperature High Pressure high drafting by Yangzhou Heng get Rong device fabrication Co., Ltd with trade name high temperature and high pressure steam drafting system product sold, draft ratio is 3 times, then use the equipment sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. to carry out drying, obtain polyacrylonitrile fibril fiber;
C, precursor are drawn into protofilament;
Use the hot-blast heater of self-control design processing, relevant design as shown in the figure, the polyacrylonitrile fibril fiber allowing step B obtain carries out stretch processing 6.0 minutes in hot-blast heater at temperature 156 DEG C with the condition of air, and stretching ratio is 1.7 times, obtains a kind of stretching protofilament;
D, fiber preoxidation and carbonization;
Use the equipment sold with trade name FRD-YYH13 by Xi'an Fu Ruida Science and Technology Ltd., the stretching protofilament allowing step C obtain carries out thermostabilization process 54min at temperature 300 DEG C, then the low temperature carbonization furnace sold with trade name FRD-LC13 by Xi'an Fu Ruida Science and Technology Ltd. is used, process 1.0min is carried out by low temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 800 DEG C, re-use the high temperature carbonization furnace sold with trade name FRD-HC13 by Xi'an Fu Ruida Science and Technology Ltd., process 0.6min is carried out by high temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 1300 DEG C, obtain described carbon fiber like this.
Under the method described to specifications determines and uses the present invention and corresponding carbonization technique condition, final carbon fiber strength is 3.93 ~ 4.42GPa, modulus 270.32 ~ 287.56GPa.
Embodiment 5: adopt the inventive method to produce high strength high modulus carbon fiber
The implementation step of this embodiment is as follows:
The preparation of A, spinning solution and wet spinning
By the weight average molecular weight of being sold with trade name acrylonitrile by Shandong Qilu Petrochemical Qi Tai petrochemical industry Co., Ltd for 3 × 10
5above polyacrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain a kind of solution containing 95.7% polyacrylonitrile and 5.0% unsaturated carboxylic acid comonomer by weight, described solution is allowed to be placed under pressure 3.4kPa to remove the monomer wherein contained and the bubble carried secretly, reach spinning solution clarification, bubble-free degree, then the candle wick formula filter sold with trade name RH-ZS candle filter by Shanghai Run Lan filter plant Co., Ltd is used to filter, the method described in description is adopted to measure, the spinning solution obtained viscosity when temperature 60 C is 680 pools, solids content is by weight 16.8%, then,
Allow described spinning solution carry out wet spinning by the spinnerets that aperture is 0.06mm, draw ratio is no more than 1.5, the hole count of spinnerets is 2000, obtain a kind of as-spun fibre;
B, as-spun fibre solidify and steam drafting process
Allow the as-spun fibre obtained in steps A by temperature 50 C, the concentration coagulating bath process 2.8min of 45% dimethyl sulfoxide (DMSO) in pure water by weight, described as-spun fibre is solidified, keep drawing of fiber rate to be-8% simultaneously; Then allow the as-spun fibre that solidifies by godet roller by temperature 36 DEG C, concentration by weight 45% the coagulating bath process 1.6min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 0% simultaneously; Again by temperature 26 DEG C, concentration by weight 8% the coagulating bath process 0.5min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 5%, so obtain a kind of coagulated fibre simultaneously; Then,
Use the hi-precision roller drawing roller of the constant temperature coagulating basin equipment sold with trade name HTCT13 by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. by the predraft 1.5 times in the water-bath of temperature 78 DEG C of described coagulated fibre, then length be in 10 meters of rinsing bowls serviceability temperature 56 DEG C washings washing remove residual solvent, solvent residual amount controls by weight 0.02%, and metal ion content is below 5ppm by weight.Finally be placed in the aminosiloxane emulsion sold with trade name 70131-67-8 by company of Pu Zhen bio tech ltd, Shanghai and process 0.6min, obtain one and to oil fiber; Then
Use the equipment sold with trade name RGWTSK-1R7TRS1 by Beijing Zhong Fangjingye electromechanical equipment mechanical & electronic equipment corporation, Ltd, the described fiber that oils is allowed at temperature 170 DEG C, to carry out compacting by drying process 35s by compacting by drying hot-rolling, then the hot bellows sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. is used to carry out hot wire-CVD process 14 seconds at temperature 104 DEG C, the degree of draft of hot wire-CVD process is zero, obtains a kind of dry heat treatment fiber;
This dry heat treatment fiber re-uses and under saturation vapor pressure is 0.05MPa, carries out the process of steam High Temperature High Pressure high drafting by Yangzhou Heng get Rong device fabrication Co., Ltd with trade name high temperature and high pressure steam drafting system product sold, draft ratio is 4 times, then use the equipment sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. to carry out drying, obtain polyacrylonitrile fibril fiber;
C, precursor are drawn into protofilament;
Use the hot-blast heater of self-control design processing, relevant design as shown in the figure, the polyacrylonitrile fibril fiber allowing step B obtain carries out stretch processing 4.6 minutes in hot-blast heater at temperature 160 DEG C with the condition of air, and stretching ratio is 1.5 times, obtains a kind of stretching protofilament;
D, fiber preoxidation and carbonization;
Use the equipment sold with trade name FRD-YYH13 by Xi'an Fu Ruida Science and Technology Ltd., the stretching protofilament allowing step C obtain carries out thermostabilization process 60min at temperature 240 DEG C, then the low temperature carbonization furnace sold with trade name FRD-LC13 by Xi'an Fu Ruida Science and Technology Ltd. is used, process 1.2min is carried out by low temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 740 DEG C, re-use the high temperature carbonization furnace sold with trade name FRD-HC13 by Xi'an Fu Ruida Science and Technology Ltd., process 0.8min is carried out by high temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 1260 DEG C, obtain described carbon fiber like this.
Under the method described to specifications determines and uses the present invention and corresponding carbonization technique condition, final carbon fiber strength is 3.55 ~ 3.97GPa, modulus 271.70 ~ 284.11GPa.
Embodiment 6: adopt the inventive method to produce high strength high modulus carbon fiber
The implementation step of this embodiment is as follows:
The preparation of A, spinning solution and wet spinning
To be produced by Xibei Chemical Inst with the weight average molecular weight of trade name PAN-P1 sale as 3 × 10
5above polyacrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain a kind of solution containing 95.4% polyacrylonitrile and 3.6% unsaturated carboxylic acid comonomer by weight, described solution is allowed to be placed under pressure 3.6kPa to remove the monomer wherein contained and the bubble carried secretly, reach spinning solution clarification, bubble-free degree, then the candle wick formula filter sold with trade name RH-ZS candle filter by Shanghai Run Lan filter plant Co., Ltd is used to filter, the method described in description is adopted to measure, the spinning solution obtained viscosity when temperature 60 C is 1400 pools, solids content is by weight 18.0%, then,
Allow described spinning solution carry out wet spinning by the spinnerets that aperture is 0.08mm, draw ratio is no more than 1.5, the hole count of spinnerets is 2400, obtain a kind of as-spun fibre;
B, as-spun fibre solidify and steam drafting process
Allow the as-spun fibre obtained in steps A by temperature 52 DEG C, the concentration coagulating bath process 1.8min of 40% dimethyl sulfoxide (DMSO) in pure water by weight, described as-spun fibre is solidified, keep drawing of fiber rate to be-8% simultaneously; Then allow the as-spun fibre that solidifies by godet roller by temperature 38 DEG C, concentration by weight 40% the coagulating bath process 1.8min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 0% simultaneously; Again by temperature 28 DEG C, concentration by weight 10% the coagulating bath process 0.8min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 5%, so obtain a kind of coagulated fibre simultaneously; Then,
Use the hi-precision roller drawing roller of the constant temperature coagulating basin equipment sold with trade name HTCT13 by Zhengzhou Hi-Tech. Heavy Industry Co., Ltd. by the predraft 1.7 times in the water-bath of temperature 82 DEG C of described coagulated fibre, then residual solvent is removed in the washings washing being serviceability temperature 50 DEG C in 12 meters of rinsing bowls in length, solvent residual amount controls by weight 0.008%, and metal ion content is below 5ppm by weight.Finally be placed in the aminosiloxane emulsion sold with trade name 70131-67-8 by company of Pu Zhen bio tech ltd, Shanghai and process 0.6min, obtain one and to oil fiber; Then
Use the equipment sold with trade name RGWTSK-1R7TRS1 by Beijing Zhong Fangjingye electromechanical equipment mechanical & electronic equipment corporation, Ltd, the described fiber that oils is allowed at temperature 180 DEG C, to carry out compacting by drying process 55s by compacting by drying hot-rolling, then the hot bellows sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. is used to carry out hot wire-CVD process 16 seconds at temperature 106 DEG C, the degree of draft of hot wire-CVD process is zero, obtains a kind of dry heat treatment fiber;
This dry heat treatment fiber re-uses and under saturation vapor pressure is 0.01MPa, carries out the process of steam High Temperature High Pressure high drafting by Yangzhou Heng get Rong device fabrication Co., Ltd with trade name high temperature and high pressure steam drafting system product sold, draft ratio is 5 times, then use the equipment sold with trade name FRD-O13 by Xi'an Fu Ruida Science and Technology Ltd. to carry out drying, obtain polyacrylonitrile fibril fiber;
C, precursor are drawn into protofilament;
Use the hot-blast heater of self-control design processing, relevant design as shown in the figure, the polyacrylonitrile fibril fiber allowing step B obtain carries out stretch processing 4.8 minutes in hot-blast heater at temperature 158 DEG C with the condition of air, and stretching ratio is 1.6 times, obtains a kind of stretching protofilament;
D, fiber preoxidation and carbonization;
Use the equipment sold with trade name FRD-YYH13 by Xi'an Fu Ruida Science and Technology Ltd., the stretching protofilament allowing step C obtain carries out thermostabilization process 55 minutes at temperature 250 DEG C, then the low temperature carbonization furnace sold with trade name FRD-LC13 by Xi'an Fu Ruida Science and Technology Ltd. is used, process 1.4min is carried out by low temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 780 DEG C, re-use the high temperature carbonization furnace sold with trade name FRD-HC13 by Xi'an Fu Ruida Science and Technology Ltd., process 0.9min is carried out by high temperature carbonization furnace under the condition of ultrapure nitrogen atmosphere and temperature 1400 DEG C, obtain described carbon fiber like this.
Under the method described to specifications determines and uses the present invention and corresponding carbonization technique condition, final carbon fiber strength is 3.74 ~ 4.00GPa, modulus 261.35 ~ 286.18GPa.
Claims (10)
1. adopt precursor stretching technique to produce a method for high strength high modulus carbon fiber, it is characterized in that the step of the method is as follows:
The preparation of A, spinning solution and wet spinning
Be 3 × 10 by weight average molecular weight
5above polyacrylonitrile polymer is dissolved in dimethyl sulfoxide solvent, obtain a kind of solution, described solution is allowed to be placed under pressure 3.0 ~ 4.0kPa to remove the monomer wherein contained and the bubble carried secretly, then use candle wick formula filter to filter, obtain the spinning solution that the viscosity when temperature 60 C is 500 ~ 1600 pools, solids content is by weight 16 ~ 20%; Then,
Allow described spinning solution by aperture be 0.05 ~ 0.08mm, the draw ratio spinnerets that is no more than 1.5 carries out wet spinning, obtains a kind of as-spun fibre;
B, as-spun fibre solidify and steam drafting process
Allow the as-spun fibre obtained in steps A by temperature 48 ~ 52 DEG C, the concentration coagulating bath process 1.5 ~ 3.0min of 35 ~ 45% dimethyl sulfoxide (DMSO)s in pure water by weight, described as-spun fibre is solidified, keep drawing of fiber rate to be-8% simultaneously; Then allow the as-spun fibre that solidifies by godet roller by temperature 32 ~ 38 DEG C, concentration by weight 35 ~ 45% the coagulating bath process 1.0 ~ 2.0min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 0% simultaneously; Again by temperature 22 ~ 28 DEG C, concentration by weight 5 ~ 10% the coagulating bath process 0.5 ~ 1.0min of dimethyl sulfoxide (DMSO) in pure water, keep drawing of fiber rate to be 5%, so obtain a kind of coagulated fibre simultaneously; Then,
Use hi-precision roller drawing roller by the predraft 1.2 ~ 1.8 times in the water-bath of temperature 75 ~ 85 DEG C of described coagulated fibre, then the washings washing of serviceability temperature 40 ~ 60 DEG C, is finally placed in aminosiloxane emulsion and processes, and obtains one and to oil fiber; Then
Allow the described fiber that oils carry out compacting by drying process at temperature 160 ~ 180 DEG C, then at temperature 100 ~ 110 DEG C, carry out hot wire-CVD process by hot bellows, obtain a kind of dry heat treatment fiber; This dry heat treatment fiber carries out the process of steam High Temperature High Pressure high drafting again, and then drying obtains polyacrylonitrile fibril fiber;
C, precursor stretching protofilament;
The polyacrylonitrile fibril fiber allowing step B obtain carries out stretch processing in hot-blast heater at temperature 150 ~ 160 DEG C with the condition of air, obtains a kind of stretching protofilament;
D, fiber preoxidation and carbonization;
The stretching protofilament allowing step C obtain carries out thermostabilization process at temperature 200 ~ 300 DEG C, then in a nitrogen atmosphere by low temperature carbonization furnace process that temperature is 600 ~ 800 DEG C, again under ultrapure nitrogen atmosphere by the high temperature carbonization furnace process that temperature is 1200 ~ 1400 DEG C, obtain described carbon fiber like this.
2. production method according to claim 1, is characterized in that in step, and described spinning solution contains more than 95% polyacrylonitrile and 0.5 ~ 5.0% unsaturated carboxylic acid comonomer by weight.
3. production method according to claim 1, it is characterized in that in step, the hole count of described spinnerets is 1000 ~ 3000.
4. method according to claim 1, is characterized in that in stepb, and the coagulated fibre of washing contains metal ion and 0.005 ~ 0.02% residual solvent of below 5ppm by weight.
5. method according to claim 1, is characterized in that in stepb, and described coagulated fibre processes 0.5 ~ 1.0min after washing in aminosiloxane emulsion.
6. method according to claim 1, is characterized in that in stepb, described in oil compacting by drying processing time of fiber be 30 ~ 60s, the hot wire-CVD processing time is 10 ~ 20 seconds.
7. method according to claim 1, is characterized in that in stepb, and the saturation vapor pressure of steam High Temperature High Pressure high drafting process is 0.5 ~-0.01MPa, and draft ratio is 1.2 ~ 2.5 times.
8. method according to claim 1, is characterized in that in step C, 4 ~ 6 minutes polyacrylonitrile fibril tensile fiber processing times, and stretching ratio is 2 ~ 5 times.
9. method according to claim 1, is characterized in that in step D, and the described stretching protofilament thermostabilization processing time is 50 ~ 60.
10. method according to claim 1, is characterized in that in step D, and described stretching precursor processes 0.5 ~ 1.5min after thermostabilization process in low temperature carbonization furnace; At high temperature carbonization furnace process 0.2 ~ 1.0min.
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| CN109402791A (en) * | 2018-09-20 | 2019-03-01 | 北京化工大学 | High-strength high-modules carbon fibre and preparation method thereof with regular table cross section structure |
| CN109440230A (en) * | 2018-11-09 | 2019-03-08 | 中国科学院山西煤炭化学研究所 | The preparation method of inexpensive carbon fiber precursor fiber, pre-oxidized fibers or carbon fiber |
| CN109537106A (en) * | 2018-11-09 | 2019-03-29 | 中国科学院山西煤炭化学研究所 | The method that high-speed dry spray spinning prepares Irregular Section Carbon Fiber precursor fibre, pre-oxidized fibers or carbon fiber |
| 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 |
| CN112226837A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Polyacrylonitrile nascent fiber and preparation method thereof |
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| CN112226851A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber |
| CN113789607A (en) * | 2021-09-22 | 2021-12-14 | 辽宁兴汇碳材料科技有限公司 | Polyacrylonitrile-based fibrofelt and preparation method and application thereof |
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| CN114108136A (en) * | 2021-07-19 | 2022-03-01 | 台湾塑胶工业股份有限公司 | Method for producing carbon fiber |
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