CN109137117A - The method of the low swelling capacity polyacrylonitrile as-spun fibre of dry-jet wet-spinning - Google Patents
The method of the low swelling capacity polyacrylonitrile as-spun fibre of dry-jet wet-spinning Download PDFInfo
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- CN109137117A CN109137117A CN201810759988.8A CN201810759988A CN109137117A CN 109137117 A CN109137117 A CN 109137117A CN 201810759988 A CN201810759988 A CN 201810759988A CN 109137117 A CN109137117 A CN 109137117A
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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
- D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
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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
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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Abstract
The invention discloses a kind of methods of the low swelling capacity polyacrylonitrile as-spun fibre of dry-jet wet-spinning.Itaconic acid ammonia and acrylonitrile, initiator ammonium persulfate are first carried out polymerization reaction by the method, the polymerization stoste of preparation is after de- single deaeration processing, the ammoniated treatment of stoste is carried out again, obtain high solids content, the high-hydrophilic spinning solution that pH value is 7~10, then spinning solution passes through dry-jet wet-spinning spinning, controlling coagulating bath pH by way of ammonium hydroxide is added dropwise in coagulating bath is 10~12, and the preparation of as-spun fibre is carried out using low temperature, high drafting rate.The present invention utilizes the hydrophilicity of amide group in monomer itaconic acid ammonia, and carries out ammoniated treatment to polymerization stoste, improves hydrophilic radical quantity in polymerization stoste, prepares high-hydrophilic spinning solution.On the basis of high-hydrophilic, high solids content stoste, the high-densit as-spun fibre of swelling capacity≤110% is made with conditions such as ultralow temperature, high magnification, high alkalinity coagulating bath atmosphere in conjunction with dry-jet wet-spinning.
Description
Technical field
The invention belongs to carbon fibre precursor preparation technical field, it is nascent to be related to a kind of low swelling capacity polyacrylonitrile of dry-jet wet-spinning
The method of fiber.
Background technique
Polyacrylonitrile-based carbon fibre is the production most promising presoma of high-performance carbon fibre, is using polyacrylonitrile fibril
Set out raw material, and carbon fiber can be made by pre-oxidation and carbonisation.The polyacrylonitrile fibril of high quality is to obtain high-quality
The key of carbon fiber.And in precursor preparation process, the compactness of fiber is improved, the porosity of precursor is reduced, is to prepare high-quality
The key of precursor.
Chinese patent application 201410164813.4 is slowed down poly- using the affinity of low-carbon fatty amine and polymers compositions
The contact for closing object and precipitating reagent water, promotes solution thread with gentle speed phase precipitating, reduces conventional wet coagulation forming mistake
The hole type defect and core-skin of Cheng Yuansi reduces the devitrification and inhomogeneity of precursor to improve the morphosis of precursor, improves
The solidification diffusion uniformity of solution thread radial direction is transparent from bath strand densification.Chinese patent 201410541140.X reports one
The preparation method of kind high compactness polyacrylonitrile-based carbon fibre, this method is after preoxidation process terminates, low-temperature carbonization process
Increase by one section of pre- carbonisation before, pre- carbonisation carries out in a nitrogen atmosphere, and temperature range is controlled at 120 DEG C 300 DEG C, leads
It stretches than controlling 5%5%, solves the low technical problem of polyacrylonitrile-based carbon fibre compactness.The above method is from raw material and increasing
Add pre- carbonation process angle to set out, improves the compactness of polyacrylonitrile-based carbon fibre.And coagulation forming as in fiberizing most
The workshop section of core determines the crystal packing formation and crystallite dimension of fiber, directly affects subsequent high power drawability.
Summary of the invention
The purpose of the present invention is to provide a kind of raising as-spun fibre compactness, the dry-jet wet-spinning of reduction fiber swelling capacity are low
The method of swelling capacity polyacrylonitrile as-spun fibre.
Realize that the technical solution of the object of the invention is as follows:
The method of the low swelling capacity polyacrylonitrile as-spun fibre of dry-jet wet-spinning, the specific steps are as follows:
Step 1, in mass ratio it is that 8~15:100 is mixed with solvent by acrylonitrile, comonomer itaconic acid ammonia is added and draws
Agent ammonium persulfate is sent out, wherein the mass ratio of itaconic acid ammonia and acrylonitrile is 0.5~3:100, the mass ratio of initiator and acrylonitrile
It for 0.2~2.5:100, stirs evenly, 12~20h of polymerization reaction at 45~65 DEG C, obtains polymerization stoste；
Step 2, in the case where vacuum absolute pressure is 0.1~30KPa, removing monomer is carried out to polymerization stoste and deaeration is handled,
Solvent is added, adjusting stoste solid content is 21%~28%, is 8~10:1 by the mass ratio of stoste and ammonia, is passed through ammonia, obtains
The high-hydrophilic spinning solution for being 7~10 to pH value；
Step 3, high-hydrophilic spinning solution is subjected to dry-jet wet-spinning spinning, high-hydrophilic spinning solution is sprayed from spinneret
Afterwards, the air layer for being 3~20mm by height, then as-spun fibre silk is formed through coagulating bath, it is used in spinning coagulation bath and ammonia is added dropwise
The mode of water, regulation coagulating bath pH value are 10~12, and coagulation bath temperature control is at -10~0 DEG C, the mass concentration of coagulating bath solution
It is 10%~25%, pre-draft multiple is 6~10 times, and polyacrylonitrile as-spun fibre is made.
Preferably, in step 1 and 2, the solvent is selected from dimethyl sulfoxide, dimethylformamide, sodium thiocyanate solution
Deng.
Preferably, in step 1, the mass ratio of the itaconic acid ammonia and acrylonitrile is 1.5~2.5:100.
Preferably, in step 3, the distribution net in the spinneret is 2000~2300 mesh, the hole diameter of spinneret 0.04
~0.20mm, draw ratio are 1.0~3.0.
Preferably, in step 3, the coagulating bath is dimethyl sulphoxide aqueous solution.
Compared with prior art, the invention has the following advantages that
The present invention utilizes the hydrophilicity of amide group in monomer itaconic acid ammonia, and carries out ammoniated treatment to polymerization stoste,
Hydrophilic radical quantity in polymerization stoste is improved, high-hydrophilic spinning solution is prepared.In high-hydrophilic, high solids content stoste basis
On, it is formd in conjunction with the superiority of dry-jet wet-spinning temperature mutagens with conditions such as ultralow temperature, high magnification, high alkalinity coagulating bath atmosphere
The high-densit forming method of as-spun fibre.Swelling capacity≤110% of polyacrylonitrile as-spun fibre made from the method for the present invention.
Specific embodiment
Below with reference to embodiment, the present invention is described in further details.
Embodiment 1
(1) after being mixed acrylonitrile according to mass ratio 15:100 with solvent dimethyl sulfoxide, comonomer is being added
The mass ratio of itaconic acid ammonia and initiator, itaconic acid ammonia and acrylonitrile is 3:100, and initiator and acrylonitrile mass ratio are 2.5:
100, after stirring, it polymerize stoste reaction temperature at 65 DEG C, the reaction time is in 12h.Carry out polymerization reaction preparation polymerization
Stoste.Under the conditions of vacuum absolute pressure 0.1KPa, polyacrylonitrile polymer solution carries out de- single deaeration by thin film evaporator and handles,
Stoste solid content is 26%.Stoste carries out ammoniated treatment, stoste and ammonia again and is added according to mass ratio 8:1, is prepared into high hydrophilic
Property spinning solution, spinning solution pH value is 7.5.
(2) spinning solution carries out spinning with dry-jet wet-spinning, and spinning solution passes through spinneret component, distributes net in spinning pack
For 2300 mesh, the hole diameter of spinneret 0.120mm, draw ratio 3.0.Air layer height 20mm.Using dropwise addition in spinning coagulation bath
The mode of ammonium hydroxide, 11, coagulation bath temperature is controlled at -10 DEG C regulation coagulating bath pH value, solidifies bath concentration 25%, pre-draft multiple
As-spun fibre is prepared at 10 times.Spinning solution passes through air layer, coagulating bath, under drafting machine driving, can prepare swelling
The as-spun fibre of degree 101%.
Embodiment 2
(1) after being mixed acrylonitrile according to mass ratio 12:100 with solvent dimethyl sulfoxide, comonomer is being added
The mass ratio of itaconic acid ammonia and initiator, itaconic acid ammonia and acrylonitrile is 2.5:100, and initiator and acrylonitrile mass ratio are 2.5:
100, after stirring, it polymerize stoste reaction temperature at 65 DEG C, the reaction time is in 16h.Carry out polymerization reaction preparation polymerization
Stoste.Under the conditions of vacuum absolute pressure 0.1KPa, polyacrylonitrile polymer solution carries out de- single deaeration by thin film evaporator and handles,
Stoste solid content is 25%.Stoste carries out ammoniated treatment, stoste and ammonia again and is added according to mass ratio 10:1, is prepared into high hydrophilic
Property spinning solution, spinning solution pH value is 10.0.
(2) spinning solution carries out spinning with dry-jet wet-spinning, and spinning solution passes through spinneret component, distributes net in spinning pack
For 2300 mesh, the hole diameter of spinneret 0.12mm, draw ratio 3.0.Air layer height 17mm.Using dropwise addition ammonia in spinning coagulation bath
The mode of water, 12, coagulation bath temperature is controlled at -10 DEG C regulation coagulating bath pH value, solidifies bath concentration 25%, pre-draft multiple exists
9 times prepare as-spun fibre.Spinning solution pass through air layer, coagulating bath, drafting machine driving under, can prepare swelling capacity≤
108% as-spun fibre.
Embodiment 3
(1) after being mixed acrylonitrile according to mass ratio 10:100 with solvent dimethyl sulfoxide, comonomer is being added
The mass ratio of itaconic acid ammonia and initiator, itaconic acid ammonia and acrylonitrile is 3:100, and initiator and acrylonitrile mass ratio are 2.5:
100, after stirring, it polymerize stoste reaction temperature at 60 DEG C, the reaction time is in 15h.Carry out polymerization reaction preparation polymerization
Stoste.Under the conditions of vacuum absolute pressure 0.1KPa, polyacrylonitrile polymer solution carries out de- single deaeration by thin film evaporator and handles,
Stoste solid content is 21%.Stoste carries out ammoniated treatment, stoste and ammonia again and is added according to mass ratio 10:1, is prepared into high hydrophilic
Property spinning solution, spinning solution pH value is 10.
(2) spinning solution carries out spinning with dry-jet wet-spinning, and spinning solution passes through spinneret component, distributes net in spinning pack
For 2300 mesh, the hole diameter of spinneret 0.12mm, draw ratio 3.0.Air layer height 10mm.Using dropwise addition ammonia in spinning coagulation bath
The mode of water, 12, coagulation bath temperature is controlled at -10 DEG C regulation coagulating bath pH value, solidifies bath concentration 23%, pre-draft multiple 8
As-spun fibre is prepared again.Spinning solution passes through air layer, coagulating bath, under drafting machine driving, can prepare swelling capacity
105% as-spun fibre.
Embodiment 4
(1) after being mixed acrylonitrile according to mass ratio 8:100 with solvent dimethyl sulfoxide, comonomer clothing is being added
The mass ratio of health acid ammonia and initiator, itaconic acid ammonia and acrylonitrile is 0.5:100, and initiator and acrylonitrile mass ratio are 0.2:
100, after stirring, it polymerize stoste reaction temperature at 45 DEG C, the reaction time is in 20h.Carry out polymerization reaction preparation polymerization
Stoste.Under the conditions of vacuum absolute pressure 30KPa, polyacrylonitrile polymer solution carries out de- single deaeration by thin film evaporator and handles,
Stoste solid content is 28%.Stoste carries out ammoniated treatment, stoste and ammonia again and is added according to mass ratio 10:1, is prepared into high hydrophilic
Property spinning solution, spinning solution pH value is 7.
(2) spinning solution carries out spinning with dry-jet wet-spinning, and spinning solution passes through spinneret component, distributes net in spinning pack
For 2000 mesh, the hole diameter of spinneret 0.04mm, draw ratio 1.0.Air layer height 3mm.Using dropwise addition ammonia in spinning coagulation bath
The mode of water, 10, coagulation bath temperature is controlled at 0 DEG C regulation coagulating bath pH value, solidification bath concentration 10%, and 6 times of pre-draft multiple
Prepare as-spun fibre.Spinning solution passes through air layer, coagulating bath, under drafting machine driving, can prepare swelling capacity 107%
As-spun fibre.
Embodiment 5
(1) after being mixed acrylonitrile according to mass ratio 10:100 with solvent dimethyl sulfoxide, comonomer is being added
The mass ratio of itaconic acid ammonia and initiator, itaconic acid ammonia and acrylonitrile is 1.5:100, and initiator and acrylonitrile mass ratio are 2.5:
100, after stirring, it polymerize stoste reaction temperature at 60 DEG C, the reaction time is in 15h.Carry out polymerization reaction preparation polymerization
Stoste.Under the conditions of vacuum absolute pressure 0.1KPa, polyacrylonitrile polymer solution carries out de- single deaeration by thin film evaporator and handles,
Stoste solid content is 21%.Stoste carries out ammoniated treatment, stoste and ammonia again and is added according to mass ratio 10:1, is prepared into high hydrophilic
Property spinning solution, spinning solution pH value is 10.
(2) spinning solution carries out spinning with dry-jet wet-spinning, and spinning solution passes through spinneret component, distributes net in spinning pack
For 2300 mesh, the hole diameter of spinneret 0.20mm, draw ratio 3.0.Air layer height 10mm.Using dropwise addition ammonia in spinning coagulation bath
The mode of water, 12, coagulation bath temperature is controlled at -10 DEG C regulation coagulating bath pH value, solidifies bath concentration 23%, pre-draft multiple 8
As-spun fibre is prepared again.Spinning solution passes through air layer, coagulating bath, under drafting machine driving, can prepare swelling capacity
102% as-spun fibre.
Comparative example 1
This comparative example is substantially the same manner as Example 1, unique the difference is that stoste does not carry out ammoniated treatment.Nascent fibre obtained
The swelling capacity of dimension is 116%.
Comparative example 2
This comparative example is substantially the same manner as Example 1, and unique the difference is that stoste carries out ammoniated treatment, spinning solution pH value is
6.The swelling capacity of as-spun fibre obtained is 120%.
Comparative example 3
This comparative example is substantially the same manner as Example 1, and unique the difference is that stoste carries out ammoniated treatment, spinning solution pH value is
11.The swelling capacity of as-spun fibre obtained is 115%.
Claims (5)
1. the method for the low swelling capacity polyacrylonitrile as-spun fibre of dry-jet wet-spinning, which is characterized in that specific step is as follows:
Step 1, in mass ratio it is that 8~15:100 is mixed with solvent by acrylonitrile, comonomer itaconic acid ammonia and initiator is added
Ammonium persulfate, wherein the mass ratio of itaconic acid ammonia and acrylonitrile is 0.5~3:100, and the mass ratio of initiator and acrylonitrile is 0.2
~2.5:100, stirs evenly, 12~20h of polymerization reaction at 45~65 DEG C, obtains polymerization stoste；
Step 2, in the case where vacuum absolute pressure is 0.1~30KPa, removing monomer is carried out to polymerization stoste and deaeration is handled, is added
Solvent, adjusting stoste solid content is 21%~28%, is 8~10:1 by the mass ratio of stoste and ammonia, is passed through ammonia, obtains pH
The high-hydrophilic spinning solution that value is 7~10；
Step 3, by high-hydrophilic spinning solution carry out dry-jet wet-spinning spinning, high-hydrophilic spinning solution from spinneret ejection after,
The air layer for being 3~20mm by height, then as-spun fibre silk is formed through coagulating bath, it is used in spinning coagulation bath and ammonium hydroxide is added dropwise
Mode, regulation coagulating bath pH value are 10~12, and coagulation bath temperature control is in -10~0 DEG C, the mass concentration of coagulating bath solution
10%~25%, pre-draft multiple is 6~10 times, and polyacrylonitrile as-spun fibre is made.
2. the method according to claim 1, wherein in step 1 and 2, the solvent be selected from dimethyl sulfoxide,
Dimethylformamide or sodium thiocyanate solution.
3. the method according to claim 1, wherein in step 1, the quality of the itaconic acid ammonia and acrylonitrile
Than for 1.5~2.5:100.
4. the method according to claim 1, wherein the distribution net in the spinneret is 2000 in step 3
~2300 mesh, the hole diameter of spinneret are 0.04~0.20mm, and draw ratio is 1.0~3.0.
5. the method according to claim 1, wherein the coagulating bath is that dimethyl sulfoxide is water-soluble in step 3
Liquid.
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Cited By (4)
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| CN114686996A (en) * | 2022-01-29 | 2022-07-01 | 军事科学院***工程研究院军需工程技术研究所 | Moisture-absorbing heating fiber and manufacturing method thereof |
| CN115976674A (en) * | 2022-12-29 | 2023-04-18 | 江苏恒神股份有限公司 | Polyacrylonitrile precursor, preparation method thereof and carbon fiber |
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| CN112921433A (en) * | 2021-01-20 | 2021-06-08 | 威海拓展纤维有限公司 | Spinning method of polyacrylonitrile-based carbon fiber precursor |
| CN113215668A (en) * | 2021-04-16 | 2021-08-06 | 山西钢科碳材料有限公司 | Polyacrylonitrile nascent fiber, polyacrylonitrile fiber and preparation method thereof |
| CN113215668B (en) * | 2021-04-16 | 2022-11-11 | 山西钢科碳材料有限公司 | Polyacrylonitrile nascent fiber, polyacrylonitrile fiber and preparation method thereof |
| CN114686996A (en) * | 2022-01-29 | 2022-07-01 | 军事科学院***工程研究院军需工程技术研究所 | Moisture-absorbing heating fiber and manufacturing method thereof |
| CN115976674A (en) * | 2022-12-29 | 2023-04-18 | 江苏恒神股份有限公司 | Polyacrylonitrile precursor, preparation method thereof and carbon fiber |
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