CN105002592A - Acetate fiber and preparation method thereof - Google Patents
Acetate fiber and preparation method thereof Download PDFInfo
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- CN105002592A CN105002592A CN201510079823.2A CN201510079823A CN105002592A CN 105002592 A CN105002592 A CN 105002592A CN 201510079823 A CN201510079823 A CN 201510079823A CN 105002592 A CN105002592 A CN 105002592A
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- nitrile
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
Abstract
The invention relates to a fiber material, in particular to an acetate fiber and a preparation method thereof. The acetate fiber is composed of polyacrylonitrile and cellulose acetate. The mass ratio of the cellulose acetate to the polyacrylonitrile is an arbitrary ratio, preferentially, the ratio is 15-35 wt%:65-85 wt%, and more preferentially, the ratio is 15-30 wt%:70-85 wt%. The acetate fiber has the advantages that the defects that the acrylic fiber is bad in hygroscopicity, and static electricity is easily generated are overcome; the defects that the pure acetate fiber is low in strength and bad in serviceability are overcome; at the same time, the combination property of the acetate fiber is good.
Description
Technical field
The present invention relates to a kind of fibrous material, specifically, relate to a kind of vinegar nitrile fiber and preparation method thereof.
Background technology
Acrylic fibers are one of world's synthetic fiber principal item, and it is soft, and bright in colour, intensity and elasticity are all relatively good, have the good reputation of " artificial wool ".But the large molecule of acrylic fiber is irregular helical conformation, does not have real crystalline texture, the brute force of fiber than natural fabric and regenerated fiber much higher, acid resistance is good, good weatherability; And owing to containing a large amount of hydrophobic groups in raw material polyacrylonitrile (PAN), the hygroscopicity of acrylic fibers is poor, very easily produces electrostatic.Electrostatic can cause Filament-wound Machine or blocking parts, affects carrying out smoothly of weaving process; Electrostatic charge is gathered and is easily made wearer produce sense of discomfort on clothes, reduces the wearability of acrylic fibers textiles, thus limits further developing of it.
By antistatic additive and Polyacrylonitrile Fiber Spinning Solution blended, being then spun into fiber is carry out antistatic modified a kind of important method to acrylic fibers.Blending type antistatic additive conventional is at present carbon black, as CN101805935A discloses the preparation method of a kind of novel antistatic acrylic fibers and antistatic acrylic fiber.These acrylic fibers contain CNT and carbon black, and wherein the percetage by weight of CNT is 1%-15%, and the percetage by weight of carbon black is 1%-3%, and the weight percent range of polyacrylonitrile is 82%-98%.But due to obtained fiber be black, its purposes is restricted.
In addition, suitable physics and chemistry method also can improve the antistatic property of acrylic fibers, but there is problem of environmental pollution in various degree.Thesis for the doctorate " acrylic fibers plasma antistatic treatment " proposes a kind of lower temperature plasma technology that adopts and carries out surface modification to improve the method for the antistatic property of acrylic fibers to acrylic fibers.Lower temperature plasma technology, as the eco-friendly new technology of one, is economized on water, energy-conservation, pollution-free, has significant economic and environmental protection effect.But the method requires higher, has certain difficulty in actual applying.
The moisture pick-up properties of acetate fiber is good, and regain is 6%, can use disperse dyeing, and tool good wear performance.Long filament gloss is graceful, soft, has good drapability, exactly likes real silk, is suitable for making underwear, bathing gown, children's garment, womenswear and indoor decorative fabric etc., also can do cigaratte filter.But the low taking of the intensity of acetate fiber is poor.
" investigation of moisture absorption acrylic fiber spinning process " " Wang Zuowu. moisture absorption acrylic fiber spinning process is discussed " disclose with polyacrylonitrile and the compounded moisture absorption acrylic fiber of cellulose acetate two kinds of raw materials.But composite fibre there is two or more immiscible polymer on same fibre section.And this moisture absorption acrylic fiber due to regain own low, in spinning processing process, each operation flyings and electrostatic phenomenon serious, especially spin in High-speed Drawing Frame, it is more outstanding that front roller exports yarn fiber electrostatic phenomenon, very easily be wound around roller, roller, not only life is rough does, and causes the dry severe exacerbation of bar.
Master's thesis " hydrophilic polymerized acrylonitrile fiber research " with acrylonitrile (AN), latent crosslinker (2-hydroxypropyl acrylate), vinylacetate (VAc) for monomer, sodium chlorate (NaClO
3) be initator, adopt aqueous precipitation polymerization to prepare copolymerized acrylonitrile.With N, N-dimethylacetylamide (DMAc) is solvent, copolymerized acrylonitrile (CPAN) fiber containing latent crosslinker and CPAN/ cellulose acetate (CA) blended fiber (CPAN-CA) is obtained through wet spinning, again through after crosslinked prepared the copolymerized acrylonitrile series fiber with cross-linked structure, to fiber basic hydrolysis, obtain having water suction more by force, water holding capacity, nonirritant and have certain powerful copolymerized acrylonitrile series fiber.But need to add front crosslinking agent and initator in the preparation of copolymerized acrylonitrile, and adopt aqueous precipitation polymerization, its preparation method is complicated; And obtaining with wet spinning after containing copolymerized acrylonitrile (CPAN) fiber of latent crosslinker and CPAN/ cellulose acetate (CA) blended fiber, need to carry out further rear crosslinked, and basic hydrolysis is carried out to fiber just can obtain having water suction more by force, water holding capacity, nonirritant and have the blended fiber of certain brute force.The method not only needs to add front crosslinking agent and initator in the preparation of copolymerized acrylonitrile, and its preparation method is complicated, aqueous deposited polymerization, wet spinning, rear crosslinked and basic hydrolysis multistep reaction need be adopted, and point out " steps necessary that hydrolysis is preparation polyacrylonitrile based hydrophilic fibre ".But in obtained blended fiber when the content of cellulose acetate is 5% intensity reach maximum, be only 1.4cN/dtex, decline along with the increase of cellulose acetate content subsequently.
Current China textile industry faces product restructuring, for adapting to domestic and international market competition and improving Business Economic Benefit, meet the need of market in the urgent need to developing a kind of fiber that not only there is acetate fiber good characteristic but also there are the improved combination properties such as acrylic fiber good characteristic, antistatic property, intensity, and need to provide one relatively simple preparation method.
In view of this, special proposition the present invention.
In prior art, the blended fiber of polyacrylonitrile and cellulose acetate is generally crosslinked after carrying out further after wet spinning, then carries out basic hydrolysis to it obtained, and to point out " steps necessary that hydrolysis is preparation polyacrylonitrile based hydrophilic fibre ".But vinegar nitrile fiber of the present invention carries out wet spinning after only polyacrylonitrile and cellulose acetate solvent need being carried out dissolving glue can obtain, do not need to carry out to be cross-linked, rear crosslinked and basic hydrolysis process, process route is simple, thus enormously simplify processing step, improve operating efficiency, be conducive to batch production, and the vinegar nitrile fibrous physics index produced is closer to conventional acrylic fiber index.
Further, described polyacrylonitrile is formed by acrylonitrile and vinyl acetate, and wherein the mass ratio of acrylonitrile and vinyl acetate is 92 ~ 94wt%:6 ~ 8wt%.
In prior art, polyacrylonitrile is normally as obtained in front crosslinking agent, initator, three single auxiliary agents, oxidant, reductant etc. by acrylonitrile, vinyl acetate and other component.In the present invention, described polyacrylonitrile is formed with the mass ratio of 92 ~ 94wt%:6 ~ 8wt% by acrylonitrile and vinyl acetate.
The quality sum of described polyacrylonitrile and cellulose acetate and the mass ratio of solvent are 20 ~ 25.5:74.5 ~ 80.
The present invention also provides the preparation method of described vinegar nitrile fiber, and the method simple possible, technique easily controls.
The preparation method of vinegar nitrile fiber provided by the present invention comprises the steps:
1) by 92 ~ 94wt% acrylonitrile and the two kinds of monomer mixing of 6 ~ 8wt% vinyl acetate, and aqueous suspension polymerization reaction is carried out continuously after its mixed concentration is adjusted to 30 ~ 40wt%; Reacted polymer stops through chelatropic reaction, deviates from unreacted monomer, then through washing filtering, granulating and forming, oven dry, obtains powdered polypropylene nitrile;
2) by powdered polypropylene nitrile, cellulose acetate and solvent, through heating, cooling, obtained spinning solution is filtered;
3) spinning solution again through temperature-adjustment pressure-adjustment, filter after carry out spinning, shaping through coagulating bath double diffusion, then through washing, drawing-off, oil, dry, curling, sizing, obtain vinegar nitrile fiber.
Disclose with acrylonitrile (AN), latent crosslinker (2-hydroxypropyl acrylate), vinylacetate (VAc) for monomer in prior art, sodium chlorate (NaClO
3) be initator, adopt aqueous precipitation polymerization to prepare copolymerized acrylonitrile.Then with N, N-dimethylacetylamide (DMAc) is solvent, copolymerized acrylonitrile (CPAN) fiber containing latent crosslinker and CPAN/ cellulose acetate (CA) blended fiber (CPAN-CA) is obtained through wet spinning, again through after crosslinked prepared the copolymerized acrylonitrile series fiber with cross-linked structure, to fiber basic hydrolysis, obtain having absorb water more by force, water holding capacity and have certain powerful copolymerized acrylonitrile series fiber.The method not only needs to add front crosslinking agent and initator in the preparation of copolymerized acrylonitrile, and its preparation method is complicated, need adopt aqueous deposited polymerization, wet spinning, rear crosslinked and basic hydrolysis multistep reaction.And emphasize " steps necessary that hydrolysis is preparation polyacrylonitrile based hydrophilic fibre ".Visible, generally believe in prior art that hydrolysis is the steps necessary of preparation polyacrylonitrile based hydrophilic fibre.
And the present invention is by adjusting process, proportioning etc., only adopt acrylonitrile and vinyl acetate two kinds of monomers, vinegar nitrile fiber can be obtained with cellulose acetate wet spinning again after obtaining polyacrylonitrile by aqueous suspension polymerization, do not need to carry out to be cross-linked, rear crosslinked and basic hydrolysis process, process route is simple, thus enormously simplify processing step, improves operating efficiency, be conducive to batch production, and the vinegar nitrile fibrous physics index produced is closer to conventional acrylic fiber index.
Further, in above-mentioned preparation method, wherein, step 1) in, described aqueous suspension polymerization reaction carries out for 2.5 ~ 3.5 times in temperature 58 ~ 62 DEG C, pH value.
Step 2) in, described cellulose acetate and the mass ratio of powdered polypropylene nitrile are any ratio, preferably 15 ~ 35wt%:65 ~ 85wt%, more preferably 15 ~ 30wt%:70 ~ 85wt%.
The mass ratio of described powdered polypropylene nitrile and the quality sum of cellulose acetate and solvent is 20 ~ 25.5:74.5 ~ 80; Described solvent is dimethylacetylamide, dimethyl sulfoxide (DMSO), dimethyl formamide or sodium sulfocyanate; Described intensification is for being warming up to 80 ~ 90 DEG C; Described cooling is for being cooled to 70 ~ 80 DEG C.
Step 3) in, described spinning carries out at pressure 0.7 ~ 0.9MPa, temperature 80 ~ 97 DEG C; Described coagulating bath is the aqueous solution of dimethylacetylamide, dimethyl sulfoxide (DMSO), dimethyl formamide or sodium sulfocyanate, and its concentration is 30 ~ 55wt%, and temperature is 25 ~ 50 DEG C; Described temperature-adjustment pressure-adjustment is for regulating temperature within the scope of 80 ~ 97 DEG C, regulating pressure within the scope of 0.7 ~ 0.9MPa; Described drafting multiple is 4 ~ 10 times; The described pressure shaping be fixed to by 200 ~ 330KPa.
Preparation method's technique simple possible of the present invention, and the good combination property of obtained vinegar nitrile fiber, its intensity is 2.3 ~ 3.0CN/dtex, and elongation is 32 ~ 40%, and regain is 2 ~ 3%, and ratio resistance is 9.0 × 10
8~ 4.8 × 10
9Ω CM.
Compared with prior art, tool of the present invention has the following advantages:
(1) the vinegar nitrile fiber that the present invention produces has some characteristics of acrylic fiber, and improves the moisture pick-up properties of acrylic fiber and easily play the defect of electrostatic.
(2) vinegar nitrile fiber provided by the present invention not only intensity be improved, and its extend, regain and ratio resistance also have good performance.
(3) the vinegar nitrile fiber that the present invention produces also has some characteristics of acetate fiber, and drapability is good, does not crease easily, and it is low to improve acetate fiber intensity, and acid resistance is poor, and weatherability is poor.
(4) present invention process simple possible, easily controls, and utilizes the existing apparatus tissues such as existing spinning to produce, can not have any impact to the continuity that lower procedure is produced.
Summary of the invention
The first object of the present invention is to provide a kind of vinegar nitrile fiber, to improve the defect that acrylic fiber hygroscopicity is poor, easily play electrostatic; Improve the shortcoming that pure acetate fiber intensity is low, taking is poor simultaneously.
The second object of the present invention is to provide the preparation method of described vinegar nitrile fiber, and the method simple possible, technique easily controls.
For realizing the first object of the present invention, the present invention adopts following technical scheme:
A kind of vinegar nitrile fiber, wherein, described vinegar nitrile fiber is made up of polyacrylonitrile and cellulose acetate, wherein said cellulose acetate and the mass ratio of polyacrylonitrile be arbitrarily than, preferably 15 ~ 35wt%:65 ~ 85wt%, more preferably 15 ~ 30wt%:70 ~ 85wt%.
The intensity of described vinegar nitrile fiber is 2.3 ~ 3.0CN/dtex, and elongation is 32 ~ 40%, and regain is 2 ~ 3%, and ratio resistance is 9.0 × 10
8~ 4.8 × 10
9Ω CM.
Described vinegar nitrile fiber obtains through wet spinning after carrying out dissolving glue by polyacrylonitrile and cellulose acetate solvent.
Described polyacrylonitrile is formed by acrylonitrile and vinyl acetate, and wherein the mass ratio of acrylonitrile and vinyl acetate is 92 ~ 94wt%:6 ~ 8wt%.
The quality sum of described polyacrylonitrile and cellulose acetate and the mass ratio of solvent are 20 ~ 25.5:74.5 ~ 80.
Vinegar nitrile fiber provided by the present invention has the advantages such as light weight is warming, good weatherability, resistance to acids and bases are good, drapability is good, do not crease easily, and has not only filled up domestic blank, and provides a kind of novel fibrous raw material for textile industry.
For realizing the second object of the present invention, the present invention adopts following technical scheme:
A preparation method for vinegar nitrile fiber of the present invention, the method comprises the steps:
1) by 92 ~ 94wt% acrylonitrile and the two kinds of monomer mixing of 6 ~ 8wt% vinyl acetate, and aqueous suspension polymerization reaction is carried out continuously after its mixed concentration is adjusted to 30 ~ 40wt%; Reacted polymer stops through chelatropic reaction, deviates from unreacted monomer, then through washing filtering, granulating and forming, oven dry, obtains powdered polypropylene nitrile;
2) by powdered polypropylene nitrile, cellulose acetate and solvent, through heating, cooling, obtained spinning solution is filtered;
3) spinning solution again through temperature-adjustment pressure-adjustment, filter after carry out spinning, shaping through coagulating bath double diffusion, then through washing, drawing-off, oil, dry, curling, sizing, obtain vinegar nitrile fiber.
In above-mentioned preparation method, wherein, step 1) in, described aqueous suspension polymerization reaction carries out for 2.5 ~ 3.5 times in temperature 58 ~ 62 DEG C, pH value.
Step 2) in, described cellulose acetate and the mass ratio of powdered polypropylene nitrile are any ratio, preferably 15 ~ 35wt%:65 ~ 85wt%, more preferably 15 ~ 30wt%:70 ~ 85wt%.
The mass ratio of described powdered polypropylene nitrile and the quality sum of cellulose acetate and solvent is 20 ~ 25.5:74.5 ~ 80; Described solvent is dimethylacetylamide, dimethyl sulfoxide (DMSO), dimethyl formamide or sodium sulfocyanate; Described intensification is for being warming up to 80 ~ 90 DEG C; Described cooling is for being cooled to 70 ~ 80 DEG C.
Step 3) in, described spinning carries out at pressure 0.7 ~ 0.9MPa, temperature 80 ~ 97 DEG C; Described coagulating bath is the aqueous solution of dimethylacetylamide, dimethyl sulfoxide (DMSO), dimethyl formamide or sodium sulfocyanate, and its concentration is 30 ~ 55wt%, and temperature is 25 ~ 50 DEG C; Described temperature-adjustment pressure-adjustment is for regulating temperature within the scope of 80 ~ 97 DEG C, regulating pressure within the scope of 0.7 ~ 0.9MPa; Described drafting multiple is 4 ~ 10 times; The described pressure shaping be fixed to by 200 ~ 330KPa.
Below technical scheme of the present invention is described in detail:
Plain polypropylene nitrile fiber due to its water suction hygroscopicity poor, the characteristics such as regain is low, antistatic behaviour constrain its range of application.The moisture absorption of fiber and antistatic behaviour have certain inner link, and the water suction hygroscopicity therefore improving polyacrylonitrile fibre can improve other performances greatly.Prior art discloses the multiple moisture-absorbing fibre be made up of polyacrylonitrile and acetyl cellulose blend, but many sections of prior aries show that intensity reaches maximum when the content of cellulose acetate is 5%, but be only 1.4cN/dtex, decline along with the increase of cellulose acetate content subsequently.Currently to meet the need of market in the urgent need to developing a kind of fiber that not only there is acetate fiber good characteristic but also there are the improved combination properties such as acrylic fiber good characteristic, antistatic property, intensity.
First the present invention provides a kind of vinegar nitrile fiber, described vinegar nitrile fiber is made up of polyacrylonitrile and cellulose acetate, wherein said cellulose acetate and the mass ratio of polyacrylonitrile are any ratio, preferably 15 ~ 35wt%:65 ~ 85wt%, more preferably 15 ~ 30wt%:70 ~ 85wt%.
The present inventor, by a large amount of tests, have employed larger cellulose acetate mass ratio, not only increases the intensity of vinegar nitrile fiber, and its elongation, regain and ratio resistance also have good performance, beyond the scope expected.
The combination property of vinegar nitrile fiber of the present invention is good, and its intensity is 2.3 ~ 3.0CN/dtex, and elongation is 32 ~ 40%, and regain is 2 ~ 3%, and ratio resistance is 9.0 × 10
8~ 4.8 × 10
9Ω CM.
Specifically, described vinegar nitrile fiber obtains through wet spinning after carrying out dissolving glue by polyacrylonitrile and cellulose acetate solvent.
Detailed description of the invention
Be below the specific embodiment of the present invention, described embodiment is to further describe the present invention, instead of restriction the present invention.
The preparation of embodiment 1, vinegar nitrile fiber
1) production of polymer: by 92wt% acrylonitrile, the two kinds of monomer mixing of 8wt% vinyl acetate, and its mixed concentration is adjusted to 30 ~ 40wt%, in 58 ~ 62 DEG C, pH carries out aqueous suspension polymerization reaction 2.5 ~ 3.5 times continuously; Reacted polymer stops through chelatropic reaction, deviates from unreacted monomer with stripper, then through water washed filter removing salinity, moisture, obtains powdered polypropylene nitrile after granulating and forming through drying;
2) powdered polypropylene nitrile, cellulose acetate are mixed in quality 20wt%:80wt% ratio with dimethylacetylamide with cellulose acetate (85wt%:15wt%) sum in powdered polypropylene nitrile with solvent dimethylacetylamide, 80 DEG C are heated to through heating up, make polyacrylonitrile, cellulose acetate is dissolved completely in solvent dimethylacetylamide, then cool to 70 DEG C and carry out filtering obtained spinning solution;
3) spinning solution carries out spinning again after temperature-adjustment pressure-adjustment, filtration at 0.7 ~ 0.9MPa pressure, temperature 80 ~ 97 DEG C, be that 85wt%:15wt% carries out spinning in powdered polypropylene nitrile and cellulose acetate ratio, through coagulating bath, (coagulating bath is the aqueous solution of dimethylacetylamide, its concentration is 30 ~ 55wt%, and temperature is 25 ~ 50 DEG C.) double diffusion is shaping, through washing, drawing-off, oil, dry, curling, its drafting multiple is 10 times, to be shaped pressure shaping by 200KPa, obtained vinegar nitrile fiber.
The preparation of embodiment 2, vinegar nitrile fiber
1) production of polymer: by 94wt% acrylonitrile, the two kinds of monomer mixing of 6wt% vinyl acetate, and its mixed concentration is adjusted to 30 ~ 40wt%, in 58 ~ 62 DEG C, pH carries out aqueous suspension polymerization reaction 2.5 ~ 3.5 times continuously; Reacted polymer stops through chelatropic reaction, deviates from unreacted monomer with stripper, then through water washed filter removing salinity, moisture, obtains powdered polypropylene nitrile after granulating and forming through drying;
2) powdered polypropylene nitrile, cellulose acetate are mixed in quality 23wt%:77wt% ratio with dimethylacetylamide with cellulose acetate (80wt%:20wt%) sum in powdered polypropylene nitrile with solvent dimethylacetylamide, 80 DEG C are heated to through heating up, make polyacrylonitrile, cellulose acetate is dissolved completely in solvent dimethylacetylamide, then cool to 70 DEG C and carry out filtering obtained spinning solution;
3) spinning solution carries out spinning again after temperature-adjustment pressure-adjustment, filtration at 0.7 ~ 0.9MPa pressure, temperature 80 ~ 97 DEG C, be that 80wt%:20wt% carries out spinning in powdered polypropylene nitrile and cellulose acetate ratio, through coagulating bath, (coagulating bath is the aqueous solution of dimethylacetylamide, its concentration is 30 ~ 55wt%, and temperature is 25 ~ 50 DEG C.) double diffusion is shaping, through washing, drawing-off, oil, dry, curling, its drafting multiple is 4 times, to be shaped pressure shaping by 330KPa, obtained vinegar nitrile fiber.
The preparation of embodiment 3, vinegar nitrile fiber
1) production of polymer: by 93wt% acrylonitrile, the two kinds of monomer mixing of 7wt% vinyl acetate, and its mixed concentration is adjusted to 30 ~ 40wt%, in 58 ~ 62 DEG C, pH carries out aqueous suspension polymerization reaction 2.5 ~ 3.5 times continuously; Reacted polymer stops through chelatropic reaction, deviates from unreacted monomer with stripper, then through water washed filter removing salinity, moisture, obtains powdered polypropylene nitrile after granulating and forming through drying;
2) powdered polypropylene nitrile, cellulose acetate are mixed in quality 25.5wt%:74.5wt% ratio with dimethylacetylamide with cellulose acetate (75wt%:25wt%) sum in powdered polypropylene nitrile with solvent dimethylacetylamide, 80 DEG C are heated to through heating up, make polyacrylonitrile, cellulose acetate is dissolved completely in solvent dimethylacetylamide, then cool to 70 DEG C and carry out filtering obtained spinning solution;
3) spinning solution carries out spinning again after temperature-adjustment pressure-adjustment, filtration at 0.7 ~ 0.9MPa pressure, temperature 80 ~ 97 DEG C, be that 75wt%:25wt% carries out spinning in powdered polypropylene nitrile and cellulose acetate ratio, through coagulating bath, (coagulating bath is the aqueous solution of dimethylacetylamide, its concentration is 30 ~ 55wt%, and temperature is 25 ~ 50 DEG C.) double diffusion is shaping, through washing, drawing-off, oil, dry, curling, its drafting multiple is 8 times, to be shaped pressure shaping by 250KPa, obtained vinegar nitrile fiber.
The preparation of embodiment 4, vinegar nitrile fiber
1) production of polymer: by 93.5wt% acrylonitrile, the two kinds of monomer mixing of 6.5wt% vinyl acetate, and its mixed concentration is adjusted to 30 ~ 40wt%, in 58 ~ 62 DEG C, pH carries out aqueous suspension polymerization reaction 2.5 ~ 3.5 times continuously; Reacted polymer stops through chelatropic reaction, deviates from unreacted monomer with stripper, then through water washed filter removing salinity, moisture, obtains powdered polypropylene nitrile after granulating and forming through drying;
2) powdered polypropylene nitrile, cellulose acetate are mixed in quality 25wt%:75wt% ratio with dimethylacetylamide with cellulose acetate (70wt%:30wt%) sum in powdered polypropylene nitrile with solvent dimethylacetylamide, 80 DEG C are heated to through heating up, make polyacrylonitrile, cellulose acetate is dissolved completely in solvent dimethylacetylamide, then cool to 70 DEG C and carry out filtering obtained spinning solution;
3) spinning solution carries out spinning again after temperature-adjustment pressure-adjustment, filtration at 0.7 ~ 0.9MPa pressure, temperature 80 ~ 97 DEG C, be that 70wt%:30wt% carries out spinning in powdered polypropylene nitrile and cellulose acetate ratio, through coagulating bath, (coagulating bath is the aqueous solution of dimethylacetylamide, its concentration is 30 ~ 55wt%, and temperature is 25 ~ 50 DEG C.) double diffusion is shaping, through washing, drawing-off, oil, dry, curling, its drafting multiple is 6 times, to be shaped pressure shaping by 280KPa, obtained vinegar nitrile fiber.
The preparation of embodiment 5, vinegar nitrile fiber
1) production of polymer: by 92.5wt% acrylonitrile, the two kinds of monomer mixing of 7.5wt% vinyl acetate, and its mixed concentration is adjusted to 30 ~ 40wt%, in 58 ~ 62 DEG C, pH carries out aqueous suspension polymerization reaction 2.5 ~ 3.5 times continuously; Reacted polymer stops through chelatropic reaction, deviates from unreacted monomer with stripper, then through water washed filter removing salinity, moisture, obtains powdered polypropylene nitrile after granulating and forming through drying;
2) powdered polypropylene nitrile, cellulose acetate are mixed in quality 25wt%:75wt% ratio with dimethylacetylamide with cellulose acetate (65wt%:35wt%) sum in powdered polypropylene nitrile with solvent dimethylacetylamide, 80 DEG C are heated to through heating up, make polyacrylonitrile, cellulose acetate is dissolved completely in solvent dimethylacetylamide, then cool to 70 DEG C and carry out filtering obtained spinning solution;
3) spinning solution carries out spinning again after temperature-adjustment pressure-adjustment, filtration at 0.7 ~ 0.9MPa pressure, temperature 80 ~ 97 DEG C, be that 65wt%:35wt% carries out spinning in powdered polypropylene nitrile and cellulose acetate ratio, through coagulating bath, (coagulating bath is the aqueous solution of dimethylacetylamide, its concentration is 30 ~ 55wt%, and temperature is 25 ~ 50 DEG C.) double diffusion is shaping, through washing, drawing-off, oil, dry, curling, its drafting multiple is 7 times, to be shaped pressure shaping by 300KPa, obtained vinegar nitrile fiber.
The preparation of embodiment 6, vinegar nitrile fiber
Change solvent into dimethyl sulfoxide (DMSO), dimethyl formamide or sodium sulfocyanate by dimethylacetylamide and repeat embodiment 1-5 test, all can obtain vinegar nitrile fiber.
Comparative example, method conventionally prepare vinegar nitrile fiber
Batch (-type) aqueous precipitation polymerization is adopted to prepare polyacrylonitrile: in four-hole boiling flask, to pass through thermostatic circulation bath control temperature at 45 ± 2 DEG C; nitrogen protection; then acrylonitrile (AN), vinylacetate (VAc), latent crosslinker (HQ) is dropped into by a certain percentage; adjust ph is about 2, then adds NaClO
3-Na
2sO
3initator initiated polymerization, controls polymerization time one and a half hours, adds NaOH with cessation reaction, dries after filtration and obtains white powder polyacrylonitrile.
By obtained white powder polyacrylonitrile and cellulose acetate blended with the mass ratio of 85/15,80/20,75/25,70/30,65/35 respectively, spinning still is put into by after 20% concentration configuration DMAc spinning solution, stir and evenly mix with certain rotating speed, obtain the homogeneous solution of amber transparent, vacuumizing and defoaming at 60 DEG C, adopt wet spinning technology, with the DMAc aqueous solution of 40% concentration for coagulating bath, spinning as-spun fibre, after coagulation forming, stretching, lax, drying, obtains blended fiber.
After above-mentioned obtained fiber natural air drying, put into 180 DEG C of temperature baking ovens and be cross-linked, process appropriate time, make the functional group of fiber macromolecule internal that dehydrated crosslinking reaction occur, obtain the blended fiber possessing cross-linked structure.
Blend staple dimension is put into the lye tank (vat) of variable concentrations different temperatures, controlled hydrolysis time, after taking-up in hydrochloric acid and fiber surface remain alkali lye, more fully wash through distilled water, naturally dry after obtain possessing the blended fiber of hydrophilicity.
Test example 1
This test example investigated when polyacrylonitrile with acetyl cellulose blend than identical, the performance of the fiber adopting the method for method of the present invention and prior art to obtain.
Test specimen: according to the method for the embodiment of the present invention 1, by polyacrylonitrile and cellulose acetate blended with the mass ratio of 85/15,80/20,75/25,70/30,65/35 respectively, obtained vinegar nitrile fiber of the present invention.
Control sample: according to the method for comparative example, by polyacrylonitrile and cellulose acetate blended with the mass ratio of 85/15,80/20,75/25,70/30,65/35 respectively, the blended fiber of obtained prior art.
The key technical indexes (specification is 1.33dtex) of the vinegar nitrile fiber adopting the method commonly used of this area to obtain the present invention and the blended fiber of prior art is tested, and the results are shown in following table 1.
Table 1
Note: wherein blending ratio is w (polyacrylonitrile)/w (cellulose acetate)
As can be seen from above-mentioned result of the test, when polyacrylonitrile with acetyl cellulose blend than identical, the good combination property of the vinegar nitrile fiber adopting method of the present invention to obtain.
Test example 2
This test example is tested with the key technical indexes of conventional acrylic fiber and acetate fiber the vinegar nitrile fiber that the present invention obtains, and see the following form 2 and table 3.
The vinegar nitrile fiber that table 2, the present invention obtain and the key technical indexes of conventional acrylic fiber
The vinegar nitrile fiber that table 3, the present invention obtain and the key technical indexes of conventional acetate fiber
Test example 3
This test example has investigated the different ratio of polyacrylonitrile and cellulose acetate to the impact of the antistatic property of obtained vinegar nitrile fiber.
Polyacrylonitrile and cellulose acetate, according to the method for embodiment 1, are obtained vinegar nitrile fiber by different ratio, and investigate its regain and ratio resistance, the results are shown in Table 4 by this test example.
Table 4, polyacrylonitrile and cellulose acetate different ratio are on the impact of vinegar nitrile fibre moisture regain rate and ratio resistance
| W (polyacrylonitrile)/w (cellulose acetate) | Moisture regain (%) | Ratio resistance (Ω CM) |
| 100/0 | 0.89 | 1.12×10 13 |
| 95/5 | 1.05 | 5.88×10 11 |
| 90/10 | 1.47 | 8.91×10 10 |
| 85/15 | 2.00 | 4.73×10 9 |
| 80/20 | 2.10 | 5.51×10 9 |
| 75/25 | 2.63 | 9.27×10 8 |
| 70/30 | 2.53 | 5.77×10 8 |
| 65/35 | 2.69 | 6.89×10 9 |
| 60/40 | 2.71 | 6.17×10 8 |
As can be seen from above-mentioned result of the test, polyacrylonitrile and cellulose acetate adopt different proportionings to have a certain impact to the regain of obtained vinegar nitrile fiber and ratio resistance tool.Along with the increase of cellulose acetate content, the regain of vinegar nitrile fiber increases, and ratio resistance reduces.But consider the content continuing to increase cellulose acetate, make blended fiber hole increase, etching degree increases the weight of relatively, and fibrous fracture intensity can be caused to decline.Therefore, the mass ratio of cellulose acetate and polyacrylonitrile preferably 15 ~ 35wt%:65 ~ 85wt%, more preferably 15 ~ 30wt%:70 ~ 85wt% in the present invention.
Claims (10)
1. a vinegar nitrile fiber, it is characterized in that, described vinegar nitrile fiber is made up of polyacrylonitrile and cellulose acetate, wherein said cellulose acetate and the mass ratio of polyacrylonitrile be arbitrarily than, preferably 15 ~ 35wt%:65 ~ 85wt%, more preferably 15 ~ 30wt%:70 ~ 85wt%.
2. vinegar nitrile fiber according to claim 1, is characterized in that, the intensity of described vinegar nitrile fiber is 2.3 ~ 3.0CN/dtex, and elongation is 32 ~ 40%, and regain is 2 ~ 3%, and ratio resistance is 9.0 × 10
8~ 4.8 × 10
9Ω CM.
3. vinegar nitrile fiber according to claim 1 and 2, is characterized in that, described vinegar nitrile fiber obtains through wet spinning after carrying out dissolving glue by polyacrylonitrile and cellulose acetate solvent.
4. vinegar nitrile fiber according to claim 3, it is characterized in that, described polyacrylonitrile is formed by acrylonitrile and vinyl acetate, and wherein the mass ratio of acrylonitrile and vinyl acetate is 92 ~ 94wt%:6 ~ 8wt%.
5. the vinegar nitrile fiber according to claim 3 or 4, is characterized in that, the quality sum of described polyacrylonitrile and cellulose acetate and the mass ratio of solvent are 20 ~ 25.5:74.5 ~ 80.
6. a preparation method for the vinegar nitrile fiber described in claim 1-5 any one, it is characterized in that, described preparation method comprises the steps:
1) by 92 ~ 94wt% acrylonitrile and the two kinds of monomer mixing of 6 ~ 8wt% vinyl acetate, and aqueous suspension polymerization reaction is carried out continuously after its mixed concentration is adjusted to 30 ~ 40wt%; Reacted polymer stops through chelatropic reaction, deviates from unreacted monomer, then through washing filtering, granulating and forming, oven dry, obtains powdered polypropylene nitrile;
2) by powdered polypropylene nitrile, cellulose acetate and solvent, through heating, cooling, obtained spinning solution is filtered;
3) spinning solution again through temperature-adjustment pressure-adjustment, filter after carry out spinning, shaping through coagulating bath double diffusion, then through washing, drawing-off, oil, dry, curling, sizing, obtain vinegar nitrile fiber.
7. preparation method according to claim 6, is characterized in that, step 1) in, described aqueous suspension polymerization reaction carries out for 2.5 ~ 3.5 times in temperature 58 ~ 62 DEG C, pH value.
8. preparation method according to claim 6, is characterized in that, step 2) in, described cellulose acetate and the mass ratio of powdered polypropylene nitrile are any ratio, preferably 15 ~ 35wt%:65 ~ 85wt%, more preferably 15 ~ 30wt%:70 ~ 85wt%.
9. preparation method according to claim 8, is characterized in that, the mass ratio of described powdered polypropylene nitrile and the quality sum of cellulose acetate and solvent is 20 ~ 25.5:74.5 ~ 80; Described solvent is dimethylacetylamide, dimethyl sulfoxide (DMSO), dimethyl formamide or sodium sulfocyanate; Described intensification is for being warming up to 80 ~ 90 DEG C; Described cooling is for being cooled to 70 ~ 80 DEG C.
10. preparation method according to claim 6, is characterized in that, step 3) in, described spinning carries out at pressure 0.7 ~ 0.9MPa, temperature 80 ~ 97 DEG C; Described coagulating bath is the aqueous solution of dimethylacetylamide, dimethyl sulfoxide (DMSO), dimethyl formamide or sodium sulfocyanate, and its concentration is 30 ~ 55wt%, and temperature is 25 ~ 50 DEG C; Described temperature-adjustment pressure-adjustment is for regulating temperature within the scope of 80 ~ 97 DEG C, regulating pressure within the scope of 0.7 ~ 0.9MPa; Described drafting multiple is 4 ~ 10 times; The described pressure shaping be fixed to by 200 ~ 330KPa.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510079823.2A CN105002592B (en) | 2015-02-13 | 2015-02-13 | A kind of vinegar nitrile fiber and preparation method thereof |
| PCT/CN2016/072777 WO2016127833A1 (en) | 2015-02-13 | 2016-01-29 | Acetic nitrile fibre and preparation method therefor |
| TR2019/09285T TR201909285T4 (en) | 2015-02-13 | 2016-01-29 | A method of preparing a polyacrylonitrile - cellulose acetate fiber. |
| EP16748634.9A EP3257975B1 (en) | 2015-02-13 | 2016-01-29 | Method of making a fiber of polyacrylonitrile - cellulose acetate |
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| CN201510079823.2A CN105002592B (en) | 2015-02-13 | 2015-02-13 | A kind of vinegar nitrile fiber and preparation method thereof |
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| CN105002592A true CN105002592A (en) | 2015-10-28 |
| CN105002592B CN105002592B (en) | 2017-10-17 |
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| EP (1) | EP3257975B1 (en) |
| CN (1) | CN105002592B (en) |
| TR (1) | TR201909285T4 (en) |
| WO (1) | WO2016127833A1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016127833A1 (en) * | 2015-02-13 | 2016-08-18 | 吉林奇峰化纤股份有限公司 | Acetic nitrile fibre and preparation method therefor |
| CN106012076A (en) * | 2016-07-15 | 2016-10-12 | 吉林富博纤维研究院有限公司 | Wet spinning method for preparing cellulose acetate fiber |
| CN107245770A (en) * | 2017-02-16 | 2017-10-13 | 王和军 | A kind of tencel for neutralizing soda acid |
| CN107385591A (en) * | 2016-05-17 | 2017-11-24 | 句容市润龙纺织品有限公司 | A kind of vinegar green grass or young crops silvalin and its processing technology |
| CN107541808A (en) * | 2016-06-29 | 2018-01-05 | 吉林富博纤维研究院有限公司 | A kind of method that vinegar nitrile filaments are prepared using wet spinning technology |
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| CN110295437A (en) * | 2018-03-23 | 2019-10-01 | 上海水星家用纺织品股份有限公司 | A kind of home textile fabric using vinegar blueness fiber |
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| CN111220657A (en) * | 2020-03-27 | 2020-06-02 | 中简科技股份有限公司 | Polyacrylonitrile carbon fiber pH test method |
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| WO2016127833A1 (en) * | 2015-02-13 | 2016-08-18 | 吉林奇峰化纤股份有限公司 | Acetic nitrile fibre and preparation method therefor |
| CN107385591A (en) * | 2016-05-17 | 2017-11-24 | 句容市润龙纺织品有限公司 | A kind of vinegar green grass or young crops silvalin and its processing technology |
| CN107541808A (en) * | 2016-06-29 | 2018-01-05 | 吉林富博纤维研究院有限公司 | A kind of method that vinegar nitrile filaments are prepared using wet spinning technology |
| CN106012076A (en) * | 2016-07-15 | 2016-10-12 | 吉林富博纤维研究院有限公司 | Wet spinning method for preparing cellulose acetate fiber |
| CN106012076B (en) * | 2016-07-15 | 2018-06-19 | 吉林富博纤维研究院有限公司 | A kind of wet spinning preparation method of acetate fiber |
| CN107245770A (en) * | 2017-02-16 | 2017-10-13 | 王和军 | A kind of tencel for neutralizing soda acid |
| CN110016728A (en) * | 2018-01-08 | 2019-07-16 | 吉林吉盟腈纶有限公司 | A kind of preparation method of polyacrylonitrile graphene fiber |
| CN110295437A (en) * | 2018-03-23 | 2019-10-01 | 上海水星家用纺织品股份有限公司 | A kind of home textile fabric using vinegar blueness fiber |
| CN109371718A (en) * | 2018-10-29 | 2019-02-22 | 绍兴文理学院 | A kind of colouring method of berberine to vinegar blueness fiber |
| CN109371718B (en) * | 2018-10-29 | 2020-11-06 | 绍兴文理学院 | Method for dyeing cellulose acetate fibers by berberine |
| CN112080830A (en) * | 2020-08-20 | 2020-12-15 | 江苏瑞康安全装备有限公司 | Elastic soft fluffy acrylic fiber yarn for satin |
| CN113373528A (en) * | 2021-06-09 | 2021-09-10 | 温州市名达服饰有限公司 | Warm-keeping western-style trousers and warm-keeping layer thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3257975A4 (en) | 2017-12-20 |
| CN105002592B (en) | 2017-10-17 |
| TR201909285T4 (en) | 2019-07-22 |
| WO2016127833A1 (en) | 2016-08-18 |
| EP3257975A1 (en) | 2017-12-20 |
| EP3257975B1 (en) | 2019-04-03 |
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