CN109234831A - A kind of high-performance conductive vinal and preparation method thereof - Google Patents
A kind of high-performance conductive vinal and preparation method thereof 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
- D01F6/50—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 polyalcohols, polyacetals or polyketals
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- 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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- 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
- D01D5/08—Melt spinning methods
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- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
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- D01D5/12—Stretch-spinning methods
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- 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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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D01F1/10—Other agents for modifying properties
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Abstract
A kind of high-performance conductive vinal disclosed by the invention is will to carry out swelling modification with composite modifier after dispersion of milling in solid state mechanochemistry reactor after various dimensions conductive powder body and polyvinyl alcohol premix, then melt spinning, stretching and thermal finalization are carried out up to the wherein evenly dispersed various dimensions conductive powder body that has that mutually overlapped, and its volume resistivity≤10 by conventional extrusion-spinning equipment5Ω .cm, intensity >=6cN/dtex vinal.Since the various dimensions conductive powder body that the present invention is added to compounding in polyvinyl alcohol base-material is conductive material, it thus both can be in the case where having reduced conductive filler usage amount, realize the connection of different shape conducting particles, three-dimensional conductive network has been constructed in fiber, is improved the electric conductivity of fiber, can also be reduced the usage amount of conductive filler to a certain extent, reduce cost, the influence to fibrous mechanical property, and simple process, economy, environmental protection are reduced, is also easy to realize industrialized production.
Description
Technical field
The invention belongs to vinal and its preparation technical fields, and in particular to a kind of high-performance conductive polyvinyl alcohol
Fiber and preparation method thereof, it is especially a kind of using the solid state mechanochemistry dispersion various dimensions conductive filler height that simultaneously prepared by melt spinning
Performance conductive polyvinyl alcohol fiber and its method.
Background technique
In recent years, synthetic fibers are widely used in every profession and trade, it has also become the indispensable a part of the national economic development.But
It is the resistivity of conventional fibrous materials mostly 1012Ω cm or more can generate electrostatic electricity because rubbing and incuding in use
Lotus, easily formation charge accumulated.Build-up of electrostatic charges can not only be detrimental to health, and also will cause electronic component destruction, interference electricity
Sub- equipment and information system cause the accidents such as fire, explosion, seriously endanger public safety, bring huge economic loss.With
High-tech development, consequence caused by electrostatic have been not limited only to safety problem, spectral interference harm caused by electric discharge,
Have become electronics, communication, Aeronautics and Astronautics and all using modern electronic equipment, instrument occasion cause equipment operation failure,
One of dropout, immediate cause of error code.In addition, in industries such as petroleum, chemical industry, precision machinery, coal mine, food, medicine
There is special requirement to the protection of electrostatic.Therefore, improve the conductivity of synthetic fibers, preparation in normal conditions (20 DEG C,
65% relative humidity) volume resistivity be lower than 108The high-performance conductive fiber of Ω .cm is to be related to the important of national economy to ask
Topic.
In order to eliminate the electrostatic of synthetic fibers and its fabric, harm is prevented, the mankind just open from the 1960s
The research work of conductive fiber is begun to develop, the method for preparing electroconductive synthetic fibre so far mainly has surface cladding process, chemistry
Post-reaction treatment method, conductive filler completion method etc., wherein filled-type composite conducting synthetic fibers because its physical mechanical property stablize,
It is easy to process, the advantages that electric conductivity is long-acting lasting and it is in widespread attention, while carbon system filler, because cheap and easy to get, electric conductivity is excellent
Different, fibre forming property is good and is widely used as conductive filler.
Polyvinyl alcohol is a kind of function admirable, widely used polymer, and high-performance synthetic fibers prepared therefrom have
Good corrosion resistance, impact resistance, with the performances such as be easily dispersed in the good caking property of matrix and processing, in building, work
There is extensive development prospect in the fields such as industry, while can also be made into the functional fibers such as water-soluble fibre, fire resistance fibre, generally answer
In clothes and interior decoration, thus this just the operation safety of vinal and anti-static electricity interference are proposed it is higher
It is required that.But the resistivity of pure vinal is up to 1011Ω .cm, it is easy to produce static electricity in production weaving, cause fiber to twine
Around or blocking parts, semi-products or the scared broken end of yarn, fabric fold phenomena such as uneven, influence going on smoothly for production；It is spinning
In fabric use, the accumulation of electrostatic charge easily causes dust to adhere to, and clothes tangle limbs and generate adherency sense of discomfort；Static discharge is also
It can cause the accidental explosion of explosive wastewater and electric initiating explosive device；The electromagnetic radiation that static discharge generates can be to various electronic equipments, information
System causes electromagnetic interference.Therefore, polyvinyl alcohol conductive fiber is studied and produced, accelerates the leakage and dispersion of electrostatic, effectively
The local accumulation of anti-electrostatic processed, disaster caused by reducing because of electrostatic have important meaning to vinal application field is expanded
Justice.To prepare high performance carbon system filled polyethylene alcohol radical conductive fiber, a large amount of manpower and material resources are put into both at home and abroad and are competitively studied.
Miaudet etc. (P.Miaudet, et al, Polymer, 2007,48:4068-4074) is prepared for PVA/ by wet spinning
CNTs (carbon nanotube) conductive fiber, although the resulting resistivity for not washing fiber can reach when adding 11%CNTs
10-1Ω cm, the fiber after washing, CNTSContent, which reaches 23% resistivity, can reach 10-1Ω cm, but water-washing process loses
A large amount of PVA matrix, controls the ratio of PVA and CNTs in fiber with being unable to strict and steady, not can be carried out serialization and stablizes life
It produces, while the fiber is not stretched so that the crystallinity and the degree of orientation of fiber is not high, has to the mechanical property of fiber very big
Loss；P.Xue etc. (Xue P, Park K H, Tao X M, et al, Composite Structures, 2007,78 (2):
It 271-277.) is prepared for PVA/CNTs conductive fiber with wet spinning and coating process respectively, adds the diameter of 10wt%CNTs
For the volume resistivity about 10 of the PVA/CNTs fiber of 0.5mm6Ω .cm adds the volume resistivity of the fiber of 40wt%CNTs
It is 104Ω.cm；But CNTs concentration under the same conditions, by being coated with PVA/ on natural fiber and other synthetic fibers
CNTs mixed liquor, available linear resistivity is the PVA/CNTs coating composite fibre of 250 Ω .cm, but the method is produced
Electrically conductive composite fibre, since conductive network is based on surface covering, producing and using, floating coat is easy to fall off, while surface covering meeting
Influence the surface uniformity and slickness of fiber.Min Ho Jee etc. (Min H J, Jin U C, Park S H, et al,
Macromolecular Research, 2012,20 (6): 650-657.) with wet spinning it is prepared for PVA/MWCNTs (multi wall carbon
Nanotube) composite fibre, it is 0.2 that additive amount, which spins the resistivity of non-stretched PVA/MWCNTs composite fibre at the beginning of being 60%MWCNTs,
Ω .cm, the resistivity for the composite fibre that draw ratio is 30% are 0.02 Ω .cm.As can be seen, the conductive fiber, due to using
Single dimension filler, will realize excellent electric conductivity, need to add a large amount of conductive filler, this is caused during the preparation process,
The stability of dispersion and the spinning of conductive filler is at problem.Li Leis etc. (Li Lei, Sichuan University's master thesis, 2007) adopt
It is prepared for PVA/ graphite fiber with wet spinning, discovery graphite particle is migrated to epidermis, and that more concentrates is distributed in fiber
Surface, and the breaking strength of fiber concentrates the increase significant decrease with content of graphite due to stress, especially when graphite contains
When amount is 24.5%, about 1.15cN/dtex, and conductivity also not substantive promotion, about 1010Ω·cm。
JP200409196A, CN101586259 etc. are also prepared for carbon system filled polyethylene alcohol radical conductive fiber using solution spinning processes,
But the conductivity of fiber is promoted less, while the dispersion of carbon system filler is also problematic, stability of spinning process is low.Existing polyethylene
The research of alcohol conductive fiber is all based on solwution method, and is all made of single conductive filler, at high cost there are filler additive amount is big, and
The problem of easy to reunite, dispersing uniformity is poor, and stress concentration, which easily occurs, in fibrous inside causes intensity to be greatly reduced, poor mechanical property,
It is difficult to the requirement that satisfaction prepares high-strength and high-modulus conductive polyvinyl alcohol fiber.
Summary of the invention
In order to solve the problems in the prior art, the purpose of the present invention is to provide a kind of using the dispersion of solid phase mechanics method first
The method that various dimensions conductive filler and melt spinning prepare high-performance conductive vinal.
It is a further object of the present invention to provide a kind of high-performance conductive vinals prepared by the above method.
The preparation method of high-performance conductive vinal provided by the invention, it is characterised in that the technique of this method walks
Rapid and condition is as follows:
(1) by after 5~12 parts and 88~95 parts of polyvinyl alcohol premixs of various dimensions conductive powder body, it is put into solid state mechanochemistry reaction
Device carries out dispersion of milling, and grinding times obtain polyvinyl alcohol based composite conductive powder for 15-25 times, and the various dimensions conductive powder body is
It is compounded by the conductive filler of the conductive filler of three-dimensional structure, the conductive filler of two-dimensional structure and one-dimentional structure；
(2) 50~70 parts of polyvinyl alcohol based composite conductive powders and 30~50 parts of composite modifiers are first carried out swelling to change
Property, melt spinning, stretching and thermal finalization are then carried out to obtain the final product by conventional extrusion-spinning equipment, the composite modifier
It is by least one of at least one of nitrogenous compound and small molecule polyol and hydrophily auxiliary additive and water group
At,
Wherein the number of the material is parts by weight.
The conductive filler of three-dimensional structure in various dimensions conductive powder body described in above method is 2~6 parts, and two-dimensional structure is led
Electric filler is 2~4 parts, and the conductive filler of one-dimentional structure is 1~2 part.
The conductive filler of three-dimensional structure described in above method is in metal powder, metal oxide or conductive black (CB)
Any, the preferred silver powder of metal powder, copper powder, zinc powder, the preferred Conductive mica of metal oxide, titanium dioxide；Two-dimensional structure
Conductive filler be expanded graphite (EG) or graphene (GR)；The conductive filler of one-dimentional structure is carbon fiber (CF) or carbon nanotube
(CNTs or MWCNTs).
Nitrogenous compound described in above method or 5~10 parts of small molecule polyol；Hydrophily auxiliary additive is 0~2
Part；Water is 25~38 parts.
Nitrogenous compound described in above method is caprolactam or acetamide；Small molecule polyol is glycerol or second two
Alcohol；Hydrophily auxiliary additive is polyethylene glycol of the molecular weight lower than 20000, polyoxyethylene of the viscosity average molecular weigh lower than 1,000,000
Alkene, polyacrylic acid and its esters, sodium alginate and polyacrylamide.
The degree of polymerization of polyvinyl alcohol described in above method is 1700~2400, and alcoholysis degree is 88~99.9%.
Solid state mechanochemistry reactor described in above method is solid state mechanochemistry reactor disclosed in ZL95111258.9.
The process conditions of the control of fusing spinning step described in above method are as follows: 130~165 DEG C of spinning temperature；Spinneret
0.12~0.4mm of aperture；1~4 times of spinneret draft ratio；10~80 DEG C of cross air blasting cooling temperature, humidity 65~85%.
The process conditions of the control of stretching step described in above method are as follows: by gained polyvinyl alcohol as-spun fibre in 150~
230 DEG C carry out 1~3 grade of stretching, and total draw ratio is 10~20 times.
The process conditions of the control of heat setting step described in above method are as follows: by fiber after resulting stretching in 200~240
DEG C carry out relaxation heat setting, heat-setting time be 0.5~5 minute.
The high-performance conductive vinal provided by the invention prepared by the above method, it is characterised in that the polyethylene
It is evenly dispersed in alcohol fiber to have mutually overlapped various dimensions conductive powder body, volume resistivity≤105Ω .cm, intensity >=6cN/
dtex。
The volume resistivity of the above vinal is 102~105Ω .cm, intensity are 6~15cN/dtex.
The present invention has the advantage that
1. since the various dimensions conductive powder body that method provided by the invention is added to compounding in polyvinyl alcohol base-material is to lead
Electric material, thus both the connection of different shape conducting particles can have been realized in the case where reducing conductive filler usage amount, in fiber
Three-dimensional conductive network has inside been constructed, the electric conductivity of fiber is improved, can also reduce the usage amount of conductive filler to a certain extent, has been dropped
Low cost reduces the influence to fibrous mechanical property.
2. since method provided by the invention is to prepare polyvinyl alcohol based conductive powder body using solid state mechanochemistry reactor,
The fine dispersion of conductive powder body thus can be not only realized in the case where not introducing solvent, and is more favorable to preparation melting and is spun
The polyvinyl alcohol based conductive powder body of silk.
3. since method provided by the invention is added to composite modifier in prepared polyvinyl alcohol based conductive powder body, and
Composite modifier also contains nitrogenous compound or small molecule polyol, thus not only realizes polyvinyl alcohol melt spinning, also presses down
The evaporation for having made plasticizer water in modifying agent realizes superheat of the water in polyvinyl alcohol, increases its boiling point, and boiling range increases
Width, moisture content explosive vaporization generates bubble when avoiding melt spinning, improves the stability of spinning.
4. the coagulating bath of wet spinning is not needed since preparation method provided by the invention is melt spinning method, thus
Technique is more simple, economical, environmentally friendly, is also easy to realize industrialized production.
5. since preparation method provided by the invention can pass through fiber to air in spinning and fiber hot-stretching step
Small molecule additive inside unidirectional mass transfer removal vinal regulates and controls the hydrogen bond density and orientation knot of vinal
Crystal structure, to prepare high performance polyvinyl alcohel fiber.
6. not only electric conductivity is excellent for high-performance conductive vinal provided by the invention, and mechanical property,
It can satisfy the requirement of the high-strength and high-modulus conduction of vinal.
Detailed description of the invention
Attached drawing 1 is the preparation process and conductive polyvinyl alcohol fiber of high-performance conductive vinal provided by the invention
Conductive network build process schematic diagram.It can be seen that compounding has different dimensions conductive powder body in polyvinyl alcohol base-material
Afterwards, these powder stuffings of different shapes can be overlapped mutually, fill up hole of the single powder stuffing in dimension, thus more
Added with constructing for three-dimensional conductive network is conducive to, the usage amount of conductive filler is reduced, successfully realizes high conductive high-performance
The preparation of vinal.
Specific embodiment
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is served only for
Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made to the present invention according to aforementioned present invention content.
Embodiment 1
900g polyvinyl alcohol (degree of polymerization 2400, alcoholysis degree 99.9%) and 50gCB, 40gEG and 10gMWCNTs are carried out just
Step mixing, then mills mixed powder 25 times in solid state mechanochemistry reactor, obtains the polyvinyl alcohol based conduction that is uniformly dispersed
Composite granule.
The composite modifier that the above-mentioned polyvinyl alcohol based conduction composite granule of 600g and 70g caprolactam and 330g water are formed
Carry out swelling modification.Modified polyvinyl alcohol based conduction composite granule is 130 DEG C in spinning temperature, and aperture is the normal of 0.12mm
The extrusion of rule-spinning equipment carries out melt spinning, and melt stream is 60 DEG C through temperature, rolls up after the side-blown air cooling that humidity is 70%
Around spinneret draft is 3 times, and as-spun fibre carries out 2 grades of stretchings, 20 times of total draw ratio, warp in 170-200 DEG C, 200-230 DEG C
220 DEG C thermal finalization 3 minutes, be made volume resistivity be 103Ω cm, intensity are the high-performance conductive polyethylene of 15cN/dtex
Alcohol fiber.
Embodiment 2
By 900g polyvinyl alcohol (degree of polymerization 1700, alcoholysis degree 97%), 60g Conductive mica, 20gEG and 20gMWCNTs
It is tentatively mixed, mixed powder is milled 15 times in solid state mechanochemistry reactor then, obtains the polyvinyl alcohol that is uniformly dispersed
Base conduction composite granule.
By the above-mentioned polyvinyl alcohol based conduction composite granule of 550g and by 60g ethylene glycol, the polyethylene glycol of 10g molecular weight 2000
Swelling modification is carried out with the composite modifier of 380g water composition.Modified polyvinyl alcohol based conduction composite granule is in spinning temperature
Spending temperature is 150 DEG C, and conventional extrusion-spinning equipment that aperture is 0.2mm carries out melt spinning, and melt stream is through temperature 50
DEG C, it is wound after the side-blown air cooling that humidity is 75%, spinneret draft is 2 times, and as-spun fibre is at 150-160 DEG C, 160-190
DEG C, 190-210 DEG C carry out 3 grades stretching, 12 times of total draw ratio, through 200 DEG C thermal finalization 5 minutes, be made volume resistivity be 103
Ω cm, intensity are the high-performance conductive vinal of 10cN/dtex.
Embodiment 3
880g polyvinyl alcohol (degree of polymerization 1700, alcoholysis degree 99%) and 60g silver powder, 40gGR and 20gCF are carried out preliminary
Mixing, then mills mixed powder 20 times in solid state mechanochemistry reactor, and the polyvinyl alcohol based conduction that obtains being uniformly dispersed is multiple
Close powder.
It is formed by the above-mentioned polyvinyl alcohol based conduction composite granule of 700g and by 50g caprolactam and 250g water composite modified
Agent carries out swelling modification.Modified polyvinyl alcohol based conduction composite granule is 165 DEG C in spinning temperature temperature, and aperture is
Conventional extrusion-spinning equipment of 0.3mm carries out melt spinning, and melt stream is 10 DEG C through temperature, humidity be 65% it is side-blown
It is wound after air cooling, spinneret draft is 1 times, and as-spun fibre carries out 3 grades of drawings in 150-160 DEG C, 160-190 DEG C, 190-210 DEG C
Stretch, 18 times of total draw ratio, through 240 DEG C thermal finalization 0.5 minute, be made volume resistivity be 102Ω cm, intensity 12cN/
The high-performance conductive vinal of dtex.
Embodiment 4
950g polyvinyl alcohol (degree of polymerization 2400, alcoholysis degree 88%) and 20gCB, 20gGR and 10gCNTs are carried out preliminary
Mixing, then mills mixed powder 18 times in solid state mechanochemistry reactor, and the polyvinyl alcohol based conduction that obtains being uniformly dispersed is multiple
Close powder.
It is formed by the above-mentioned polyvinyl alcohol based conduction composite granule of 650g and by 50g glycerol, 280g water and 20g sodium alginate
Composite modifier carries out swelling modification.Modified polyvinyl alcohol based conduction composite granule is 160 DEG C in spinning temperature temperature, hole
Conventional extrusion-spinning equipment that diameter is 0.4mm carries out melt spinning, and melt stream is 80 DEG C through temperature, and humidity is 85%
It is wound after side-blown air cooling, spinneret draft is 4 times, and as-spun fibre carries out 3 in 150-160 DEG C, 160-190 DEG C, 190-220 DEG C
Grade stretch, 15 times of total draw ratio, through 220 DEG C thermal finalization 3 minutes, be made volume resistivity be 105Ω cm, intensity 9cN/
The high-performance conductive vinal of dtex.
Embodiment 5
920g polyvinyl alcohol (degree of polymerization 1700, alcoholysis degree 99%) and 40gCB, 28gEG and 12gCNTs are carried out preliminary
Mixing, then mills mixed powder 23 times in solid state mechanochemistry reactor, and the polyvinyl alcohol based conduction that obtains being uniformly dispersed is multiple
Close powder.
Compound change by the above-mentioned polyvinyl alcohol based conduction composite granule of 600g and by what 100g caprolactam and 300g water formed
Property agent carries out swelling modification.Modified polyvinyl alcohol based conduction composite granule is 155 DEG C in spinning temperature temperature, and aperture is
Conventional extrusion-spinning equipment of 0.25mm carries out melt spinning, and melt stream is 60 DEG C through temperature, humidity be 80% it is side-blown
It is wound after air cooling, spinneret draft is 3 times, and as-spun fibre carries out 2 grades of stretchings in 160-190 DEG C, 190-210 DEG C, total to stretch
12 times of multiple, through 220 DEG C thermal finalization 2 minutes, be made volume resistivity be 104Ω cm, intensity are the high property of 11cN/dtex
It can conductive polyvinyl alcohol fiber.
Embodiment 6
910g polyvinyl alcohol (degree of polymerization 1700, alcoholysis degree 99%) and 50g copper powder, 25gGR and 15gMWCNTs are carried out
Preliminary mixing, then mills mixed powder 20 times in solid state mechanochemistry reactor, and the polyvinyl alcohol based that obtains being uniformly dispersed is led
Electric composite granule.
By the above-mentioned polyvinyl alcohol based conduction composite granule of 500g and by 100g acetamide 380g water and 20g polyacrylamide group
At composite modifier carry out swelling modification.Modified polyvinyl alcohol based conduction composite granule is 160 in spinning temperature temperature
DEG C, conventional extrusion-spinning equipment that aperture is 0.15mm carries out melt spinning, and melt stream is 50 DEG C through temperature, and humidity is
It is wound after 65% side-blown air cooling, spinneret draft is 2 times, and as-spun fibre is at 170-190 DEG C, 190-200 DEG C, 200-220
DEG C carry out 3 grades stretching, 12 times of total draw ratio, through 230 DEG C thermal finalization 1 minute, be made volume resistivity be 104Ω cm, by force
Degree is the high-performance conductive vinal of 13cN/dtex.
Embodiment 7
By 930g polyvinyl alcohol (degree of polymerization 1700, alcoholysis degree 88%) and 23g titanium dioxide, 35gGR and 12gCNTs
It is tentatively mixed, mixed powder is milled 17 times in solid state mechanochemistry reactor then, obtains the polyvinyl alcohol that is uniformly dispersed
Base conduction composite granule.
By the above-mentioned polyvinyl alcohol based conduction composite granule of 620g and by 80g glycerol, 285g water and 15g viscosity average molecular weigh
The composite modifier of 100000 polyethylene glycol oxides composition carries out swelling modification.Modified polyvinyl alcohol based conduction composite granule
It is 165 DEG C in spinning temperature temperature, conventional extrusion-spinning equipment that aperture is 0.3mm carries out melt spinning, melt stream warp
Temperature be 75 DEG C, humidity be 80% side-blown air cooling after wind, spinneret draft be 2 times, as-spun fibre 180-200 DEG C into
1 grade of row stretching, 10 times of total draw ratio, through 225 DEG C thermal finalization 2.5 minutes, be made volume resistivity be 105Ω cm, intensity
For the high-performance conductive vinal of 6cN/dtex.
Claims (10)
1. a kind of preparation method of high-performance conductive vinal, it is characterised in that the processing step and condition of this method are such as
Under:
(1) will after 5~12 parts of various dimensions conductive powder body and 88~95 parts of polyvinyl alcohol premixs, be put into solid state mechanochemistry reactor into
Capable dispersion of milling, grinding times obtain polyvinyl alcohol based composite conductive powder for 15-25 times, and the various dimensions conductive powder body is by three
Conductive filler, the conductive filler of two-dimensional structure and the conductive filler of one-dimentional structure of dimension structure compound；
(2) 50~70 parts of polyvinyl alcohol based composite conductive powders and 30~50 parts of composite modifiers are first subjected to swelling modification, so
Melt spinning, stretching and thermal finalization are carried out to obtain the final product by conventional extrusion-spinning equipment afterwards, the composite modifier is by containing
At least one of at least one of nitrogen compound and small molecule polyol and hydrophily auxiliary additive and water composition,
Wherein the number of the material is parts by weight.
2. the preparation method of high-performance conductive vinal according to claim 1, it is characterised in that this method institute
The conductive filler for stating the three-dimensional structure in various dimensions conductive powder body is 2~6 parts, and the conductive filler of two-dimensional structure is 2~4 parts, one
The conductive filler for tieing up structure is 1~2 part.
3. the preparation method of high-performance conductive vinal according to claim 1 or 2, it is characterised in that this method
Described in the conductive filler of three-dimensional structure be any one of metal powder, metal oxide or conductive black (CB)；Two dimension knot
The conductive filler of structure is expanded graphite (EG) or graphene (GR)；The conductive filler of one-dimentional structure is carbon fiber (CF) or carbon nanometer
It manages (CNTs or MWCNTs).
4. the preparation method of high-performance conductive vinal according to claim 1 or 2, it is characterised in that this method
Described in nitrogenous compound or small molecule polyol be 5~10 parts；Hydrophily auxiliary additive is 0~2 part；Water is 25~38
Part.
5. the preparation method of high-performance conductive vinal according to claim 3, it is characterised in that in this method
The nitrogenous compound or small molecule polyol are 5~10 parts；Hydrophily auxiliary additive is 0~2 part；Water is 25~38 parts.
6. the preparation method of high-performance conductive vinal according to claim 1 or 2, it is characterised in that this method
Described in nitrogenous compound be caprolactam or acetamide；Small molecule polyol is glycerol or ethylene glycol；Hydrophily auxiliary addition
Agent is polyethylene glycol of the molecular weight lower than 20000, polyethylene glycol oxide, polyacrylic acid and its salt of the viscosity average molecular weigh lower than 1,000,000
Class, sodium alginate and polyacrylamide.
7. the preparation method of high-performance conductive vinal according to claim 5, it is characterised in that in this method
The nitrogenous compound is caprolactam or acetamide；Small molecule polyol is glycerol or ethylene glycol；Hydrophily auxiliary additive
For molecular weight lower than 20000 polyethylene glycol, viscosity average molecular weigh lower than 1,000,000 polyethylene glycol oxide, polyacrylic acid and its esters,
Sodium alginate and polyacrylamide.
8. the preparation method of high-performance conductive vinal according to claim 1 or 2, it is characterised in that this method
Described in fusing spinning step control process conditions are as follows: 130~165 DEG C of spinning temperature；0.12~0.4mm of the hole diameter of spinneret；
1~4 times of spinneret draft ratio；10~80 DEG C of cross air blasting cooling temperature, humidity 65~85%；
The process conditions of the stretching step control are as follows: gained polyvinyl alcohol as-spun fibre is carried out 1~3 grade in 150~230 DEG C
It stretches, total draw ratio is 10~20 times；
The process conditions of the heat setting step control are as follows: fiber after resulting stretching is subjected to relaxation heat in 200~240 DEG C and is determined
Type, heat-setting time are 0.5~5 minute.
9. the preparation method of high-performance conductive vinal according to claim 7, it is characterised in that in this method
The process conditions of the fusing spinning step control are as follows: 130~165 DEG C of spinning temperature；0.12~0.4mm of the hole diameter of spinneret；Spray
1~4 times of draw ratio of head of silk；10~80 DEG C of cross air blasting cooling temperature, humidity 65~85%；
The process conditions of the stretching step control are as follows: gained polyvinyl alcohol as-spun fibre is carried out 1~3 grade in 150~230 DEG C
It stretches, total draw ratio is 10~20 times；
The process conditions of the heat setting step control are as follows: fiber after resulting stretching is subjected to relaxation heat in 200~240 DEG C and is determined
Type, heat-setting time are 0.5~5 minute.
10. the high-performance conductive vinal of any one of -9 the methods preparation, feature exist according to claim 1
It is evenly dispersed in the vinal to have mutually overlapped various dimensions conductive powder body, volume resistivity≤105Ω .cm,
Intensity >=6cN/dtex.
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| CN111155189A (en) * | 2019-10-14 | 2020-05-15 | 四川大学 | Preparation method of melt-spun profiled polyvinyl alcohol fiber |
| CN116574413A (en) * | 2023-05-31 | 2023-08-11 | 湖州乐通新材料科技有限公司 | Preparation method of conductive ink |
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