CN103233291B - Preparation method of moisture-absorption polyacrylonitrile fiber - Google Patents
Preparation method of moisture-absorption polyacrylonitrile fiber Download PDFInfo
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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 fiber.
Background technology
Polyacrylonitrile fibre is one of three large synthetic fiber, has the features such as excellent warmth retention property, dyeability and simulate wool, has the title of artificial wool, be widely used in the fields of taking such as knitted underwear, woollen blanket, Fake Furss.But, along with people's living standard to improve constantly with clothing design growing, warming is no longer the unitary request of clothes, people 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 represent with official regain.The official regain of natural fabric is about 8 ~ 15%, and polyacrylonitrile fibre is only 2%, the performance that hygroscopicity, poisture-penetrability etc. are relevant to human body skin-friendly shows serious defect, the clothing dress making it make has feeling of oppression and heat, sweat are not easily absorbed and distribute, static behaviour is strong, often need additional functionality process or spin blending ratio after reducing, not only increase processing cost, and the durability for the treatment of effect is lower, thus greatly reduce the wearability of polyacrylonitrile fibre, more limited in the field application that some has antistatic behaviour to require.
In order to improve the hygroscopicity of acrylic fibers, improve the wearing comfort of acrylic fibers, researcher have employed multiple method and carries out modification to the moisture pick-up properties of acrylic fibers.Such as CN1900413A provides a kind of acrylic fiber surface graft protein that adopts and carries out modification, first under certain condition acrylic fiber is hydrolyzed, then hydrolysis fiber and thionyl chloride are reacted to obtain chloride fiber, again with protein grafting, making superficial layer is phytoprotein grafting cover layer, core is the modified fibre of acrylic fiber, improves the hygroscopicity of acrylic fibers.But because graft numbers is limited, make the hygroscopic raising of acrylic fibers limited, modified effect is not obvious.Abroad employing chemical modification method carry out moisture absorption polyacrylonitrile prepare in research comparatively early.Polyacrylonitrile fibre to be hydrolyzed and the method for water absorbent fiber is prepared in compound crosslink process as Japan patent discloses at CN1239775C, CN1247849C, CN1230585C, CN101023212B and CN101914852A etc. that China applies for, and to improve on fibre whiteness and fire resistance respectively.The durability of these methods is better, but shortcoming is because the chemical process time be hydrolyzed and be cross-linked is longer, batch process is spun after can only being applied to staple fibre, belong to the manufacture method that a kind of off-line produces water absorbent fiber, thus the moisture absorption of fiber treatment and the inhomogeneity of fibrous physics mechanical performance higher, production efficiency is low.
In addition, also the method for monomer or latent crosslinker by adding hygroscopicity group in polymerization formula is had to prepare the report of similar hygroscopicity polyacrylonitrile fibre, but because the change of copolymerization process is on the impact being polymerized production control and polymerizate performance, and the follow-up basic hydrolysis process spinning the long period indispensable in journey, make these class methods not have the condition of online production moisture-absorption polyacrylonitrile fiber.
Summary of the invention
The present invention is directed to the above-mentioned state of the art, take requirement from what meet polyacrylonitrile fibre, a kind of online production method obtaining moisture-absorption polyacrylonitrile fiber in conventional polypropylene nitrile fiber manufacture process is provided.Under the prerequisite not changing polymerization technique, polyacrylonitrile basic hydrolysis solution and the conventional polyacrylonitrile matrix obtained of producing is adopted to carry out a certain proportion of blended and spinning, thus preparation moisture-absorption polyacrylonitrile fiber.
The preparation method of a kind of moisture-absorption polyacrylonitrile fiber of the present invention, comprises the steps:
(1) acrylonitrile copolymer hydrolysis
With the aqueous solution of alkaline metal salt, polymer is hydrolyzed process;
The mass ratio of acrylonitrile copolymer and alkaline metal salt is 1:0.5 ~ 1:2.0, and hydrolysising reacting temperature is 80 ~ 110 DEG C, and hydrolysis time is 1 ~ 10 hour;
Cyano group in acrylonitrile copolymer has greater activity, and cyano group reacts under the effect of alkalinous metal saline solution, can be hydrolyzed and generate the moisture absorption such as amide groups, carboxyl group;
(2) precipitating
In order to improve the concentration of hydrolysate polyacrylonitrile in hydrolyzate, by 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 hydrolysate polyacrylonitrile;
(3) hydrolyzed polyacrylonitrile stoste is prepared
For the ease of adding, realizing with conventional stoste evenly blended further, hydrolysate polyacrylonitrile need be mixed with solution.Described hydrolysate polyacrylonitrile spin solvent is deployed into hydrolyzed polyacrylonitrile stoste, and adjustment solid content is 10 ~ 40wt%;
(4) moisture absorption polyacrylonitrile matrix is prepared
The molecular weight and molecular weight of polyacrylonitrile after hydrolysis, water-solublely greatly to improve, cannot meet wet spinning requirement, by hydrolyzed polyacrylonitrile stoste and conventional polypropylene nitrile stoste with the blended stoste obtaining stable and uniform, meet spinning fibre requirement of certain proportion.
By described hydrolyzed polyacrylonitrile stoste temperature adjustment to 70 ~ 80 DEG C, the polyacrylonitrile matrix produced with routine fully mixes, and prepares moisture absorption polyacrylonitrile matrix; Wherein, described hydrolyzed polyacrylonitrile stoste accounts for 5 ~ 40wt% of described moisture absorption polyacrylonitrile matrix.More conventional stoste, the hydrolysising original liquid of moisture absorption polyacrylonitrile matrix a large amount of moisture absorption group because blended molecular structure contains, thus there is water suction moisture pick-up properties;
(5) spinning solidification forming
Spinning solution is extruded from spinnerets, in coagulating bath, form as-spun fibre;
(6) preliminary draft
As-spun fibre preliminary draft after coagulation forming 1.0 ~ 3.5 times;
(7) wash
As-spun fibre after preliminary draft washes away spin solvent, and water temperature is 45 ~ 65 DEG C;
(8) hydrophily process
Carry out hydrophilicity-imparting treatment with the method that cushioning liquid floods and spray combines that pH is 9 ~ 12, make the H type converting carboxylate groups on fiber be salt form carboxyl;
(9) hot gas spring
The water-bath drawing-off of 2.5 ~ 5.0 times is carried out in the hot water of 98 ~ 100 DEG C;
(10) densification-crosslinked
Fiber after hot gas spring is carried out thermal crosslinking treatment at 105 ~ 145 DEG C;
(11) curling and sizing
Adopt hot bath or decatize mode preheating tow to carry out machine crimp, the fiber after curling carries out the process of saturated vapor HEAT SETTING, and heat setting temperature is 120 ~ 135 DEG C;
(12) oil and oven dry
After HEAT SETTING, fiber carries out dipping and oils, and concentration of oil trough, 1.0 ~ 3.0%, afterwards, is lax in second drying machine of 90 ~ 120 DEG C oven dry in temperature.
As preferred technical scheme:
The preparation method of a kind of moisture-absorption polyacrylonitrile fiber as above, 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 a kind of moisture-absorption polyacrylonitrile fiber as above, 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 a kind of moisture-absorption polyacrylonitrile fiber as above, described acrylonitrile copolymer is the copolymer of acrylonitrile monemer and other the second comonomer and/or the 3rd comonomer; Other second comonomer described is the one in acrylate monomer, methacrylate monomers or vinyl acetate, and the 3rd comonomer is the one in methylpropene sodium sulfonate, Sodium styrene sulfonate, sodium vinyl sulfonate or 2-acrylamide-2-methylpro panesulfonic acid.
The preparation method of a kind of moisture-absorption polyacrylonitrile fiber as above, 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 a kind of moisture-absorption polyacrylonitrile fiber as above, 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 a kind of moisture-absorption polyacrylonitrile fiber as above, 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 a kind of moisture-absorption polyacrylonitrile fiber as above, described solvent is absolute ethyl alcohol, acetone or methyl alcohol.
The preparation method of a kind of moisture-absorption polyacrylonitrile fiber as above, in described moisture absorption polyacrylonitrile matrix, acrylonitrile copolymer main chain is C-C singly-bound, contains carboxyl, amide groups and a large amount of cyano group in the large molecule of acrylonitrile copolymer simultaneously.Described moisture absorption polyacrylonitrile matrix is by conventional polypropylene nitrile stoste, 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 a kind of moisture-absorption polyacrylonitrile fiber as above, described cushioning liquid is sodium carbonate-bicarbonate, NaOH-boric acid-potassium chloride, NaOH-amion acetic acid-sodium chloride or potassium chloride-sodium hydroxide buffer solution; The described method combined with dipping and spray instigates fiber impregnation by the bath of an above-mentioned cushioning liquid, and cushioning liquid is circulated to by pump one group of shower ejection that bath tow runs top, strengthens reduction effect.
The preparation method of a kind of moisture-absorption polyacrylonitrile fiber as above, described moisture-absorption polyacrylonitrile fiber is endless tow or staple fibre.
The preparation method of a kind of moisture-absorption polyacrylonitrile fiber as above, described fiber hygroscopicity index regain records as follows: a kind of moisture-absorption polyacrylonitrile fiber sample (about 5 grams) is dried to constant weight and weighs its weight in the electric drying oven with forced convection of 105 DEG C is W1(g), then sample to be placed in the climatic chamber remaining on 20 DEG C and 65%RH condition 24 hours, the weight weighing the sample after moisture absorption is W2(g).Undertaken calculating sample regain by formula below:
Regain (%)=[(W2-W1)/W1] × 100%
Beneficial effect:
The preparation method of a kind of moisture-absorption polyacrylonitrile fiber provided by the present invention, obtains moisture-absorption polyacrylonitrile fiber in conventional polypropylene nitrile fiber manufacture process.The moisture-absorption polyacrylonitrile fiber obtained by the present invention not only has good moisture pick-up properties, and uniformity is good, and durability is good, and not by the restriction of fibre number, length, production efficiency is high.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
The acrylonitrile copolymers be made up of acrylonitrile, methyl acrylate and methylpropene sodium sulfonate is hydrolyzed in 1wt% sodium hydrate aqueous solution, the mass ratio of acrylonitrile copolymer and NaOH is 1:0.5, hydrolysis temperature is 90 DEG C, hydrolysis time is 2 hours, then by the hydrolyzate of hydrolysis process gained absolute ethyl alcohol precipitating, after filtering by nitric acid adjust ph to 4, then become by obtained hydrolysate polyacrylonitrile NaSCN preparing solution solid content to be the hydrolyzed polyacrylonitrile stoste of 13wt%.By this hydrolyzed polyacrylonitrile stoste temperature adjustment to 70 DEG C, fully mix with the conventional polyacrylonitrile matrix produced, obtain moisture absorption polyacrylonitrile matrix, wherein hydrolyzed polyacrylonitrile stoste accounts for the 5wt% of described moisture absorption polyacrylonitrile matrix.Moisture absorption polyacrylonitrile matrix is extruded from spinnerets, formation as-spun fibre is solidified in coagulating bath, then as-spun fibre is through 1.5 times of preliminary drafts, after through 45 DEG C of washings, hydrophilicity-imparting treatment is carried out with the NaOH-boric acid-potassium chloride buffer solution of pH=9, in the hot water of 98 DEG C, carry out the hot water drawing-off of 4.0 times again, the fiber after hot gas spring carries out thermal crosslinking treatment at 105 DEG C.Then carry out curling, shape, oil, dry.Heat setting temperature is 120 DEG C, and the oil concentration oiled is 1.2%, and bake out temperature is 100 DEG C.Obtain moisture-absorption polyacrylonitrile fiber.This fiber can be cut off on request, make the moisture absorption Orlon of different length.The regain recording this fiber is 16%.
Embodiment 2
The acrylonitrile copolymers be made up of acrylonitrile and methyl methacrylate is hydrolyzed in 8wt% potassium hydroxide aqueous solution, the mass ratio of acrylonitrile copolymer and potassium hydroxide is 1:0.8, hydrolysis temperature is 100 DEG C, hydrolysis time is 3 hours, then by the hydrolyzate of hydrolysis process gained absolute ethyl alcohol precipitating, use formic acid adjust ph to 5 after filtering, then obtained hydrolysate polyacrylonitrile dimethyl sulfoxide (DMSO) is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 12wt%.By this hydrolyzed polyacrylonitrile stoste temperature adjustment to 70 DEG C, fully mix with the conventional polyacrylonitrile matrix produced, obtain moisture absorption polyacrylonitrile matrix, wherein hydrolyzed polyacrylonitrile stoste accounts for the 15wt% of described moisture absorption polyacrylonitrile matrix.Moisture absorption polyacrylonitrile matrix is extruded from spinnerets, formation as-spun fibre is solidified in coagulating bath, then as-spun fibre is through 1.0 times of preliminary drafts, after through 50 DEG C of washings, hydrophilicity-imparting treatment is carried out with the sodium carbonate-bicarbonate cushioning liquid of pH=9.5, in the hot water of 100 DEG C, carry out the hot water drawing-off of 5.0 times again, the fiber after hot gas spring carries out thermal crosslinking treatment at 120 DEG C.Then carry out curling, shape, oil, dry.Heat setting temperature is 125 DEG C, and the oil concentration oiled is 1.0%, and bake out temperature is 110 DEG C.Obtain moisture-absorption polyacrylonitrile fiber.This fiber can be cut off on request, make the moisture absorption Orlon of different length.The regain recording this fiber is 23%.
Embodiment 3
The acrylonitrile copolymers be made up of acrylonitrile and ethyl acrylate is hydrolyzed in 10wt% sodium hydrate aqueous solution, the mass ratio of acrylonitrile copolymer and NaOH is 1:1.0, hydrolysis temperature is 105 DEG C, hydrolysis time is 1 hour, then by the hydrolyzate of hydrolysis process gained acetone precipitating, use salt acid for adjusting pH value to 5 after filtering, then obtained hydrolysate polyacrylonitrile solder(ing)acid is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 15wt%.By this hydrolyzed polyacrylonitrile stoste temperature adjustment to 70 DEG C, fully mix with the conventional polyacrylonitrile matrix produced, obtain moisture absorption polyacrylonitrile matrix, wherein hydrolyzed polyacrylonitrile stoste accounts for the 10wt% of described moisture absorption polyacrylonitrile matrix.Moisture absorption polyacrylonitrile matrix is extruded from spinnerets, formation as-spun fibre is solidified in coagulating bath, then as-spun fibre is through 2.3 times of preliminary drafts, after through 58 DEG C of washings, hydrophilicity-imparting treatment is carried out with the NaOH-amion acetic acid-sodium chloride buffer solution of pH=11, in the hot water of 99 DEG C, carry out the hot water drawing-off of 4.0 times again, the fiber after hot gas spring carries out thermal crosslinking treatment at 110 DEG C.Then carry out curling, shape, oil, dry.Heat setting temperature is 120 DEG C, and the oil concentration oiled is 2.3%, and bake out temperature is 110 DEG C.Obtain moisture-absorption polyacrylonitrile fiber.The regain recording this fiber is 28%.
Embodiment 4
Receive formed acrylonitrile copolymers by acrylonitrile, ethyl acrylate and vinyl sulfonic acid to be hydrolyzed in 12wt% magnesium hydroxide aqueous solution, the mass ratio of acrylonitrile copolymer and magnesium hydroxide is 1:1.2, hydrolysis temperature is 95 DEG C, hydrolysis time is 2 hours, then by the hydrolyzate of hydrolysis process gained acetone precipitating, use sulfuric acid adjust ph to 6 after filtering, then obtained hydrolysate polyacrylonitrile dimethylacetylamide is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 15wt%.By this hydrolyzed polyacrylonitrile stoste temperature adjustment to 80 DEG C, fully mix with the conventional polyacrylonitrile matrix produced, obtain moisture absorption polyacrylonitrile matrix, wherein hydrolyzed polyacrylonitrile stoste accounts for the 5wt% of described moisture absorption polyacrylonitrile matrix.Moisture absorption polyacrylonitrile matrix is extruded from spinnerets, formation as-spun fibre is solidified in coagulating bath, then as-spun fibre is through 2.5 times of preliminary drafts, after through 53 DEG C of washings, hydrophilicity-imparting treatment is carried out with the NaOH-boric acid-Klorvess Liquid of pH=9.8, in the hot water of 99 DEG C, carry out the hot water drawing-off of 3.0 times again, the fiber after hot gas spring carries out thermal crosslinking treatment at 130 DEG C.Then carry out curling, shape, oil, dry.Heat setting temperature is 120 DEG C, and the oil concentration oiled is 3.0%, and bake out temperature is 90 DEG C.Obtain moisture-absorption polyacrylonitrile fiber.The regain recording this fiber is 15%.
Embodiment 5
The acrylonitrile copolymers be made up of acrylonitrile, butyl acrylate and Sodium styrene sulfonate is hydrolyzed in 15wt% calcium hydroxide aqueous solution, the mass ratio of acrylonitrile copolymer and calcium hydroxide is 1:1.5, hydrolysis temperature is 95 DEG C, hydrolysis time is 4 hours, then by the hydrolyzate of hydrolysis process gained methyl alcohol precipitating, after filtering by acetic acid adjust ph to 6, then become by obtained hydrolysate polyacrylonitrile NaSCN preparing solution solid content to be the hydrolyzed polyacrylonitrile stoste of 13wt%.By this hydrolyzed polyacrylonitrile stoste temperature adjustment to 80 DEG C, fully mix with the conventional polyacrylonitrile matrix produced, obtain moisture absorption polyacrylonitrile matrix, wherein hydrolyzed polyacrylonitrile stoste accounts for the 20wt% of described moisture absorption polyacrylonitrile matrix.Moisture absorption polyacrylonitrile matrix is extruded from spinnerets, formation as-spun fibre is solidified in coagulating bath, then as-spun fibre is through 2.6 times of preliminary drafts, after through 55 DEG C of washings, hydrophilicity-imparting treatment is carried out with the potassium chloride-sodium hydroxide buffer solution of pH=13, in the hot water of 100 DEG C, carry out the hot water drawing-off of 3.5 times again, the fiber after hot gas spring carries out thermal crosslinking treatment at 145 DEG C.Then carry out curling, shape, oil, dry.Heat setting temperature is 130 DEG C, and the oil concentration oiled is 2.0%, and bake out temperature is 110 DEG C.Obtain moisture-absorption polyacrylonitrile fiber.The regain recording this fiber is 19%.
Embodiment 6
The acrylonitrile copolymers be made up of acrylonitrile, butyl acrylate and 2-acrylamide-2-methylpro panesulfonic acid is hydrolyzed in 30wt% sodium bicarbonate aqueous solution, the mass ratio of acrylonitrile copolymer and sodium bicarbonate is 1:1.8, hydrolysis temperature is 110 DEG C, hydrolysis time is 5 hours, then by the hydrolyzate of hydrolysis process gained methyl alcohol precipitating, use ethanedioic acid adjust ph to 7 after filtering, then obtained hydrolysate polyacrylonitrile dimethyl formamide is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 40wt%.By this hydrolyzed polyacrylonitrile stoste temperature adjustment to 80 DEG C, fully mix with the conventional polyacrylonitrile matrix produced, obtain moisture absorption polyacrylonitrile matrix, wherein hydrolyzed polyacrylonitrile stoste accounts for the 25wt% of described moisture absorption polyacrylonitrile matrix.Moisture absorption polyacrylonitrile matrix is extruded from spinnerets, formation as-spun fibre is solidified in coagulating bath, then as-spun fibre is through 2.8 times of preliminary drafts, after through 65 DEG C of washings, hydrophilicity-imparting treatment is carried out with the NaOH-amion acetic acid-sodium chloride buffer solution of pH=12, in the hot water of 100 DEG C, carry out the hot water drawing-off of 3.5 times again, the fiber after hot gas spring carries out thermal crosslinking treatment at 145 DEG C.Then carry out curling, shape, oil, dry.Heat setting temperature is 135 DEG C, and the oil concentration oiled is 2.5%, and bake out temperature is 110 DEG C.Obtain moisture-absorption polyacrylonitrile fiber.The regain recording this fiber is 17%.
Embodiment 7
The acrylonitrile copolymers be made up of acrylonitrile, vinyl acetate and methylpropene sodium sulfonate is hydrolyzed in 40wt% potassium bicarbonate aqueous solution, the mass ratio of acrylonitrile copolymer and saleratus is 1:2.0, hydrolysis temperature is 80 DEG C, hydrolysis time is 10 hours, then by the hydrolyzate of hydrolysis process gained methyl alcohol precipitating, use salt acid for adjusting pH value to 7 after filtering, then obtained hydrolysate polyacrylonitrile dimethyl formamide is deployed into the hydrolyzed polyacrylonitrile stoste that solid content is 20wt%.By this hydrolyzed polyacrylonitrile stoste temperature adjustment to 80 DEG C, fully mix with the conventional polyacrylonitrile matrix produced, obtain moisture absorption polyacrylonitrile matrix, wherein hydrolyzed polyacrylonitrile stoste accounts for the 40wt% of described moisture absorption polyacrylonitrile matrix.Moisture absorption polyacrylonitrile matrix is extruded from spinnerets, formation as-spun fibre is solidified in coagulating bath, then as-spun fibre is through 1.8 times of preliminary drafts, after through 50 DEG C of washings, hydrophilicity-imparting treatment is carried out with the NaOH-boric acid-potassium chloride buffer solution of pH=10, in the hot water of 98 DEG C, carry out the hot water drawing-off of 2.5 times again, the fiber after hot gas spring carries out thermal crosslinking treatment at 125 DEG C.Then carry out curling, shape, oil, dry.Heat setting temperature is 120 DEG C, and the oil concentration oiled is 2.3%, and bake out temperature is 120 DEG C.Obtain moisture-absorption polyacrylonitrile fiber.The regain recording this fiber is 25%.
Claims (10)
1. a preparation method for moisture-absorption polyacrylonitrile fiber, is characterized in that comprising the steps:
(1) acrylonitrile copolymer hydrolysis;
With the aqueous solution of alkaline metal cpds, polymer is hydrolyzed process;
The mass ratio of acrylonitrile copolymer and alkaline metal cpds is 1:0.5 ~ 1:2.0, and hydrolysising reacting temperature is 80 ~ 110 DEG C, and hydrolysis time is 1 ~ 10 hour; Described alkaline metal cpds is alkali metal hydroxide, alkaline earth metal hydroxide or alkali carbonate;
(2) precipitating;
By the hydrolyzate solvent precipitation of described hydrolysis process gained, after filtration, add acid for adjusting pH value to 4 ~ 7, the hydrolysate polyacrylonitrile obtained;
(3) hydrolyzed polyacrylonitrile stoste is prepared;
Described hydrolysate polyacrylonitrile spin solvent is deployed into hydrolyzed polyacrylonitrile stoste, and adjustment solid content is 10 ~ 40wt%;
(4) moisture absorption polyacrylonitrile matrix is prepared;
By described hydrolyzed polyacrylonitrile stoste temperature adjustment to 70 ~ 80 DEG C, the polyacrylonitrile matrix produced with routine fully mixes, and prepares moisture absorption polyacrylonitrile matrix; Wherein, described hydrolyzed polyacrylonitrile stoste accounts for 5 ~ 40wt% of described moisture absorption polyacrylonitrile matrix;
(5) spinning solidification forming;
Described moisture absorption polyacrylonitrile matrix is extruded from spinnerets, forms as-spun fibre through coagulating bath;
(6) preliminary draft;
By as-spun fibre preliminary draft 1.0 ~ 3.5 times;
(7) wash;
Then wash away spin solvent, washing temperature is 45 ~ 65 DEG C;
(8) hydrophilicity-imparting treatment;
With pH be 9 ~ 12 cushioning liquid with dipping and spray combine method carry out hydrophilicity-imparting treatment;
(9) hot gas spring;
The water-bath drawing-off of 2.5 ~ 5.0 times is carried out in the hot water of 98 ~ 100 DEG C;
(10) densification-crosslinked;
Fiber after hot gas spring is carried out thermal crosslinking treatment at 105 ~ 145 DEG C;
(11) curling and sizing;
Adopt hot bath or decatize mode preheating tow to carry out machine crimp, the fiber after curling carries out the process of saturated vapor HEAT SETTING, and heat setting temperature is 120 ~ 135 DEG C;
(12) oil and oven dry;
After HEAT SETTING, fiber carries out dipping and oils, and concentration of oil trough, 1.0 ~ 3.0%, afterwards, is lax in second drying machine of 90 ~ 120 DEG C oven dry in temperature;
Obtain moisture-absorption polyacrylonitrile fiber.
2. the preparation method of a kind of moisture-absorption polyacrylonitrile fiber according to claim 1, is characterized in that, the concentration of aqueous solution of described alkaline metal cpds is 1 ~ 40wt%.
3. the preparation method of a kind of moisture-absorption polyacrylonitrile fiber according to claim 1, 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 fiber according to claim 1, is characterized in that, described acrylonitrile copolymer is the copolymer of acrylonitrile monemer and other the second comonomer and/or the 3rd comonomer; Other second comonomer described is the one in acrylate monomer, methacrylate monomers or vinyl acetate, and the 3rd comonomer is the one in methylpropene sodium sulfonate, Sodium styrene sulfonate, sodium vinyl sulfonate or 2-acrylamide-2-methylpro panesulfonic acid.
5. the preparation method of a kind of moisture-absorption polyacrylonitrile fiber 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 fiber 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 fiber 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 fiber 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 fiber according to claim 1, it is characterized in that, described cushioning liquid is sodium carbonate-bicarbonate, NaOH-boric acid-potassium chloride, NaOH-amion acetic acid-sodium chloride or potassium chloride-sodium hydroxide buffer solution; The described method combined with dipping and spray instigates fiber impregnation by the bath of an above-mentioned cushioning liquid, and cushioning liquid is circulated to by pump one group of shower ejection that bath tow runs top, strengthens reduction effect.
10. the preparation method of a kind of moisture-absorption polyacrylonitrile fiber according to claim 1, is characterized in that, described moisture-absorption polyacrylonitrile fiber is endless tow or staple fibre; It is 15 ~ 28% that described moisture-absorption polyacrylonitrile fiber has regain under 20 DEG C and 65%RH condition.
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| 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 |
| WO2019058966A1 (en) * | 2017-09-22 | 2019-03-28 | 日本エクスラン工業株式会社 | Moisture absorbent acrylonitrile-based fiber, method for producing same and fiber structure containing same |
| 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 |
| 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 |
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| US5458968A (en) * | 1994-01-26 | 1995-10-17 | Monsanto Company | Fiber bundles including reversible crimp filaments having improved dyeability |
| 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 |
| 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 |
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