CN106192362A - A kind of preparation method of sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber - Google Patents
A kind of preparation method of sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber Download PDFInfo
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- CN106192362A CN106192362A CN201610568576.7A CN201610568576A CN106192362A CN 106192362 A CN106192362 A CN 106192362A CN 201610568576 A CN201610568576 A CN 201610568576A CN 106192362 A CN106192362 A CN 106192362A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/008—Treatment with radioactive elements or with neutrons, alpha, beta or gamma rays
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
- D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Abstract
The invention discloses the preparation method of a kind of sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber, belong to fibre technology field.The present invention is with polyacrylonitrile as raw material, mix to obtain transparent and homogeneous spinning liquid with organic solvent after pretreatment, carried out being vacuum dried, deaeration, spinning, solidification, lyophilizing obtain polyacrylonitrile fibril, then precursor modification is obtained modified polyacrylonitrile precursor, finally by the stretching of modification precursor, pre-oxidation, sulfuric acid treatment, wash, be dried to obtain sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber, solve conventional polypropylene nitrile wearability and the defect such as fatigue resistance is poor, enhance the toughness of fiber after acidified modified, there is preferably application prospect.
Description
Technical field
The invention discloses the preparation method of a kind of sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber, belong to fiber
Technical field.
Background technology
High intensity, Large strain carbon fiber are important feature and the functional materials of Aeronautics and Astronautics industry in modern age.Carbon fiber has
High intensity, high-modulus, low-density, the advantage such as heat-resist, be preferable composite material reinforcement body.Polyacrylonitrile fibre is as
Important presoma, just need to can obtain high-performance carbon fibre through non-fusible, carbonization treatment.Carbon fiber is to be passed through by organic fiber
The phosphorus content that a series of heat treatments are transformed fragile material more than 90%, is that the one risen the sixties in last century is novel
Material with carbon element, is that a kind of preferably functional material and structural material are military and each in civilian industry to sports equipment and leisure goods etc.
Individual field obtains and is widely applied.The precursor preparing high-performance carbon fibre mainly has polyacrylonitrile fibre, viscose fiber and Colophonium
Base fiber three major types.Comparatively speaking, owing to PAN fiber has the highest molecularly oriented, higher fusing point and higher carbon
Fiber yield, and when low temperature carries out heat treatment to PAN fiber, can be formed a kind of that there is Heat stability is good, highly take
To the pre-oxidized fibers of molecular structure.
Pre-oxidation is the critical stage that polypropylene fine (PAN) fiber is changed into high-performance carbon fibre, along with highly exothermic and
Complicated chemically and physically transition process, easily produces and pre-oxidizes the uneven skin-core structure caused, thus leverage carbon
The performance of fiber.Traditional pre-oxidation process is usually taken the mode being slowly heated to suppress the concentration of heat to discharge, substantial amounts of
Time and the consumption of energy so that the cost of carbon fiber remains high, greatly inhibit it to wait extensively answering of field civilian
With.Traditional curing process generally use the mode being slowly heated to suppress the concentration of heat to discharge, consume the plenty of time and
Energy consumption, carbon fiber production cost remains high, it is suppressed that it is in the application of civil area.Wear-resisting, heat-resisting quantity and fatigue resistance
The existence of the defect such as poor, causes the modification being correlated with polyacrylonitrile fibril, becomes problem demanding prompt solution.
Summary of the invention
The technical problem that present invention mainly solves: for current conventional polypropylene nitrile carbon fiber wear-resisting, heat-resisting quantity and
Fatigue resistance is poor, causes carbon fiber to consume the defect of substantial amounts of energy resources in process of production, it is provided that at a kind of sulphuric acid
The preparation method of reason radiation modification pre-oxidized polyacrylonitrile fiber.The present invention is with polyacrylonitrile as raw material, with organic after pretreatment
Solvent mixes to obtain transparent and homogeneous spinning liquid, is carried out being vacuum dried, deaeration, spinning, solidification, lyophilizing obtain polyacrylonitrile fibril,
Then precursor modification is obtained modified polyacrylonitrile precursor, finally by the stretching of modification precursor, pre-oxidation, sulfuric acid treatment, washing,
It is dried and to obtain sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber, solve conventional polypropylene nitrile wearability and fatigue resistance relatively
The defects such as difference, acidified modified after enhance the toughness of fiber, there is preferably application prospect.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
(1) weighing 50 ~ 80g molecular weight is 50000 ~ 90000 polyacrylonitrile powder, adds in air dry oven, at 80 ~ 85 DEG C
It is dried to constant weight, the polyacrylonitrile powder being fully dried is added in 80 ~ 100mL dimethyl sulfoxide, is placed in constant water bath box
In, bath temperature is heated to 80 ~ 90 DEG C with 2 DEG C/min from room temperature, with the continuously stirred 4 ~ 5h of 80 ~ 100r/min, obtains transparent and homogeneous
Spinning liquid；
(2) above-mentioned transparent and homogeneous spinning liquid is placed in 80 ~ 85 DEG C of vacuum drying ovens, under 50 ~ 100Pa vacuum, at deaeration
Reason 8 ~ 10h, then spinning liquid addition is preheated in 80 ~ 85 DEG C of spinning-drawing machines, through spinning mouth extrusion filamentation, spinning speed is 2.5m/
Min, it is solidification 10 ~ 15min in 50% dimethyl sulphoxide aqueous solution that spinning is placed in 10 ~ 12 DEG C of mass fractions, takes out, spend from
Sub-water washs 3 ~ 5 times, then is immersed in 10 ~ 15min in boiling water, takes out, is placed in lyophilizing in freeze drying box, obtains polyacrylonitrile former
Silk；
(3) above-mentioned polyacrylonitrile fibril being immersed in 150 ~ 200mL mass fraction is 20 ~ 30min in 30% ethylenediamine solution, takes
Go out precursor, and to be washed with deionized precursor to cleaning mixture be neutrality, natural air drying, add in irradiation tube, be evacuated in pipe
Vacuum is 0.01 ~ 0.05Pa, seals irradiation tube, is 180 ~ 200kGy with gamma-rays to precursor vacuum irradiation to close rate,
Modified polyacrylonitrile precursor；
(4) above-mentioned modified polyacrylonitrile precursor is placed in drawing by high temperature machine fixes with fixture, at 140 ~ 150 DEG C, with 25mm/
Min Drawing rate carries out constant temperature extension, proceeds to fix with fixture in air dry oven, with 5 DEG C/min from room temperature liter after extending 8 times
Temperature, to 160 ~ 180 DEG C, pre-oxidizes 8 ~ 10h, and it is 98% sulphuric acid that pre-oxidized polyacrylonitrile fiber is immersed in 50 ~ 80mL mass fraction
1 ~ 2min in solution, adds 3 ~ 5L deionized water, filters, and spending ion-cleaning pre-oxidized fibers to cleaning mixture is neutrality, proceeds to
100 ~ 105 DEG C of drying baker are dried to constant weight, obtain sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber.
The application process of the present invention is: by prepared sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber, at nitrogen
High temperature cabonization under atmosphere, prepares polyacrylonitrile carbon fiber, the polypropylene carbon fibers of preparation use temperature up to 1000 ~ 1200 DEG C,
Hot strength reaches 240 ~ 250Mpa, and percentage elongation reaches 150 ~ 200%, extends 5 ~ 10 years service life.
The invention has the beneficial effects as follows:
(1) the sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber that the present invention prepares both had solved the high temperature resistant of traditional fibre
Property difference defect, also solve the problems such as fiber weatherability difference service life is shorter, extend 5 ~ 10 years service life.
(2) present invention achieves the controlled pre-oxidation of low cost of polyacrylonitrile, reduce the pre-oxidation stage production cost,
Decrease skin-core structure, can be used for producing high-performance carbon fibre.
Detailed description of the invention
First weighing 50 ~ 80g molecular weight is 50000 ~ 90000 polyacrylonitrile powder, adds in air dry oven, 80 ~
It is dried at 85 DEG C to constant weight, the polyacrylonitrile powder being fully dried is added in 80 ~ 100mL dimethyl sulfoxide, is placed in constant temperature
In water bath, bath temperature is heated to 80 ~ 90 DEG C with 2 DEG C/min from room temperature, with the continuously stirred 4 ~ 5h of 80 ~ 100r/min, obtains all
One transparent spinning liquid；Above-mentioned transparent and homogeneous spinning liquid is placed in 80 ~ 85 DEG C of vacuum drying ovens, under 50 ~ 100Pa vacuum,
Deaeration processes 8 ~ 10h, then spinning liquid addition is preheated in 80 ~ 85 DEG C of spinning-drawing machines, and through spinning mouth extrusion filamentation, spinning speed is
2.5m/min, it is solidification 10 ~ 15min in 50% dimethyl sulphoxide aqueous solution that spinning is placed in 10 ~ 12 DEG C of mass fractions, takes out, uses
Deionized water wash 3 ~ 5 times, then it is immersed in 10 ~ 15min in boiling water, take out, be placed in lyophilizing in freeze drying box, obtain polyacrylonitrile
Precursor；It is 20 ~ 30min in 30% ethylenediamine solution that above-mentioned polyacrylonitrile fibril is immersed in 150 ~ 200mL mass fraction, takes out
Precursor, and to be washed with deionized precursor to cleaning mixture be neutrality, natural air drying, adds in irradiation tube, evacuation the most pure virginity in pipe
Reciprocal of duty cycle is 0.01 ~ 0.05Pa, seals irradiation tube, is 180 ~ 200kGy with gamma-rays to precursor vacuum irradiation to close rate, must change
Property polyacrylonitrile fibril；Above-mentioned modified polyacrylonitrile precursor is placed in drawing by high temperature machine and fixes with fixture, at 140 ~ 150 DEG C
Under, carry out constant temperature extension with 25mm/min Drawing rate, proceed to air dry oven is fixed with fixture after extending 8 times, with 5 DEG C/
Min, from room temperature to 160 ~ 180 DEG C, pre-oxidizes 8 ~ 10h, pre-oxidized polyacrylonitrile fiber is immersed in 50 ~ 80mL mass and divides
Number is 1 ~ 2min in 98% sulfuric acid solution, adds 3 ~ 5L deionized water, filters, spends ion-cleaning pre-oxidized fibers to cleaning mixture
In neutrality, proceed to 100 ~ 105 DEG C of drying baker are dried to constant weight, obtain sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber.
Example 1
First weighing 50g molecular weight is 50000 polyacrylonitrile powder, adds in air dry oven, is dried to constant weight at 80 DEG C,
Being added in 80mL dimethyl sulfoxide by the polyacrylonitrile powder being fully dried, be placed in constant water bath box, bath temperature is with 2
DEG C/min is heated to 80 DEG C from room temperature, with the continuously stirred 4h of 80r/min, obtains transparent and homogeneous spinning liquid；Above-mentioned transparent and homogeneous is spun
Silk liquid is placed in 80 DEG C of vacuum drying ovens, and under 50Pa vacuum, deaeration processes 8h, then is added by spinning liquid and be preheated to 80 DEG C and spin
In silk machine, through spinning mouth extrusion filamentation, spinning speed is 2.5m/min, and it is that 50% dimethyl is sub-that spinning is placed in 10 DEG C of mass fractions
Sulfone aqueous solution solidifies 10min, takes out, be washed with deionized 3 times, then be immersed in 10min in boiling water, take out, be placed in freezing
Lyophilizing in drying baker, obtains polyacrylonitrile fibril；It is 30% ethylenediamine that above-mentioned polyacrylonitrile fibril is immersed in 150mL mass fraction
20min in solution, takes out precursor, and to be washed with deionized precursor to cleaning mixture is neutrality, and natural air drying adds irradiation tube
In, being evacuated to vacuum in pipe is 0.01Pa, seals irradiation tube, with gamma-rays to precursor vacuum irradiation to close rate is
180kGy, obtains modified polyacrylonitrile precursor；Above-mentioned modified polyacrylonitrile precursor is placed in drawing by high temperature machine and fixes with fixture,
At 140 DEG C, carry out constant temperature extension with 25mm/min Drawing rate, proceed to air dry oven is fixed with fixture after extending 8 times, with
5 DEG C/min, from room temperature to 160 DEG C, pre-oxidizes 8h, and it is 98% that pre-oxidized polyacrylonitrile fiber is immersed in 50mL mass fraction
1min in sulfuric acid solution, adds 3L deionized water, filters, and spending ion-cleaning pre-oxidized fibers to cleaning mixture is neutrality, proceeds to
100 DEG C of drying baker are dried to constant weight, obtain sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber.
The application process of the present invention is: by prepared sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber, at nitrogen
High temperature cabonization under atmosphere, prepares polyacrylonitrile carbon fiber, and the polypropylene carbon fibers of preparation uses temperature up to 1000 DEG C, and stretching is strong
Degree reaches 240Mpa, and percentage elongation reaches 150%, extends 5 years service life.
Example 2
First weighing 65g molecular weight is 70000 polyacrylonitrile powder, adds in air dry oven, is dried to constant weight at 83 DEG C,
Being added in 90mL dimethyl sulfoxide by the polyacrylonitrile powder being fully dried, be placed in constant water bath box, bath temperature is with 2
DEG C/min is heated to 85 DEG C from room temperature, with the continuously stirred 4.5h of 90r/min, obtains transparent and homogeneous spinning liquid；By above-mentioned transparent and homogeneous
Spinning liquid is placed in 83 DEG C of vacuum drying ovens, and under 70Pa vacuum, deaeration processes 9h, then spinning liquid addition is preheated to 83 DEG C
In spinning-drawing machine, through spinning mouth extrusion filamentation, spinning speed is 2.5m/min, and it is 50% dimethyl that spinning is placed in 11 DEG C of mass fractions
Sulfoxide aqueous solution solidifies 13min, takes out, be washed with deionized 4 times, then be immersed in 13min in boiling water, take out, be placed in cold
Freeze lyophilizing in drying baker, obtain polyacrylonitrile fibril；It is 30% second two that above-mentioned polyacrylonitrile fibril is immersed in 170mL mass fraction
25min in amine aqueous solution, takes out precursor, and to be washed with deionized precursor to cleaning mixture is neutrality, and natural air drying adds irradiation tube
In, being evacuated to vacuum in pipe is 0.03Pa, seals irradiation tube, with gamma-rays to precursor vacuum irradiation to close rate is
190kGy, obtains modified polyacrylonitrile precursor；Above-mentioned modified polyacrylonitrile precursor is placed in drawing by high temperature machine and fixes with fixture,
At 145 DEG C, carry out constant temperature extension with 25mm/min Drawing rate, proceed to air dry oven is fixed with fixture after extending 8 times, with
5 DEG C/min, from room temperature to 170 DEG C, pre-oxidizes 9h, and it is 98% that pre-oxidized polyacrylonitrile fiber is immersed in 65mL mass fraction
1.5min in sulfuric acid solution, adds 4L deionized water, filters, and spending ion-cleaning pre-oxidized fibers to cleaning mixture is neutrality, turns
Enter in 103 DEG C of drying baker and be dried to constant weight, obtain sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber.
The application process of the present invention is: by prepared sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber, at nitrogen
High temperature cabonization under atmosphere, prepares polyacrylonitrile carbon fiber, and the polypropylene carbon fibers of preparation uses temperature up to 1100 DEG C, and stretching is strong
Degree reaches 245Mpa, and percentage elongation reaches 180%, extends 7 years service life.
Example 3
First weighing 80g molecular weight is 90000 polyacrylonitrile powder, adds in air dry oven, is dried to constant weight at 85 DEG C,
Being added in 100mL dimethyl sulfoxide by the polyacrylonitrile powder being fully dried, be placed in constant water bath box, bath temperature is with 2
DEG C/min is heated to 90 DEG C from room temperature, with the continuously stirred 5h of 100r/min, obtains transparent and homogeneous spinning liquid；Above-mentioned transparent and homogeneous is spun
Silk liquid is placed in 85 DEG C of vacuum drying ovens, and under 100Pa vacuum, deaeration processes 10h, then spinning liquid addition is preheated to 85 DEG C
In spinning-drawing machine, through spinning mouth extrusion filamentation, spinning speed is 2.5m/min, and it is 50% dimethyl that spinning is placed in 12 DEG C of mass fractions
Sulfoxide aqueous solution solidifies 15min, takes out, be washed with deionized 5 times, then be immersed in 15min in boiling water, take out, be placed in cold
Freeze lyophilizing in drying baker, obtain polyacrylonitrile fibril；It is 30% second two that above-mentioned polyacrylonitrile fibril is immersed in 200mL mass fraction
30min in amine aqueous solution, takes out precursor, and to be washed with deionized precursor to cleaning mixture is neutrality, and natural air drying adds irradiation tube
In, being evacuated to vacuum in pipe is 0.05Pa, seals irradiation tube, with gamma-rays to precursor vacuum irradiation to close rate is
200kGy, obtains modified polyacrylonitrile precursor；Above-mentioned modified polyacrylonitrile precursor is placed in drawing by high temperature machine and fixes with fixture,
At 150 DEG C, carry out constant temperature extension with 25mm/min Drawing rate, proceed to air dry oven is fixed with fixture after extending 8 times, with
5 DEG C/min, from room temperature to 180 DEG C, pre-oxidizes 10h, and pre-oxidized polyacrylonitrile fiber is immersed in 80mL mass fraction is
2min in 98% sulfuric acid solution, adds 5L deionized water, filters, and spending ion-cleaning pre-oxidized fibers to cleaning mixture is neutrality, turns
Enter in 105 DEG C of drying baker and be dried to constant weight, obtain sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber.
The application process of the present invention is: by prepared sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber, at nitrogen
High temperature cabonization under atmosphere, prepares polyacrylonitrile carbon fiber, and the polypropylene carbon fibers of preparation uses temperature up to 1200 DEG C, and stretching is strong
Degree reaches 250Mpa, and percentage elongation reaches 200%, service life prolonged for another ten years.
Claims (1)
1. the preparation method of a sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber, it is characterised in that concrete preparation process
For:
(1) weighing 50 ~ 80g molecular weight is 50000 ~ 90000 polyacrylonitrile powder, adds in air dry oven, at 80 ~ 85 DEG C
It is dried to constant weight, the polyacrylonitrile powder being fully dried is added in 80 ~ 100mL dimethyl sulfoxide, is placed in constant water bath box
In, bath temperature is heated to 80 ~ 90 DEG C with 2 DEG C/min from room temperature, with the continuously stirred 4 ~ 5h of 80 ~ 100r/min, obtains transparent and homogeneous
Spinning liquid；
(2) above-mentioned transparent and homogeneous spinning liquid is placed in 80 ~ 85 DEG C of vacuum drying ovens, under 50 ~ 100Pa vacuum, at deaeration
Reason 8 ~ 10h, then spinning liquid addition is preheated in 80 ~ 85 DEG C of spinning-drawing machines, through spinning mouth extrusion filamentation, spinning speed is 2.5m/
Min, it is solidification 10 ~ 15min in 50% dimethyl sulphoxide aqueous solution that spinning is placed in 10 ~ 12 DEG C of mass fractions, takes out, spend from
Sub-water washs 3 ~ 5 times, then is immersed in 10 ~ 15min in boiling water, takes out, is placed in lyophilizing in freeze drying box, obtains polyacrylonitrile former
Silk；
(3) above-mentioned polyacrylonitrile fibril being immersed in 150 ~ 200mL mass fraction is 20 ~ 30min in 30% ethylenediamine solution, takes
Go out precursor, and to be washed with deionized precursor to cleaning mixture be neutrality, natural air drying, add in irradiation tube, be evacuated in pipe
Vacuum is 0.01 ~ 0.05Pa, seals irradiation tube, is 180 ~ 200kGy with gamma-rays to precursor vacuum irradiation to close rate,
Modified polyacrylonitrile precursor；
(4) above-mentioned modified polyacrylonitrile precursor is placed in drawing by high temperature machine fixes with fixture, at 140 ~ 150 DEG C, with 25mm/
Min Drawing rate carries out constant temperature extension, proceeds to fix with fixture in air dry oven, with 5 DEG C/min from room temperature liter after extending 8 times
Temperature, to 160 ~ 180 DEG C, pre-oxidizes 8 ~ 10h, and it is 98% sulphuric acid that pre-oxidized polyacrylonitrile fiber is immersed in 50 ~ 80mL mass fraction
1 ~ 2min in solution, adds 3 ~ 5L deionized water, filters, and spending ion-cleaning pre-oxidized fibers to cleaning mixture is neutrality, proceeds to
100 ~ 105 DEG C of drying baker are dried to constant weight, obtain sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber.
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| CN201610568576.7A CN106192362A (en) | 2016-07-19 | 2016-07-19 | A kind of preparation method of sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber |
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| CN201610568576.7A CN106192362A (en) | 2016-07-19 | 2016-07-19 | A kind of preparation method of sulfuric acid treatment radiation modification pre-oxidized polyacrylonitrile fiber |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112936504A (en) * | 2021-02-24 | 2021-06-11 | 上海城建预制构件有限公司 | Bridge member and manufacturing method |
| CN115304082A (en) * | 2022-10-11 | 2022-11-08 | 山东鲁泰化学有限公司 | Process for recovering NaCl in salt mud for chlor-alkali production |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619509A (en) * | 2009-08-14 | 2010-01-06 | 东华大学 | Carbon nanotube modified polyacrylonitrile-based carbon fibre precursor and preparation method thereof |
| CN101798392A (en) * | 2009-12-11 | 2010-08-11 | 中国科学院上海应用物理研究所 | Method for modifying polyacrylonitrile by using gamma ray irradiation |
| CN103924440A (en) * | 2014-05-07 | 2014-07-16 | 中国科学院上海应用物理研究所 | Method for preparing crosslinking polyacrylonitrile fibers |
| CN104790070A (en) * | 2015-04-17 | 2015-07-22 | 东华大学 | Method for preparing polyacrylonitrile carbon fiber with gamma ray irradiation |
| CN105603543A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Fibre spinning method for polyacrylonitrile solution |
| CN105671651A (en) * | 2014-11-20 | 2016-06-15 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile fibers |
| CN105755581A (en) * | 2016-02-26 | 2016-07-13 | 中复神鹰碳纤维有限责任公司 | Wet-spinning preparation method for polyacrylonitrile-based carbon fiber precursor |
-
2016
- 2016-07-19 CN CN201610568576.7A patent/CN106192362A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619509A (en) * | 2009-08-14 | 2010-01-06 | 东华大学 | Carbon nanotube modified polyacrylonitrile-based carbon fibre precursor and preparation method thereof |
| CN101798392A (en) * | 2009-12-11 | 2010-08-11 | 中国科学院上海应用物理研究所 | Method for modifying polyacrylonitrile by using gamma ray irradiation |
| CN103924440A (en) * | 2014-05-07 | 2014-07-16 | 中国科学院上海应用物理研究所 | Method for preparing crosslinking polyacrylonitrile fibers |
| CN105603543A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Fibre spinning method for polyacrylonitrile solution |
| CN105671651A (en) * | 2014-11-20 | 2016-06-15 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile fibers |
| CN104790070A (en) * | 2015-04-17 | 2015-07-22 | 东华大学 | Method for preparing polyacrylonitrile carbon fiber with gamma ray irradiation |
| CN105755581A (en) * | 2016-02-26 | 2016-07-13 | 中复神鹰碳纤维有限责任公司 | Wet-spinning preparation method for polyacrylonitrile-based carbon fiber precursor |
Non-Patent Citations (2)
| Title |
|---|
| 宗亚宁: "《新型纺织材料及应用》", 31 October 2009, 中国纺织出版社 * |
| 江驰: "硫酸处理聚丙烯腈预氧化纤维的研究", 《合成纤维工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112936504A (en) * | 2021-02-24 | 2021-06-11 | 上海城建预制构件有限公司 | Bridge member and manufacturing method |
| CN115304082A (en) * | 2022-10-11 | 2022-11-08 | 山东鲁泰化学有限公司 | Process for recovering NaCl in salt mud for chlor-alkali production |
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Application publication date: 20161207 |