CN109295523A - A kind of permanent anti-static acrylonitrile copolymer and its fiber producing processes - Google Patents
A kind of permanent anti-static acrylonitrile copolymer and its fiber producing processes Download PDFInfo
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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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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Abstract
The invention discloses a kind of permanent anti-static acrylonitrile copolymer and its fiber producing processes.The preparation principle of permanent anti-static acrylonitrile copolymer fiber are as follows: be copolymerized first with the monomers such as acrylonitrile and the ionic liquid containing unsaturated double-bond and the polyethyleneglycol derivative containing unsaturated double-bond, permanent anti-static acrylonitrile copolymer is obtained, then directly prepares permanent anti-static acrylonitrile copolymer fiber using spin processes processing.Since the antistatic agent used takes part in polymerization reaction, solves the problems, such as small molecule migration precipitation, so obtained acrylonitrile copolymer fiber has permanent antistatic performance.
Description
Technical field
The present invention relates to technical field of fiber preparation, and in particular to a kind of permanent anti-static acrylonitrile copolymer and its fibre
Tie up preparation method.
Background technique
The electrical property of high molecular material depends primarily on two physical quantitys, i.e. resistivity and dielectric constant, the resistance of material
Rate is lower, and the ability of dissipation electrostatic is stronger, and dielectric constant is lower, is often more easy to produce electrostatic.However, most of macromolecule materials
Expect surface resistivity (> 10 all with higher12Ω) with lower dielectric constant, therefore, this kind of material does not have antistatic property
Can, cause it to cause various problems and difficulty because of accumulation of static electricity in practical applications, for example, communication apparatus computer room can be because of electrostatic
There is random fault, malfunction or run-time error when computer being caused to run in accumulation, it is also possible to lead to certain components (MOS electricity
Road, bipolar circuit etc.) breakdown and breaking-up；Coal production and petrochemical industry production inventory transportational process can be led because of accumulation of static electricity
Cause fire explosion；Electrostatic caused by clothes friction can be such that the blood alkalinity of people increases, and cause pruitus, pigment heavy
, interfere the mood etc. of people.Make high molecular material that there is antistatic effect, most efficient method is exactly into high molecular material
Antistatic agent is added, to reduce its resistivity, improves conductive capability.
Currently, the antistatic agent of commercialization is many kinds of, wherein there is ionic liquid hardly possible to volatilize, steam forces down, ion-conductance
Conductance height, electrochemical window mouth width, the advantages that optical clarity is high are a kind of antistatic agents haveing excellent performance, therefore by people
Extensive concern.Application No. is a kind of polyacrylonitrile/ionic liquid is disclosed in 201510146416.9 Chinese invention patent
Body/polyaniline composite material preparation method, should be the preparation method comprises the following steps: right after first mixing aniline monomer with ionic liquid
Polyacrylonitrile plasticising and machine-shaping；Then shaped article is post-processed, i.e., under the acid condition containing oxidant, made
The aniline of interiors of products after molding occurs polymerization reaction and generates polyaniline, finally obtains polyacrylonitrile/ionic liquid/polyaniline
Conducing composite material.Application No. is disclosed in 201110237446.2 Chinese invention patent a kind of High-elasticity conductive fiber and
Preparation method, this method are to be uniformly mixed carbon nanotube with ionic liquid, are then blended again with strong flexible polymer, finally
Spinning is carried out, High-elasticity conductive fiber is obtained.But above-mentioned patent is all made of the mode system that ionic liquid is blended with macromolecule matrix
Standby conductive fiber, can not fundamentally solve the problems, such as ionic liquid precipitation easy to migrate, so can not achieve the permanent anti-of fiber
Electrostatic.In addition, polyaniline and carbon nanotube color are deeper, influence fiber can dyeability.
Application No. is disclosing in 201510449504.6 Chinese invention patent, a kind of permanent anti-static ionic liquid is high
Ionic liquid is grafted in a manner of being graft-polymerized and is total to by the block of monomer and acid anhydrides preparation by the preparation method of polymers masterbatch
On polymers, ionic liquid migration precipitation is solved the problems, such as with this, the high polymer masterbatch obtained using this method can effectively be dropped
The surface resistivity of low high molecular material makes material reach antistatic ability, in addition, high polymer masterbatch and a variety of high polymers are all
With good compatibility.Although the electric conductivity of ionic liquid is excellent, used using ionic liquid as single antistatic agent
In producing and exploitation antistatic products are primarily present two problems: on the one hand, ionic liquid as a kind of ionic anti-static agent,
It is influenced by ambient temperature and humidity than more serious；On the other hand, the ionic liquid largely haveing excellent performance is expensive, and adding proportion is big
Cause production cost excessively high.Application No. is disclosing in 02111399.8 Chinese invention patent, a kind of anti-static polyacrylonitrile is fine
The preparation method of dimension, has used that cost is lower, the stronger polyethylene glycol of wettability power is as antistatic agent.But the patent is only
It is that polyethylene glycol and polyacrylonitrile blended, the problem of equally existing antistatic agent migration precipitation be cannot achieve into permanent anti-static
Performance.Use polyethylene glycol to be primarily present following problems as antistatic agent: when additive amount is lower, antistatic property is poor；Addition
When measuring too high, water sorption is strong, causes material surface viscosity too high, influences following process and use.
Summary of the invention
The technical issues of present invention intends to solve is: providing a kind of permanent anti-static acrylonitrile copolymer, and provides one
The preparation method of the kind easily acrylonitrile copolymer fiber of preparation processing.The acrylonitrile copolymer has lower sheet resistance
Rate can be prepared into copolymer fibre by spinning processing technology.The fiber not only has excellent mechanical property, chemical stabilization
Property, can dyeability, and have permanent antistatic performance, widened the application field of polyacrylonitrile fibre.
The purpose of the present invention is in this way to reach, a kind of permanent anti-static acrylonitrile copolymer fiber, first with
The monomers such as acrylonitrile and ionic liquid containing unsaturated double-bond are copolymerized, and obtain permanent anti-static acrylonitrile copolymer, it is described forever
The surface resistivity of long antistatic acrylonitrile copolymer is 6.1 × 105~9.2 × 1010Ω.Then directly being total to using what is prepared
Polymers is processed into permanent anti-static acrylonitrile copolymer fiber, the fiber number of the acrylonitrile copolymer fiber by spin processes
For 0.8~4.5dtex, breaking strength is 1.5~4.7cN/dtex, and elongation at break is 14.5%~27.8%, sheet resistance
Rate is 6.1 × 105~9.2 × 1010Ω.Fiber is placed in 60 DEG C of hot water and impregnates 30min, taking-up is dried, and repetition is impregnated-dried in the air
After dry run 50 times, measurement fiber surface resistivity is 1.2 × 106~9.9 × 1010Ω still can reach antistatic requirement.
A kind of preparation method of permanent anti-static acrylonitrile copolymer fiber, it is characterised in that the following steps are included:
(1) preparation of permanent anti-static acrylonitrile copolymer
A certain amount of solvent is added into reaction vessel, then by 40~97mol% acrylonitrile monemer, 20~1mol% second
Monomer, 20~1mol% Third monomer, 20~1mol% ionic liquid monomer and a certain amount of initiator pour into after mixing
In reaction vessel, wherein the sum of all monomer molar percentages are 100mol%, and the additional amount of the initiator is all monomers
1~4mol% of total amount, monomer concentration control is 3~6mol/L, is heated to 50~110 DEG C while stirring, temperature is constant
6~15h is reacted afterwards, then reaction solution is poured into distilled water and is precipitated, is stood, is filtered, and vacuum drying obtains acrylonitrile group copolymerization
Object, the copolymer fusing point are 150~265 DEG C, and surface resistivity is 6.1 × 105~9.2 × 1010Ω；
(2) preparation of permanent anti-static acrylonitrile copolymer fiber
By the acrylonitrile copolymer of 100 mass parts, the antioxidant of 0.05~0.5 mass parts, 0.2~1 mass parts
Heat stabilizer, 0~3 mass parts filler by high speed blender after mixing, obtain permanent anti-static third using spin processes
Alkene itrile group copolymer fibre, the fiber number of the copolymer fibre are 0.8~4.5dtex, and breaking strength is 1.5~3.7cN/dtex,
Elongation at break is 14.5%~27.8%, and sheet resistance is 6.1 × 105~9.2 × 1010Ω.Fiber is placed in 60 DEG C of heat
30min is impregnated in water, taking-up is dried, and after operation 50 times are impregnated-dried to repetition, measurement fiber surface resistivity is 1.2 × 106~
9.9×1010Ω still can reach antistatic requirement.
In a specific embodiment of the invention, solvent described in step (1) is dimethylformamide, dimethyl Asia
The mixture of one of sulfone, sulfolane, nitric acid ethylidene ester, ethylene carbonate or any several any ratios.
In another specific embodiment of the invention, step (1) second comonomer is that acrylic acid or acrylic acid spread out
One of biology, the acrylic acid derivative preferably are selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid
Isobutyl ester, tert-butyl acrylate, Isooctyl acrylate monomer, dodecyl acrylate, 2-Hydroxy ethyl acrylate, methyl methacrylate
Ester, ethyl methacrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, metering system
The different monooctyl ester of acid, lauryl methacrylate, methacrylic acid -2- hydroxy methacrylate, sodium acrylate, potassium acrylate, methacrylic acid
Sodium, methacrylic acid potassium.
In another specific embodiment of the invention, Third monomer described in step (1) is poly- containing unsaturated bond
One of ethylene glycol derivative, the polyethyleneglycol derivative preferably is selected from polyethylene glycol methacrylate-styrene polymer, and (molecular weight is preferred
From 350~2400), polyethylene glycol acrylate (molecular weight is preferably 350~2400), (molecular weight is excellent for allyl polyglycol
Be selected as 350~2400), methacrylic polyethylene glycol (molecular weight is preferably 350~2400), isopentene group polyethylene glycol (point
Son amount preferably 350~2400), polyethylene glycol monomethyl ethermethacrylic acid esters (molecular weight is preferably 350~2400), poly- second two
Alcohol monomethyl ether acrylate (molecular weight is preferably 350~2400), (molecular weight is preferably 350 to allyl polyethylene glycol monomethyl ether
~2400), methacrylic poly glycol monomethyl ether (molecular weight is preferably 350~2400), isopentene group polyethyleneglycol first
Ether (molecular weight is preferably 350~2400), polyethylene glycol dimethacrylate (molecular weight is preferably 350~2400), poly- second
Omega-diol diacrylate (molecular weight is preferably 350~2400).
In another specific embodiment of the invention, ionic liquid described in step (1) is to contain as shown in formula M1
The imidazole type ion liquid of unsaturated bond, the pyrrolidines type ionic liquid as shown in formula M2 containing unsaturated bond, as shown in formula M3
The pyridine type ionic liquid containing unsaturated bond, the piperidines type ionic liquid as shown in formula M4 containing unsaturated bond, such as formula M5 institute
Show containing unsaturated bond season phosphine type ionic liquid, the quaternary ammonium salt ion liquid as shown in formula M6 containing unsaturated bond, such as formula
The mixture of one of morpholine type ionic liquid shown in M7 containing unsaturated bond or any several any ratios,
Wherein, X1 -、X2 -、X3 -、X4 -、X5 -、X6 -、X7 -Respectively Cl-、Br-、I-、BF4 -、PF6 -、SCN-、(CN)2N-、
CF3SO3 -、(CF3SO2)2N-、(CF3CF2SO2)2N-、NO3 -、AlCl4 -In any one；R1、R3、R5、R6、R8、R12、R16Respectively
For CH2=CH (CH2)n, n is any integer in 0~15；R2、R4、R7、R9、R10、R11、R13、R14、R15、R11Respectively CH2=CH
(CH2)n, n is any integer or CH in 0~153(CH2) n, n is any integer or H, NH in 0~202、(CH3)2CH、CH3O、
(CH3)2Any one in N.
Of the invention there are one in specific embodiment, initiator described in step (1) is azodiisobutyronitrile, idol
The different heptonitrile of nitrogen two, azo-bis-iso-dimethyl, dibenzoyl peroxide, dilauroyl peroxide, peroxidating -2 ethyl hexanoic acid
The tert-butyl ester, peroxidating tert-butyl isobutyrate, peroxide acetic acid butyl ester, 1,1- be bis--(tert-butyl hydroperoxide) -3,3,5- trimethyls
Hexamethylene, peroxidating -3,3,5- trimethylhexanoate, cumyl peroxide, di-t-butyl peroxide, peroxidating 12
The mixture of one of acyl or any several any ratios.
In a still more specific embodiment of the invention, the volume ratio of distilled water and reaction solution described in step (1)
It is 1: 1~100: 1；The vacuum drying temperature is 60~90 DEG C.
In a specific embodiment in turn of the invention, antioxidant described in step (2) is thio-2 acid two
Lauryl, 2, bis- [2,2 '-di-2-ethylhexylphosphine oxide (4, the 6- di-t-butyls of 4,6- tri-tert pentaerythritol bis-phosphites, spiral shell ethylene glycol
Phenyl)] phosphite ester, one of double diphosphorous acid two (2,4- di-tert-butyl-phenyl) esters of pentaerythrite or any several any
The mixture of ratio；One of the heat stabilizer calcium stearate, zinc stearate, magnesium stearate, Methyl stannum mercaptide are any several
The mixture of any ratio of kind；The filler is talcum powder, mica, quartz, bauxite, bentonite, montmorillonite, diatomite, nanometer
The mixture of one of calcium carbonate, nepheline, white carbon black, starch, Cellulose nanocrystal palpus or any several any ratios.
Compared with prior art, technical solution provided by the invention has the advantages that
(1) used the ionic liquid containing unsaturated double-bond and the polyethyleneglycol derivative containing unsaturated bond anti-as two kinds
Electrostatic agent, and by it in a manner of copolymerization with the monomer reactions such as acrylonitrile, solve the problems, such as antistatic agent migration precipitation, because
This, the copolymer of preparation has permanent antistatic performance；
(2) in the application of antistatic aspect, ionic liquid and polyethyleneglycol derivative can make up mutually other side not
Foot and defect improve antistatic property to achieve the effect that collaboration reduces surface resistivity；
(3) introducing of ionic liquid and polyethyleneglycol derivative has dual function: first is that improving as antistatic agent poly-
Close the conductivity of object；Second is that effectively improving the plasticity and toughness of polyacrylonitrile as the reactive plasticizer haveing excellent performance；
(4) compared with polyaniline and carbon nanotube, the color of ionic liquid and polyethyleneglycol derivative is extremely shallow, does not change substantially
Become the color of polyacrylonitrile fibre, thus do not influence fiber can dyeability.
The surface resistivity of heretofore described antistatic acrylonitrile copolymer and acrylonitrile copolymer fiber is pressed
It is tested according to GB/T1410-2006 " solid insulating material volume resistivity and surface resistivity test method " standard.It is described
The antistatic permanent method of acrylonitrile copolymer fiber are as follows: fiber is placed in 60 DEG C of hot water and impregnates 30min, taking-up is dried in the air
It is dry, after operation 50 times are impregnated-dried to repetition, measure fiber surface resistivity.
Specific embodiment
The present invention is described further below with reference to embodiment, but the contents of the present invention are not limited to this.
Embodiment 1
(1) preparation of permanent anti-static acrylonitrile copolymer
1L dimethylformamide is poured into reaction kettle, then by 3.75mol acrylonitrile monemer, 0.3mol acrylic acid first
Ester, 0.45mol polyethylene glycol methacrylate-styrene polymer 400,0.5mol 1- allyl -3- butyl imidazole hexafluorophosphate and
0.1mol azodiisobutyronitrile pours into reaction kettle after mixing, is heated to 65 DEG C while stirring, after temperature is constant instead
10h is answered, then reaction solution is poured into 5L distilled water and is precipitated, is stood, is filtered, is dried in vacuo in 85 DEG C, it is total to obtain acrylonitrile group
Polymers, copolymer fusing point are 215 DEG C；
(2) preparation of permanent anti-static acrylonitrile copolymer fiber
By the acrylonitrile copolymer of 100 mass parts, the dilauryl thiodipropionate of 0.2 mass parts, 0.3 mass parts
Zinc stearate, 1 mass parts Cellulose nanocrystal must permanently be resisted by high speed blender after mixing using spin processes
Electrostatic acrylonitrile copolymer fiber, the fiber number of copolymer fibre are 2.1dtex, breaking strength 2.9cN/dtex, and fracture is stretched
Long rate is 19.6%, and sheet resistance is 3.2 × 107Ω.Fiber is placed in 60 DEG C of hot water and impregnates 30min, taking-up is dried, weight
After impregnating-drying operation 50 times again, measurement fiber surface resistivity is 3.8 × 107Ω。
Embodiment 2
(1) preparation of permanent anti-static acrylonitrile copolymer
0.5L dimethylformamide and 0.5L dimethyl sulfoxide are poured into reaction kettle, then by 3.5mol acrylonitrile list
1- allyl -3- the fourth of body, 0.5mol methyl acrylate, 0.5mol polyethylene glycol monomethyl ethermethacrylic acid esters 400,0.5mol
Base imidazoles villaumite and 0.1mol azodiisobutyronitrile pour into reaction kettle after mixing, are heated to 60 while stirring
DEG C, 10h is reacted after temperature is constant, then reaction solution is poured into 7L distilled water and is precipitated, is stood, is filtered, is dried in vacuo in 80 DEG C,
Acrylonitrile copolymer is obtained, copolymer fusing point is 188 DEG C；
(2) preparation of permanent anti-static acrylonitrile copolymer fiber
By bis- [2, the 2 '-di-2-ethylhexylphosphine oxides (4,6- of the spiral shell ethylene glycol of the acrylonitrile copolymer of 100 mass parts, 0.2 mass parts
Di-tert-butyl-phenyl)] phosphite ester, the zinc stearate of 0.2 mass parts, 1 mass parts Cellulose nanocrystal must by high speed altogether
Mixed machine obtains permanent anti-static acrylonitrile copolymer fiber after mixing, using spin processes, and the fiber number of copolymer fibre is
2.3dtex, breaking strength 2.6cN/dtex, elongation at break 24.5%, sheet resistance are 9.5 × 106Ω.Fiber is set
30min is impregnated in 60 DEG C of hot water, taking-up is dried, and after operation 50 times are impregnated-dried to repetition, measurement fiber surface resistivity is
9.8×106Ω。
Embodiment 3
(1) preparation of permanent anti-static acrylonitrile copolymer
1L dimethylformamide is poured into reaction kettle, then by 3.75mol acrylonitrile monemer, 0.5mol acrylic acid first
Ester, 0.25mol polyethylene glycol acrylate 400,0.5mol 1- allyl -3- butyl imidazole tetrafluoroborate and 0.1mol
Azodiisobutyronitrile pours into reaction kettle after mixing, is heated to 65 DEG C while stirring, reacts 10h after temperature is constant,
Then reaction solution is poured into 5L distilled water and is precipitated, is stood, is filtered, is dried in vacuo in 85 DEG C, obtains acrylonitrile copolymer, altogether
Polymers fusing point is 202 DEG C；
(2) preparation of permanent anti-static acrylonitrile copolymer fiber
By bis- [2, the 2 '-di-2-ethylhexylphosphine oxides (4,6- of the spiral shell ethylene glycol of the acrylonitrile copolymer of 100 mass parts, 0.1 mass parts
Di-tert-butyl-phenyl)] phosphite ester, the zinc stearate of 0.2 mass parts, 1.2 mass parts Cellulose nanocrystal must pass through high speed
Blender obtains permanent anti-static acrylonitrile copolymer fiber, the fiber number of copolymer fibre after mixing, using spin processes
For 2.0dtex, breaking strength 2.7cN/dtex, elongation at break 21.3%, sheet resistance is 9.8 × 107Ω.By fiber
It is placed in 60 DEG C of hot water and impregnates 30min, taking-up is dried, and after operation 50 times are impregnated-dried to repetition, measures fiber surface resistivity
It is 1.2 × 108Ω。
Embodiment 4
(1) preparation of permanent anti-static acrylonitrile copolymer
1L dimethylformamide is poured into reaction kettle, then by 3mol acrylonitrile monemer, 0.5mol methacrylic acid,
0.5mol polyethylene glycol monomethyl ethermethacrylic acid esters 400, the dimethyl diallyl ammonium chloride of 0.5mol and 0.1mol are even
The different heptonitrile of nitrogen two pours into reaction kettle after mixing, is heated to 65 DEG C while stirring, reacts 10h after temperature is constant, with
Reaction solution is poured into 5L distilled water afterwards and is precipitated, is stood, is filtered, is dried in vacuo in 80 DEG C, obtains acrylonitrile copolymer, is copolymerized
Object fusing point is 167 DEG C；
(2) preparation of permanent anti-static acrylonitrile copolymer fiber
By the acrylonitrile copolymer of 100 mass parts, the dilauryl thiodipropionate of 0.1 mass parts, 0.3 mass parts
Calcium stearate, 1.2 mass parts white carbon black by high speed blender after mixing, obtain permanent anti-static third using spin processes
Alkene itrile group copolymer fibre, the fiber number of copolymer fibre are 2.2dtex, breaking strength 2.5cN/dtex, and elongation at break is
24.0%, sheet resistance is 4.2 × 106Ω.Fiber is placed in 60 DEG C of hot water and impregnates 30min, taking-up is dried, and repeats to soak
After steeping-drying operation 50 times, measurement fiber surface resistivity is 4.8 × 106Ω。
Embodiment 5
(1) preparation of permanent anti-static acrylonitrile copolymer
1.5L dimethylformamide is poured into reaction kettle, then by 4.5mol acrylonitrile monemer, 0.5mol metering system
The double trifluoro methylsulphurs of 1- allyl -3- butyl imidazole of acid, 0.6mol polyethylene glycol monomethyl ethermethacrylic acid esters 400,0.4mol
Imide salts and 0.1mol azobisisoheptonitrile are poured into reaction kettle after mixing, are heated to 65 DEG C while stirring,
10h is reacted after temperature is constant, then reaction solution is poured into 7L distilled water and is precipitated, is stood, is filtered, and is dried in vacuo, is obtained in 80 DEG C
To acrylonitrile copolymer, copolymer fusing point is 235 DEG C；
(2) preparation of permanent anti-static acrylonitrile copolymer fiber
By the acrylonitrile copolymer of 100 mass parts, the dilauryl thiodipropionate of 0.2 mass parts, 0.3 mass parts
Calcium stearate, 1.1 mass parts white carbon black by high speed blender after mixing, obtain permanent anti-static third using spin processes
Alkene itrile group copolymer fibre, the fiber number of copolymer fibre are 2.4dtex, breaking strength 3.3cN/dtex, and elongation at break is
18.2%, sheet resistance is 7.7 × 108Ω.Fiber is placed in 60 DEG C of hot water and impregnates 30min, taking-up is dried, and repeats to soak
After steeping-drying operation 50 times, measurement fiber surface resistivity is 8.3 × 108Ω。
Embodiment 6
(1) preparation of permanent anti-static acrylonitrile copolymer
0.5L dimethylformamide and 0.7L dimethyl sulfoxide are poured into reaction kettle, then by 3.6mol acrylonitrile list
1- allyl -3- the fourth of body, 0.4mol methacrylic acid, 0.6mol polyethylene glycol monomethyl ethermethacrylic acid esters 400,0.4mol
Base imidazoles bis-trifluoromethylsulfoandimide salt and 0.1mol azodiisobutyronitrile pour into reaction kettle after mixing, while stirring
65 DEG C are heated to, 10h is reacted after temperature is constant, then reaction solution is poured into 5L distilled water and is precipitated, stand, filter, in
80 DEG C of vacuum drying, obtain acrylonitrile copolymer, and copolymer fusing point is 193 DEG C；
(2) preparation of permanent anti-static acrylonitrile copolymer fiber
By bis- [2, the 2 '-di-2-ethylhexylphosphine oxides (4,6- of the spiral shell ethylene glycol of the acrylonitrile copolymer of 100 mass parts, 0.2 mass parts
Di-tert-butyl-phenyl)] phosphite ester, the calcium stearate of 0.1 mass parts, 1 mass parts white carbon black pass through high speed blender mix
After uniformly, permanent anti-static acrylonitrile copolymer fiber is obtained using spin processes, the fiber number of copolymer fibre is 2.3dtex,
Breaking strength is 2.8cN/dtex, and elongation at break 20.8%, sheet resistance is 6.5 × 107Ω.Fiber is placed in 60 DEG C
30min is impregnated in hot water, taking-up is dried, and after operation 50 times are impregnated-dried to repetition, measurement fiber surface resistivity is 6.8 × 107
Ω。
Embodiment 7
(1) preparation of permanent anti-static acrylonitrile copolymer
1.2L dimethylformamide is poured into reaction kettle, then by 4.0mol acrylonitrile monemer, 0.2mol acrylic acid,
1- allyl -3- butyl imidazole the villaumite and 0.1mol of 0.5mol polyethylene glycol monomethyl ethermethacrylic acid esters 400,0.5mol
Azodiisobutyronitrile pours into reaction kettle after mixing, is heated to 60 DEG C while stirring, reacts 10h after temperature is constant,
Then reaction solution is poured into 7L distilled water and is precipitated, is stood, is filtered, is dried in vacuo in 80 DEG C, obtains acrylonitrile copolymer, altogether
Polymers fusing point is 221 DEG C；
(2) preparation of permanent anti-static acrylonitrile copolymer fiber
By bis- [2, the 2 '-di-2-ethylhexylphosphine oxides (4,6- of the spiral shell ethylene glycol of the acrylonitrile copolymer of 100 mass parts, 0.2 mass parts
Di-tert-butyl-phenyl)] phosphite ester, the calcium stearate of 0.1 mass parts, 1 mass parts white carbon black pass through high speed blender mix
After uniformly, permanent anti-static acrylonitrile copolymer fiber is obtained using spin processes, the fiber number of copolymer fibre is 2.1dtex,
Breaking strength is 3.2cN/dtex, and elongation at break 18.3%, sheet resistance is 4.5 × 108Ω.Fiber is placed in 60 DEG C
30min is impregnated in hot water, taking-up is dried, and after operation 50 times are impregnated-dried to repetition, measurement fiber surface resistivity is 5.0 × 108
Ω。
Claims (9)
1. a kind of permanent anti-static acrylonitrile copolymer and its fiber, it is characterised in that first with acrylonitrile and containing unsaturation
The copolymerization of the monomers such as the ionic liquid of double bond, obtains permanent anti-static acrylonitrile copolymer, the permanent anti-static acrylonitrile group
The surface resistivity of copolymer is 6.1 × 105~9.2 × 1010Ω；Then directly added using the copolymer of preparation by spin processes
Work is 0.8~4.5dtex at permanent anti-static acrylonitrile copolymer fiber, the fiber number of the acrylonitrile copolymer fiber,
Breaking strength is 1.5~4.7cN/dtex, and elongation at break is 14.5%~27.8%, and surface resistivity is 6.1 × 105~
9.2×1010Ω；Fiber being placed in 60 DEG C of hot water and impregnates 30min, taking-up is dried, after operation 50 times are impregnated-dried to repetition,
Measuring fiber surface resistivity is 1.2 × 106~9.9 × 1010Ω still can reach antistatic requirement.
2. the preparation method of a kind of permanent anti-static acrylonitrile copolymer as described in claim 1 and its fiber, feature
Be the following steps are included:
(1) preparation of permanent anti-static acrylonitrile copolymer
A certain amount of solvent is added into reaction vessel, it is then that 40~97mol% acrylonitrile monemer, 20~1mol% second is single
Body, 20~1mol% Third monomer, 20~1mol% ionic liquid monomer and a certain amount of initiator pour into instead after mixing
It answers in container, wherein the sum of all monomer molar percentages are 100mol%, and the additional amount of the initiator is that all monomers are total
1~4mol% of amount, monomer concentration control is 3~6mol/L, is heated to 50~110 DEG C, after temperature is constant while stirring
6~15h is reacted, then reaction solution is poured into distilled water and is precipitated, is stood, is filtered, vacuum drying obtains acrylonitrile group copolymerization
Object, the copolymer fusing point are 150~265 DEG C, and surface resistivity is 6.1 × 105~9.2 × 1010Ω；
(2) preparation of permanent anti-static acrylonitrile copolymer fiber
The heat of the acrylonitrile copolymer of 100 mass parts, the antioxidant of 0.05~0.5 mass parts, 0.2~1 mass parts is steady
Determine agent, 0~3 mass parts filler by high speed blender after mixing, obtain permanent anti-static acrylonitrile using spin processes
Base co-polymer fiber, the fiber number of the copolymer fibre are 0.8~4.5dtex, and breaking strength is 1.5~3.7cN/dtex, fracture
Elongation is 14.5%~27.8%, and sheet resistance is 6.1 × 105~9.2 × 1010Ω.Fiber is placed in 60 DEG C of hot water
30min is impregnated, taking-up is dried, and after operation 50 times are impregnated-dried to repetition, measurement fiber surface resistivity is 1.2 × 106~9.9
×1010Ω still can reach antistatic requirement.
3. the preparation method of a kind of permanent anti-static acrylonitrile copolymer according to claim 2 and its fiber, special
Sign is that solvent described in step (1) is dimethylformamide, dimethyl sulfoxide, sulfolane, nitric acid ethylidene ester, ethylene carbonate
The mixture of one of ester or any several any ratios.
4. the preparation method of a kind of permanent anti-static acrylonitrile copolymer according to claim 2 and its fiber, special
Sign is that step (1) second comonomer is one of acrylic acid or acrylic acid derivative, and the acrylic acid derivative is preferred
From methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer,
The positive fourth of dodecyl acrylate, 2-Hydroxy ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid
Ester, Isobutyl methacrylate, Tert-butyl Methacrylate, isooctyl methacrylate, lauryl methacrylate, methyl-prop
Olefin(e) acid -2- hydroxy methacrylate, sodium acrylate, potassium acrylate, Sodium methacrylate, methacrylic acid potassium.
5. the preparation method of a kind of permanent anti-static acrylonitrile copolymer according to claim 2 and its fiber, special
Sign is that Third monomer described in step (1) is one of the polyethyleneglycol derivative containing unsaturated bond, the polyethylene glycol
Derivative preferably is selected from polyethylene glycol methacrylate-styrene polymer (molecular weight preferably is selected from 350~2400), polyethylene glycol acrylate (molecule
Amount preferably 350~2400), allyl polyglycol (molecular weight is preferably 350~2400), methacrylic polyethylene glycol
(molecular weight is preferably 350~2400), isopentene group polyethylene glycol (molecular weight is preferably 350~2400), polyethyleneglycol first
Ether metacrylic acid ester (molecular weight is preferably 350~2400), (molecular weight is preferably 350 to monomethyl polyethylene glycol acrylate ester
~2400), allyl polyethylene glycol monomethyl ether (molecular weight is preferably 350~2400), methacrylic poly glycol monomethyl ether
(molecular weight is preferably 350~2400), isopentene group poly glycol monomethyl ether (molecular weight is preferably 350~2400), poly- second two
Alcohol dimethylacrylate (molecular weight is preferably 350~2400), polyethyleneglycol diacrylate (molecular weight is preferably 350~
2400)。
6. the preparation method of a kind of permanent anti-static acrylonitrile copolymer according to claim 2 and its fiber, special
Sign be ionic liquid described in step (1) for as shown in formula M1 containing unsaturated bond imidazole type ion liquid, such as formula M2 institute
The pyrrolidines type ionic liquid containing unsaturated bond that shows, the pyridine type ionic liquid as shown in formula M3 containing unsaturated bond, such as formula
Piperidines type ionic liquid shown in M4 containing unsaturated bond, the season phosphine type ionic liquid, such as shown in formula M5 containing unsaturated bond
Quaternary ammonium salt ion liquid shown in formula M6 containing unsaturated bond, the morpholine type ionic liquid as shown in formula M7 containing unsaturated bond
One of or any several any ratios mixture,
Wherein, X1 -、X2 -、X3 -、X4 -、X5 -、X6 -、X7 -Respectively Cl-、Br-、I-、BF4 -、PF6 -、SCN-、(CN)2N-、CF3SO3 -、
(CF3SO2)2N-、(CF3CF2SO2)2N-、NO3 -、AlCl4 -In any one；R1、R3、R5、R6、R8、R12、R16Respectively CH2=
CH(CH2)n, n is any integer in 0~15；R2、R4、R7、R9、R10、R11、R13、R14、R15、R11Respectively CH2=CH (CH2)n, n
For any integer or CH in 0~153(CH2) n, n is any integer or H, NH in 0~202、(CH3)2CH、CH3O、(CH3)2In N
Any one.
7. the preparation method of a kind of permanent anti-static acrylonitrile copolymer according to claim 2 and its fiber, special
Sign is that initiator described in step (1) is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, peroxide
Change dibenzoyl, dilauroyl peroxide, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating tert-butyl isobutyrate, peroxidating second
Tert-butyl acrylate, 1,1- be bis--(tert-butyl hydroperoxide) -3,3,5- trimethyl-cyclohexanes, peroxidating -3,3, and the tertiary fourth of 5- tri-methyl hexanoic acid
The mixing of one of ester, cumyl peroxide, di-t-butyl peroxide, dilauroyl peroxide or any several any ratios
Object.
8. the preparation method of a kind of permanent anti-static acrylonitrile copolymer according to claim 2 and its fiber, special
Sign is that the volume ratio of distilled water described in step (1) and reaction solution is 1: 1~100: 1；The vacuum drying temperature be 60~
90℃。
9. the preparation method of a kind of permanent anti-static acrylonitrile copolymer according to claim 2 and its fiber, special
Sign is that antioxidant described in step (2) is dilauryl thiodipropionate, 2, the double phosphorous of 4,6- tri-tert pentaerythrites
The double diphosphorous acids two of bis- [2,2 '-di-2-ethylhexylphosphine oxides (4,6- the di-tert-butyl-phenyl)] phosphite esters of acid esters, spiral shell ethylene glycol, pentaerythrite
The mixture of one of (2,4- di-tert-butyl-phenyl) ester or any several any ratios；It is the heat stabilizer calcium stearate, hard
The mixture of one of resin acid zinc, magnesium stearate, Methyl stannum mercaptide or any several any ratios；The filler be talcum powder,
Mica, quartz, bauxite, bentonite, montmorillonite, diatomite, nanometer calcium carbonate, nepheline, white carbon black, starch, cellulose nanometer
The mixture of one of whisker or any several any ratios.
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