CN105002592B - A kind of vinegar nitrile fiber and preparation method thereof - Google Patents
A kind of vinegar nitrile fiber and preparation method thereof Download PDFInfo
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- CN105002592B CN105002592B CN201510079823.2A CN201510079823A CN105002592B CN 105002592 B CN105002592 B CN 105002592B CN 201510079823 A CN201510079823 A CN 201510079823A CN 105002592 B CN105002592 B CN 105002592B
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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 present invention relates to a kind of fibrous material, specifically, it is related to a kind of vinegar nitrile fiber and preparation method thereof.Described vinegar nitrile fiber is made up of polyacrylonitrile and cellulose acetate, wherein described cellulose acetate and the mass ratio of polyacrylonitrile are any ratio, preferably 15~35wt%：65~85wt%, more preferably 15~30wt%：70~85wt%.Vinegar nitrile fiber provided by the present invention improve acrylic fiber hygroscopicity it is poor, easily rise electrostatic defect；Improve pure acetate fiber low intensity, the shortcoming of taking difference；The combination property of vinegar nitrile fiber provided by the present invention is good simultaneously.
Description
Technical field
The present invention relates to a kind of fibrous material, specifically, it is related to a kind of vinegar nitrile fiber and preparation method thereof.
Background technology
Acrylic fibers are one of world's synthetic fibers principal item, and it is soft, bright in colour, and intensity and elasticity all compare
It is good, there is the good reputation of " artificial wool ".But acrylic fiber macromolecular is in irregular helical conformation, without real crystallization knot
Structure, the strength of fiber is more much higher than natural fiber and regenerated fiber, and acid resistance is good, good weatherability；And due to raw material polypropylene
Contain substantial amounts of hydrophobic group in nitrile (PAN), the hygroscopicity of acrylic fibers is poor, easily produces electrostatic.Electrostatic can cause fiber to twine
Around or block parts, influence weaving process is smoothed out；Electrostatic charge is gathered on clothes easily to be enabled a wearer to produce sense of discomfort,
The wearability of acrylic fibers textile is reduced, so as to limit its further development.
Antistatic additive and Polyacrylonitrile Fiber Spinning Solution are blended, it is to carry out antistatic modified one to acrylic fibers to be then spun into fiber
Plant important method.Conventional blending type antistatic additive is carbon black at present, and such as CN101805935A discloses a kind of novel antistatic
The preparation method of acrylic fibers and antistatic acrylic fiber.The acrylic fibers contain the percetage by weight of CNT and carbon black, wherein CNT
It is 1%-15%, the percetage by weight of carbon black is 1%-3%, and the weight percent range of polyacrylonitrile is 82%-98%.But
Because obtained fiber is black, its purposes is restricted.
In addition, appropriate physics and chemical method can also improve the antistatic property of acrylic fibers, but exist in various degree
Problem of environmental pollution.Thesis for the doctorate《Acrylic fibers plasma antistatic treatment》Propose a kind of using lower temperature plasma technology pair
The method that acrylic fibers carry out the antistatic property that surface is modified to improve acrylic fibers.Lower temperature plasma technology is environment-friendly as one kind
New technology, economize on water, energy-conservation is pollution-free, with significant economic and environmental protection effect.But this method requires higher, in reality
There is certain difficulty in the popularization and application of border.
The moisture pick-up properties of acetate fiber is good, and regain is 6%, can use disperse dyeing, and have good dressing
Energy.Long filament gloss is graceful, soft, has good drapability, exactly likes silk, suitable for making underwear, bathing gown, children's garment, women
Clothes and indoor decorative fabric etc., can also do cigaratte filter.But the low intensity taking of acetate fiber is poor.
" investigation of moisture absorption acrylic fiber spinning process "《King's assistant force moisture absorption acrylic fibers spinning process investigation》Disclose with poly-
Acrylonitrile and the compounded moisture absorption acrylic fiber of two kinds of raw materials of cellulose acetate.But composite fibre is cut in same fiber
There is two or more immiscible polymer on face.And this moisture absorption acrylic fiber is low due to regain itself,
During spinning processing, each operation flyings and electrostatic phenomenon are serious, are spinned especially in High-speed Drawing Frame, front roller output palpus
Bar fiber electrostatic phenomenon is more prominent, easily winds roller, roller, not only life is rough does, and causes the dry severe exacerbation of bar.
Master's thesis《Hydrophilic polymerized acrylonitrile fiber is studied》With acrylonitrile (AN), latent crosslinker (acrylic acid -2- hydroxypropyls
Ester), vinylacetate (VAc) be monomer, sodium chlorate (NaClO3) it is initiator, copolymerization third is prepared using aqueous precipitation polymerization
Alkene nitrile.With DMA (DMAc) for solvent, the copolymerized acrylonitrile containing latent crosslinker is made through wet spinning
(CPAN) fiber and CPAN/ cellulose acetates (CA) blended fiber (CPAN-CA), then be prepared for through post-crosslinking with crosslinking knot
The copolymerized acrylonitrile series fiber of structure, to fiber basic hydrolysis, obtains having relatively strong water suction, water holding capacity, nonirritant and have one
Determine the copolymerized acrylonitrile series fiber of strength.However, crosslinking agent and initiator before needing to add in the preparation of copolymerized acrylonitrile, and
Using aqueous precipitation polymerization, its preparation method is complicated；And the copolymerized acrylonitrile containing latent crosslinker is being made with wet spinning
(CPAN) after fiber and CPAN/ cellulose acetates (CA) blended fiber, it is necessary to further carry out post-crosslinking, and alkali is carried out to fiber
Property hydrolysis can just obtain that there is relatively strong water suction, water holding capacity, blended fiber that is nonirritant and having certain strength.This method is not only
Crosslinking agent and initiator before needing to add in the preparation of copolymerized acrylonitrile, and its preparation method is complicated, need to use aqueous phase precipitation
Polymerization, wet spinning, post-crosslinking and basic hydrolysis multistep reaction, and point out that " hydrolysis prepares polyacrylonitrile hydrophilic fibre
Steps necessary ".But when the content of cellulose acetate is 5%, intensity reaches maximum in obtained blended fiber, is only
1.4cN/dtex, then declines with the increase of cellulose acetate content.
Current China textile industry faces product restructuring, to adapt to domestic and international market competition and improving business economic effect
Benefit, had not only had acetate fiber good characteristic again with acrylic fiber good characteristic, antistatic property, by force in the urgent need to exploitation is a kind of
The fiber of the improved combination properties such as degree meets the market demand, and needs to provide a kind of relatively simple preparation method.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of vinegar nitrile fiber, and to improve, acrylic fiber hygroscopicity is poor, easily play electrostatic
Defect；Improve pure acetate fiber low intensity, the shortcoming of taking difference simultaneously.
The second object of the present invention is the preparation method of the vinegar nitrile fiber described in offer, this method simple possible, technique
It is easily controlled.
To realize the first object of the present invention, the present invention is adopted the following technical scheme that：
A kind of vinegar nitrile fiber, wherein, described vinegar nitrile fiber is made up of polyacrylonitrile and cellulose acetate, wherein described
The mass ratio of cellulose acetate and polyacrylonitrile is any ratio, preferably 15~35wt%：65~85wt%, more preferably 15~
30wt%：70~85wt%.
The intensity of described vinegar nitrile fiber is 2.3~3.0CN/dtex, is extended for 32~40%, and regain is 2~3%,
Ratio resistance is 9.0 × 108~4.8 × 109Ω·CM。
Described vinegar nitrile fiber is to be carried out by polyacrylonitrile and cellulose acetate with solvent after dissolving glue through wet spinning
It is obtained.
Described polyacrylonitrile is formed by acrylonitrile and vinyl acetate, wherein the mass ratio of acrylonitrile and vinyl acetate
For 92~94wt%：6~8wt%.
The mass ratio of described polyacrylonitrile and the quality sum of cellulose acetate and solvent is 20~25.5：74.5~
80。
Vinegar nitrile fiber provided by the present invention has that warming light weight, good weatherability, resistance to acids and bases are good, drapability is good, be difficult
The advantages of corrugation, domestic blank is not only filled up, and a kind of new fibrous raw material is provided for textile industry.
To realize the second object of the present invention, the present invention is adopted the following technical scheme that：
A kind of preparation method of vinegar nitrile fiber of the present invention, this method comprises the following steps：
1) two kinds of monomers of 92~94wt% acrylonitrile and 6~8wt% vinyl acetates are mixed, and the concentration after being mixed
It is adjusted to be carried out continuously aqueous suspension polymerization reaction after 30~40wt%；Reacted polymer is terminated through chelatropic reaction, and abjection is not
The monomer of reaction, then through washing filtering, granulating and forming, drying, obtains powdered polypropylene nitrile；
2) powdered polypropylene nitrile, cellulose acetate and solvent are mixed, through heating, cooling, spinning solution is made in filtering；
3) spinning solution again through temperature-adjustment pressure-adjustment, filtering after carry out spinning, through coagulating bath double diffusion be molded, then through washing,
Drawing-off, oil, dry, crimping, shaping, vinegar nitrile fiber is made.
In above-mentioned preparation method, wherein, step 1) in, described aqueous suspension polymerization reaction be 58~62 DEG C of temperature,
2.5~3.5 times progress of pH value.
Step 2) in, the mass ratio of described cellulose acetate and powdered polypropylene nitrile is 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；The solvent is dimethyl acetamide, dimethyl sulfoxide (DMSO), dimethylformamide or sodium sulfocyanate；Described heating is
It is warming up to 80~90 DEG C；Described cooling is to be cooled to 70~80 DEG C.
Step 3) in, described spinning is carried out at 0.7~0.9MPa of pressure, 80~97 DEG C of temperature；Described solidification
To bathe as the aqueous solution of dimethyl acetamide, dimethyl sulfoxide (DMSO), dimethylformamide or sodium sulfocyanate, its concentration is 30~
55wt%, temperature is 25~50 DEG C；Described temperature-adjustment pressure-adjustment for regulation temperature in the range of 80~97 DEG C, regulation pressure 0.7
In the range of~0.9MPa；Described drafting multiple is 4~10 times；The described pressure shaping being fixed to by 200~330KPa.
Technical scheme is described in detail below：
Hygroscopicity is poor because it absorbs water for plain polypropylene nitrile fiber, and regain is low, and the characteristic such as antistatic behaviour constrains it should
Use scope.The moisture absorption of fiber has certain inner link with antistatic behaviour, therefore improves the water suction hygroscopicity of polyacrylonitrile fibre
Other performances can be substantially improved.Prior art discloses a variety of hygroscopicity being made up of polyacrylonitrile and acetyl cellulose blend
Fiber, but many prior art indicate that when cellulose acetate content be 5% when intensity reach maximum, but only 1.4cN/
Dtex, then declines with the increase of cellulose acetate content.It is current both to have had acetate fiber excellent in the urgent need to exploitation is a kind of
There is good characteristic the fiber of the improved combination properties such as acrylic fiber good characteristic, antistatic property, intensity to meet market need again
Ask.
Present invention firstly provides a kind of vinegar nitrile fiber, described vinegar nitrile fiber is made up of polyacrylonitrile and cellulose acetate,
Wherein described cellulose acetate and the mass ratio of polyacrylonitrile are any ratio, preferably 15~35wt%：65~85wt%, it is more excellent
Select 15~30wt%：70~85wt%.
The present inventor employs larger cellulose acetate mass ratio by substantial amounts of experiment, not only increases vinegar nitrile fine
The intensity of dimension, and its elongation, regain and ratio resistance also have preferable performance, beyond the scope of expectation.
The combination property of vinegar nitrile fiber of the present invention is good, and its intensity is 2.3~3.0CN/dtex, extend for 32~
40%, regain is 2~3%, and ratio resistance is 9.0 × 108~4.8 × 109Ω·CM。
Specifically, described vinegar nitrile fiber be by polyacrylonitrile and cellulose acetate carry out dissolving glue with solvent after pass through
Made from wet spinning.
In the prior art, the blended fiber of polyacrylonitrile and cellulose acetate is usually and further carried out after wet spinning
Post-crosslinking, is then carried out made from basic hydrolysis to it, and points out that " hydrolysis is the necessity for preparing polyacrylonitrile hydrophilic fibre
Step ".But vinegar nitrile fiber of the present invention only need to be carried out polyacrylonitrile and cellulose acetate after dissolving glue with solvent
It is that can obtain to carry out wet spinning, it is not necessary to be crosslinked, post-crosslinking and basic hydrolysis are handled, process route is simple, so that significantly
Processing step is simplified, operating efficiency is improved, is conducive to batch production, and the vinegar nitrile fibrous physics index produced is closer
In conventional acrylic fiber index.
Further, described polyacrylonitrile is formed by acrylonitrile and vinyl acetate, wherein acrylonitrile and acetic acid second
The mass ratio of alkene is 92~94wt%：6~8wt%.
In the prior art, polyacrylonitrile is typically by acrylonitrile, vinyl acetate and for example preceding crosslinking agent of other components, initiation
Made from agent, three single auxiliary agents, oxidant, reducing agent etc..In the present invention, described polyacrylonitrile is by acrylonitrile and vinyl acetate
With 92~94wt%：6~8wt% mass ratio formation.
The mass ratio of described polyacrylonitrile and the quality sum of cellulose acetate and solvent is 20~25.5：74.5~
80。
The present invention also provides the preparation method of described vinegar nitrile fiber, and this method simple possible, technique is easily controlled.
The preparation method of vinegar nitrile fiber provided by the present invention comprises the following steps：
1) two kinds of monomers of 92~94wt% acrylonitrile and 6~8wt% vinyl acetates are mixed, and the concentration after being mixed
It is adjusted to be carried out continuously aqueous suspension polymerization reaction after 30~40wt%；Reacted polymer is terminated through chelatropic reaction, and abjection is not
The monomer of reaction, then through washing filtering, granulating and forming, drying, obtains powdered polypropylene nitrile；
2) powdered polypropylene nitrile, cellulose acetate and solvent are mixed, through heating, cooling, spinning solution is made in filtering；
3) spinning solution again through temperature-adjustment pressure-adjustment, filtering after carry out spinning, through coagulating bath double diffusion be molded, then through washing,
Drawing-off, oil, dry, crimping, shaping, vinegar nitrile fiber is made.
Disclose in the prior art with acrylonitrile (AN), latent crosslinker (2-hydroxypropyl acrylate), vinylacetate
(VAc) it is monomer, sodium chlorate (NaClO3) it is initiator, copolymerized acrylonitrile is prepared using aqueous precipitation polymerization.Then with N,
N- dimethyl acetamides (DMAc) are solvent, through wet spinning be made copolymerized acrylonitrile (CPAN) fiber containing latent crosslinker and
CPAN/ cellulose acetates (CA) blended fiber (CPAN-CA), then it is prepared for the co-polypropylene with cross-linked structure through post-crosslinking
Nitrile series fiber, to fiber basic hydrolysis, obtains with relatively strong water suction, water holding capacity and has the copolymerized acrylonitrile system of certain strength fine
Dimension.Crosslinking agent and initiator before this method not only needs to add in the preparation of copolymerized acrylonitrile, and its preparation method is complicated,
Aqueous deposited polymerization, wet spinning, post-crosslinking and basic hydrolysis multistep reaction need to be used.And emphasize that " hydrolysis is to prepare polypropylene
The steps necessary of nitrile system hydrophilic fibre ".It can be seen that, it is to prepare polyacrylonitrile hydrophily fibre that hydrolysis is generally believed in the prior art
The steps necessary of dimension.
It is outstanding by aqueous phase only with two kinds of monomers of acrylonitrile and vinyl acetate and the present invention is by adjusting process, proportioning etc.
Floating polymerization obtains can obtain vinegar nitrile fiber after polyacrylonitrile with cellulose acetate wet spinning again, it is not necessary to be crosslinked, after
Crosslinking and basic hydrolysis processing, process route are simple, so as to enormously simplify processing step, improve operating efficiency, are conducive to criticizing
Amount 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 is in temperature
58~62 DEG C, 2.5~3.5 times progress of pH value.
Step 2) in, the mass ratio of described cellulose acetate and powdered polypropylene nitrile is 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；The solvent is dimethyl acetamide, dimethyl sulfoxide (DMSO), dimethylformamide or sodium sulfocyanate；Described heating is
It is warming up to 80~90 DEG C；Described cooling is to be cooled to 70~80 DEG C.
Step 3) in, described spinning is carried out at 0.7~0.9MPa of pressure, 80~97 DEG C of temperature；Described solidification
To bathe as the aqueous solution of dimethyl acetamide, dimethyl sulfoxide (DMSO), dimethylformamide or sodium sulfocyanate, its concentration is 30~
55wt%, temperature is 25~50 DEG C；Described temperature-adjustment pressure-adjustment for regulation temperature in the range of 80~97 DEG C, regulation pressure 0.7
In the range of~0.9MPa；Described drafting multiple is 4~10 times；The described pressure shaping being fixed to by 200~330KPa.
The preparation method technique simple possible of the present invention, and the good combination property of obtained vinegar nitrile fiber, its intensity are 2.3
~3.0CN/dtex, extends for 32~40%, and regain is 2~3%, and ratio resistance is 9.0 × 108~4.8 × 109Ω·CM。
Compared with prior art, the invention has the advantages that：
(1) vinegar nitrile fiber produced by the invention has some characteristics of acrylic fiber, and improves the moisture absorption of acrylic fiber
Performance and the defect for easily playing electrostatic.
(2) not only intensity is improved vinegar nitrile fiber provided by the present invention, and its elongation, regain and ratio resistance
Also there is preferable performance.
(3) vinegar nitrile fiber produced by the invention also has some characteristics of acetate fiber, and drapability is good, does not crease easily, and change
Acetate fiber low intensity has been apt to it, acid resistance is poor, and weatherability is poor.
(4) present invention process simple possible, is easily controlled, and is produced using the existing apparatus such as existing spinning tissue, to downstream
The continuity of process production does not result in any influence.
Embodiment
Be below the embodiment of the present invention, described embodiment be in order to further describe the present invention, rather than
The limitation present invention.
The preparation of embodiment 1, vinegar nitrile fiber
1) production of polymer：92wt% acrylonitrile, two kinds of monomers of 8wt% vinyl acetates are mixed, and after being mixed
Concentration be adjusted to 30~40wt%, in 58~62 DEG C, pH is to be carried out continuously aqueous suspension polymerization reaction under 2.5~3.5；After reaction
Polymer terminated through chelatropic reaction, deviate from unreacted monomer with stripper, then remove salinity, water through water washed filter
Point, obtain powdered polypropylene nitrile through drying after granulating and forming；
2) powdered polypropylene nitrile, cellulose acetate and solvent dimethyl acetamide are pressed into powdered polypropylene nitrile and acetate fiber
Element (85wt%：15wt%) sum presses quality 20wt% with dimethyl acetamide：80wt% ratios are mixed, and 80 are heated to through heating
DEG C, polyacrylonitrile, cellulose acetate is dissolved completely in solvent dimethyl acetamide, then cool to 70 DEG C carry out filtering be made
Spinning solution；
3) spinning solution is spun through temperature-adjustment pressure-adjustment, filtering after at 0.7~0.9MPa pressure, 80~97 DEG C of temperature again
Silk, is 85wt% in powdered polypropylene nitrile and cellulose acetate ratio：15wt% carries out spinning, and through coagulating bath, (coagulating bath is two
The aqueous solution of methylacetamide, its concentration is 30~55wt%, and temperature is 25~50 DEG C.) double diffusion shaping, through washing, drawing-off,
Oil, dry, crimp, its drafting multiple is 10 times, by 200KPa sizing pressure shapings, vinegar nitrile fiber is made.
The preparation of embodiment 2, vinegar nitrile fiber
1) production of polymer：94wt% acrylonitrile, two kinds of monomers of 6wt% vinyl acetates are mixed, and after being mixed
Concentration be adjusted to 30~40wt%, in 58~62 DEG C, pH is to be carried out continuously aqueous suspension polymerization reaction under 2.5~3.5；After reaction
Polymer terminated through chelatropic reaction, deviate from unreacted monomer with stripper, then remove salinity, water through water washed filter
Point, obtain powdered polypropylene nitrile through drying after granulating and forming；
2) powdered polypropylene nitrile, cellulose acetate and solvent dimethyl acetamide are pressed into powdered polypropylene nitrile and acetate fiber
Element (80wt%：20wt%) sum presses quality 23wt% with dimethyl acetamide：77wt% ratios are mixed, and 80 are heated to through heating
DEG C, polyacrylonitrile, cellulose acetate is dissolved completely in solvent dimethyl acetamide, then cool to 70 DEG C carry out filtering be made
Spinning solution；
3) spinning solution is spun through temperature-adjustment pressure-adjustment, filtering after at 0.7~0.9MPa pressure, 80~97 DEG C of temperature again
Silk, is 80wt% in powdered polypropylene nitrile and cellulose acetate ratio：20wt% carries out spinning, and through coagulating bath, (coagulating bath is two
The aqueous solution of methylacetamide, its concentration is 30~55wt%, and temperature is 25~50 DEG C.) double diffusion shaping, through washing, drawing-off,
Oil, dry, crimp, its drafting multiple is 4 times, by 330KPa sizing pressure shapings, vinegar nitrile fiber is made.
The preparation of embodiment 3, vinegar nitrile fiber
1) production of polymer：93wt% acrylonitrile, two kinds of monomers of 7wt% vinyl acetates are mixed, and after being mixed
Concentration be adjusted to 30~40wt%, in 58~62 DEG C, pH is to be carried out continuously aqueous suspension polymerization reaction under 2.5~3.5；After reaction
Polymer terminated through chelatropic reaction, deviate from unreacted monomer with stripper, then remove salinity, water through water washed filter
Point, obtain powdered polypropylene nitrile through drying after granulating and forming；
2) powdered polypropylene nitrile, cellulose acetate and solvent dimethyl acetamide are pressed into powdered polypropylene nitrile and acetate fiber
Element (75wt%：25wt%) sum presses quality 25.5wt% with dimethyl acetamide：74.5wt% ratios are mixed, and are heated through heating
To 80 DEG C, make polyacrylonitrile, cellulose acetate be dissolved completely in solvent dimethyl acetamide, then cool to 70 DEG C to be filtered
Spinning solution is made；
3) spinning solution is spun through temperature-adjustment pressure-adjustment, filtering after at 0.7~0.9MPa pressure, 80~97 DEG C of temperature again
Silk, is 75wt% in powdered polypropylene nitrile and cellulose acetate ratio：25wt% carries out spinning, and through coagulating bath, (coagulating bath is two
The aqueous solution of methylacetamide, its concentration is 30~55wt%, and temperature is 25~50 DEG C.) double diffusion shaping, through washing, drawing-off,
Oil, dry, crimp, its drafting multiple is 8 times, by 250KPa sizing pressure shapings, vinegar nitrile fiber is made.
The preparation of embodiment 4, vinegar nitrile fiber
1) production of polymer：93.5wt% acrylonitrile, two kinds of monomers of 6.5wt% vinyl acetates are mixed, and mixed
Concentration after conjunction is adjusted to 30~40wt%, in 58~62 DEG C, and pH is to be carried out continuously aqueous suspension polymerization reaction under 2.5~3.5；Instead
Should after polymer terminated through chelatropic reaction, deviate from unreacted monomer with stripper, then through water washed filter remove salinity,
After moisture, granulating and forming powdered polypropylene nitrile is obtained through drying；
2) powdered polypropylene nitrile, cellulose acetate and solvent dimethyl acetamide are pressed into powdered polypropylene nitrile and acetate fiber
Element (70wt%：30wt%) sum presses quality 25wt% with dimethyl acetamide：75wt% ratios are mixed, and 80 are heated to through heating
DEG C, polyacrylonitrile, cellulose acetate is dissolved completely in solvent dimethyl acetamide, then cool to 70 DEG C carry out filtering be made
Spinning solution；
3) spinning solution is spun through temperature-adjustment pressure-adjustment, filtering after at 0.7~0.9MPa pressure, 80~97 DEG C of temperature again
Silk, is 70wt% in powdered polypropylene nitrile and cellulose acetate ratio：30wt% carries out spinning, and through coagulating bath, (coagulating bath is two
The aqueous solution of methylacetamide, its concentration is 30~55wt%, and temperature is 25~50 DEG C.) double diffusion shaping, through washing, drawing-off,
Oil, dry, crimp, its drafting multiple is 6 times, by 280KPa sizing pressure shapings, vinegar nitrile fiber is made.
The preparation of embodiment 5, vinegar nitrile fiber
1) production of polymer：92.5wt% acrylonitrile, two kinds of monomers of 7.5wt% vinyl acetates are mixed, and mixed
Concentration after conjunction is adjusted to 30~40wt%, in 58~62 DEG C, and pH is to be carried out continuously aqueous suspension polymerization reaction under 2.5~3.5；Instead
Should after polymer terminated through chelatropic reaction, deviate from unreacted monomer with stripper, then through water washed filter remove salinity,
After moisture, granulating and forming powdered polypropylene nitrile is obtained through drying；
2) powdered polypropylene nitrile, cellulose acetate and solvent dimethyl acetamide are pressed into powdered polypropylene nitrile and acetate fiber
Element (65wt%：35wt%) sum presses quality 25wt% with dimethyl acetamide：75wt% ratios are mixed, and 80 are heated to through heating
DEG C, polyacrylonitrile, cellulose acetate is dissolved completely in solvent dimethyl acetamide, then cool to 70 DEG C carry out filtering be made
Spinning solution；
3) spinning solution is spun through temperature-adjustment pressure-adjustment, filtering after at 0.7~0.9MPa pressure, 80~97 DEG C of temperature again
Silk, is 65wt% in powdered polypropylene nitrile and cellulose acetate ratio：35wt% carries out spinning, and through coagulating bath, (coagulating bath is two
The aqueous solution of methylacetamide, its concentration is 30~55wt%, and temperature is 25~50 DEG C.) double diffusion shaping, through washing, drawing-off,
Oil, dry, crimp, its drafting multiple is 7 times, by 300KPa sizing pressure shapings, vinegar nitrile fiber is made.
The preparation of embodiment 6, vinegar nitrile fiber
Solvent is changed to dimethyl sulfoxide (DMSO), dimethylformamide or sodium sulfocyanate by dimethyl acetamide and repeats embodiment
1-5 experiments, can be made vinegar nitrile fiber.
Comparative example, vinegar nitrile fiber is prepared according to the method for prior art
Polyacrylonitrile is prepared using batch (-type) aqueous precipitation polymerization：Pass through thermostatic circulation bath control in four-hole boiling flask
Temperature is at 45 ± 2 DEG C, and then nitrogen protection puts into acrylonitrile (AN), vinylacetate (VAc), latent crosslinker by a certain percentage
(HQ), regulation pH value is 2 or so, adds NaClO3-Na2SO3Initiator initiated polymerization, controls polymerization time one and half
Hour, plus NaOH obtain white powder polyacrylonitrile with terminating reaction through filtering drying.
By obtained white powder polyacrylonitrile and cellulose acetate respectively with 85/15,80/20,75/25,70/30,
65/35 mass ratio blending, is put into spinning kettle after configuring DMAc spinning solutions by 20% concentration, mixed with the stirring of certain rotating speed
It is even, vacuumizing and defoaming at the homogeneous solution of amber transparent, 60 DEG C is obtained, using wet spinning technology, with the DMAc of 40% concentration
The aqueous solution is coagulating bath, spins as-spun fibre, after coagulation forming, stretching, relaxation, drying, obtains blended fiber.
After fiber natural air drying obtained above, it is put into 180 DEG C of temperature baking ovens and is crosslinked, handles appropriate time, make fibre
Dehydrated crosslinking reaction occurs for the functional group for tieing up macromolecule internal, obtains the blended fiber for possessing cross-linked structure.
Blend staple dimension is put into the lye tank (vat) of various concentrations different temperatures, hydrolysis time is controlled, through hydrochloric acid after taking-up
Neutralize fiber surface residual alkali lye, then fully wash through distilled water, dry naturally after obtain the blended fiber that possesses hydrophilicity.
Test example 1
This test example has been investigated in the case of polyacrylonitrile and acetyl cellulose blend ratio identical, using the side of the present invention
The performance of fiber made from the method for method and prior art.
Test specimen：According to the method for the embodiment of the present invention 1, by polyacrylonitrile and cellulose acetate respectively with 85/15,
80/20th, 75/25,70/30,65/35 mass ratio blending, is made the vinegar nitrile fiber of the present invention.
Control sample：According to the method for comparative example, by polyacrylonitrile and cellulose acetate respectively with 85/15,80/20,75/
25th, 70/30,65/35 mass ratio blending, is made the blended fiber of prior art.
Using method commonly used in the art to the main of vinegar nitrile fiber produced by the present invention and the blended fiber of prior art
Technical indicator (specification is 1.33dtex) is tested, and as a result see the table below 1.
Table 1
Note：Wherein blending ratio is w (polyacrylonitrile)/w (cellulose acetate)
It can be seen that in the case of polyacrylonitrile and acetyl cellulose blend ratio identical, use from above-mentioned result of the test
The good combination property of vinegar nitrile fiber made from the method for the present invention.
Test example 2
This test example refers to the major technique of vinegar nitrile fiber produced by the present invention and conventional acrylic fiber and acetate fiber
Mark is tested, and see the table below 2 and table 3.
The key technical indexes of table 2, vinegar nitrile fiber produced by the present invention and conventional acrylic fiber
The key technical indexes of table 3, vinegar nitrile fiber produced by the present invention and conventional acetate fiber
Test example 3
The test example has investigated the different ratio of polyacrylonitrile and cellulose acetate to the anti-quiet of obtained vinegar nitrile fiber
The influence of electrical property.
According to the method for embodiment 1 vinegar nitrile fibre is made by different ratio in polyacrylonitrile and cellulose acetate by this test example
Dimension, and its regain and ratio resistance are investigated, it the results are shown in Table 4.
The influence of table 4, polyacrylonitrile and cellulose acetate different ratio to vinegar nitrile fiber regain and ratio resistance
| W (polyacrylonitrile)/w (cellulose acetate) | Get damp again (%) | Ratio resistance (Ω CM) |
| 100/0 | 0.89 | 1.12×1013 |
| 95/5 | 1.05 | 5.88×1011 |
| 90/10 | 1.47 | 8.91×1010 |
| 85/15 | 2.00 | 4.73×109 |
| 80/20 | 2.10 | 5.51×109 |
| 75/25 | 2.63 | 9.27×108 |
| 70/30 | 2.53 | 5.77×108 |
| 65/35 | 2.69 | 6.89×109 |
| 60/40 | 2.71 | 6.17×108 |
Polyacrylonitrile and cellulose acetate are can be seen that using different with comparing obtained vinegar nitrile from above-mentioned result of the test
Regain and the ratio resistance tool of fiber have a certain impact.With the increase of cellulose acetate content, the regain of vinegar nitrile fiber
Increase, ratio resistance reduces.But the content in view of continuing increase cellulose acetate so that blended fiber hole increases, etches journey
Degree is relative to be aggravated, and fibrous fracture intensity can be caused to decline.Therefore, the mass ratio of cellulose acetate and polyacrylonitrile is excellent in the present invention
Select 15~35wt%：65~85wt%, more preferably 15~30wt%：70~85wt%.
Claims (8)
1. a kind of vinegar nitrile fiber, it is characterised in that the fiber number of described vinegar nitrile fiber is 1.33dtex, by polyacrylonitrile and acetic acid
Cellulose is constituted, wherein described cellulose acetate and the mass ratio of polyacrylonitrile are 15~35wt%：65~85wt%；Described
The preparation method of vinegar nitrile fiber comprises the following steps：
1）Two kinds of monomers of 92~94wt% acrylonitrile and 6~8wt% vinyl acetates are mixed, and the concentration after being mixed is adjusted to 30
Aqueous suspension polymerization reaction is carried out continuously after~40wt%；Reacted polymer is terminated through chelatropic reaction, deviates from unreacted list
Body, then through washing filtering, granulating and forming, drying, obtains powdered polypropylene nitrile；
2）Powdered polypropylene nitrile, cellulose acetate are mixed with solvent, through heating, cooling, spinning solution is made in filtering；
3）Spinning solution again through temperature-adjustment pressure-adjustment, filtering after carry out spinning, through coagulating bath double diffusion be molded, then through washing, drawing-off,
Oil, dry, crimp, shape, vinegar nitrile fiber is made.
2. vinegar nitrile fiber according to claim 1, it is characterised in that described cellulose acetate and the quality of polyacrylonitrile
Than for 15~30wt%：70~85wt%.
3. vinegar nitrile fiber according to claim 1 or 2, it is characterised in that the intensity of described vinegar nitrile fiber is 2.3~
3.0CN/dtex, extends for 32~40%, and regain is 2~3%, and ratio resistance is 9.0 × 108~4.8 × 109Ω•cm。
4. vinegar nitrile fiber according to claim 1 or 2, it is characterised in that described polyacrylonitrile and cellulose acetate
The mass ratio of quality sum and solvent is 20~25.5：74.5~80.
5. a kind of preparation method of the vinegar nitrile fiber described in claim 1-3 any one, it is characterised in that described preparation side
Method comprises the following steps：
1）Two kinds of monomers of 92~94wt% acrylonitrile and 6~8wt% vinyl acetates are mixed, and the concentration after being mixed is adjusted to 30
Aqueous suspension polymerization reaction is carried out continuously after~40wt%；Reacted polymer is terminated through chelatropic reaction, deviates from unreacted list
Body, then through washing filtering, granulating and forming, drying, obtains powdered polypropylene nitrile；
2）Powdered polypropylene nitrile, cellulose acetate are mixed with solvent, through heating, cooling, spinning solution is made in filtering；
3）Spinning solution again through temperature-adjustment pressure-adjustment, filtering after carry out spinning, through coagulating bath double diffusion be molded, then through washing, drawing-off,
Oil, dry, crimp, shape, vinegar nitrile fiber is made.
6. preparation method according to claim 5, it is characterised in that step 1）In, described aqueous suspension polymerization reaction
It is in 58~62 DEG C of temperature, 2.5~3.5 times progress of pH value.
7. preparation method according to claim 6, it is characterised in that described powdered polypropylene nitrile and cellulose acetate
The mass ratio of quality sum and solvent is 20~25.5：74.5~80；The solvent be dimethyl acetamide, dimethyl sulfoxide (DMSO) or
Dimethylformamide；Described heating is to be warming up to 80~90 DEG C；Described cooling is to be cooled to 70~80 DEG C.
8. preparation method according to claim 5, it is characterised in that step 3）In, described spinning be pressure 0.7~
Carried out at 0.9MPa, 80~97 DEG C of temperature；Described coagulating bath is dimethyl acetamide, dimethyl sulfoxide (DMSO), dimethylformamide
Or the aqueous solution of sodium sulfocyanate, its concentration is 30~55wt%, and temperature is 25~50 DEG C；Described temperature-adjustment pressure-adjustment is regulation temperature
Degree is in the range of 80~97 DEG C, regulation pressure is in the range of 0.7~0.9MPa；Drafting multiple is 4~10 times；Described is fixed to
Pass through 200~330kPa pressure shaping.
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 |
| EP16748634.9A EP3257975B1 (en) | 2015-02-13 | 2016-01-29 | Method of making a fiber of polyacrylonitrile - cellulose acetate |
| 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. |
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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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| CN105002592B true CN105002592B (en) | 2017-10-17 |
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| EP (1) | EP3257975B1 (en) |
| CN (1) | CN105002592B (en) |
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| CN105002592B (en) * | 2015-02-13 | 2017-10-17 | 吉林奇峰化纤股份有限公司 | A kind of vinegar nitrile fiber and preparation method thereof |
| 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 |
| CN107541808B (en) * | 2016-06-29 | 2020-08-04 | 吉林富博纤维研究院有限公司 | Method for preparing vinyl acetate filaments by adopting wet spinning process |
| 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 |
| CN110016728B (en) * | 2018-01-08 | 2022-04-22 | 吉林吉盟腈纶有限公司 | 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 |
| CN109371718B (en) * | 2018-10-29 | 2020-11-06 | 绍兴文理学院 | Method for dyeing cellulose acetate fibers by berberine |
| CN111220657A (en) * | 2020-03-27 | 2020-06-02 | 中简科技股份有限公司 | Polyacrylonitrile carbon fiber pH test method |
| 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 |
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| CH432721A (en) * | 1964-01-25 | 1967-03-31 | Rhodiaceta | Process for preparing spinnable mixtures of high molecular weight materials |
| JPH0299609A (en) * | 1988-10-03 | 1990-04-11 | Mitsubishi Rayon Co Ltd | Production method for novel acrylic synthetic fiber |
| JP3851192B2 (en) * | 2001-07-11 | 2006-11-29 | 三菱レイヨン株式会社 | Method for producing acrylic composite fiber |
| CN100491608C (en) * | 2007-06-12 | 2009-05-27 | 天津工业大学 | Method for preparing hydrophilic polymerized acrylonitrile fiber |
| CN100535210C (en) * | 2007-07-31 | 2009-09-02 | 浙江杭州湾腈纶有限公司 | Method for preparing acrylic fibre used for building |
| CN103498208B (en) * | 2013-09-26 | 2016-03-30 | 吉林奇峰化纤股份有限公司 | Thermal storage fiber and preparation method thereof |
| CN103882547B (en) * | 2014-02-27 | 2016-07-06 | 宁波中新腈纶有限公司 | A kind of flat acrylic fiber and production method thereof |
| CN105002592B (en) * | 2015-02-13 | 2017-10-17 | 吉林奇峰化纤股份有限公司 | A kind of vinegar nitrile fiber and preparation method thereof |
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| CN105002592A (en) | 2015-10-28 |
| WO2016127833A1 (en) | 2016-08-18 |
| EP3257975B1 (en) | 2019-04-03 |
| EP3257975A1 (en) | 2017-12-20 |
| TR201909285T4 (en) | 2019-07-22 |
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Effective date of registration: 20180327 Address after: 052160 Hebei Province, Shijiazhuang city Gaocheng District East Road No. 2 Patentee after: Hebei Acu-Rite Fiber Co. Ltd. Address before: 132115 Jilin province Jilin City nine Street No. 516-1 Patentee before: Jilin Qifeng Chemical Fibre Stock Co., Ltd. |