CN109321994A - A kind of polyacrylonitrile-based carbon fibre dry-wet spinning stoste and preparation method thereof - Google Patents
A kind of polyacrylonitrile-based carbon fibre dry-wet spinning stoste and preparation method thereof Download PDFInfo
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- CN109321994A CN109321994A CN201811160027.1A CN201811160027A CN109321994A CN 109321994 A CN109321994 A CN 109321994A CN 201811160027 A CN201811160027 A CN 201811160027A CN 109321994 A CN109321994 A CN 109321994A
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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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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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
- 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
- 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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Abstract
Present invention relates particularly to a kind of polyacrylonitrile-based carbon fibre dry-wet spinning stostes and preparation method thereof, using dimethyl sulfoxide as reaction medium, azo compound is initiator, acrylonitrile is the 1st monomer, itaconic acid or derivatives thereof is the 2nd monomer, acrylic acid or derivatives thereof is the 3rd monomer, it is aggregated, de- dullness viscosity, deaeration is made, it is arranged by regulation system component proportion combination speed of agitator, preparation inherent viscosity is 1.6-5dL/g high viscosity polymerization system, the high molecular weight copolymer for being suitble to dry-wet spinning is obtained in polymerization stage, then utilize the dynamic viscosity of plus solvent regulation system to 120-600Pas in de- single phase, the spinning solution system for being suitble to dry-wet spinning is obtained after deaeration.Technical indicator needed for present invention substep regulation spinning solution, is easier to the uniform spinning solution of processability, with being conducive to wet-dry change steady and continuous spinning carbon fibers precursor.
Description
Technical field
The invention belongs to technical field of carbon fiber preparation, and in particular to a kind of polyacrylonitrile-based carbon fibre dry-wet spinning is former
Liquid and preparation method thereof.
Background technique
Polyacrylonitrile-based carbon fibre has high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, endurance, conduction, heat transfer
Etc. a series of excellent properties, have in the army and the people's industries such as aerospace, national defence, nuclear energy, communications and transportation, body articles, medical instruments
Be widely applied.The characteristics of dry-wet spinning, can be achieved on high speed spinning, improves equipment efficiency of usage and reduces cost, and
And the carbon fiber surface defect of wet-dry change spinning is few, is conducive to prepare high-performance carbon fibre, is technical field of carbon fiber preparation hair
The important directions of exhibition.But dry-wet spinning has higher requirements to dope viscosity and polymer molecule figureofmerit, and preparation is stablized
Spinning solution be the most important condition that wet-dry change industrializes continuous spinning carbon fibers precursor.Patent 200710056083.6 proposes one
The method that kind prepares high-molecular weight vinyl cyanide copolymer spinning fluid as initiator using azobisisoheptonitrile, gained molecular weight of copolymer
System viscosity is excessive between 10-90 ten thousand, but when the polymerization-filling object molecular weight is larger, and spinnability is poor.Patent
201310514386.3 providing a kind of preparation method of polyacrylonitrile carbon fiber spinning solution that viscosity is controllable, this method is main
The spinning solution of viscosity 20-120Pas, the spinning solution molecular weight of this method preparation are obtained by preparation low molecular weight product
It is lower with viscosity, it is difficult to guarantee the stable operation of dry-wet spinning, and second comonomer uses sodium allylsulfonate or metering system
Sodium sulfonate, the stability and carbon fiber structural of the presence injury spinning solution of sodium element, is unfavorable for the preparation of carbon fiber.Patent
201410584734.9 propose to prepare super high molecular weight spinning solution using batch charging method, and patent 200910234653.5 proposes
A kind of method for preparing high viscosity spinning solution using step-by-step polymerization, patent 200510016572.X with acrylonitrile, itaconic acid and
β-itaconic acid amide is that monomer carries out copolymerization, prepares a kind of high-performance polyacrylonitrile-based carbon fiber spinning solution.These systems
Preparation Method lacks the Effective Regulation means of dope viscosity in polymer molecular weight compared with Gao Shijun, is unfavorable for continuously and stably
Spinning carbon fibers precursor.
Summary of the invention
Viscosity not easy-regulating, provides when higher the purpose of the present invention is to solve existing spinning solution polymer molecular weight
A kind of polyacrylonitrile-based carbon fibre dry-wet spinning stoste and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of polyacrylonitrile-based carbon fibre dry-wet spinning stoste is the azo using dimethyl sulfoxide as reaction medium
Conjunction object is initiator, and acrylonitrile is the 1st monomer, and itaconic acid or derivatives thereof is the 2nd monomer, and acrylic acid or derivatives thereof is the 3rd
Monomer carries out copolymerization, is then made through de- dullness viscosity, deaeration.
Further, the addition parts by weight of each component raw material are as follows: 200 parts of dimethyl sulfoxide, azo compound 0.05-
0.5 part, 30-80 parts of acrylonitrile, 0.1-2 parts of itaconic acid or derivatives thereof, acrylic acid or derivatives thereof be 0.01-2 parts.Match at this
Than under, can effectively acquired character viscosity be 1.6-5dL/g high viscosity polyacrylonitrile copolymer polymer fluid system, and system is solid
Content is high, is conducive to improve productivity.
Further, the azo compound is two isobutyric acid two of azodiisobutyronitrile, azobisisovaleronitrile or azo
One of methyl esters.It is appropriate that above compound decomposes velocity of initiation under polymerization conditions, reacts easy to control.
Further, the derivative of the itaconic acid is one of itaconic acid ammonium, itaconic acid methyl esters or itaconic acid ethyl ester
Or several mixtures with any ratio.
Further, the derivative of the acrylic acid is methyl acrylate, ethyl acrylate, methyl methacrylate or first
One or more of base ethyl acrylate is with the mixture of any ratio.
A kind of preparation method of polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under inert gas shielding state, by dimethyl sulfoxide, azo compound, acrylonitrile, itaconic acid
Or derivatives thereof, acrylic acid or derivatives thereof be added in the reactor with stirring and carry out copolymerization, until combined polymerization product
Inherent viscosity when being 1.6-5dL/g, ammonia is added and adjusts polymer fluid pH value to 8-9；
2) take off single phase: the polymer fluid after adjusting pH value removes unreacted monomer 1-8h with rotating thin film evaporation, until residual
It stays acrylonitrile mass concentration less than 0.1%, and adjusts polymer fluid dynamic viscosity to 120-600Pas using dimethyl sulfoxide；
3) the deaeration stage: deaeration unit is evacuated to 0.01-30kPa, and the polymer fluid for mixing up viscosity is introduced deaeration
Unit, continuous or standing and defoaming obtain polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
Further, the addition parts by weight of the polymerization stage each component raw material are as follows: 200 parts of dimethyl sulfoxide, azo
0.1-2 parts of object 0.05-0.5 parts of conjunction, 30-80 parts of acrylonitrile, itaconic acid or derivatives thereof, acrylic acid or derivatives thereof are 0.1-2
Part.Under the proportion, the high viscosity polymer fluid system that combined polymerization product property viscosity is 1.6-5dL/g can be effectively obtained, and
System solid content is high, is conducive to improve productivity.
Further, the reaction temperature of the copolymerization is 45-75 DEG C, stirring rate 20-150r/min.Polymerization
Temperature is more than 75 DEG C, and polymerization rate is fast, easily leads to implode or polymer molecular weight is lower；Stirring rate is more than 150r/
Min, shearing force is big, is not easy to obtain high molecular weight polymerization product, stirring rate is lower than 20r/min, and polymerization reaction heat is not easy in time
It removes.
Further, de- single temperature in the kettle of the de- single phase is 60-80 DEG C, the temperature of the dimethyl sulfoxide of addition and de-
Temperature in one-pot is identical.Temperature is more than 80 DEG C, and polymer is unstable, and temperature is lower than 60 DEG C, and de- single speed is spent slowly, takes off single-action rate
It is low.
Further, polymer fluid is viscous when the de- single stage polymerisation hydraulic power viscosity is 40 DEG C measured using falling ball method
Degree.
The present invention by regulation system component proportion combination speed of agitator in view of the deficienciess of the prior art, set first
It sets, using the inherent viscosity of combined polymerization product as index, prepares high molecular weight high viscosity polymerization system, be suitble in polymerization stage
Then the high molecular weight copolymer of dry-wet spinning utilizes the dynamic viscosity of plus solvent regulation system, deaeration in de- single phase
The spinning solution system for being suitble to dry-wet spinning is obtained afterwards.
Compared with the prior art, the present invention has the following beneficial effects:
Polymerization stage regulates and controls the molecular weight of copolymer, takes off the viscosity of single phase adjustment and control system, and substep regulates and controls spinning solution institute
The technical indicator needed, is easier to the uniform spinning solution of processability, with being conducive to wet-dry change steady and continuous spinning carbon fibers precursor.
Using the solution of the present invention, the inherent viscosity of the spinning solution of preparation is 1.6-5dL/g, dynamic viscosity 120-
600Pas, residual propylene nitrile mass concentration achieve preferable technical effect less than 0.1%.
Specific embodiment
The present invention is described further with reference to embodiments, the given examples are served only to explain the present invention, is not intended to
It limits the scope of protection of the present invention.
Embodiment 1
One of the present embodiment polyacrylonitrile-based carbon fibre dry-wet spinning stoste, is to be prepared from the following raw materials: diformazan
Base sulfoxide 200kg, azodiisobutyronitrile 0.05kg, acrylonitrile 40kg, itaconic acid 0.15kg, acrylic acid 0.01kg.
The preparation method of above-mentioned polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under nitrogen protection state, by dimethyl sulfoxide 200kg, azodiisobutyronitrile 0.05kg, acrylonitrile
30kg, itaconic acid 0.1kg, acrylic acid 0.01kg, which are added in the reactor with stirring, carries out copolymerization, polymerization reaction temperature
Degree is 75 DEG C, stirring rate 150r/min, using the inherent viscosity of determination of ubbelohde viscometer combined polymerization product, until combined polymerization produces
When the inherent viscosity of object is 1.6dL/g, ammonia is added and adjusts polymer fluid pH value to 8；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, and taking off list temperature in the kettle is 80 DEG C, with rotation
Film evaporation method removes unreacted monomer 1h, and residual propylene nitrile mass concentration is 0.1%, and adjusts polymerization using dimethyl sulfoxide
Hydraulic power viscosity is to 120Pas, wherein the addition temperature of dimethyl sulfoxide is 80 DEG C, and polymer fluid dynamic viscosity is to use falling sphere
Method measurement 40 DEG C when polymer fluid viscosity；
3) the deaeration stage: deaeration unit is evacuated to 5kPa, and the polymer fluid for mixing up viscosity introducing deaeration unit is set
It is standby, it is further evacuated to 0.01kPa, standing and defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
The inherent viscosity of the combined polymerization product of gained spinning solution is 1.6dL/g, dynamic viscosity 120Pas.
Embodiment 2
One of the present embodiment polyacrylonitrile-based carbon fibre dry-wet spinning stoste, is to be prepared from the following raw materials: diformazan
Base sulfoxide 200kg, azobisisovaleronitrile 0.5kg, acrylonitrile 65kg, itaconic acid 2kg, methyl acrylate 2kg.
The preparation method of above-mentioned polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under nitrogen protection state, by dimethyl sulfoxide 200kg, azobisisovaleronitrile 0.5kg, acrylonitrile
65kg, itaconic acid 2kg, methyl acrylate 2kg, which are added in the reactor with stirring, carries out copolymerization, polymeric reaction temperature
It is 45 DEG C, stirring rate 20r/min, using the inherent viscosity of determination of ubbelohde viscometer combined polymerization product, until combined polymerization product
Inherent viscosity when being 5dL/g, ammonia is added and adjusts polymer fluid pH value to 8.5；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, and taking off list temperature in the kettle is 70 DEG C, with rotation
Film evaporation method removes unreacted monomer 8h, and residual propylene nitrile mass concentration is 0.095%, is adjusted later using dimethyl sulfoxide
Polymer fluid dynamic viscosity is to 600Pas, wherein the addition temperature of dimethyl sulfoxide is 70 DEG C, and polymer fluid dynamic viscosity is to use
Falling ball method measurement 40 DEG C when polymer fluid viscosity；
3) the deaeration stage: deaeration unit is evacuated to 30kPa, and the polymer fluid for mixing up viscosity introducing deaeration unit is set
Standby, continuous defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
The inherent viscosity of the combined polymerization product of gained spinning solution is 5dL/g, dynamic viscosity 600Pas.
Embodiment 3
One of the present embodiment polyacrylonitrile-based carbon fibre dry-wet spinning stoste, is to be prepared from the following raw materials: diformazan
Base sulfoxide 200kg, azo-bis-iso-dimethyl 0.12kg, acrylonitrile 60kg, itaconic acid 0.6kg, methyl acrylate 0.2kg,
Methyl methacrylate 0.8kg.
The preparation method of above-mentioned polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under nitrogen protection state, by dimethyl sulfoxide 200kg, azo-bis-iso-dimethyl 0.12kg,
The reaction with stirring is added in acrylonitrile 60kg, itaconic acid 0.6kg, methyl acrylate 0.2kg, methyl methacrylate 0.8kg
Copolymerization is carried out in device, polymeric reaction temperature is 58 DEG C, stirring rate 80r/min, total using determination of ubbelohde viscometer
The inherent viscosity of polymerizate, until ammonia is added and adjusts polymer fluid pH value to 9 when the inherent viscosity of combined polymerization product is 4.0dL/g；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, and taking off list temperature in the kettle is 75 DEG C, with rotation
Film evaporation method removes unreacted monomer 8h, and residual propylene nitrile mass concentration is 0.096%, is adjusted later using dimethyl sulfoxide
Polymer fluid dynamic viscosity is to 420Pas, wherein the addition temperature of dimethyl sulfoxide is 75 DEG C, and polymer fluid dynamic viscosity is to use
Falling ball method measurement 40 DEG C when polymer fluid viscosity；
3) the deaeration stage: deaeration unit is evacuated to 30kPa, and the polymer fluid for mixing up viscosity introducing deaeration unit is set
It is standby, it is evacuated to 5kPa, standing and defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
The inherent viscosity of the combined polymerization product of gained spinning solution is 4.0dL/g, dynamic viscosity 420Pas.
Embodiment 4
One of the present embodiment polyacrylonitrile-based carbon fibre dry-wet spinning stoste, is to be prepared from the following raw materials: diformazan
Base sulfoxide 200kg, azobisisovaleronitrile 0.14kg, acrylonitrile 40kg, itaconic acid ammonium 0.9kg, acrylic acid 0.9kg.
The preparation method of above-mentioned polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under nitrogen protection state, by dimethyl sulfoxide 200kg, azobisisovaleronitrile 0.14kg, acrylonitrile
40kg, itaconic acid ammonium 0.9kg, acrylic acid 0.9kg, which are added in the reactor with stirring, carries out copolymerization, polymerization reaction temperature
Degree is 62 DEG C, stirring rate 80r/min, using the inherent viscosity of determination of ubbelohde viscometer combined polymerization product, until combined polymerization produces
When the inherent viscosity of object is 3.8dL/g, ammonia is added and adjusts polymer fluid pH value to 8.7；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, and taking off list temperature in the kettle is 80 DEG C, with rotation
Film evaporation method removes unreacted monomer 5h, and residual propylene nitrile mass concentration is 0.092%, is adjusted later using dimethyl sulfoxide
Polymer fluid dynamic viscosity is to 280PaS, wherein the addition temperature of dimethyl sulfoxide is 80 DEG C, and polymer fluid dynamic viscosity is to use
Falling ball method measurement 40 DEG C when polymer fluid viscosity；
3) the deaeration stage: deaeration unit is evacuated to 18kPa, and the polymer fluid for mixing up viscosity introducing deaeration unit is set
It is standby, it is evacuated to 3kPa, standing and defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
The inherent viscosity of the combined polymerization product of gained spinning solution is 3.8dL/g, dynamic viscosity 280Pas.
Embodiment 5
One of the present embodiment polyacrylonitrile-based carbon fibre dry-wet spinning stoste, is to be prepared from the following raw materials: diformazan
Base sulfoxide 200kg, azo-bis-iso-dimethyl 0.09kg, acrylonitrile 40kg, itaconic acid methyl esters 1.2kg, ethyl acrylate
0.9kg。
The preparation method of above-mentioned polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under nitrogen protection state, by dimethyl sulfoxide 200kg, azo-bis-iso-dimethyl 0.09kg,
It is anti-that progress combined polymerization in the reactor with stirring is added in acrylonitrile 40kg, itaconic acid methyl esters 1.2kg, ethyl acrylate 0.9kg
It answers, polymeric reaction temperature is 60 DEG C, stirring rate 85r/min, viscous using the characteristic of determination of ubbelohde viscometer combined polymerization product
Degree, until ammonia is added and adjusts polymer fluid pH value to 8.3 when the inherent viscosity of combined polymerization product is 3dL/g；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, and taking off list temperature in the kettle is 70 DEG C, with rotation
Film evaporation method removes unreacted monomer 4.5h, and residual propylene nitrile mass concentration is 0.081%, utilizes dimethyl sulfoxide tune later
Polymer fluid dynamic viscosity is saved to 328PaS, wherein the addition temperature of dimethyl sulfoxide is 70 DEG C, and polymer fluid dynamic viscosity is to make
With falling ball method measure 40 DEG C when polymer fluid viscosity；
3) the deaeration stage: deaeration unit is evacuated to 18kPa, and the polymer fluid for mixing up viscosity introducing deaeration unit is set
It is standby, it is evacuated to 3kPa, standing and defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
The inherent viscosity of the combined polymerization product of gained spinning solution is 3dL/g, dynamic viscosity 328Pas.
Embodiment 6
One of the present embodiment polyacrylonitrile-based carbon fibre dry-wet spinning stoste, is to be prepared from the following raw materials: diformazan
Base sulfoxide 200kg, azodiisobutyronitrile 0.2kg, acrylonitrile 50kg, itaconic acid ethyl ester 1.5kg, methyl methacrylate 0.1kg,
Ethyl methacrylate 0.8kg.
The preparation method of above-mentioned polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under nitrogen protection state, by dimethyl sulfoxide 200kg, azodiisobutyronitrile 0.2kg, acrylonitrile
50kg, itaconic acid ethyl ester 1.5kg, methyl methacrylate 0.1kg, ethyl methacrylate 0.8kg are added with the anti-of stirring
It answers and carries out copolymerization in device, polymeric reaction temperature is 65 DEG C, and stirring rate 100r/min uses determination of ubbelohde viscometer
The inherent viscosity of combined polymerization product, until the inherent viscosity of combined polymerization product be 2.8dL/g when, be added ammonia adjust polymer fluid pH value to
8.8；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, and taking off list temperature in the kettle is 65 DEG C, with rotation
Film evaporation method removes unreacted monomer 6h, and residual propylene nitrile mass concentration is 0.075%, is adjusted later using dimethyl sulfoxide
Polymer fluid dynamic viscosity is to 220Pas, wherein the addition temperature of dimethyl sulfoxide is 65 DEG C, and polymer fluid dynamic viscosity is to use
Falling ball method measurement 40 DEG C when polymer fluid viscosity；
3) the deaeration stage: deaeration unit is evacuated to 18kPa, and the polymer fluid for mixing up viscosity introducing deaeration unit is set
It is standby, it is evacuated to 3kPa, standing and defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
The inherent viscosity of the combined polymerization product of gained spinning solution is 2.8dL/g, dynamic viscosity 220Pas.
Embodiment 7
One of the present embodiment polyacrylonitrile-based carbon fibre dry-wet spinning stoste, is to be prepared from the following raw materials: diformazan
Base sulfoxide 200kg, azodiisobutyronitrile 0.1kg, acrylonitrile 80kg, itaconic acid ammonium 0.2kg, itaconic acid methyl esters 0.1kg, acrylic acid
0.5kg。
The preparation method of above-mentioned polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under nitrogen protection state, by dimethyl sulfoxide 200kg, azodiisobutyronitrile 0.1kg, acrylonitrile
80kg, itaconic acid ammonium 0.2kg, itaconic acid methyl esters 0.1kg, acrylic acid 0.5kg are added in the reactor with stirring and are copolymerized
Reaction is closed, polymeric reaction temperature is 65 DEG C, and stirring rate 150r/min uses the spy of determination of ubbelohde viscometer combined polymerization product
Property viscosity, until ammonia is added and adjusts polymer fluid pH value to 8.5 when the inherent viscosity of combined polymerization product is 4.5dL/g；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, and taking off list temperature in the kettle is 60 DEG C, with rotation
Film evaporation method removes unreacted monomer 8h, and residual propylene nitrile mass concentration is 0.094%, is adjusted later using dimethyl sulfoxide
Polymer fluid dynamic viscosity is to 400PaS, wherein the addition temperature of dimethyl sulfoxide is 80 DEG C, and polymer fluid dynamic viscosity is to use
Falling ball method measurement 40 DEG C when polymer fluid viscosity；
3) the deaeration stage: deaeration unit is evacuated to 2kPa, and the polymer fluid for mixing up viscosity introducing deaeration unit is set
Standby, continuous defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
The inherent viscosity of the combined polymerization product of gained spinning solution is 4.5dL/g, dynamic viscosity 400Pas.
Embodiment 8
One of the present embodiment polyacrylonitrile-based carbon fibre dry-wet spinning stoste, is to be prepared from the following raw materials: diformazan
Base sulfoxide 200kg, azobisisovaleronitrile 0.05kg, acrylonitrile 35kg, itaconic acid 1.2kg, itaconic acid ethyl ester 0.8kg, methyl-prop
Olefin(e) acid ethyl ester 0.01kg.
The preparation method of above-mentioned polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under nitrogen protection state, by dimethyl sulfoxide 200kg, azobisisovaleronitrile 0.05kg, acrylonitrile
35kg, itaconic acid 1.2kg, itaconic acid ethyl ester 0.8kg, ethyl methacrylate 0.01kg be added with stirring reactor in into
Row copolymerization, polymeric reaction temperature are 58 DEG C, and stirring rate 120r/min is produced using determination of ubbelohde viscometer combined polymerization
The inherent viscosity of object, until ammonia is added and adjusts polymer fluid pH value to 8.9 when the inherent viscosity of combined polymerization product is 3.5dL/g；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, and taking off list temperature in the kettle is 80 DEG C, with rotation
Film evaporation method removes unreacted monomer 6h, and residual propylene nitrile mass concentration is 0.088%, is adjusted later using dimethyl sulfoxide
Polymer fluid dynamic viscosity is to 260PaS, wherein the addition temperature of dimethyl sulfoxide is 80 DEG C, and polymer fluid dynamic viscosity is to use
Falling ball method measurement 40 DEG C when polymer fluid viscosity；
3) the deaeration stage: deaeration unit is evacuated to 10kPa, and the polymer fluid for mixing up viscosity introducing deaeration unit is set
It is standby, it is evacuated to 1kPa, standing and defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
The inherent viscosity of the combined polymerization product of gained spinning solution is 3.5dL/g, dynamic viscosity 260Pas.
Embodiment 9
One of the present embodiment polyacrylonitrile-based carbon fibre dry-wet spinning stoste, is to be prepared from the following raw materials: diformazan
Base sulfoxide 200kg, azo-bis-iso-dimethyl 0.4kg, acrylonitrile 30kg, itaconic acid methyl esters 1kg, itaconic acid ethyl ester 0.5kg,
Ethyl acrylate 0.01kg, methyl methacrylate 0.01kg.
The preparation method of above-mentioned polyacrylonitrile-based carbon fibre dry-wet spinning stoste, comprising the following steps:
1) polymerization stage: under nitrogen protection state, by dimethyl sulfoxide 200kg, azo-bis-iso-dimethyl 0.4kg,
Acrylonitrile 30kg, itaconic acid methyl esters 1kg, itaconic acid ethyl ester 0.5kg, ethyl acrylate 0.01kg, methyl methacrylate
0.01kg, which is added in the reactor with stirring, carries out copolymerization, and polymeric reaction temperature is 60 DEG C, stirring rate 120r/
Min, using the inherent viscosity of determination of ubbelohde viscometer combined polymerization product, until when the inherent viscosity of combined polymerization product is 2.4dL/g,
Ammonia is added and adjusts polymer fluid pH value to 8.2；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, and taking off list temperature in the kettle is 70 DEG C, with rotation
Film evaporation method removes unreacted monomer 6h, and residual propylene nitrile mass concentration is 0.081%, is adjusted later using dimethyl sulfoxide
Polymer fluid dynamic viscosity is to 160PaS, wherein the addition temperature of dimethyl sulfoxide is 70 DEG C, and polymer fluid dynamic viscosity is to use
Falling ball method measurement 40 DEG C when polymer fluid viscosity；
3) the deaeration stage: deaeration unit is evacuated to 10kPa, and the polymer fluid for mixing up viscosity introducing deaeration unit is set
It is standby, it is evacuated to 1kPa, standing and defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste afterwards completely.
The inherent viscosity of the combined polymerization product of gained spinning solution is 2.4dL/g, dynamic viscosity 160Pas.
The spinning solution of embodiment 1-9 preparation leads through dry-jet wet-spinning spinning, coagulation forming, washing, heat, oils, drying cause
Densification, steam drafting, laxation shaping prepare polyacrylonitrile fibril, and control precursor diameter is 8-9 μm, the degree of orientation >=94%.Gained
Polyacrylonitrile fibril is through 210 DEG C -220 DEG C -230 DEG C -240 DEG C -250 DEG C -260 DEG C six grades of pre-oxidation, 350 DEG C -400 DEG C -500
DEG C of -600 DEG C -700 DEG C of -800 DEG C of six grade low-temps carbonizations, 1000 DEG C -1200 DEG C -1400 DEG C of three-level high temperature cabonizations obtain high-intensitive poly-
The test result of acrylic carbon fibre, polyacrylonitrile fibril and carbon fiber is shown in Table 1.
1 polyacrylonitrile fibril performance of table and carbon fiber tensile strength
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of polyacrylonitrile-based carbon fibre dry-wet spinning stoste, it is characterised in that: be using dimethyl sulfoxide as reaction medium,
Azo compound is initiator, and acrylonitrile is the 1st monomer, and itaconic acid or derivatives thereof is the 2nd monomer, acrylic acid or its derivative
Object is that the 3rd monomer carries out copolymerization, is then made through de- single, modulation viscosity, deaeration.
2. a kind of polyacrylonitrile-based carbon fibre dry-wet spinning stoste according to claim 1, it is characterised in that: described each
The additive amount of component raw material are as follows: 200 parts of dimethyl sulfoxide, 0.05-0.5 parts of azo compound, 30-80 parts of acrylonitrile, clothing health
0.1-2 parts of acid or derivatives thereof, acrylic acid or derivatives thereof are 0.01-2 parts.
3. a kind of polyacrylonitrile-based carbon fibre dry-wet spinning stoste according to claim 1, it is characterised in that: the idol
Nitrogen compound is one of azodiisobutyronitrile, azobisisovaleronitrile or azo-bis-iso-dimethyl.
4. a kind of polyacrylonitrile-based carbon fibre dry-wet spinning stoste according to claim 1, it is characterised in that: the clothing
The derivative of health acid is one or more of itaconic acid ammonium, itaconic acid methyl esters or itaconic acid ethyl ester with the mixture of any ratio.
5. described in any item a kind of polyacrylonitrile-based carbon fibre dry-wet spinning stostes according to claim 1, it is characterised in that:
The derivative of the acrylic acid is in methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate
One or more are with the mixture of any ratio.
6. a kind of preparation method of polyacrylonitrile-based carbon fibre dry-wet spinning stoste as described in any one in claim 1-5,
It is characterized by comprising following steps:
1) polymerization stage: under inert gas shielding state, by dimethyl sulfoxide, azo compound, acrylonitrile, itaconic acid or its
Derivative, acrylic acid or derivatives thereof are added in the reactor with stirring and carry out copolymerization, until the spy of combined polymerization product
Property viscosity when being 1.6-5dL/g, ammonium hydroxide is added and adjusts polymer fluid pH value to 8-9；
2) take off single phase: the polymer fluid pump after adjusting pH value squeezes into de- one-pot, removes unreacted list with rotating thin film evaporation
Body 1-8h, until residual propylene nitrile mass concentration is less than 0.1%, later using dimethyl sulfoxide adjust polymer fluid dynamic viscosity to
120-600Pa·s；
3) the deaeration stage: deaeration unit is evacuated to 0.01-30kPa, and the polymer fluid for mixing up viscosity is introduced deaeration unit
Equipment continuously or after standing and defoaming obtains polyacrylonitrile-based carbon fibre dry-wet spinning stoste.
7. a kind of preparation method of polyacrylonitrile-based carbon fibre dry-wet spinning stoste according to claim 6, feature
Be: the additive amount of the polymerization stage each component raw material are as follows: 200 parts of dimethyl sulfoxide, 0.05-0.5 parts of azo compound,
0.1-2 parts of 30-80 parts of acrylonitrile, itaconic acid or derivatives thereof, acrylic acid or derivatives thereof are 0.01-2 parts.
8. a kind of preparation method of polyacrylonitrile-based carbon fibre dry-wet spinning stoste according to claim 6, feature
Be: the polymeric reaction temperature is 45-75 DEG C, stirring rate 20-150r/min.
9. a kind of preparation method of polyacrylonitrile-based carbon fibre dry-wet spinning stoste according to claim 6, feature
Be: the de- single phase, de- single temperature in the kettle was 60-80 DEG C, the temperature in the temperature of the dimethyl sulfoxide of addition and de- one-pot
It is identical.
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