CN110055601A - A kind of wet spinning process and polyacrylonitrile fibre of polyacrylonitrile fibre - Google Patents
A kind of wet spinning process and polyacrylonitrile fibre of polyacrylonitrile fibre Download PDFInfo
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- CN110055601A CN110055601A CN201910403489.XA CN201910403489A CN110055601A CN 110055601 A CN110055601 A CN 110055601A CN 201910403489 A CN201910403489 A CN 201910403489A CN 110055601 A CN110055601 A CN 110055601A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
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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
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
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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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
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- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The present invention relates to a kind of wet spinning process of polyacrylonitrile fibre and polyacrylonitrile fibres.The technical solution mainly used are as follows: a kind of wet spinning process of polyacrylonitrile fibre includes the following steps: spinneret: spinning solution is squeezed out through the spinneret orifice of spinning pack, obtains dynamic analysis of spinning；Coagulation forming: the dynamic analysis of spinning enters coagulation forming in coagulating bath, obtains as-spun fibre；Hot gas spring processing: multistage hot gas spring processing is carried out to the as-spun fibre；Washing process: washing process is carried out to hot gas spring treated fiber；Dry, thermal finalization processing: the fiber after washing is successively dried, thermal finalization processing, obtains polyacrylonitrile fibre.A kind of polyacrylonitrile fibre is prepared by the wet spinning process of above-mentioned polyacrylonitrile fibre.Present invention is mainly used for ensure spinning solution in the spinnability of spinning process, and the mechanical property of raising polyacrylonitrile fibre.
Description
Technical field
The present invention relates to a kind of polyacrylonitrile fibre technical fields, more particularly to a kind of Wet-spinning of polyacrylonitrile fibre
Silk method and polyacrylonitrile fibre.
Background technique
Polyacrylonitrile fibre is one of big synthetic fibers in the world three, and it is excellent to have that elasticity is good, soft, warmth retention property is good etc.
Point has the title of " synthetic wool ", therefore is widely used in the fields such as clothes, decoration, outdoor textile.But polyacrylonitrile is fine
The limit oxygen index LOI value of dimension is only 17~18.5%, is one of extremely incendive synthetic fibers, is easy to draw in use
Play the security of the lives and property of fire threat people.Therefore, flame-resistant polyacrylonitrile fiber also becomes opening for various countries' synthetic fiber industry
Hair and research hotspot.
Since the modified method of polymer chemistry has the advantages that flame-retardant monomer dosage is few, flame retardant effect is most lasting, cost is relatively low,
The companies such as U.S. Yi Siman, Britain's Courtaulds, Japan Zhong Yuan use the method to produce flame-resistant polyacrylonitrile fiber.Though China
Right the 1960s begins to the production technology of research flame-retardant acrylic fibre fiber, but since production technology and the problems such as equipment develop
Slowly, the spining technology of flame-retardant acrylic fibre fiber almost blank fails extensive industrialization so far.
It was found by the inventors of the present invention that the research of the prior art focuses on that (limit oxygen refers to by the LOI of polyacrylonitrile fibre substantially
Number) raising, still, thus bring spinning solution is spinning process spinnability is poor and manufactured polyacrylonitrile fibre mechanics
The decline of performance is less to be taken into account.
Summary of the invention
In view of this, the present invention provides the wet spinning process and polyacrylonitrile fibre of a kind of polyacrylonitrile fibre, mainly
Purpose is to ensure that spinning solution in the spinnability of spinning process, improves the mechanical property of fiber.
In order to achieve the above objectives, present invention generally provides following technical solutions:
On the one hand, the embodiment of the present invention provides a kind of wet spinning process of polyacrylonitrile fibre comprising following step
It is rapid:
Spinneret: spinning solution is squeezed out through the spinneret orifice of spinning pack, obtains dynamic analysis of spinning；
Coagulation forming: the dynamic analysis of spinning enters coagulation forming in coagulating bath, obtains as-spun fibre；
Hot gas spring processing: hot gas spring processing is carried out to the as-spun fibre；
Washing process: washing process is carried out to hot gas spring treated fiber；
Dry, thermal finalization processing: the fiber after washing is successively dried, thermal finalization processing, obtains polyacrylonitrile fibre
Dimension.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, in the step of hot gas spring is handled, drawing-off medium selects glycerol；And/or the hot gas spring processing
For the processing of multistage hot gas spring；Wherein, the temperature of previous stage hot gas spring is lower than the temperature of rear stage hot gas spring；Preferably, the heat
The temperature of drawing-off processing is 100~130 DEG C.
Preferably, in the step of hot gas spring is handled, the processing of three-level hot gas spring is carried out to the as-spun fibre；Its
In, the temperature of first order hot gas spring is 100~105 DEG C, and the multiple of first order hot gas spring is 1.2~2 times；And/or second level heat
The temperature of drawing-off is 110~120 DEG C, and the multiple of second level hot gas spring is 2~3 times；And/or the temperature of third level hot gas spring is
125~130 DEG C, the multiple of third level hot gas spring is 1.2~2 times.
Preferably, in the washing process the step of: the temperature of the washing process is 50~70 DEG C, washing process
Time is 1~3min.
Preferably, the drying, the drying steps in thermal finalization processing step are as follows: to the fiber after the washing process into
Row vacuum drying treatment；Preferably, 40~50 DEG C of the temperature of drying process, time of drying process is 12~for 24 hours；And/or
Thermal finalization processing step in the drying, thermal finalization processing step includes:
Relaxation heat setting: relaxation heat setting is carried out to the fiber after drying；Preferably, the step of relaxation heat setting
In, the medium of negative drawing-off selects glycerol；Preferably, in the step of relaxation heat setting, temperature is 140~150 DEG C, negative drawing-off
Rate is -30% to -10%；
Washing: to relaxation heat setting, treated that fiber is washed；Preferably, 60~80 DEG C of the temperature of the washing,
The time of the washing is 3~5min；
Dry thermal finalization: thermal finalization is dried to the fiber after washing；Preferably, the temperature of the dry thermal finalization is
50~60 DEG C, time of the dry thermal finalization be 12~for 24 hours；Preferably, the dry thermal finalization carries out under vacuum conditions.
Preferably, the aperture of the spinneret is 0.065~0.1mm.
Preferably, in institute's coagulation forming the step of: the coagulating bath includes:
Level-one coagulating bath: the level-one coagulating bath includes solvent and water；Wherein, the solvent in level-one coagulating bath selects diformazan
It is one or more in base sulfoxide, dimethylformamide and dimethyl acetamide；Preferably, the solvent content in level-one coagulating bath is
30~60%；Preferably, the temperature of level-one coagulating bath is 30~60 DEG C；
Second level coagulating bath: the second level coagulating bath includes solvent and water；Wherein, the solvent in second level coagulating bath selects diformazan
It is one or more in base sulfoxide, dimethylformamide and dimethyl acetamide；Preferably, the solvent content in second level coagulating bath is
15~25%；Preferably, the temperature of second level coagulating bath is 60~80 DEG C；
Wherein, the dynamic analysis of spinning is introduced into coagulation forming in level-one coagulating bath and obtains solidification strand, the solidification strand
Enter back into coagulation forming in second level coagulating bath.
Preferably, setting time of the dynamic analysis of spinning in level-one coagulating bath is 20~100s, negative degree of draft is -50%
To -20%；And/or
Setting time of the solidification strand in second level coagulating bath is 30~120s, draw ratio is 1.2~1.5 times.
Preferably, the spinning solution is made by main monomer acrylonitrile, comonomer, solvent and initiator polymerization reaction；
Preferably, the comonomer selects halogen element content greater than the alkenyl halide of content of Cl element in vinyl chloride；It is excellent
Choosing, the comonomer selects one or both of vinylidene chloride, dibromoethylene；
Preferably, acrylonitrile accounts for the 40~60% of total monomer quality, and comonomer accounts for the 40~60% of total monomer quality；Its
In, total monomer quality is the quality sum of main monomer and comonomer；
Preferably, the solvent is one or more in dimethyl sulfoxide, dimethylformamide and dimethyl acetamide；
Preferably, the initiator is azodiisobutyronitrile；
Preferably, the conversion ratio of the polymerization reaction is greater than 90%；
Preferably, the spinning fluid solid content is 30~40%；
Preferably, the use temperature of the spinning solution is 30~60 DEG C.
On the other hand, the embodiment of the present invention provides a kind of polyacrylonitrile fibre, wherein the fibre of the polyacrylonitrile fibre
Degree is 1.7~2.2dtex；The intensity of the polyacrylonitrile fibre is 2.2~3.2cN/dtex；The polyacrylonitrile fibre is stretched
Long rate is 26~38%；Preferably, the limit oxygen index LOI value of the polyacrylonitrile fibre is 26.5~30%；Preferably, institute
Polyacrylonitrile fibre is stated to be prepared by the wet spinning process of polyacrylonitrile fibre described in any of the above embodiments.
Compared with prior art, the wet spinning process of polyacrylonitrile fibre of the invention and polyacrylonitrile fibre at least have
Have it is following the utility model has the advantages that
1. the wet spinning process of polyacrylonitrile fibre proposed by the present invention using " the step of first hot gas spring is washed again " and
It is not " the step of first washing first break draft " in the prior art.The inventors discovered that " first washing and leading afterwards using in the prior art
The method stretched ", in hot water drawing-off and high temperature drawing-off, fiber drawability is very poor, i.e., spinning solution can be gone out using existing spinning process
The situation of existing spinnability difference.And inventor is put forward for the first time after coagulation forming, first carry out drawing-off, after washed；In this way from solidifying
Gu solvent content is higher in the as-spun fibre that bath comes out, solvent can play the plasticization of molecule interchain in the fibre, be conducive to
The raising of the drafting multiple of hot gas spring, to solve the technical problem of spinnability difference.
2. the wet spinning process of polyacrylonitrile fibre proposed by the present invention is by " the hot water drawing-off " in prior art processes
" steam drafting " is combined into one (that is, hot gas spring processing).Strand pine in long process is reduced compared with the existing technology
It relaxes the time, improves the degree of orientation, be conducive to improve fibre property.Further, different from " steam drafting " of the prior art, originally
Application is using three-level hot gas spring and glycerol is used to carry out high temperature drawing-off to fiber as drawing-off medium, and classification drawing-off is available higher
It leads again, while, strong operability low relative to steam drafting equipment requirement.
3. the drying process step in the wet spinning process of polyacrylonitrile fibre proposed by the present invention uses vacuum drying,
The dry micropore closure be conducive in fiber of vacuum environment, reduces fiber defect and further increases fibre property, and vacuum item
Drying temperature reduces under part, can prevent fiber premature oxidation.
4. the suitable spinning solution of the wet spinning process selection of polyacrylonitrile fibre proposed by the present invention using temperature and coagulates
Gu the conditions such as bath temperature, concentration substantially increase the spinnability of fire-retardant polyacrylonitrile spinning solution, while making in hot gas spring process
Multistage high drafting is carried out with glycerol medium, improves the mechanical property of fiber.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention, detailed description is as follows below.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to specific embodiment, structure, feature and its effect applied according to the present invention, detailed description is as follows.Under
It states in bright, what different " embodiment " or " embodiment " referred to is not necessarily the same embodiment.In addition, one or more embodiments
In special characteristic, structure or feature can be combined by any suitable form.
The wet spinning technology of the polyacrylonitrile fibre of the prior art is as follows: 1 spinneret, 2 coagulation formings, 3, washing 4, hot water
Drawing-off, 5 dry, 6, steam drafting, 7, relaxation heat setting.
The inventors found that: while improving the anti-flammability of polyacrylonitrile fibre using macromolecule modified method, spin
Silk liquid can have the mechanical property that spinning properties are poor, obtain polyacrylonitrile fibre according to above-mentioned existing spinning technique spinning
The technical problem of difference.
In order to solve the above technical problems, the present invention proposes a kind of wet spinning process of polyacrylonitrile fibre, according to
It is secondary to include the following steps:
Spinneret: using wet spinning, and spinneret orifice diameter is 0.065~0.1mm.
Coagulation forming: the dynamic analysis of spinning formed after spinneret orifice is left, is sequentially entered in the coagulating bath of various concentration.Level-one is solidifying
Gu bath includes solvent and water；Wherein, the solvent in level-one coagulating bath selects dimethyl sulfoxide, dimethylformamide and dimethyl second
It is one or more in amide.Second level coagulating bath includes solvent and water；Wherein, the solvent in second level coagulating bath selects dimethyl sub-
It is one or more in sulfone, dimethylformamide and dimethyl acetamide.
Wherein, in a coagulating bath solvent content be 30~60%, temperature be 30~60 DEG C, negative drawing-off -50% to -
20%, setting time is 20~100s.The content of solvent is 15~25% in two coagulating baths, and temperature is 60~80 DEG C, stretches 1.2
~1.5 times, setting time is 30~120s, obtains as-spun fibre.
Hot gas spring processing: as-spun fibre passes through three-level hot gas spring, and from low to high, drawing-off medium is glycerol to temperature, and first
Grade temperature is 100~105 DEG C, 1.2~2 times of drawing-off；Second level temperature is 110~120 DEG C, 2~3 times of drawing-off；Third level temperature
It is 125~130 DEG C, 1.2~2 times of drawing-off.
Washing process: by hot gas spring, treated that fiber is washed, and 50~70 DEG C of washing temperature, washing time is 1~
3min。
Dry, thermal finalization processing: including dry and thermal finalization processing step；Wherein, dry: by the fiber after washing process
It is dried in vacuo, 40~50 DEG C of temperature, dry 12~for 24 hours.
Thermal finalization processing step includes: relaxation heat setting, washing, dry thermal finalization.Specifically: by the fiber after drying into
Row relaxation heat setting, medium are glycerol, and temperature is 140~150 DEG C, negative drawing-off -30% to -10%.And then it is fixed to relaxation heat
Fiber after type is washed, and 60~80 DEG C of washing temperature, washing time is 3~5min；Finally, the fiber after washing is done
Scorching sizing, 50~60 DEG C of temperature, dry 12~for 24 hours, obtain polyacrylonitrile fibre；Preferably, dry thermal finalization is in vacuum item
It is carried out under part；Vacuum condition is conducive to the evolution of hydrone in fiber, and porosity further decreases, and it is preferable can to prepare consistency
Polyacrylonitrile fibre.
By comparing the technique of the application and the prior art, it can be found that the spinning process of the application and the prior art just like
Lower distinctive points:
(1) " the step of first the washing first break draft " of the present invention using " the step of first hot gas spring is washed again " rather than in the past.
The inventors discovered that using previous " first washing the method for first break draft ", the fiber drawability in hot water drawing-off and high temperature drawing-off
It is very poor, i.e. the spinning solution situation that will appear spinnability difference using previous spinning process.And the present inventor is put forward for the first time and is being frozen into
After type, first carry out drawing-off, after washed；Solvent content is higher from the as-spun fibre that coagulating bath comes out in this way, and solvent is in fibre
The plasticization that molecule interchain can be played in dimension, is conducive to the raising of the drafting multiple of hot gas spring, so that it is poor to solve spinnability
The technical issues of.
(2) " the hot water drawing-off " and " steam drafting " in prior art processes is combined into one (that is, at hot gas spring by the present invention
Reason).Strand slack time in long process is reduced compared with the existing technology, improves the degree of orientation, is conducive to improve fine
Tie up performance.
(3) it is different from " steam drafting " of the prior art, the application is using three-level hot gas spring and uses glycerol as drawing-off
Medium carries out high temperature drawing-off to fiber, classification drawing-off it is available it is higher lead times, while it is low relative to steam drafting equipment requirement, can
Strong operability.
(4) compared with constant pressure and dry in the prior art, drying process step of the invention is using vacuum drying, vacuum ring
The dry micropore closure be conducive in fiber in border reduces fiber defect and further increases performance, and drying temperature reduces under vacuum condition
It can prevent fiber premature oxidation.
(5) in existing technology, fiber is just collecting fibrous finished product after " relaxation heat setting " step.Due to this
It is also washed after invention " relaxation heat setting " step, the purpose of drying thermal finalization is: on the fiber after cleaning relaxation heat setting
Glycerol finally need to carry out the dry thermal finalization of a step while in order to reduce water content.
Preferably, the wet spinning process of polyacrylonitrile fibre proposed by the present invention, used spinning solution is by main list
(vinylidene chloride or dibromoethylene or other halogen element contents are greater than content of Cl element in vinyl chloride for body polyacrylonitrile, comonomer
Alkenyl halide；That is, as long as the alkenyl halide that halogen element content is higher than content of Cl element in vinyl chloride can be used as the application
Comonomer), initiator and solvent copolyreaction preparation.
Preferably, acrylonitrile be total monomer weight 40~60%, the comonomer be total monomer weight 40~
60%；It is further preferred that institute's comonomer is the 50~60% of total monomer weight.Here, the embodiment of the present invention uses inclined chlorine
Ethylene and/or dibromoethylene are as comonomer and acrylonitrile progress combined polymerization, relative to vinyl chloride used in traditional handicraft
For, not only reaction condition is mild for vinylidene chloride, dibromoethylene, simple process is safe, and halogen amount is twice in itself monomer
Vinyl chloride can reach high flame resistance in the case where lower monomeric charge amount.
Preferably, the initiator in the embodiment of the present invention selects azodiisobutyronitrile；Preferably, the initiator is total single
The 0.8~1% of weight；It is further preferred that the initiator is the 0.91~1% of total monomer quality.Here, the present invention is real
Applying initiator A IBN used in example is azo-initiator, and decomposition of initiator temperature is 35 DEG C or more, and efficiency of initiation is high, instead
13 hours conversion ratios that just can reach 93.15% are answered, are suitable for high-efficiency and low-cost industrialized production.
Preferably, solvent selects one or more in dimethyl sulfoxide, dimethylformamide and dimethyl acetamide mix
Bonding solvent.Preferably, in the reactive mixture, the mass percent concentration of copolymerization component is 30~40%；Preferably 33~
40%.
Preferably, spinning fluid solid content is 30~40% in spinneret step.
Preferably, the use temperature of spinning solution is 30~60 DEG C.
It is further described below by specific experiment embodiment:
Embodiment 1
It prepares spinning solution: using initiator azodiisobutyronitrile, making main monomer acrylonitrile, comonomer vinylidene chloride molten
Polymerization reaction is carried out in agent dimethyl sulfoxide, and (wherein, acrylonitrile accounts for the 60% of total monomer quality, vinylidene chloride and accounts for total monomer quality
40%, initiator amount be total monomer quality 0.8%, solvent usage accounts for polymerization system quality (that is, reactant gross mass)
70%, 70 DEG C of polymeric reaction temperature, reaction time 20h), obtain polymer fluid；Polymer fluid is spun after de- single deaeration processing
Silk liquid.Wherein, polymerization conversion 96.2%, the solid content of spinning solution are 30%, and the use temperature of spinning solution is 60 DEG C,
Spinning is carried out to this spinning solution.
Spinneret: using wet spinning, and the aperture of spinneret orifice is 0.065mm.
Coagulation forming: after dynamic analysis of spinning leaves spinneret orifice, sequentially entering level-one coagulating bath, (content of dimethyl sulfoxide is
30%, temperature is 60 DEG C) and second level coagulating bath (content of dimethyl sulfoxide is 15%, temperature be 60 DEG C) in coagulation forming, obtain
To as-spun fibre.Wherein, setting time of the dynamic analysis of spinning in level-one coagulating bath is 20s, negative degree of draft is -50%, is coagulated
Gu strand；Setting time of the solidification strand in second level coagulating bath is 30s, draw ratio is 1.5 times.
Hot gas spring: as-spun fibre item passes through three-level hot gas spring, and from low to high, drawing-off medium is glycerol, the first order to temperature
Temperature is 100 DEG C, 1.2 times of drawing-off；Second level temperature is 110 DEG C, 3 times of drawing-off；Third level temperature is 125 DEG C, 1.8 times of drawing-off.
Primary washing: the fiber after hot gas spring is washed, 50 DEG C of washing temperature, washing time 1min.
Primary drying: the fiber after primary washing is dried in vacuo, 40 DEG C of temperature, drying is for 24 hours.
Relaxation heat setting: carrying out relaxation heat setting for the strand after primary drying, and medium is glycerol, and temperature is 150 DEG C, is born
Degree of draft is -30%.
Secondary washing: carrying out secondary washing to the fiber after relaxation heat setting, and 60 DEG C of washing temperature, washing time is
5min。
Dry thermal finalization: thermal finalization, temperature 50 C are dried to the fiber after secondary washing, drying for 24 hours, obtains fire-retardant
Polyacrylonitrile fibre.
Embodiment 2
It prepares spinning solution: using initiator azodiisobutyronitrile, making main monomer acrylonitrile, comonomer dibromoethylene molten
Polymerization reaction is carried out in agent dimethyl sulfoxide, and (wherein, acrylonitrile accounts for the 55% of total monomer quality, dibromoethylene and accounts for total monomer quality
45%, initiator amount be total monomer quality 0.8%, solvent usage accounts for the 65% of polymerization system quality, polymerization reaction temperature
65 DEG C of degree, reaction time 16h), obtain polymer fluid；Polymer fluid obtains spinning solution after de- single deaeration processing.Wherein, polymerization is anti-
Answering conversion ratio is 93.5%, and the solid content of spinning solution is 35%, and the use temperature of spinning solution is 50 DEG C, is spun to this spinning solution
Silk.
Spinneret: using wet spinning, and the aperture of spinneret orifice is 0.075mm.
Coagulation forming: after dynamic analysis of spinning leaves spinneret orifice, sequentially entering level-one coagulating bath, (content of dimethyl sulfoxide is
60%, temperature is 55 DEG C) and second level coagulating bath (content of dimethyl sulfoxide is 25%, temperature be 60 DEG C) in coagulation forming, obtain
To as-spun fibre.Wherein, setting time of the dynamic analysis of spinning in level-one coagulating bath is 60s, negative degree of draft is -35%, is coagulated
Gu strand；Setting time of the solidification strand in second level coagulating bath is 120s, draw ratio is 1.2 times.
Hot gas spring: as-spun fibre item passes through three-level hot gas spring, and from low to high, drawing-off medium is glycerol, the first order to temperature
Temperature is 102 DEG C, 1.5 times of drawing-off；Second level temperature is 115 DEG C, 2.5 times of drawing-off；Third level temperature is 128 DEG C, 2 times of drawing-off.
Primary washing: the fiber after hot gas spring is washed, 70 DEG C of washing temperature, washing time 2min.
Primary drying: the fiber after primary washing being dried in vacuo, temperature 50 C, dry 12h.
Relaxation heat setting: carrying out relaxation heat setting for the strand after primary drying, and medium is glycerol, and temperature is 145 DEG C, is born
Degree of draft is -20%.
Secondary washing: carrying out secondary washing to the fiber after relaxation heat setting, and 80 DEG C of washing temperature, washing time is
3min。
Dry thermal finalization: thermal finalization, temperature 60 C are dried to the fiber after secondary washing, dry 12h is obtained fire-retardant
Polyacrylonitrile fibre.
Embodiment 3
It prepares spinning solution: using initiator azodiisobutyronitrile, making main monomer acrylonitrile, comonomer vinylidene chloride molten
Polymerization reaction is carried out in agent dimethyl acetamide, and (wherein, acrylonitrile accounts for the 60% of total monomer quality, vinylidene chloride and accounts for total monomer matter
The 40% of amount, initiator amount are the 0.8% of total monomer quality, and solvent usage accounts for the 60% of polymerization system quality, polymerization reaction
65 DEG C of temperature, reaction time 20h), obtain polymer fluid；Polymer fluid obtains spinning solution after de- single deaeration processing.Wherein, it polymerize
Reaction conversion ratio is 91.8%, and the solid content of spinning solution is 40%, and the use temperature of spinning solution is 30 DEG C, is carried out to this spinning solution
Spinning.
Spinneret: using wet spinning, and the aperture of spinneret orifice is 0.1mm.
Coagulation forming: after dynamic analysis of spinning leaves spinneret orifice, sequentially entering level-one coagulating bath, (content of dimethyl acetamide is
56%, temperature is 30 DEG C) and second level coagulating bath (content of dimethyl acetamide is 20%, temperature be 80 DEG C) in coagulation forming,
Obtain as-spun fibre.Wherein, setting time of the dynamic analysis of spinning in level-one coagulating bath is 100s, negative degree of draft is -20%, is obtained
Solidify strand；Setting time of the solidification strand in second level coagulating bath is 60s, draw ratio is 1.4 times.
Hot gas spring: as-spun fibre item passes through three-level hot gas spring, and from low to high, drawing-off medium is glycerol, the first order to temperature
Temperature is 105 DEG C, 2 times of drawing-off；Second level temperature is 120 DEG C, 2 times of drawing-off；Third level temperature is 130 DEG C, 1.2 times of drawing-off.
Primary washing: the fiber after hot gas spring is washed, 60 DEG C of washing temperature, washing time 3min.
Primary drying: the fiber after primary washing being dried in vacuo, temperature 45 C, dry 18h.
Relaxation heat setting: carrying out relaxation heat setting for the strand after primary drying, and medium is glycerol, and temperature is 150 DEG C, is born
Degree of draft is -10%.
Secondary washing: carrying out secondary washing to the fiber after relaxation heat setting, and 70 DEG C of washing temperature, washing time is
4min。
Dry thermal finalization: thermal finalization is dried to the fiber after secondary washing, 55 DEG C of temperature, dry 18h is obtained fire-retardant
Polyacrylonitrile fibre.
Embodiment 4
It prepares spinning solution: using initiator azodiisobutyronitrile, making main monomer acrylonitrile, comonomer vinylidene chloride molten
Polymerization reaction is carried out in agent dimethylformamide, and (wherein, acrylonitrile accounts for the 50% of total monomer quality, vinylidene chloride and accounts for total monomer matter
The 50% of amount, initiator amount are the 0.9% of total monomer quality, and solvent usage accounts for the 65% of polymerization system quality, polymerization reaction
68 DEG C of temperature, reaction time 22h), obtain polymer fluid；Polymer fluid obtains spinning solution after de- single deaeration processing.Wherein, it polymerize
Reaction conversion ratio is 92.4%, and the solid content of spinning solution is 35%, and the use temperature of spinning solution is 40 DEG C, is carried out to this spinning solution
Spinning.
Spinneret: using wet spinning, and the aperture of spinneret orifice is 0.1mm.
Coagulation forming: after dynamic analysis of spinning leaves spinneret orifice, sequentially entering level-one coagulating bath, (content of dimethylformamide is
40%, temperature is 50 DEG C) and second level coagulating bath (content of dimethylformamide is 15%, temperature be 70 DEG C) in coagulation forming,
Obtain as-spun fibre.Wherein, setting time of the dynamic analysis of spinning in level-one coagulating bath is 80s, negative degree of draft is -25%, is obtained
Solidify strand；Setting time of the solidification strand in second level coagulating bath is 80s, draw ratio is 1.3 times.
Hot gas spring: as-spun fibre item passes through three-level hot gas spring, and from low to high, drawing-off medium is glycerol, the first order to temperature
Temperature is 103 DEG C, 1.8 times of drawing-off；Second level temperature is 118 DEG C, 2.6 times of drawing-off；Third level temperature is 122 DEG C, drawing-off 1.5
Times.
Primary washing: the fiber after hot gas spring is washed, 65 DEG C of washing temperature, washing time 3min.
Primary drying: the fiber after primary washing being dried in vacuo, 48 DEG C of temperature, dry 20h.
Relaxation heat setting: carrying out relaxation heat setting for the strand after primary drying, and medium is glycerol, and temperature is 140 DEG C, is born
Degree of draft is -15%.
Secondary washing: carrying out secondary washing to the fiber after relaxation heat setting, and 65 DEG C of washing temperature, washing time is
5min。
Dry thermal finalization: thermal finalization is dried to the fiber after secondary washing, 58 DEG C of temperature, dry 20h is obtained fire-retardant
Polyacrylonitrile fibre.
To fiber number, intensity, elongation, the limit oxygen index LOI value of polyacrylonitrile fibre prepared by embodiment 1- embodiment 4
Test, test result ginseng are shown in Table 1.
Table 1 is the Vinyon N fibre of the polyacrylonitrile fibre of embodiment 1-4 preparation and the Velicern FR trade mark of the prior art
The performance data of dimension
| Fiber number | Intensity | Elongation | LOI value | |
| Embodiment 1 | 1.7dtex | 2.2cN/dtex | 38% | 30% |
| Embodiment 2 | 2.0dtex | 2.8cN/dtex | 30% | 29.5% |
| Embodiment 3 | 2.2dtex | 3.2cN/dtex | 26% | 26.5% |
| Embodiment 4 | 2.1dtex | 3.0cN/dtex | 35% | 28% |
| The Vinyon N of the FR trade mark | 2.2-22dtex | 2.5-2.6cN/dtex | 30-35% | 26-30% |
The Vinyon N of the Velicern FR trade mark of largest domestic Vinyon N producer Fushun Vinyon N laboratory production at present is fine
Dimension intensity is 2.5-2.6cN/dtex, elongation 30-35%.
As can be seen from Table 1: the fibre strength of the application preparation is 2.2~3.2cN/dtex, and elongation is 26~38%,
Compared with the fiber of the Velicern FR trade mark, maximum intensity improves 23%, and maximum elongation rate improves 8%.It can be seen that this
The better performances of the polyacrylonitrile fibre for the polyacrylonitrile fibre spinning process preparation that inventive embodiments provide, and the present invention is implemented
The flame retardant property of the polyacrylonitrile fibre of example preparation is also suitable with the flame retardant property of the fiber of the Velicern FR trade mark.Therefore, originally
Not only flame retardant property is preferable for the polypropylene fibre of inventive embodiments preparation, and key also ensures the mechanical property of polyacrylonitrile fibre
Energy.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within
In the range of bright technical solution.
Claims (10)
1. a kind of wet spinning process of polyacrylonitrile fibre, which is characterized in that it includes the following steps:
Spinneret: spinning solution is squeezed out through the spinneret orifice of spinning pack, obtains dynamic analysis of spinning；
Coagulation forming: the dynamic analysis of spinning enters coagulation forming in coagulating bath, obtains as-spun fibre；
Hot gas spring processing: hot gas spring processing is carried out to the as-spun fibre；
Washing process: washing process is carried out to hot gas spring treated fiber；
Dry, thermal finalization processing: the fiber after washing is successively dried, thermal finalization processing, obtains polyacrylonitrile fibre.
2. the wet spinning process of polyacrylonitrile fibre according to claim 1, which is characterized in that at the hot gas spring
In the step of reason,
Drawing-off medium selects glycerol；And/or
The hot gas spring processing is multistage hot gas spring processing；Wherein, the temperature of previous stage hot gas spring is lower than rear stage hot gas spring
Temperature；Preferably, the temperature of the hot gas spring processing is 100~130 DEG C.
3. the wet spinning process of polyacrylonitrile fibre according to claim 1 or 2, which is characterized in that led in the heat
In the step of stretching processing, the processing of three-level hot gas spring is carried out to the as-spun fibre；Wherein,
The temperature of first order hot gas spring is 100~105 DEG C, and the multiple of first order hot gas spring is 1.2~2 times；And/or
The temperature of second level hot gas spring is 110~120 DEG C, and the multiple of second level hot gas spring is 2~3 times；And/or
The temperature of third level hot gas spring is 125~130 DEG C, and the multiple of third level hot gas spring is 1.2~2 times.
4. the wet spinning process of polyacrylonitrile fibre according to claim 1-3, which is characterized in that described
In the step of washing process: the temperature of the washing process is 50~70 DEG C, the time of washing process is 1~3min.
5. the wet spinning process of polyacrylonitrile fibre according to claim 1-4, which is characterized in that described dry
Drying steps dry, in thermal finalization processing step are as follows: vacuum drying treatment is carried out to the fiber after the washing process；It is preferred that
, 40~50 DEG C of the temperature of drying process, time of drying process is 12~for 24 hours；And/or
Thermal finalization processing step in the drying, thermal finalization processing step includes:
Relaxation heat setting: relaxation heat setting is carried out to the fiber after drying；Preferably, it in the step of relaxation heat setting, bears
The medium of drawing-off selects glycerol；Preferably, in the step of relaxation heat setting, temperature be 140~150 DEG C, negative degree of draft be-
30% to -10%；
Washing: to relaxation heat setting, treated that fiber is washed；Preferably, 60~80 DEG C of the temperature of the washing, it is described
The time of washing is 3~5min；
Dry thermal finalization: thermal finalization is dried to the fiber after washing；Preferably, the temperature of the dry thermal finalization be 50~
60 DEG C, time of the dry thermal finalization be 12~for 24 hours；
Preferably, the dry thermal finalization carries out under vacuum conditions.
6. the wet spinning process of polyacrylonitrile fibre according to claim 1-5, which is characterized in that the spray
The aperture of filament plate is 0.065~0.1mm.
7. the wet spinning process of polyacrylonitrile fibre according to claim 1-6, which is characterized in that coagulating
Admittedly in the step of molding: the coagulating bath includes:
Level-one coagulating bath: the level-one coagulating bath includes solvent and water；Wherein, the solvent in level-one coagulating bath selects dimethyl sub-
It is one or more in sulfone, dimethylformamide and dimethyl acetamide；Preferably, the solvent content in level-one coagulating bath be 30~
60%；Preferably, the temperature of level-one coagulating bath is 30~60 DEG C；
Second level coagulating bath: the second level coagulating bath includes solvent and water；Wherein, the solvent in second level coagulating bath selects dimethyl sub-
It is one or more in sulfone, dimethylformamide and dimethyl acetamide；Preferably, the solvent content in second level coagulating bath be 15~
25%；Preferably, the temperature of second level coagulating bath is 60~80 DEG C；
Wherein, the dynamic analysis of spinning be introduced into coagulation forming in level-one coagulating bath obtain solidification strand, the solidification strand again into
Enter coagulation forming in second level coagulating bath.
8. the wet spinning process of polyacrylonitrile fibre according to claim 7, which is characterized in that the dynamic analysis of spinning exists
Setting time in level-one coagulating bath is 20~100s, negative degree of draft is -50% to -20%；And/or
Setting time of the solidification strand in second level coagulating bath is 30~120s, draw ratio is 1.2~1.5 times.
9. the wet spinning process of polyacrylonitrile fibre according to claim 1-8, which is characterized in that the spinning
Silk liquid is made by main monomer acrylonitrile, comonomer, solvent and initiator polymerization reaction；
Preferably, the comonomer selects halogen element content greater than the alkenyl halide of content of Cl element in vinyl chloride；Preferably,
The comonomer selects one or both of vinylidene chloride, dibromoethylene；
Preferably, acrylonitrile accounts for the 40~60% of total monomer quality, and comonomer accounts for the 40~60% of total monomer quality；Wherein,
Total monomer quality is the quality sum of main monomer and comonomer；
Preferably, the solvent is one or more in dimethyl sulfoxide, dimethylformamide and dimethyl acetamide；
Preferably, the initiator is azodiisobutyronitrile；
Preferably, the conversion ratio of the polymerization reaction is greater than 90%；
Preferably, the spinning fluid solid content is 30~40%；
Preferably, the use temperature of the spinning solution is 30~60 DEG C.
10. a kind of polyacrylonitrile fibre, which is characterized in that the fiber number of the polyacrylonitrile fibre is 1.7~2.2dtex；It is described
The intensity of polyacrylonitrile fibre is 2.2~3.2cN/dtex；The elongation of the polyacrylonitrile fibre is 26~38%；
Preferably, the limit oxygen index LOI value of the polyacrylonitrile fibre is 26.5~30%；
Preferably, the polyacrylonitrile fibre by the described in any item polyacrylonitrile fibres of claim 1-9 wet spinning side
Method is prepared.
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