CN101067214B - Dry-jet wet-spinning technique for producing polyacrylonitrile fibre - Google Patents
Dry-jet wet-spinning technique for producing polyacrylonitrile fibre Download PDFInfo
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- CN101067214B CN101067214B CN2007100418898A CN200710041889A CN101067214B CN 101067214 B CN101067214 B CN 101067214B CN 2007100418898 A CN2007100418898 A CN 2007100418898A CN 200710041889 A CN200710041889 A CN 200710041889A CN 101067214 B CN101067214 B CN 101067214B
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Abstract
The present invention relates to dry spraying and wet spinning process for preparing polyacrylonitrile fiber. The dry spraying and wet spinning process includes the following steps: 1. preparing spinning solution comprising polyacrylonitrile and ionic liquid; 2. extruding the spinning solution, treated through debubbling, filtering and metering, with the spinning jet to form fine spinning flow passing through the wet air layer and entering to the solidifying bath for solidifying to form; and 3. pre-stretching, water washing, drying and hot setting to form polyacrylonitrile filament or short polyacrylonitrile fiber. The present invention has the advantages of high production efficiency, easy fiber formation, capacity of forming homogeneous fiber with high strength, environment friendship, etc.
Description
Technical field
The invention belongs to the polyacrylonitrile solution dry-jet wet-spinning technique, particularly relating to the ionic liquid is the dry-jet wet-spinning technique that solvent prepares polyacrylonitrile fibre.
Background technology
Polyacrylonitrile fibre has been widely used in textile garment and industrial field; Its ripe process route is the solvent spinning method, and the solvent that is adopted comprises dimethyl formamide (DMF), sodium thiocyanate water solution, dimethyl sulfoxide (DMSO) (DMSO), dimethylacetylamide (DMAc), nitric acid, α-pyridine alkane ketone, sulfolane etc.Because used these corrosive inorganic solvent or volatile organic solvents in a large number in the polyacrylonitrile process, except equipment being had the very high requirement, the processing of waste gas or waste water has brought very big pressure to environmental protection.
Recent years, a kind of new solvent---ionic liquid begins to be applied to the polymerization and the spinning of polyacrylonitrile, has opened up the new technology that polyacrylonitrile fibre cleans processing.We the patent ZL200410016369.8 of application discloses the preparation method of a kind of acrylonitrile polymer in ionic liquid; Patent 200410066610.8; 200410066608.0; 200410066609.5 200410066607.6 further to disclose with the ionic liquid be the wet spinning process of the polyacrylonitrile fibre of solvent.But the spinning speed of wet spinning process is low, and polyacrylonitrile ionic liquid solution system viscosity is relatively large, needs higher spinning temperature.In addition, wet spinning directly immerses spinning head in the lower coagulating bath of temperature, and the rapid reduction of spinning solution temperature causes easily extrudes difficulty, influences spinning technique.
Summary of the invention
The purpose of this invention is to provide a kind of dry-jet wet-spinning technique for preparing polyacrylonitrile fibre, this technology production efficiency is high, be easy to spinning technique, and environmental pollution is little.
A kind of dry-jet wet-spinning technique for preparing polyacrylonitrile fibre of the present invention comprises the following steps:
(1) preparation polyacrylonitrile ionic liquid spinning solution;
(2) after the deaeration of spinning solution process, filtration, the metering, extrude the back through spinning head and form dynamic analysis of spinning,, get into the coagulating bath solidification forming through the humid air layer;
(3) carry out predraft, stretching, washing, dried heat typing back one-tenth fibre, preparation polyacrylonitrile long filament or short silk.
Said polyacrylonitrile ionic liquid spinning solution is meant the solution be made up of the polyacrylonitrile of mass percent 5～30%, 70～95% ionic liquid or the solution of being made up of the water of the polyacrylonitrile of mass percent 5～30%, 67～95% ionic liquid and 0～3%;
The preparation method of said polyacrylonitrile ionic liquid spinning solution is meant polyacrylonitrile is dissolved in the ionic liquid preparation spinning solution or is that solvent carries out polymerization of acrylonitrile and directly prepares spinning solution with the ionic liquid;
Described ionic liquid is made up of CATION and anion;
Described CATION is selected from a kind of in the following CATION:
Alkyl quaternary ammonium ion ethoxy alkyl quaternary ammonium ion alkyl sulfonium cation alkyl quaternary phosphonium ion
Alkyl pyridinium ion alkyl pyrroles ion alkyl pyrazoles ion alkyl imidazol ion
Wherein: R1, R2, R3, R4, R5 and R6 can be identical, also can be different, be respectively that H or carbon number are the alkyl of 1-8;
Described anion is selected from Cl
-, Br
-, BF
4 -, PF
6 -, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-, or (CF
3SO
2)
3C
-In a kind of;
Described polyacrylonitrile is selected from copolymer or the copolymer of first and second monomer or the homopolymers of acrylonitrile of first, second and third monomer, and viscosity average molecular weigh is 2.0 * 10
4～2.0 * 10
5
The copolymer of described first, second and third monomer is meant that the mass percent of second monomer in the copolymer is 3～18wt%, and the content of the 3rd monomer is 0.1～1.0wt%;
The copolymer of described first and second monomer or acrylonitrile homopolymer are meant that the content of second monomer in the polymer is 0～18wt%;
Described first monomer is an acrylonitrile; Second monomer is selected from a kind of in methyl acrylate, methyl methacrylate, methacrylonitrile, vinylacetate or the acrylamide, and the 3rd monomer is taken from a kind of in the amino ethyl ester of itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine, 2-methyl-5-vinylpyridine or dimethylaminoethyl acrylate methyl;
Described spinning solution temperature is 70～120 ℃;
Described humid air layer is meant in spinnerets and the coagulating bath that the distance of air layer is 1～10cm between the liquid level, and the temperature of air layer is 5～30 ℃, and relative humidity is 60～95%;
Described coagulating bath is made up of ionic liquid and water, and temperature is 5～35 ℃, and wherein ion liquid mass percent is 0～20%, and the mass percent of water is 80～100%;
Described predraft is bathed and is water, 40～65 ℃ of temperature;
Described stretch bath is a water, 80～99 ℃ of water temperatures.
Said washing is meant the spray washing, 25～50 ℃ of temperature or the washing of water at atmospheric pressure steam;
Described drying is meant hot-air dry, and baking temperature is 120～165 ℃;
Described spinning speed is 20～200m/min;
Described polyacrylonitrile fibre is meant that filament number is 1.5～5.0dtex, intensity 2.0～4.2cN/dtex.
Beneficial effect of the present invention:
(1) with the ionic liquid be solvent, ionic liquid is easy to recycle, and has the characteristic of environmental protection;
(2) adopt dry-jet wet-spinning technique, spinning speed is high, and production efficiency improves;
(3) fiber is easy to be shaped;
(4) shaping back fiber is even, and intensity is high.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Raw material: polyacrylonitrile, viscosity average molecular weigh are 5.0 * 10
4, be a kind of copolymer that comprises first monomer, second monomer and the 3rd monomer, wherein first monomer is that the mass percent of acrylonitrile is that the mass percent of 81.8%, the second monomer methyl acrylate is that the content of 18%, the three monomer itaconic acid is 0.2%.Ionic liquid, 1-butyl-3-methylimidazole chloride.
20% polyacrylonitrile is added in 1-butyl-3-methylimidazole chloride,, 78 ℃ of dissolvings 3 hours down, be mixed with solution then 20 ℃ of following swellings 2 hours; Filter deaeration down at 78 ℃, extrude through measuring pump and spinnerets, through the humid air layer of 1cm; Temperature is 10 ℃, and humidity 60% gets into 20 ℃ coagulating bath; Coagulating bath is a water, and the predraft water-bath through 40 ℃ of deflector roll entering gets into 90 ℃ hot water stretch bath then; Total draw ratio is 4 times, is wound into long filament through the speed with 100m/min behind the washing of 25 ℃ sprays and the 120 ℃ of hot-air dries, obtains the polyacrylonitrile fibre that filament number is 1.5dtex, intensity 3.2cN/dtex.
Embodiment 2
Raw material: polyacrylonitrile, viscosity average molecular weigh 2.0 * 10
5, be a kind of copolymer that comprises first monomer and second monomer, wherein first monomer is that the content of acrylonitrile is that the content of 90%, the second monomers methyl methacrylate is 10%.Ionic liquid, 1-allyl-3-methylimidazole chloride.
8% polyacrylonitrile added contain in the 1-allyl-3-methylimidazole chloride of 3% water, 25 ℃ of following swellings 2 hours, then 70 ℃ of dissolvings 4 hours down; Be mixed with solution, under 70 ℃ of degree, filter deaeration, extrude through measuring pump and spinnerets; Through the humid air layer of 10cm, temperature is 5 ℃, humidity 95%; Get into 30 ℃ coagulating bath, coagulation bath composition is to contain 1-allyl-muriatic aqueous solution of 3-methylimidazole of 5%, gets into 55 ℃ predraft bath water through deflector roll; Get into 99 ℃ hot water stretch bath then, 12 times of total draw ratios are washed and 165 ℃ hot-air dry through the normal pressure steam water; Speed with 200m/min is wound into long filament, obtains the polyacrylonitrile fibre that filament number is 2.5dtex, intensity 4.2cN/dtex.
Embodiment 3
Raw material: polyacrylonitrile, viscosity average molecular weigh 2.0 * 10
4, be acrylonitrile homopolymer.Ionic liquid, 1-butyl-3-methyl imidazolium tetrafluoroborate.
Polyacrylonitrile with 5% adds in ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate, and swelling is 1.5 hours under 25 ℃ of degree, under 70 ℃ of degree, dissolves 6 hours then; Be mixed with solution, filter deaeration down, extrude through measuring pump and spinnerets at 70 ℃; Through the humid air layer of 2cm, temperature is 10 ℃, humidity 88%; Get into 10 ℃ coagulating bath, coagulating bath is a water, gets into 50 ℃ predraft bath water through deflector roll; Get into 85 ℃ hot water stretch bath then; Total draw ratio is .3.5, through 30 ℃ spray woodss wash and 130 ℃ hot-air dry after be wound into long filament with 80m/min speed, obtaining filament number is that 2.8dtex, intensity are the polyacrylonitrile fibre of 3.0cN/dtex.
Embodiment 4
Raw material: polyacrylonitrile, viscosity average molecular weigh 6.0 * 10
4, be a kind of copolymer that comprises first monomer and second monomer, the content of the first monomer acrylonitrile is 86wt%, the content of the second monomer methacrylonitrile is 14wt%.Ionic liquid, 3-methyl-N-butyl-pyridinium chloride.
10% polyacrylonitrile is added in ionic liquid 3-methyl-N-butyl-pyridinium chloride,, under 80 ℃ of degree, dissolved 2.5 hours then 30 ℃ of following swellings 1.5 hours; Be mixed with solution, filter deaeration down, extrude through measuring pump and spinnerets at 80 ℃; Through the humid air layer of 3cm, temperature is 15 ℃, humidity 81%; Get into 15 ℃ coagulating bath, coagulating bath is a water, gets into 55 ℃ predraft water-bath through deflector roll; Get into 90 ℃ hot water stretch bath then; Total draw ratio is 4 times, through the water at atmospheric pressure vapor water wash with 135 ℃ hot-air dry after be wound into long filament with the speed of temperature 100m/min, obtaining filament number is that 2.5dtex, intensity are the polyacrylonitrile fibre of 2.5cN/dtex.
Embodiment 5
Raw material: polyacrylonitrile, viscosity average molecular weigh 8.0 * 10
4, be a kind of copolymer that comprises first monomer, second monomer and the 3rd monomer, the content of the first monomer acrylonitrile is 83.6wt%, and the content of the second monomer vinylacetate is 16wt%, and the content of the 3rd monomer sodium allylsulfonate is 0.4wt%.Ionic liquid, benzyl dimethyl myristyl ammonium chloride.
15% polyacrylonitrile is added in the ionic liquid benzyl dimethyl myristyl ammonium chloride, 25 ℃ of following swellings 1.5 hours, then 90 ℃ of dissolvings 3 hours down; Be mixed with solution, filter deaeration down, extrude through measuring pump and spinnerets at 90 ℃; Through the humid air layer of 4cm, temperature is 20 ℃, humidity 74%; Get into 20 ℃ coagulating bath, coagulation bath composition is a water, gets into 60 ℃ predraft bath water through deflector roll; Get into 95 ℃ hot water stretch bath then, total draw ratio be .4.5 doubly, through the normal pressure steam water wash with 140 ℃ of hot-air dries after be wound into long filament with the speed of 120m/min; Obtaining filament number is 3.0dtex,, the polyacrylonitrile fibre of intensity 4.0cN/dtex.
Embodiment 6
Raw material: polyacrylonitrile, viscosity average molecular weigh 1.0 * 10
5, be acrylonitrile homopolymer.Ionic liquid, trimethyl butyl phosphorus bromide.
12% polyacrylonitrile added contain in the trimethyl butyl phosphorus bromide of 2% water, 30 ℃ of following swellings 1 hour, then 100 ℃ of dissolvings 5 hours down; Be mixed with solution, filter deaeration down, extrude through measuring pump and spinnerets at 100 ℃; Through the humid air layer of 5cm, temperature is 25 ℃, humidity 67%; Get into 25 ℃ coagulating bath, coagulation bath composition is the aqueous solution that contains 20% trimethyl butyl phosphorus bromide, gets into 65 ℃ predraft water-bath through deflector roll; Get into 90 ℃ hot water stretch bath then, total draw ratio is 2.5, through 40 ℃ spray woods washings and 145 ℃ hot-air dry; Speed with 60m/min is wound into long filament, and obtaining filament number is that 3.5dtex, intensity are the polyacrylonitrile fibre of 2.8cN/dtex.
Embodiment 7
Raw material: polyacrylonitrile, viscosity average molecular weigh 8 * 10
4, be a kind of copolymer that comprises first monomer and second monomer, wherein the content of the first monomer acrylonitrile is that the content of 88%, the second monomer methacrylonitrile is 12%.Ionic liquid, N-ethylpyridine trifluoromethyl sulfonic acid.
20% polyacrylonitrile is added in ionic liquid N-ethylpyridine trifluoromethyl sulfonic acid,, under 110 ℃ of degree, dissolved 3 hours then, be mixed with solution 25 ℃ of swellings 2 hours; Filter deaeration down at 110 ℃, extrude through measuring pump and spinnerets, through the humid air layer of 6cm; Temperature is 30 ℃, and humidity 60% gets into 30 ℃ coagulating bath; Coagulation bath composition is a water, gets into 70 ℃ predraft bath water through deflector roll, gets into 95 ℃ hot water stretch bath then; Total draw ratio is 7, through the water at atmospheric pressure steam water wash with 150 ℃ hot-air dry after be wound into long filament with 150m/min speed, obtain the polyacrylonitrile fibre that filament number is 2.5dtex, intensity 4.0cN/dtex.
Embodiment 8
Raw material: polyacrylonitrile, viscosity average molecular weigh 1.2 * 10
5, be a kind of copolymer that comprises first monomer and second monomer, the content 90wt% of the first monomer acrylonitrile wherein, the content of the second monomer vinylacetate is 10%.Ionic liquid, N, N '-dimethyl pyrrole trifluoromethane sulfonic acid acid imide.
6% polyacrylonitrile is added ionic liquid N, in N '-dimethyl pyrrole trifluoromethane sulfonic acid acid imide, 20 ℃ of following swellings 3 hours; Under 120 ℃ of degree, dissolved 4 hours then, be mixed with solution, filter deaerations down at 120 ℃; Extrude through measuring pump and spinnerets, through the humid air layer of 7cm, temperature is 25 ℃; Humidity 67% gets into 35 ℃ coagulating bath, and coagulating bath is a water; Predraft water-bath through 75 ℃ of deflector roll entering gets into 90 ℃ hot water stretch bath then, and the temperature draw ratio is 7.5; Speed with 155m/min behind the hot-air dry of the washing of 50 ℃ spray woodss and 155 ℃ is wound into long filament, obtains the polyacrylonitrile fibre that filament number is 2.0dtex, intensity 3.8cN/dtex.
Embodiment 9
Ionic liquid, 1-butyl-2-methylpyrazole bromide.
The first monomer acrylonitrile that accounts for total monomer 90%, 10% the second monomer methyl acrylate, 0.5% initator dilauroyl peroxide, 1% light-colored agent stannous chloride, 1% molecular weight regulator isopropyl alcohol are added stirring and dissolving in ionic liquid 1-butyl-2-methylpyrazole bromide successively; Wherein to account for the mass percent of solution be 30% to total monomer; 72 ℃ of following polymerisations 2 hours, viscosity average molecular weigh be 2.0 * 10
4The ionic liquid solution of acrylonitrile copolymer.Under 72 ℃, take off list, 120 ℃ are filtered deaeration down, extrude through measuring pump and spinnerets; Through the humid air layer of 1cm, temperature is 5 ℃, humidity 95%; Get into 5 ℃ coagulating bath, coagulating bath is 20% ionic liquid aqueous solution, gets into 40 ℃ predraft water-bath through deflector roll; Get into 80 ℃ hot water stretch bath then; Total draw ratio is 3, through the water at atmospheric pressure vapor water wash with 165 ℃ hot-air dry after be wound into long filament with the speed of 50m/min, filament number be the polyacrylonitrile fibre of 2.0dtex, intensity 2.2cN/dtex.
Embodiment 10
Ionic liquid, 1-butyl-3-methylimidazole hexafluorophosphate.
The first monomer acrylonitrile that accounts for total monomer 89.8%, 10% second monomers methyl methacrylate, 0.2% the 3rd monomer dimethylaminoethyl acrylate methyl are added stirring and dissolving in the ionic liquid successively for amino ethyl ester, 1% initator peroxidating decoyl, 1.5% light-colored agent thiourea dioxide, 1% molecular weight regulator isopropyl alcohol; Wherein to account for the mass percent of solution be 5% to total monomer; 65 ℃ of following polymerisations 3 hours, viscosity average molecular weigh be 2.0 * 10
5The ionic liquid solution of acrylonitrile copolymer.Under 65 ℃, take off list, 65 ℃ are filtered deaeration down, extrude through measuring pump and spinnerets, through the humid air layer of 10cm; Temperature is 10 ℃, and humidity 90% gets into 10 ℃ coagulating bath; Coagulating bath is a water, and the predraft water-bath through 50 ℃ of deflector roll entering gets into 85 ℃ hot water stretch bath then; Draw ratio is 3.5, and the speed with 80m/min behind the washing of 25 ℃ spray woodss and 160 ℃ hot-air dry is wound into long filament, must filament number be the polyacrylonitrile fibre of 2.2dtex, intensity 4.0cN/dtex.
Embodiment 11
Ionic liquid, triethyl group ethanol ammonium chloride.
Monomer acrylonitrile, 1% initator ABVN are added stirring and dissolving in the ionic liquid successively, and wherein to account for the mass percent of solution be 15% to monomer, 75 ℃ of following polymerisations 3.5 hours, viscosity average molecular weigh be 4.0 * 10
4The ionic liquid solution of acrylonitrile copolymer.Under 75 ℃, take off list, 75 ℃ are filtered deaeration down, extrude through measuring pump and spinnerets; Through the humid air layer of 2cm, temperature is 15 ℃, humidity 85%; Get into 15 ℃ coagulating bath, coagulating bath is the ionic liquid aqueous solution of 15wt%, gets into 45 ℃ predraft water-bath through deflector roll; Get into 80 ℃ hot water stretch bath then; Draw ratio is 2.5, through the water at atmospheric pressure vapor water wash with 155 ℃ hot-air dry after be wound into long filament with the speed of 60m/min, filament number be the polyacrylonitrile fibre of 4.4dtex, intensity 2.0cN/dtex.
Embodiment 12
Ionic liquid, N, N '-dimethyl pyrrole bromide.
With the first monomer acrylonitrile that accounts for total monomer 85.2%, 14% the second monomer vinylacetate, the 3rd monomer 2-methyl-5-vinylpyridine of 0.8%, 1.0% di-isopropyl peroxydicarbonate; 1.5% initator thiourea dioxide, 1% light-colored agent, 1.0% molecular weight regulator isopropyl alcohol add stirring and dissolving in the ionic liquid successively; Wherein to account for the mass percent of solution be 10% to total monomer; 75 ℃ of following polymerisations 3 hours, viscosity average molecular weigh be 8.0 * 10
4The ionic liquid solution of acrylonitrile copolymer.Under 80 ℃, take off list, 80 ℃ are filtered deaeration down, extrude through measuring pump and spinnerets, through the humid air layer of 3cm; Temperature is 20 ℃, and humidity 80% gets into 20 ℃ coagulating bath; Coagulating bath is a water, and the predraft water-bath through 40 ℃ of deflector roll entering gets into 80 ℃ hot water stretch bath then; Draw ratio is 9, and the speed with 140m/min behind the washing of 30 ℃ spray woodss and 150 ℃ hot-air dry is wound into long filament, must filament number be the polyacrylonitrile fibre of 2.4dtex, intensity 3.6cN/dtex.
Embodiment 13
Ionic liquid, 1-ethyl-3-methylimidazole bromide.
The first monomer acrylonitrile that accounts for total monomer 84%, 16% the second monomer acrylamide, 1% initator azodiisobutyronitrile, 1% light-colored agent stannous chloride, 1% molecular weight regulator isopropyl alcohol are added stirring and dissolving in the ionic liquid successively; Wherein the mass percent of total monomer is 8%; 70 ℃ of following polymerisations 4 hours, viscosity average molecular weigh be 1.0 * 10
5The ionic liquid solution of acrylonitrile copolymer.Take off list at 70 ℃, 70 ℃ are filtered deaeration down, extrude through measuring pump and spinnerets; Through the humid air layer of 4cm, temperature is 25 ℃, humidity 75%; Get into 25 ℃ coagulating bath, the ionic liquid aqueous solution of coagulating bath 10wt% is through the predraft water-bath of 45 ℃ of deflector roll entering; Get into 85 ℃ hot water stretch bath then; Draw ratio is 6, through the water at atmospheric pressure vapor water wash with 145 ℃ hot-air dry after be wound into long filament with the speed of 120m/min, filament number be the polyacrylonitrile fibre of 2.6dtex, intensity 3.4cN/dtex.
Embodiment 14
Ionic liquid, N-ethylpyridine chloride.
With monomer acrylonitrile, 0.8% initator dibenzoyl peroxide, add stirring and dissolving in the ionic liquid successively, wherein to account for the mass percent of solution be 8% to monomer, 70 ℃ of following polymerisations 4.5 hours, viscosity average molecular weigh be 2.8 * 10
4The ionic liquid solution of acrylonitrile copolymer.Under 70 ℃, take off list, 70 ℃ are filtered deaeration down, extrude through measuring pump and spinnerets; Through the humid air layer of 5cm, temperature is 30 ℃, humidity 70%; Get into 30 ℃ coagulating bath, coagulating bath is 5% ionic liquid aqueous solution, gets into 50 ℃ predraft water-bath through deflector roll; Get into 90 ℃ hot water stretch bath then; Draw ratio is 2, and the speed with 55m/min behind the washing of 35 ℃ spray woodss and 140 ℃ hot-air dry is wound into long filament, must filament number be the polyacrylonitrile fibre of 4.8dtex, intensity 2.2cN/dtex.
Embodiment 15
Ionic liquid, 3-methyl-N-butyl-pyridinium trifluoroacetate.
The first monomer acrylonitrile that accounts for total monomer 82%, 18% the second monomer methyl acrylate, 1.0% initator ABVN, 1.5% light-colored agent thiourea dioxide, 1.0wt% molecular weight regulator isopropyl alcohol are added stirring and dissolving in the ionic liquid successively; Wherein to account for the mass percent of solution be 6wt% to total monomer; 70 ℃ of following polymerisations 5 hours, viscosity average molecular weigh be 8.4 * 10
4The ionic liquid solution of acrylonitrile copolymer.Under 70 ℃, take off list, 70 ℃ are filtered deaeration down, extrude through measuring pump and spinnerets, through the humid air layer of 6cm; Temperature is 25 ℃, and humidity 75% gets into 35 ℃ coagulating bath; Coagulating bath is a water, and the predraft water-bath through 55 ℃ of deflector roll entering gets into 95 ℃ hot water stretch bath then; Draw ratio is 3, through the water at atmospheric pressure vapor water wash with 100 ℃ hot-air dry after be wound into long filament with the speed of 85m/min, filament number be the polyacrylonitrile fibre of 4.0dtex, intensity 2.0cN/dtex.
Embodiment 16
Ionic liquid, 1-ethyl-3-methyl imidazolium tetrafluoroborate.
The first monomer acrylonitrile that accounts for total monomer 89.6%, 10% the second monomer methyl acrylate and 0.4% the 3rd monomer metering system benzene sulfonic acid sodium salt, 1.0% initator peroxidating decoyl, 1.5% light-colored agent thiourea dioxide, 1.0% molecular weight regulator isopropyl alcohol are added stirring and dissolving in the ionic liquid successively; Wherein to account for the mass percent of solution be 5% to total monomer; 70 ℃ of following polymerisations 6 hours, viscosity average molecular weigh be 2.6 * 10
4The ionic liquid solution of acrylonitrile copolymer.Under 70 ℃, take off list, 70 ℃ are filtered deaeration down, extrude through measuring pump and spinnerets, through the humid air layer of 7cm; Temperature is 20 ℃, and humidity 80% gets into 40 ℃ coagulating bath; Coagulating bath is a water, and the predraft water-bath through 60 ℃ of deflector roll entering gets into 90 ℃ hot water stretch bath then; Draw ratio is 2, and the speed with 20m/min behind the washing of 50 ℃ spray woodss and 120 ℃ hot-air dry is wound into long filament, must filament number be the polyacrylonitrile fibre of 5.0dtex, intensity 2.0cN/dtex.
Claims (11)
1. a dry-jet wet-spinning method for preparing polyacrylonitrile fibre comprises the following steps:
(1) preparation polyacrylonitrile ionic liquid spinning solution; The wherein solution formed by the polyacrylonitrile of mass percent 5～30%, 70～95% ionic liquid of polyacrylonitrile ionic liquid spinning solution or the solution formed by the water of the polyacrylonitrile of mass percent 5～30%, 67～95% ionic liquid and 0～3%; Ionic liquid is made up of CATION and anion, and CATION is selected from a kind of in the following CATION:
Alkyl quaternary ammonium ion ethoxy alkyl quaternary ammonium ion alkyl sulfonium cation alkyl quaternary phosphonium ion
Alkyl pyridinium ion alkyl pyrroles ion alkyl pyrazoles ion alkyl imidazol ion
Wherein: R1, R2, R3, R4, R5 and R6 can be identical, also can be different, be respectively that H or carbon number are the alkyl of 1-8; Anion is selected from Cl
-, Br
-, BF
4 -, PF
6 -, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-Or (CF
3SO
2)
3C
-In a kind of;
(2) after the deaeration of spinning solution process, filtration, the metering, extrude the back through spinning head and form dynamic analysis of spinning,, get into the coagulating bath solidification forming through the humid air layer; Wherein the humid air layer is meant in spinnerets and the coagulating bath that the distance of air layer is 1～10cm between the liquid level, and the temperature of air layer is 5～30 ℃, and relative humidity is 60～95%;
(3) carry out predraft, stretching, washing, dried heat typing back one-tenth fibre, preparation polyacrylonitrile long filament or short silk.
2. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1 is characterized in that: the preparation method of said polyacrylonitrile ionic liquid spinning solution is meant polyacrylonitrile is dissolved in the ionic liquid preparation spinning solution or is that solvent carries out polymerization of acrylonitrile and directly prepares spinning solution with the ionic liquid.
3. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1; It is characterized in that: described polyacrylonitrile is copolymer or the copolymer of first and second monomer or the homopolymers of acrylonitrile of first, second and third monomer, and viscosity average molecular weigh is 2.0 * 10
4～2.0 * 10
5The copolymer of first, second and third monomer is meant that the mass percent of second monomer in the copolymer is 3～18wt%, and the content of the 3rd monomer is 0.1～1.0wt%; The copolymer of first and second monomer or acrylonitrile homopolymer are meant that the content of second monomer in the polymer is 0～18wt%; First monomer is an acrylonitrile; Second monomer is a kind of in methyl acrylate, methyl methacrylate, methacrylonitrile, vinylacetate or the acrylamide, and what the 3rd monomer was itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine, 2-methyl-5-vinylpyridine or dimethylaminoethyl acrylate methyl in the amino ethyl ester is a kind of.
4. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1, it is characterized in that: described spinning solution temperature is 70～120 ℃.
5. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1; It is characterized in that: described coagulating bath is made up of ionic liquid and water; Temperature is 5～35 ℃, 0＜ionic liquid≤20% (mass percent) wherein, and the mass percent of water is 80～100%.
6. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1 is characterized in that: described coagulating bath is by being water, and temperature is 5～35 ℃.
7. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1 is characterized in that: the predraft that described predraft is adopted is bathed and is water, 40～65 ℃ of temperature.
8. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1 is characterized in that: the stretch bath that described stretching is adopted is a water, 80～99 ℃ of water temperatures.
9. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1 is characterized in that: said washing is meant the spray washing, 25～50 ℃ of temperature or the washing of water at atmospheric pressure steam.
10. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1, it is characterized in that: described drying is meant hot-air dry, baking temperature is 120～165 ℃.
11. a kind of dry-jet wet-spinning method for preparing polyacrylonitrile fibre according to claim 1 is characterized in that: described polyacrylonitrile fibre is meant that filament number is 1.5～5.0dtex, intensity 2.0～4.2cN/dtex.
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| CN101724922B (en) * | 2009-11-26 | 2012-09-05 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber |
| CN101818380B (en) * | 2010-02-05 | 2013-05-22 | 金发科技股份有限公司 | Method for preparing polyacrylonitrile carbon fiber precursor by adopting dry-jet wet spinning method |
| CN102277629B (en) * | 2011-06-10 | 2013-04-17 | 金发科技股份有限公司 | Dry-jet wet-spinning method for preparing polyacrylonitrile carbon fiber precursor |
| DE102012004118A1 (en) * | 2011-10-26 | 2013-05-02 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Carbon fibers, carbon fiber precursors and their production |
| CN102732981A (en) * | 2012-06-21 | 2012-10-17 | 精源(南通)化纤制品有限公司 | Polyacrylonitrile artificial hair and preparation method thereof |
| CN104562270A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Wet spinning method for improving acrylic fiber glossiness |
| CN104313717B (en) * | 2014-11-06 | 2018-01-12 | 西安元创化工科技股份有限公司 | A kind of production method with high-strength polypropylene nitrile fiber |
| JP6909453B2 (en) * | 2015-02-04 | 2021-07-28 | 三菱ケミカル株式会社 | High-performance fiber manufacturing method |
| CN105350115A (en) * | 2015-12-15 | 2016-02-24 | 常熟市金羽纤维制品厂 | Preparation method of pre-oxidized fibre |
| CN106048741B (en) * | 2016-07-15 | 2019-03-05 | 吉林富博纤维研究院有限公司 | A kind of method that dry-wet spinning prepares cellulose fibre |
| CN107557882A (en) * | 2017-09-12 | 2018-01-09 | 中安信科技有限公司 | Prepare the dry-jet wet-spinning spinning process of high performance carbon fiber used polyacrylonitrile precursor |
| CN107988707A (en) * | 2017-12-25 | 2018-05-04 | 合肥洁诺无纺布制品有限公司 | A kind of non-woven fabrics neonate blanket of fluffy antibacterial and preparation method thereof |
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