CN103233291A - Preparation method of moisture-absorption polyacrylonitrile fiber - Google Patents
Preparation method of moisture-absorption polyacrylonitrile fiber Download PDFInfo
- Publication number
- CN103233291A CN103233291A CN2013102167917A CN201310216791A CN103233291A CN 103233291 A CN103233291 A CN 103233291A CN 2013102167917 A CN2013102167917 A CN 2013102167917A CN 201310216791 A CN201310216791 A CN 201310216791A CN 103233291 A CN103233291 A CN 103233291A
- Authority
- CN
- China
- Prior art keywords
- polyacrylonitrile
- moisture absorption
- preparation
- acid
- hydrolyzed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a preparation method of moisture-absorption polyacrylonitrile fiber. The preparation method comprises the following steps of: (1) carrying out hydrolysis treatment on an acrylonitrile copolymer by using an alkaline metal salt solution; (2) settling out by using a solvent, filtering and adjusting pH value; (3) blending polyacrylonitrile hydrolysate into a hydrolyzed polyacrylonitrile stock solution by using a spinning solvent; (4) adjusting the temperature of the hydrolyzed polyacrylonitrile stock solution, and sufficiently and uniformly mixing the hydrolyzed polyacrylonitrile stock solution and a conventionally produced polyacrylonitrile stock solution to prepare a moisture-absorption polyacrylonitrile stock solution; and (5) enabling the moisture-absorption polyacrylonitrile stock solution to be subjected to working procedures, namely extruding, solidifying and forming, pre-drafting, water washing, hydrophilic treatment, thermal drafting, densifying-crosslinking, sizing, oiling and drying to obtain the moisture-absorption polyacrylonitrile fiber. According to the preparation method, the moisture-absorption polyacrylonitrile fiber is favorable in moisture-absorption property, good in uniformity, excellent in durability, free of limit from fiber number and length and high in production efficiency.
Description
Technical field
The invention belongs to chemical fibre manufacturing technology field, be specifically related to a kind of manufacture method of moisture absorption polyacrylonitrile fibre.
Background technology
Polyacrylonitrile fibre is one of three big synthetic fiber, has characteristics such as good warmth retention property, dyeability and simulate wool, and the title of artificial wool is arranged, and is widely used in the fields of taking such as knitted underwear, woollen blanket, Fake Furss.But along with growing with clothing design of improving constantly of people's living standard, warming no longer is the unitary request of clothes, and people are to its comfort level, functional and security requirement is more and more higher.The gender gap comfortable and easy to wear of different fibrous material clothes is relevant with the moisture pick-up properties of fiber, and moisture pick-up properties can be represented with official regain.The official regain of natural fabric is about 8～15%, and polyacrylonitrile fibre only is 2%, show serious defective in performances relevant with the human body skin-friendly such as hygroscopicity, poisture-penetrabilitys, make its clothing dress of making have feeling of oppression and heat, sweat to be difficult for being absorbed and distributing, static behaviour is strong, often need to spin the blend ratio after additional functionality processing or the minimizing, not only increase processing cost, and the durability for the treatment of effect is lower, thereby greatly reduce the wearability of polyacrylonitrile fibre, more use limited in some field that has antistatic behaviour to require.
In order to improve the hygroscopicity of acrylic fibers, improve the wearing comfort of acrylic fibers, the researcher has adopted several different methods that the moisture pick-up properties of acrylic fibers is carried out modification.For example CN1900413A provides a kind of employing acrylic fiber surface graft protein to carry out modification, at first under certain condition with the acrylic fiber hydrolysis, then hydrolysis fiber and thionyl chloride are reacted the chloride fiber, again with the protein grafting, making superficial layer is phytoprotein grafting cover layer, core is the modified fibre of acrylic fiber, has improved the hygroscopicity of acrylic fibers.But because the grafting limited amount makes that the hygroscopic raising of acrylic fibers is limited, modified effect is not obvious.Abroad adopt chemical modification method carry out the moisture absorption polyacrylonitrile prepare aspect research early.As Japan in the patent disclosures such as CN1239775C, CN1247849C, CN1230585C, CN101023212B and CN101914852A of China application polyacrylonitrile fibre is hydrolyzed and the method for compound crosslink Processing of Preparation water absorbent fiber, and improve at fibre whiteness and fire resistance respectively.The durability of these methods is better, but shortcoming be since hydrolysis and crosslinked chemical treatment time longer, can only be applied to spin process in batches behind the staple fibre, belong to a kind of off-line and produce the manufacture method of water absorbent fiber, thereby the inhomogeneity of the moisture absorption of fiber treatment and fibrous physics mechanical performance is higher, and production efficiency is low.
In addition, also there is the method for monomer by adding the hygroscopicity group in the polymerization formula or latent crosslinker to prepare the report of similar hygroscopicity polyacrylonitrile fibre, but because the change of copolymerization process is to polymerization production control and polymerizate Effect on Performance, and the follow-up basic hydrolysis processing of spinning the long period indispensable on the journey, make these class methods not have the condition of online production moisture absorption polyacrylonitrile fibre.
Summary of the invention
The present invention is directed to the above-mentioned state of the art, from satisfying the requirement of taking of polyacrylonitrile fibre, provide a kind of online production method that in conventional polyacrylonitrile fibre manufacture process, obtains the moisture absorption polyacrylonitrile fibre.Under the prerequisite that does not change polymerization technique, adopt polyacrylonitrile basic hydrolysis solution and the conventional polyacrylonitrile stoste that obtains of producing to carry out a certain proportion of blend and spinning, thus preparation moisture absorption polyacrylonitrile fibre.
The preparation method of a kind of moisture absorption polyacrylonitrile fibre of the present invention comprises the steps:
(1) acrylonitrile copolymer hydrolysis
With the aqueous solution of alkaline metal salt to the polymer processing that is hydrolyzed;
Acrylonitrile copolymer is 1:0.5～1:2.0 with the ratio of the quality of alkaline metal salt, and hydrolysising reacting temperature is 80～110 ℃, and hydrolysis time is 1～10 hour;
Cyano group in the acrylonitrile copolymer has greater activity, and cyano group reacts under the effect of alkalinous metal saline solution, can hydrolysis generate moisture absorption groups such as amide groups, carboxyl;
(2) precipitating
In order to improve the concentration of polyacrylonitrile hydrolyzed thing in hydrolyzate, with the hydrolyzate solvent precipitation of described hydrolysis process gained, polyacrylonitrile hydrolyzed liquid after filtering shows as alkalescence, adds acid for adjusting pH value to 4～7, obtains polyacrylonitrile hydrolyzed thing;
(3) preparation hydrolyzed polyacrylonitrile stoste
For the ease of adding, further realize and the even blend of conventional stoste, need polyacrylonitrile hydrolyzed thing is mixed with solution.Described polyacrylonitrile hydrolyzed thing is deployed into hydrolyzed polyacrylonitrile stoste with spin solvent, and the adjusting solid content is 10～40wt%;
(4) preparation moisture absorption polyacrylonitrile stoste
Polyacrylonitrile is through the molecular weight and molecular weight after the hydrolysis, water-solublely improves greatly, can't satisfy the wet spinning requirement, and hydrolyzed polyacrylonitrile stoste and conventional polyacrylonitrile stoste can be obtained stable and uniform, satisfy the stoste of spinning fibre requirement with the certain proportion blend.
With described hydrolyzed polyacrylonitrile stoste temperature adjustment to 70～80 ℃, the polyacrylonitrile stoste of producing with routine fully mixes, and prepares moisture absorption polyacrylonitrile stoste; Wherein, described hydrolyzed polyacrylonitrile stoste accounts for 5～40wt% of described moisture absorption polyacrylonitrile stoste.More conventional stoste, moisture absorption polyacrylonitrile stoste contains the hydrolysising original liquid of a large amount of moisture absorption groups owing to the blend molecular structure, thereby has the suction moisture pick-up properties;
(5) spinning solidification forming
Spinning solution is extruded from spinnerets, forms as-spun fibre in coagulating bath;
(6) preliminary draft
1.0～3.5 times of as-spun fibre preliminary drafts behind the coagulation forming;
(7) washing
As-spun fibre washing flush away spin solvent behind the preliminary draft, water temperature is 45～65 ℃;
(8) hydrophily is handled
Be that 9～12 cushioning liquid carries out hydrophilicity-imparting treatment with the method for dipping and spray combination with pH, make the H type carboxyl on the fiber be converted into salt type carboxyl;
(9) hot drawing-off
In 98～100 ℃ hot water, carry out 2.5～5.0 times water-bath drawing-off;
(10) densification-crosslinked
Fiber after the hot drawing-off is carried out heat cross-linking under 105～145 ℃ handle;
(11) curling and typing
Adopt hot bath or decatize mode preheating tow to carry out machine crimp, the fiber after curling carries out the saturated vapor HEAT SETTING to be handled, and heat setting temperature is 120～135 ℃;
(12) oil and dry
Fiber floods and oils after the HEAT SETTING, and oil groove concentration is 1.0～3.0%, afterwards, is lax oven dry in 90～120 ℃ second drying machine in temperature.
As optimized technical scheme:
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described alkaline metal salt is alkali metal hydroxide, alkaline earth metal hydroxide or alkali carbonate; The concentration of aqueous solution of described alkaline metal salt is 1～40wt%.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described alkali metal hydroxide is NaOH or potassium hydroxide; Described alkaline earth metal hydroxide is magnesium hydroxide or calcium hydroxide; Described alkali carbonate is sodium bicarbonate or saleratus.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described acrylonitrile copolymer is the copolymer of acrylonitrile monemer and other second comonomer and/or the 3rd comonomer; Described other second comonomer is a kind of in acrylate monomer, methacrylate monomers or the vinyl acetate, and the 3rd comonomer is a kind of in methylpropene sodium sulfonate, Sodium styrene sulfonate, sodium vinyl sulfonate or the 2-acrylamido-2-methyl propane sulfonic acid.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described acrylate monomer is methyl acrylate, ethyl acrylate or butyl acrylate; Described methacrylate monomers is methyl methacrylate, ethyl methacrylate or butyl methacrylate.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described acid is inorganic acid or the organic acid aqueous solution; Described inorganic acid is nitric acid, hydrochloric acid or sulfuric acid, and described organic acid is formic acid, acetic acid or ethanedioic acid.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described spin solvent is organic solvent or inorganic solvent; Described organic solvent is dimethyl formamide, dimethyl sulfoxide (DMSO) or dimethylacetylamide, and described inorganic solvent is sodium thiocyanate water solution or solder(ing)acid.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described solvent is absolute ethyl alcohol, acetone or methyl alcohol.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, in the described moisture absorption polyacrylonitrile stoste, the acrylonitrile copolymer main chain is the C-C singly-bound, contains carboxyl, amide groups and a large amount of cyano group in the big molecule of acrylonitrile copolymer simultaneously.Described moisture absorption polyacrylonitrile stoste is by conventional polyacrylonitrile stoste, the 5～40wt% hydrolyzed polyacrylonitrile stoste of 60～95wt%, and when adopting inorganic solvent, wherein polyacrylonitrile is 10～24.4wt%, and solvent is 38～45wt%, and water is 30.6～52wt%; When adopting organic solvent, wherein polyacrylonitrile is 20～30wt%, and solvent is 70～80wt%.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described cushioning liquid is sodium carbonate-sodium bicarbonate, NaOH-boric acid-potassium chloride, NaOH-amion acetic acid-sodium chloride or potassium chloride-sodium hydroxide buffer solution; Described method with dipping and spray combination is to instigate fiber impregnation to pass through the bath of an above-mentioned cushioning liquid, and cushioning liquid is circulated to one group of shower ejection of bath tow operation top by pump, strengthens reduction effect.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described moisture absorption polyacrylonitrile fibre is endless tow or staple fibre.
The preparation method of aforesaid a kind of moisture absorption polyacrylonitrile fibre, described fiber hygroscopicity index regain records as follows: a kind of moisture absorption polyacrylonitrile fibre sample (about 5 gram) is dried to constant weight and its weight of weighing is W1(g in 105 ℃ electric drying oven with forced convection), then sample was placed in the climatic chamber that remains on 20 ℃ and 65%RH condition 24 hours, the weight of the sample after the weighing moisture absorption is W2(g).Calculate the sample regain by following formula:
Regain (%)=[(W2-W1)/W1] * 100%
Beneficial effect:
The preparation method of a kind of moisture absorption polyacrylonitrile fibre provided by the present invention obtains the moisture absorption polyacrylonitrile fibre in conventional polyacrylonitrile fibre manufacture process.The moisture absorption polyacrylonitrile fibre that is obtained by the present invention not only has good moisture pick-up properties, and good uniformity, and durability is good, is not subjected to the restriction of fibre number, length, the production efficiency height.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications 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
The acrylonitrile compolymer body of being made up of acrylonitrile, methyl acrylate and methylpropene sodium sulfonate is hydrolyzed in the 1wt% sodium hydrate aqueous solution, the mass ratio of acrylonitrile copolymer and NaOH is 1:0.5, hydrolysis temperature is 90 ℃, hydrolysis time is 2 hours, then with the hydrolyzate of hydrolysis process gained absolute ethyl alcohol precipitating, filter back nitre acid for adjusting pH value to 4, then resulting polyacrylonitrile hydrolyzed thing being become solid content with the NaSCN preparing solution is the hydrolyzed polyacrylonitrile stoste of 13wt%.With this hydrolyzed polyacrylonitrile stoste temperature adjustment to 70 ℃, fully mix with conventional polyacrylonitrile stoste of producing, obtain moisture absorption polyacrylonitrile stoste, wherein hydrolyzed polyacrylonitrile stoste accounts for the 5wt% of described moisture absorption polyacrylonitrile stoste.Moisture absorption polyacrylonitrile stoste is extruded from spinnerets, in coagulating bath, solidify the formation as-spun fibre, as-spun fibre is through 1.5 times of preliminary drafts then, afterwards through 45 ℃ of washings, NaOH-boric acid-potassium chloride buffer solution with pH=9 carries out hydrophilicity-imparting treatment, through carrying out 4.0 times hot water drawing-off in 98 ℃ the hot water, the fiber after the hot drawing-off carries out heat cross-linking under 105 ℃ handles again.Curl then, finalize the design, oil, dry.Heat setting temperature is 120 ℃, and the oil concentration that oils is 1.2%, and bake out temperature is 100 ℃.Obtain the moisture absorption polyacrylonitrile fibre.This fiber can be cut off on request, make the moisture absorption Orlon of different length.The regain that records this fiber is 16%.
Embodiment 2
The acrylonitrile compolymer body of being made up of acrylonitrile and methyl methacrylate is hydrolyzed in the 8wt% potassium hydroxide aqueous solution, the mass ratio of acrylonitrile copolymer and potassium hydroxide is 1:0.8, hydrolysis temperature is 100 ℃, hydrolysis time is 3 hours, then with the hydrolyzate of hydrolysis process gained absolute ethyl alcohol precipitating, filter the back with first acid for adjusting pH value to 5, then resulting polyacrylonitrile hydrolyzed thing is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 12wt% with dimethyl sulfoxide (DMSO).With this hydrolyzed polyacrylonitrile stoste temperature adjustment to 70 ℃, fully mix with conventional polyacrylonitrile stoste of producing, obtain moisture absorption polyacrylonitrile stoste, wherein hydrolyzed polyacrylonitrile stoste accounts for the 15wt% of described moisture absorption polyacrylonitrile stoste.Moisture absorption polyacrylonitrile stoste is extruded from spinnerets, in coagulating bath, solidify the formation as-spun fibre, as-spun fibre is through 1.0 times of preliminary drafts then, afterwards through 50 ℃ of washings, sodium carbonate-sodium bicarbonate buffer solution with pH=9.5 carries out hydrophilicity-imparting treatment, through carrying out 5.0 times hot water drawing-off in 100 ℃ the hot water, the fiber after the hot drawing-off carries out heat cross-linking under 120 ℃ handles again.Curl then, finalize the design, oil, dry.Heat setting temperature is 125 ℃, and the oil concentration that oils is 1.0%, and bake out temperature is 110 ℃.Obtain the moisture absorption polyacrylonitrile fibre.This fiber can be cut off on request, make the moisture absorption Orlon of different length.The regain that records this fiber is 23%.
Embodiment 3
The acrylonitrile compolymer body of being made up of acrylonitrile and ethyl acrylate is hydrolyzed in the 10wt% sodium hydrate aqueous solution, the mass ratio of acrylonitrile copolymer and NaOH is 1:1.0, hydrolysis temperature is 105 ℃, hydrolysis time is 1 hour, then with the hydrolyzate of hydrolysis process gained acetone precipitating, filter the back with salt acid for adjusting pH value to 5, then resulting polyacrylonitrile hydrolyzed thing is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 15wt% with solder(ing)acid.With this hydrolyzed polyacrylonitrile stoste temperature adjustment to 70 ℃, fully mix with conventional polyacrylonitrile stoste of producing, obtain moisture absorption polyacrylonitrile stoste, wherein hydrolyzed polyacrylonitrile stoste accounts for the 10wt% of described moisture absorption polyacrylonitrile stoste.Moisture absorption polyacrylonitrile stoste is extruded from spinnerets, in coagulating bath, solidify the formation as-spun fibre, as-spun fibre is through 2.3 times of preliminary drafts then, afterwards through 58 ℃ of washings, NaOH-amion acetic acid-sodium chloride cushioning liquid with pH=11 carries out hydrophilicity-imparting treatment, through carrying out 4.0 times hot water drawing-off in 99 ℃ the hot water, the fiber after the hot drawing-off carries out heat cross-linking under 110 ℃ handles again.Curl then, finalize the design, oil, dry.Heat setting temperature is 120 ℃, and the oil concentration that oils is 2.3%, and bake out temperature is 110 ℃.Obtain the moisture absorption polyacrylonitrile fibre.The regain that records this fiber is 28%.
Embodiment 4
Receiving the acrylonitrile compolymer body of forming by acrylonitrile, ethyl acrylate and vinyl sulfonic acid is hydrolyzed in the 12wt% magnesium hydroxide aqueous solution, the mass ratio of acrylonitrile copolymer and magnesium hydroxide is 1:1.2, hydrolysis temperature is 95 ℃, hydrolysis time is 2 hours, then with the hydrolyzate of hydrolysis process gained acetone precipitating, filter the back with sulphur acid for adjusting pH value to 6, then resulting polyacrylonitrile hydrolyzed thing is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 15wt% with dimethylacetylamide.With this hydrolyzed polyacrylonitrile stoste temperature adjustment to 80 ℃, fully mix with conventional polyacrylonitrile stoste of producing, obtain moisture absorption polyacrylonitrile stoste, wherein hydrolyzed polyacrylonitrile stoste accounts for the 5wt% of described moisture absorption polyacrylonitrile stoste.Moisture absorption polyacrylonitrile stoste is extruded from spinnerets, in coagulating bath, solidify the formation as-spun fibre, as-spun fibre is through 2.5 times of preliminary drafts then, afterwards through 53 ℃ of washings, NaOH-boric acid-Klorvess Liquid with pH=9.8 carries out hydrophilicity-imparting treatment, through carrying out 3.0 times hot water drawing-off in 99 ℃ the hot water, the fiber after the hot drawing-off carries out heat cross-linking under 130 ℃ handles again.Curl then, finalize the design, oil, dry.Heat setting temperature is 120 ℃, and the oil concentration that oils is 3.0%, and bake out temperature is 90 ℃.Obtain the moisture absorption polyacrylonitrile fibre.The regain that records this fiber is 15%.
Embodiment 5
The acrylonitrile compolymer body of being made up of acrylonitrile, butyl acrylate and Sodium styrene sulfonate is hydrolyzed in the 15wt% calcium hydroxide aqueous solution, the mass ratio of acrylonitrile copolymer and calcium hydroxide is 1:1.5, hydrolysis temperature is 95 ℃, hydrolysis time is 4 hours, then with the hydrolyzate of hydrolysis process gained methyl alcohol precipitating, filter back second acid for adjusting pH value to 6, then resulting polyacrylonitrile hydrolyzed thing being become solid content with the NaSCN preparing solution is the hydrolyzed polyacrylonitrile stoste of 13wt%.With this hydrolyzed polyacrylonitrile stoste temperature adjustment to 80 ℃, fully mix with conventional polyacrylonitrile stoste of producing, obtain moisture absorption polyacrylonitrile stoste, wherein hydrolyzed polyacrylonitrile stoste accounts for the 20wt% of described moisture absorption polyacrylonitrile stoste.Moisture absorption polyacrylonitrile stoste is extruded from spinnerets, in coagulating bath, solidify the formation as-spun fibre, as-spun fibre is through 2.6 times of preliminary drafts then, afterwards through 55 ℃ of washings, potassium chloride-sodium hydroxide buffer solution with pH=13 carries out hydrophilicity-imparting treatment, through carrying out 3.5 times hot water drawing-off in 100 ℃ the hot water, the fiber after the hot drawing-off carries out heat cross-linking under 145 ℃ handles again.Curl then, finalize the design, oil, dry.Heat setting temperature is 130 ℃, and the oil concentration that oils is 2.0%, and bake out temperature is 110 ℃.Obtain the moisture absorption polyacrylonitrile fibre.The regain that records this fiber is 19%.
Embodiment 6
The acrylonitrile compolymer body of being made up of acrylonitrile, butyl acrylate and 2-acrylamido-2-methyl propane sulfonic acid is hydrolyzed in the 30wt% sodium bicarbonate aqueous solution, the mass ratio of acrylonitrile copolymer and sodium bicarbonate is 1:1.8, hydrolysis temperature is 110 ℃, hydrolysis time is 5 hours, then with the hydrolyzate of hydrolysis process gained methyl alcohol precipitating, filter the back and regulate pH value to 7 with ethanedioic acid, then resulting polyacrylonitrile hydrolyzed thing is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 40wt% with dimethyl formamide.With this hydrolyzed polyacrylonitrile stoste temperature adjustment to 80 ℃, fully mix with conventional polyacrylonitrile stoste of producing, obtain moisture absorption polyacrylonitrile stoste, wherein hydrolyzed polyacrylonitrile stoste accounts for the 25wt% of described moisture absorption polyacrylonitrile stoste.Moisture absorption polyacrylonitrile stoste is extruded from spinnerets, in coagulating bath, solidify the formation as-spun fibre, as-spun fibre is through 2.8 times of preliminary drafts then, afterwards through 65 ℃ of washings, NaOH-amion acetic acid-sodium chloride cushioning liquid with pH=12 carries out hydrophilicity-imparting treatment, through carrying out 3.5 times hot water drawing-off in 100 ℃ the hot water, the fiber after the hot drawing-off carries out heat cross-linking under 145 ℃ handles again.Curl then, finalize the design, oil, dry.Heat setting temperature is 135 ℃, and the oil concentration that oils is 2.5%, and bake out temperature is 110 ℃.Obtain the moisture absorption polyacrylonitrile fibre.The regain that records this fiber is 17%.
Embodiment 7
The acrylonitrile compolymer body of being made up of acrylonitrile, vinyl acetate and methylpropene sodium sulfonate is hydrolyzed in the 40wt% potassium bicarbonate aqueous solution, the mass ratio of acrylonitrile copolymer and saleratus is 1:2.0, hydrolysis temperature is 80 ℃, hydrolysis time is 10 hours, then with the hydrolyzate of hydrolysis process gained methyl alcohol precipitating, filter the back with salt acid for adjusting pH value to 7, then resulting polyacrylonitrile hydrolyzed thing is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 20wt% with dimethyl formamide.With this hydrolyzed polyacrylonitrile stoste temperature adjustment to 80 ℃, fully mix with conventional polyacrylonitrile stoste of producing, obtain moisture absorption polyacrylonitrile stoste, wherein hydrolyzed polyacrylonitrile stoste accounts for the 40wt% of described moisture absorption polyacrylonitrile stoste.Moisture absorption polyacrylonitrile stoste is extruded from spinnerets, in coagulating bath, solidify the formation as-spun fibre, as-spun fibre is through 1.8 times of preliminary drafts then, afterwards through 50 ℃ of washings, NaOH-boric acid-potassium chloride buffer solution with pH=10 carries out hydrophilicity-imparting treatment, through carrying out 2.5 times hot water drawing-off in 98 ℃ the hot water, the fiber after the hot drawing-off carries out heat cross-linking under 125 ℃ handles again.Curl then, finalize the design, oil, dry.Heat setting temperature is 120 ℃, and the oil concentration that oils is 2.3%, and bake out temperature is 120 ℃.Obtain the moisture absorption polyacrylonitrile fibre.The regain that records this fiber is 25%.
Claims (10)
1. the preparation method of a moisture absorption polyacrylonitrile fibre is characterized in that comprising the steps:
(1) acrylonitrile copolymer hydrolysis;
With the aqueous solution of alkaline metal salt to the polymer processing that is hydrolyzed;
Acrylonitrile copolymer is 1:0.5～1:2.0 with the ratio of the quality of alkaline metal salt, and hydrolysising reacting temperature is 80～110 ℃, and hydrolysis time is 1～10 hour;
(2) precipitating;
With the hydrolyzate solvent precipitation of described hydrolysis process gained, filter the back and add acid for adjusting pH value to 4～7, the polyacrylonitrile hydrolyzed thing that obtains;
(3) preparation hydrolyzed polyacrylonitrile stoste;
Described polyacrylonitrile hydrolyzed thing is deployed into hydrolyzed polyacrylonitrile stoste with spin solvent, and the adjusting solid content is 10～40wt%;
(4) preparation moisture absorption polyacrylonitrile stoste;
With described hydrolyzed polyacrylonitrile stoste temperature adjustment to 70～80 ℃, the polyacrylonitrile stoste of producing with routine fully mixes, and prepares moisture absorption polyacrylonitrile stoste; Wherein, described hydrolyzed polyacrylonitrile stoste accounts for 5～40wt% of described moisture absorption polyacrylonitrile stoste;
(5) spinning solidification forming;
Described moisture absorption polyacrylonitrile stoste is extruded from spinnerets, formed as-spun fibre through coagulating bath;
(6) preliminary draft;
With 1.0～3.5 times of as-spun fibre preliminary drafts;
(7) washing;
Wash the flush away spin solvent then, washing temperature is 45～65 ℃;
(8) hydrophilicity-imparting treatment;
Be that 9～12 cushioning liquid carries out hydrophilicity-imparting treatment with the method for dipping and spray combination with pH;
(9) hot drawing-off;
In 98～100 ℃ hot water, carry out 2.5～5.0 times water-bath drawing-off;
(10) densification-crosslinked;
Fiber after the hot drawing-off is carried out heat cross-linking under 105～145 ℃ handle;
(11) curling and typing;
Adopt hot bath or decatize mode preheating tow to carry out machine crimp, the fiber after curling carries out the saturated vapor HEAT SETTING to be handled, and heat setting temperature is 120～135 ℃;
(12) oil and dry;
Fiber floods and oils after the HEAT SETTING, and oil groove concentration is 1.0～3.0%, afterwards, is lax oven dry in 90～120 ℃ second drying machine in temperature;
Obtain the moisture absorption polyacrylonitrile fibre.
2. the preparation method of a kind of moisture absorption polyacrylonitrile fibre according to claim 1 is characterized in that, described alkaline metal salt is alkali metal hydroxide, alkaline earth metal hydroxide or alkali carbonate; The concentration of aqueous solution of described alkaline metal salt is 1～40wt%.
3. the preparation method of a kind of moisture absorption polyacrylonitrile fibre according to claim 2 is characterized in that, described alkali metal hydroxide is NaOH or potassium hydroxide; Described alkaline earth metal hydroxide is magnesium hydroxide or calcium hydroxide; Described alkali carbonate is sodium bicarbonate or saleratus.
4. the preparation method of a kind of moisture absorption polyacrylonitrile fibre according to claim 1 is characterized in that, described acrylonitrile copolymer is the copolymer of acrylonitrile monemer and other second comonomer and/or the 3rd comonomer; Described other second comonomer is a kind of in acrylate monomer, methacrylate monomers or the vinyl acetate, and the 3rd comonomer is a kind of in methylpropene sodium sulfonate, Sodium styrene sulfonate, sodium vinyl sulfonate or the 2-acrylamido-2-methyl propane sulfonic acid.
5. the preparation method of a kind of moisture absorption polyacrylonitrile fibre according to claim 4 is characterized in that, described acrylate monomer is methyl acrylate, ethyl acrylate or butyl acrylate; Described methacrylate monomers is methyl methacrylate, ethyl methacrylate or butyl methacrylate.
6. the preparation method of a kind of moisture absorption polyacrylonitrile fibre according to claim 1 is characterized in that, described acid is inorganic acid or the organic acid aqueous solution; Described inorganic acid is nitric acid, hydrochloric acid or sulfuric acid, and described organic acid is formic acid, acetic acid or ethanedioic acid.
7. the preparation method of a kind of moisture absorption polyacrylonitrile fibre according to claim 1 is characterized in that, described spin solvent is organic solvent or inorganic solvent; Described organic solvent is dimethyl formamide, dimethyl sulfoxide (DMSO) or dimethylacetylamide, and described inorganic solvent is sodium thiocyanate water solution or solder(ing)acid.
8. the preparation method of a kind of moisture absorption polyacrylonitrile fibre according to claim 1 is characterized in that, described solvent is absolute ethyl alcohol, acetone or methyl alcohol.
9. the preparation method of a kind of moisture absorption polyacrylonitrile fibre according to claim 1, it is characterized in that described cushioning liquid is sodium carbonate-sodium bicarbonate, NaOH-boric acid-potassium chloride, NaOH-amion acetic acid-sodium chloride or potassium chloride-sodium hydroxide buffer solution; Described method with dipping and spray combination is to instigate fiber impregnation to pass through the bath of an above-mentioned cushioning liquid, and cushioning liquid is circulated to one group of shower ejection of bath tow operation top by pump, strengthens reduction effect.
10. the preparation method of a kind of moisture absorption polyacrylonitrile fibre according to claim 1 is characterized in that, described moisture absorption polyacrylonitrile fibre is endless tow or staple fibre; Described moisture absorption polyacrylonitrile fibre has regain under 20 ℃ and 65%RH condition be 15～28%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310216791.7A CN103233291B (en) | 2013-05-31 | 2013-05-31 | Preparation method of moisture-absorption polyacrylonitrile fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310216791.7A CN103233291B (en) | 2013-05-31 | 2013-05-31 | Preparation method of moisture-absorption polyacrylonitrile fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103233291A true CN103233291A (en) | 2013-08-07 |
| CN103233291B CN103233291B (en) | 2015-04-08 |
Family
ID=48881355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310216791.7A Expired - Fee Related CN103233291B (en) | 2013-05-31 | 2013-05-31 | Preparation method of moisture-absorption polyacrylonitrile fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103233291B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103726182A (en) * | 2013-12-19 | 2014-04-16 | 苏州丽绣纺织有限公司 | Fleece fabric made of fibers with high moisture absorption |
| CN105088407A (en) * | 2015-09-15 | 2015-11-25 | 苏州顺唐化纤有限公司 | Preparation method for hydrophilic polyacrylonitrile fibers |
| CN105088378A (en) * | 2015-09-17 | 2015-11-25 | 无锡市长安曙光手套厂 | Method for preparing polyacrylonitrile nanofibers through electrostatic spinning technology |
| CN105113042A (en) * | 2015-09-15 | 2015-12-02 | 苏州顺唐化纤有限公司 | Moisture-absorption polyacrylonitrile fiber |
| CN107503136A (en) * | 2017-08-30 | 2017-12-22 | 广州弘雅服装科技有限公司 | Antistatic moisture-absorption polyacrylonitrile fiber, antistatic Hygroscopic material and preparation method and application |
| CN111133137A (en) * | 2017-09-22 | 2020-05-08 | 日本爱克兰工业株式会社 | Hygroscopic acrylic fiber, method for producing the fiber, and fiber structure containing the fiber |
| CN113882153A (en) * | 2021-11-02 | 2022-01-04 | 中国船舶重工集团公司第七一八研究所 | Method for preparing carboxylic acid fiber by catalytic hydrolysis of polyacrylonitrile |
| CN114573362A (en) * | 2022-01-26 | 2022-06-03 | 河南三林建设集团有限公司 | Green energy-saving resource brick making process for municipal sludge |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5458968A (en) * | 1994-01-26 | 1995-10-17 | Monsanto Company | Fiber bundles including reversible crimp filaments having improved dyeability |
| CN101818380A (en) * | 2010-02-05 | 2010-09-01 | 金发科技股份有限公司 | Method for preparing polyacrylonitrile carbon fiber precursor by adopting dry-jet wet spinning method |
| CN102733170A (en) * | 2012-07-06 | 2012-10-17 | 山东理工大学 | Method for preparing acrylic fibers with high water absorptivity and moisture absorptivity through acetalation |
| CN102953140A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method for polyacrylonitrile-based carbon fiber protofilament |
-
2013
- 2013-05-31 CN CN201310216791.7A patent/CN103233291B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5458968A (en) * | 1994-01-26 | 1995-10-17 | Monsanto Company | Fiber bundles including reversible crimp filaments having improved dyeability |
| CN101818380A (en) * | 2010-02-05 | 2010-09-01 | 金发科技股份有限公司 | Method for preparing polyacrylonitrile carbon fiber precursor by adopting dry-jet wet spinning method |
| CN102953140A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method for polyacrylonitrile-based carbon fiber protofilament |
| CN102733170A (en) * | 2012-07-06 | 2012-10-17 | 山东理工大学 | Method for preparing acrylic fibers with high water absorptivity and moisture absorptivity through acetalation |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103726182A (en) * | 2013-12-19 | 2014-04-16 | 苏州丽绣纺织有限公司 | Fleece fabric made of fibers with high moisture absorption |
| CN105088407A (en) * | 2015-09-15 | 2015-11-25 | 苏州顺唐化纤有限公司 | Preparation method for hydrophilic polyacrylonitrile fibers |
| CN105113042A (en) * | 2015-09-15 | 2015-12-02 | 苏州顺唐化纤有限公司 | Moisture-absorption polyacrylonitrile fiber |
| CN105088378A (en) * | 2015-09-17 | 2015-11-25 | 无锡市长安曙光手套厂 | Method for preparing polyacrylonitrile nanofibers through electrostatic spinning technology |
| CN107503136A (en) * | 2017-08-30 | 2017-12-22 | 广州弘雅服装科技有限公司 | Antistatic moisture-absorption polyacrylonitrile fiber, antistatic Hygroscopic material and preparation method and application |
| CN111133137A (en) * | 2017-09-22 | 2020-05-08 | 日本爱克兰工业株式会社 | Hygroscopic acrylic fiber, method for producing the fiber, and fiber structure containing the fiber |
| CN111133137B (en) * | 2017-09-22 | 2022-05-10 | 日本爱克兰工业株式会社 | Hygroscopic acrylic fiber, method for producing the fiber, and fiber structure containing the fiber |
| CN113882153A (en) * | 2021-11-02 | 2022-01-04 | 中国船舶重工集团公司第七一八研究所 | Method for preparing carboxylic acid fiber by catalytic hydrolysis of polyacrylonitrile |
| CN113882153B (en) * | 2021-11-02 | 2023-06-06 | 中国船舶重工集团公司第七一八研究所 | Method for preparing carboxylic acid fiber by polyacrylonitrile catalytic hydrolysis |
| CN114573362A (en) * | 2022-01-26 | 2022-06-03 | 河南三林建设集团有限公司 | Green energy-saving resource brick making process for municipal sludge |
| CN114573362B (en) * | 2022-01-26 | 2022-11-25 | 河南三林建设集团有限公司 | Green energy-saving resource brick making process for municipal sludge |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103233291B (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103233291B (en) | Preparation method of moisture-absorption polyacrylonitrile fiber | |
| CN103266381B (en) | Preparation method for moisture-absorbing and heat-radiating polyacrylonitrile yarn | |
| CN103205821B (en) | Preparation method of moisture-absorption flat polyacrylonitrile fiber | |
| CN107237004B (en) | Crosslinked acrylate fiber and fiber structure containing the same | |
| CN102493016B (en) | Porous superfine polyamide 6 fully-drawn yarn, preparation method thereof, and equipment thereof | |
| WO2016127833A1 (en) | Acetic nitrile fibre and preparation method therefor | |
| CN102277644B (en) | Polyacrylonitrile-based protofilaments modified by phenolic resin and preparation method thereof | |
| CN100579997C (en) | Functionalization polyacrylonitrile resin, production and application of the same in fibre | |
| CN103882547A (en) | Flat acrylic fiber and production method thereof | |
| CN101696517B (en) | Method for manufacturing adsorption transfer fiber | |
| CN103498208A (en) | Thermal storage fiber and preparation method thereof | |
| CN111334880B (en) | Photochromic lyocell fibers and method for making same | |
| CN100368608C (en) | Method for preparing copolymerized acrylonitrile high water-absorption fiber | |
| CN101392456A (en) | Method for preparing super absorbent fiber by modification of polyvinyl alcohol fiber | |
| CN108851257A (en) | A kind of moisture absorption heating heat-preserving function panty hose | |
| CN102864521B (en) | Cortex-core protein and polyacrylonitrile compound fiber and method for wigs | |
| CN108342786B (en) | Acrylic fiber with magnet physiotherapy health-care function and preparation method thereof | |
| CN110453306A (en) | Apery hair functional protein fiber and its wet spinning process | |
| CN103205823B (en) | Preparation method of hydrophilic polyacrylonitrile fiber | |
| CN101240462B (en) | Method for preparing acrylics-protein-copper salt composite antistatic fiber | |
| CN103205822A (en) | Preparation method for hydrophilic polyacrylonitrile stoste | |
| CN117568986A (en) | Fabric with flame retardance and crease resistance and preparation method thereof | |
| CN108532065A (en) | A kind of spinning process of modified cotton fiber and modified flax fiber blending yarn | |
| JP4128024B2 (en) | Fiber for artificial hair with improved devitrification and method for producing the same | |
| CN103668531B (en) | Method for preparing anti-pilling acrylic fibers from acrylonitrile and vinyl chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150408 Termination date: 20210531 |