CN107794589A - The preparation method of graphene polyvinyl alcohol function and service fiber - Google Patents
The preparation method of graphene polyvinyl alcohol function and service fiber Download PDFInfo
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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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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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
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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
- D01F1/10—Other agents for modifying properties
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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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Abstract
The invention discloses a kind of high-strength and high-modulus amount, antibacterial, ultra-violet radiation resisting graphene polyvinyl alcohol function and service fiber preparation method.It is first that graphene and polyvinyl alcohol is uniform in the mixed solvent dispersion mixing, then gel is added to stir to form coagulant liquid, and coagulant liquid spinneret is formed into gel fiber into low temperature coagulating bath, most afterwards through more times of hot-stretch obtain high-strength and high-modulus amount, antibacterial, ultra-violet radiation resisting graphene polyvinyl alcohol function and service fiber.The present invention is raw materials used cheap, simple production process, easily realizes industrial mass production.1.4~2.2GPa of tensile strength of prepared graphene polyvinyl alcohol function and service fiber, Young's modulus 36GPa, elongation at break 10%, fiber surface is smooth, section is rounded form, can meet the requirement of special dimension, building and industrial circle to high-strength and high-modulus amount, antibacterial, anti-ultraviolet radiation poly vinyl alcohol composite fibre.
Description
Technical field
The present invention relates to a kind of preparation method of graphene-polyvinyl alcohol function and service fiber, belong to complex fiber material
Technical field.
Background technology
High strength poly vinyl alcohol (PVA) fiber has in good hydrophily, caking property, impact resistance and process easily
In scattered etc., so existing in cement, Ashestos plate, ceramic building material and polymer matrix composite etc. as reinforcing material
Many applications.It is tired the shock resistance of material, elastoresistance can effectively to be improved with high intensity PVA fibre reinforced concretes and construction material
The performance such as labor and anti-cracking.Geotextiles tensile strength is high made of high intensity PVA fibers, and creep resistance is good, wear-resisting, chemically-resistant
The resistance to microorganism of burn into and transmissibility are excellent, and reinforcement, isolation, protection, draining and leakproof effect can be played in engineering construction, can
For the pressure sand water proof of the engineering such as various dams and highway, railway, bridge, tunnel, slurry, sand ground, reinforcing, place mat, firm
Basic and anti-water segregation etc., construction quality can be significantly improved, reduce engineering cost.With epoxy resin by high intensity PVA fibers
Shaft is bonded into instead of the reinforcing bar in concrete, as civil construction project material, the deadweight of building element can be substantially reduced.
It is suitable to use because the fracture strength of high intensity PVA fibers, impact strength, against weather, resistance to corrosion seawater etc. are all relatively good
Make various types of fishing nets, fishing gear, fishing line, cable etc., have good application market in marine fishing and means of transport etc..
Although still not as Kevlar, UHMW-PE fiber etc., its breaking work is big, viscous for the tensile strength and modulus of high intensity PVA fibers
Connecing property is good, cheap etc. is possible to the higher Kevlar fibers of part fictitious hosts in terms of strengthening and protecting composite
Deng.Therefore, the exploitation of poly- graphene-polyvinyl alcohol (Graphene-PVA) composite fibre of high-strength and high-modulus amount has important research
Value and huge application prospect and market potential.
With the continuous progress of society, the requirement more and more higher to material property, existing vinal can not
Meet require, therefore high-strength and high-modulus amount Graphene-PVA composite fibres prepare it is particularly important.The high-strength and high-modulus of fiber quantifies
Both its chemical constitution and molecular structure are depended on, it is also related to its supramolecular structure.PVA theoretical limit intensity is respectively
27GPa, crystallization modulus is respectively 255GPa.And the highest modulus that PVA fibers are made so far is 115GPa.In order to obtain height
The fibrous material of performance, expands its application, the space that the intensity and moduluss of PVA fibers is also further lifted, thus such as
, by design on material structure and recombination process, the nano composite material for obtaining high-strength and high-modulus amount is necessary and urgent for what.
Carbon is widely present in nature, is one of basic element for forming living organism.Graphene (Graphene)
As a kind of carbonaceous new material, by one layer of carbon atom that is intensive, being wrapped in honeycomb crystal lattice with sp2Hydridization is formed by connecting
Monoatomic layer composition.It is the elementary cell for forming other carbon allotropes.It can be folded into the fullerene of zero dimension, is curled into
One-dimensional CNT, it is stacked to the graphite and diamond of three-dimensional.With fabulous crystallinity and electricity and excellent mechanical property
Energy.Graphene intensity is high, and performance can match in excellence or beauty with diamond, and it is respectively 125GPa and 1.1T to survey tensile strength and modulus of elasticity
Pa, graphene platelet only have an atomic layers thick (0.335nm), only 20 a ten thousandths of hair, are known in the world at present
Most thin most hard material.In addition, the specific surface area of graphene super large, the mechanical performance of protrusion, excellent ultraviolet isolating and anti-
Bacterium performance, it is widely used among novel high-strength and multifunctional nanocomposites.The present invention utilizes the ratio of graphene super large
Surface area and excellent mechanical performance and multifunctionality, prepare high-strength and high-modulus amount, antibacterial with the method for gel-gel spinning, resist
The Graphene-PVA function and service fibers of ultraviolet radiation.
The content of the invention
It is an object of the invention to provide the low high-strength and high-modulus amount of a kind of simple production process, cost, antibacterial, uvioresistant
Radiate the preparation method of graphene-polyvinyl alcohol function and service fiber.
The present invention is achieved by the following technical solutions：
The invention provides a kind of preparation method of graphene-polyvinyl alcohol function and service fiber, it comprises the following steps：
By graphene or Graphene derivative and polyvinyl alcohol after in the mixed solvent mixing, gel is added, is coagulated
Glue, coagulant liquid can form more preferable gel structure during gel spinning, and gel structure can effectively reduce macromolecular chain
Entanglement, be fully extended strand by ultra-drawing, formed effectively orientation and greatly improve the intensity of fiber；
By the coagulant liquid spinneret into coagulating bath, gel fiber is obtained；
By the gel fiber through more times of hot-stretch, the graphene-polyvinyl alcohol function and service fiber is obtained.
Preferably, the mixed solvent is the mixture of organic solvent and water, wherein, the weight of organic solvent and water
Amount is than being 95:5~70:30.
Preferably, the organic solvent is selected from dimethyl sulfoxide (DMSO), ethylene glycol, propane diols, glycerine, n-butanol, different
One or more in butanol, triethylene-glycol, tetrahydrofuran.
Preferably, the preparation method of the gel fiber is：
The coagulant liquid is filtered at 80~120 DEG C, after deaeration, in the methanol coagulating bath through spinneret to -15~5 DEG C,
The coagulant liquid forms gel fiber by chilling.
Preferably, the gel in glutaraldehyde, epoxychloropropane, silicate, borate at least one
Kind.
Preferably, the aperture of the spinneret of spinning process selection is 0.06~0.15mm, hole count 1500
~6000.
Preferably, the more times of hot-stretching steps are specially：The gel fiber is extracted successively, dried
Afterwards, 120~240 DEG C of hot-stretch temperature, 8~36 times of draw ratio, 1~15min heat-setting time under conditions of enter
Row hot-stretch is shaped.
Preferably, the temperature of the extraction is 20~80 DEG C, and the time is 2~60min, and the drying temperature is 60
~120 DEG C.
Preferably, the extractant of the extraction is methanol or ethanol.
Preferably, the degree of polymerization of the polyvinyl alcohol is 1750~2488, and alcoholysis degree is 80~99%.
Preferably, in the coagulant liquid, the weight fraction of polyvinyl alcohol is 10~25%, graphene or graphene
The dosage of derivative is the 0.1~10% of PVA-based weight, and the dosage of gel is the 0.1 of PVA-based weight
~5%.
The Graphene derivative is selected from graphene oxide, or derives through surface hydrophilic sex modification or modified graphene
One kind in material；The polyvinyl alcohol degree of polymerization is 1750~2488, and alcoholysis degree is 80~99% (i.e. by polyvinyl acetate
The alcoholysis in the aqueous solution of methanol, in polyvinyl acetate ester molecule 80~99% acetate alcoholysis is changed into hydroxyl).Work as selection
Polyvinyl alcohol degree of polymerization when being less than 1750, because polyvinyl alcohol molecule chain is short, after gel spinning can draw ratio it is smaller, multiple
The strand of polyvinyl alcohol could not be effectively from the orderly regular stretch-like condensed state of random coil shape arrangement form in condensating fiber
Structure.When the degree of polymerization of polyvinyl alcohol is higher than 2488, because molecular weight causes greatly gel fluid viscosity too big, it is highly detrimental to freeze
Glue spinning, and cost of spinning is high, operating difficulties.In addition, according to polyvinyl alcohol alcoholysis degree be less than 80%, polyvinyl alcohol is not
It can be completely dissolved in the mixed solvent used in this patent, spinning process is difficult to be smoothed out.
The mass percent concentration of polyvinyl alcohol is 10~25% in the coagulant liquid, graphene or Graphene derivative
Dosage is the 0.1~10% of PVA-based weight.Gel is the 0.1~5% of PVA-based weight, works as coagulant liquid
When middle polyvinyl alcohol selects above-mentioned concentration, graphene plural gel fluid viscosity is moderate, is advantageous to gel spinning processing efficient, stably
Ground is carried out, and Cheng Sizhong fault of construction is few, and the performance of composite fibre is good.Meanwhile when graphene in coagulant liquid or graphene derive
When thing selects above-mentioned concentration, graphene or Graphene derivative can be thoroughly dispersed in polyvinyl alcohol matrix, the stacking of graphene
Less, uniform dispersion is high, enhancing effect is obvious, while the ropiness of composite fibre can be good.In addition, graphene oxide, graphene
Or surface modification and this concentration range of modified graphene addition, will not be to the intrinsic machinery such as the toughness of vinal
Performance is impacted and lost.
By more times of hot-stretch (8~36 times), fibre crystallinity and the degree of orientation can be improved, makes to stretch in the piece crystal orientation of folded chain
Straight chain converts, so as to obtain graphene-polyvinyl alcohol function and service fiber of the strong high-modulus of superelevation, antibacterial, ultra-violet radiation resisting.
When stretching for more times, it can not only make macromolecular chain in composite fibre that the extended configuration of regular arrangement be presented, while can also make
Graphene film Linear Dichroism Studies of The Orientation in fibrous matrix is obtained, forms the brick wall topological structure similar to mollusk nacre, this
One organic and inorganic layer structure is very beneficial for scattered and transmits extraneous gravitation, can effectively absorb, shifts and transmit load
Lotus, so as to significantly increase the comprehensive mechanical performance of graphene-polyvinyl alcohol function and service fiber.
Compared with prior art, the present invention has following beneficial effect：
1st, polyvinyl alcohol can be used as dispersant, graphene or Graphene derivative is dispersed in the mixed solvent；
2nd, graphene or Graphene derivative and polyvinyl alcohol are well mixed in the mixed solvent, are added gel, are made to gather
Certain crosslinking is produced between vinyl alcohol strand, avoids intermolecular random entanglement, while polyvinyl alcohol molecule and graphene
Crosslinked between edge hydrophilic group on piece, form coagulant liquid.In more times of follow-up drawing process, graphene film is with poly-
Vinyl alcohol strand displacement, it can not only make the extended configuration of the regular orientations of macromolecular chain presentation in composite fibre,
Cause that rules orientation arranges graphene film in the fibre simultaneously, both cooperative effects assign the compound fibre of graphene-polyvinyl alcohol
Dimension higher mechanical property and feature.
Brief description of the drawings
The detailed description made by reading with reference to the following drawings to non-limiting example, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is high-strength and high-modulus amount, antibacterial, the preparation original of ultra-violet radiation resisting graphene-polyvinyl alcohol function and service fiber
Reason figure.
Fig. 2 is that the SEM of graphene-polyvinyl alcohol function and service fibre section schemes.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
The preparation of the high-strength and high-modulus amount, antibacterial, ultra-violet radiation resisting graphene-polyvinyl alcohol function and service fiber of the present invention
Schematic diagram as shown in figure 1, the present invention by graphene or Graphene derivative and polyvinyl alcohol after in the mixed solvent is well mixed,
Gel is added, forms gel.By gel spinneret into low temperature coagulating bath, gel fiber is formed, by surpassing times hot-stretch, is improved fine
Crystallinity and the degree of orientation are tieed up, makes to convert in the piece crystal orientation extended chain of folded chain, so as to obtain high-strength and high-modulus amount graphene-polyethylene
Alcohol function and service fiber.When stretching for more times, it can not only make the stretch-like of the regular arrangement of macromolecular chain presentation in composite fibre
State, while be advantageous to graphene film Linear Dichroism Studies of The Orientation and improve the performance of composite fibre.It is specifically shown in following embodiment.
Embodiment 1
The present embodiment is related to a kind of high-strength and high-modulus amount, antibacterial, graphene-polyvinyl alcohol function and service of ultra-violet radiation resisting
The preparation method of fiber.By graphene and polyvinyl alcohol after in the mixed solvent is well mixed, gel is added, stirring forms solidifying
Glue, by coagulant liquid spinneret into low temperature coagulating bath, form gel fiber.Then through more times of hot-stretch obtain high-strength and high-modulus, antibacterial,
The graphene of ultra-violet radiation resisting-polyvinyl alcohol function and service fiber.Specifically include following steps：
(1) it is 90 in weight ratio:The in the mixed solvent of 10 dimethyl sulfoxide (DMSO) and water composition adds graphene oxide, ultrasound
Scattered 3h, adds polyvinyl alcohol (degree of polymerization 2488 ± 50, alcoholysis degree 95%), and solution temperature is 100 DEG C；Add polyethylene
The Boratex of the quality 1% of alcohol, stirring form coagulant liquid.The weight percent concentration of polyvinyl alcohol is 15% in the coagulant liquid,
Graphene oxide mass percent is the 1% of PVA-based weight.
(2) by the coagulant liquid of configuration at 100 DEG C of temperature, after filtering, vacuum defoamation, through spinneret (spinneret hole
Footpath 0.1mm, hole count 2000~2500) it is ejected into -5~0 DEG C of methanol coagulating bath, coagulant liquid is formed by chilling and frozen at low temperature
Collodion silk.
(3) above-mentioned gel fiber is extracted, dry and hot-stretch sizing, high-strength and high-modulus amount graphene-polyethylene is made
Alcohol function and service fiber.Extractant uses methanol, 50 DEG C of extraction temperature, time 30min；Drying temperature is 100 DEG C, drying time
For 12h；180 DEG C of hot-stretch temperature, 30 times of draw ratio, heat-setting time 8min.
High-strength and high-modulus amount manufactured in the present embodiment, antibacterial, graphene-polyvinyl alcohol function and service of ultra-violet radiation resisting are fine
The SEM photograph for tieing up section is as shown in Figure 2.As shown in Figure 2, the cross sectional shape of composite fibre is not received typically substantially close to circle
Rice Material cladding fiber is also easy to produce the phase separation structure of core-skin layer when preparing.In addition, from the visible present invention of composite fibre SEM photograph
Obvious fault of construction is not present in the graphene nano composite fibre of preparation, composite fiber surface is smooth, is evenly distributed, polyethylene
Alcohol and graphenic surface be firmly combined with, uniform in the absence of being separated and the defects of empty, graphene dispersion occur.This method simultaneously
Can continuous prepare with scale, be a kind of comparatively ideal method for preparing nano-composite fiber.
Embodiment 2
The present embodiment is related to a kind of high-strength and high-modulus amount, antibacterial, graphene-polyvinyl alcohol function and service of ultra-violet radiation resisting
The preparation method of fiber.By graphene and polyvinyl alcohol after in the mixed solvent is well mixed, gel is added, stirring forms solidifying
Glue, by coagulant liquid spinneret into low temperature coagulating bath, gel fiber is formed, more times of hot-stretch obtain high-strength and high-modulus, antibacterial, uvioresistant
The graphene of beta radiation-polyvinyl alcohol function and service fiber.Specifically include following steps：
(1) it is 95 in weight ratio:The in the mixed solvent of 5 ethylene glycol and water composition adds surface modification and modified graphite
Alkene, ultrasonic disperse 1h add polyvinyl alcohol (degree of polymerization 1750 ± 50, alcoholysis degree 80%), and solution temperature is 50 DEG C；Add
The glutaraldehyde of polyvinyl alcohol quality 0.5%, stirring form coagulant liquid.The weight percent concentration of polyvinyl alcohol is in the coagulant liquid
10%, surface modification and modified graphene mass percent are the 10% of PVA-based weight.
(2) by the coagulant liquid of configuration at 80 DEG C of temperature, after filtering, normal pressure standing and defoaming, through spinneret (spinneret
Aperture 0.06mm, hole count 200~1000) it is ejected into -15~-10 DEG C of methanol coagulating bath, spinning solution is by urgency at low temperature
Cold formation gel fiber.
(3) above-mentioned spinning post processing：The gel fiber is extracted, dry and hot-stretch sizing, high-strength and high-modulus is made
Measure graphene-polyvinyl alcohol function and service fiber.Extractant uses methanol, 20 DEG C, time 2min of extraction temperature, and drying temperature is
60 DEG C, drying time 2h, 120 DEG C of hot-stretch temperature, 8 times of draw ratio, heat-setting time 1min.
It is fine to graphene-polyvinyl alcohol function and service of high-strength and high-modulus manufactured in the present embodiment, antibacterial, ultra-violet radiation resisting
Dimension carries out sem analysis and characterizes discovery, and fiber surface is smooth, and no skin-core structure defect, complex structure of filament are uniform, polyvinyl alcohol point
Son and graphene be firmly combined with, in the absence of be separated and there is the defects of empty, filler is uniformly dispersed；Cross sectional shape subcircular.
Embodiment 3
The present embodiment is related to a kind of high-strength and high-modulus amount, antibacterial, graphene-polyvinyl alcohol function and service of ultra-violet radiation resisting
The preparation method of fiber, by graphene and polyvinyl alcohol after in the mixed solvent is well mixed, gel is added, stirring forms solidifying
Glue, by coagulant liquid spinneret into low temperature coagulating bath, gel fiber is formed, high-strength and high-modulus, antibacterial, anti-purple are obtained through more times of hot-stretch
The graphene of UV radiation-polyvinyl alcohol function and service fiber.Specifically include following steps：
(1) it is 70 in weight ratio:The in the mixed solvent that 30 tetrahydrofuran, n-butanol and water forms adds electrochemical method
The graphene of stripping, ultrasonic disperse 6h, add polyvinyl alcohol (degree of polymerization 2488 ± 50, alcoholysis degree 95%), solution temperature
For 120 DEG C；The epoxychloropropane of the quality 1% of polyvinyl alcohol is added, stirring forms coagulant liquid.Polyvinyl alcohol in the spinning solution
Weight percent concentration be 25%, electrochemical stripping graphene mass percent be PVA-based weight 0.1%.
(2) by the coagulant liquid of configuration at 120 DEG C of temperature, after filtering, vacuum defoamation, through spinneret (spinneret hole
Footpath 0.15mm, hole count 5000~6000) it is ejected into -10~-5 DEG C of methanol coagulating bath, coagulant liquid is by chilling shape at low temperature
Into gel fiber.
(3) above-mentioned spinning post processing：The gel fiber is extracted, dry and hot-stretch sizing, obtained high-strength and high-modulus,
Graphene-polyvinyl alcohol function and service fiber of antibacterial, ultra-violet radiation resisting.Extractant uses ethanol, 80 DEG C of extraction temperature, when
Between 60min, drying temperature be 120 DEG C, drying time 24h, 240 DEG C of hot-stretch temperature, 36 times of draw ratio, heat-setting time
15min。
To high-strength and high-modulus manufactured in the present embodiment, antibacterial, ultra-violet radiation resisting graphene-polyvinyl alcohol function and service fiber
Carry out sem analysis characterize find, fiber surface is smooth, in the absence of obvious fault of construction, complex structure of filament uniformly, organic phase
It is firmly combined with Nano filling, is not separated and the defects of empty occur, filler is uniformly dispersed；Cross sectional shape is closely round.
Embodiment 4
This present embodiment is related to a kind of high-strength and high-modulus amount, antibacterial, graphene-polyvinyl alcohol function of ultra-violet radiation resisting and answered
The preparation method of condensating fiber, by graphene and polyvinyl alcohol after in the mixed solvent is well mixed, gel is added, stirring is formed
Coagulant liquid, by coagulant liquid spinneret into low temperature coagulating bath, gel fiber is formed, obtain high-strength and high-modulus, antibacterial through more times of hot-stretch, resist
The graphene of ultraviolet radiation-polyvinyl alcohol function and service fiber.Specifically include following steps：
(1) it is 80 in weight ratio:The in the mixed solvent of 20 G ＆ W composition adds graphite prepared by mechanical stripping method
Alkene, ultrasonic disperse 2h add polyvinyl alcohol (degree of polymerization 2088 ± 50, alcoholysis degree 90%), and solution temperature is 80 DEG C；Add
The glutaraldehyde of the quality 0.8% of polyvinyl alcohol, stirring form coagulant liquid.The weight percent concentration of polyvinyl alcohol in the coagulant liquid
For 20%, graphene mass percent is the 2% of PVA-based weight.
(2) by the coagulant liquid of configuration at 105 DEG C of temperature, after filtering, normal pressure standing and defoaming, through spinneret (spinneret
Panel aperture 0.12mm, hole count 2000~2500) it is ejected into 0~5 DEG C of methanol coagulating bath, coagulant liquid is by chilling shape at low temperature
Into gel fiber.
(3) above-mentioned spinning post processing：The gel fiber is extracted, dry and hot-stretch sizing, high-strength and high-modulus is made
Measure graphene-polyvinyl alcohol function and service fiber.Extractant uses ethanol, 60 DEG C, time 25min of extraction temperature, drying temperature
For 80 DEG C, drying time 20h, 180 DEG C of hot-stretch temperature, 20 times of draw ratio, heat-setting time 10min.
It is fine to graphene-polyvinyl alcohol function and service of high-strength and high-modulus manufactured in the present embodiment, antibacterial, ultra-violet radiation resisting
Dimension carries out sem analysis and characterizes discovery, and fiber surface is smooth, and no fault of construction, complex structure of filament are uniform, organic phase and nanometer are filled out
Material be firmly combined with, in the absence of be separated and there is the defects of empty, filler is uniformly dispersed；Cross sectional shape is circle.
Embodiment 5
1st, to high-strength and high-modulus amount, antibacterial, ultra-violet radiation resisting graphene-polyvinyl alcohol work(made from above example 1~4
Can composite fibre progress Mechanics Performance Testing；As a result it is as shown in table 1.
Table 1
In table 1, with embodiment 1, institute's difference is the preparation method that reference examples 1 use, and use only polyvinyl alcohol
And gel, graphene is not added.With embodiment 1, institute's difference is the preparation method that reference examples 2 use, and use only
Polyvinyl alcohol, graphene and gel are not added.As shown in Table 1, polyvinyl alcohol-graphene nano made from method of the invention
Composite fibre has excellent tensile strength and Young's modulus, and special dimension, building and industrial circle can be met to high-strength and high-modulus
Amount, the requirement of polyvinyl alcohol composite fiber.
2nd, to high-strength and high-modulus amount, antibacterial, ultra-violet radiation resisting graphene-polyvinyl alcohol work(made from above example 1~4
Can composite fibre progress anti-microbial property test；By graphene-polyvinyl alcohol function and service fibrous woven into cloth, antibacterial test according to
National standard FZ/T 73023-2006, as a result as shown in table 2.
Table 2
In table 2, with embodiment 1, institute's difference is the preparation method that reference examples use, and use only polyvinyl alcohol,
Graphene oxide, gel are not added.As shown in Table 2, graphene made from method of the invention-polyvinyl alcohol function and service is fine
Dimension has excellent anti-microbial property, and health, health-care textile field, building and industrial circle can be met to high-strength and high-modulus amount, antibacterial
The requirement of polyvinyl alcohol composite fiber.
3rd, to high-strength and high-modulus amount made from above example 1~4, antibacterial, ultra-violet radiation resisting graphene-polyvinyl alcohol
Function and service fiber carries out anti-ultraviolet property test；By graphene-polyvinyl alcohol function and service fibrous woven into cloth, uvioresistant
Line test is according to national standard GB/T 18830-2009, as a result as shown in table 3.
Table 3
In table 3, with embodiment 1, institute's difference is the preparation method that reference examples use, and use only polyvinyl alcohol,
Graphene, gel are not added.As shown in Table 3, graphene made from method of the invention-polyvinyl alcohol function and service fiber tool
There is excellent resistance to ultraviolet radiation energy (in general products of the UPF more than 40 just has resistance to ultraviolet radiation energy), can expire
Sufficient special dimension, building and industrial circle are wanted to high-strength and high-modulus amount, antibacterial, anti-ultraviolet radiation poly vinyl alcohol composite fibre
Ask.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. the preparation method of a kind of graphene-polyvinyl alcohol function and service fiber, it is characterised in that comprise the following steps：
By graphene or Graphene derivative and polyvinyl alcohol after in the mixed solvent mixing, gel is added, obtains coagulant liquid；
By the coagulant liquid spinneret into coagulating bath, gel fiber is obtained；
By the gel fiber through more times of hot-stretch, the graphene-polyvinyl alcohol function and service fiber is obtained.
2. the preparation method of graphene as claimed in claim 1-polyvinyl alcohol function and service fiber, it is characterised in that described
Mixed solvent is the mixture of organic solvent and water, wherein, the weight ratio of organic solvent and water is 95:5~70:30.
3. the preparation method of graphene as claimed in claim 2-polyvinyl alcohol function and service fiber, it is characterised in that described
Organic solvent is selected from dimethyl sulfoxide (DMSO), ethylene glycol, propane diols, glycerine, n-butanol, isobutanol, triethylene-glycol, tetrahydrofuran
In one or more.
4. the preparation method of graphene as claimed in claim 1-polyvinyl alcohol function and service fiber, it is characterised in that described
The preparation method of gel fiber is：
The coagulant liquid is filtered at 80~120 DEG C, after deaeration, it is described in the methanol coagulating bath through spinneret to -15~5 DEG C
Coagulant liquid forms gel fiber by chilling.
5. the preparation method of graphene as claimed in claim 1-polyvinyl alcohol function and service fiber, it is characterised in that described
Gel is selected from least one of glutaraldehyde, epoxychloropropane, silicate, borate.
6. the preparation method of graphene as claimed in claim 1-polyvinyl alcohol function and service fiber, it is characterised in that described
The aperture of the spinneret of spinning process selection is 0.06~0.15mm, and hole count is 1500~6000.
7. the preparation method of graphene as claimed in claim 1-polyvinyl alcohol function and service fiber, it is characterised in that described
More times of hot-stretching steps are specially：The gel fiber is extracted successively, after drying, in 120~240 DEG C of hot-stretch temperature
Hot-stretch sizing is carried out under conditions of degree, 8~36 times of draw ratio, 1~15min heat-setting time.
8. the preparation method of graphene as claimed in claim 7-polyvinyl alcohol function and service fiber, it is characterised in that described
The temperature of extraction is 20~80 DEG C, and the time is 2~60min, and the drying temperature is 60~120 DEG C, the extractant of the extraction
For methanol or ethanol.
9. the preparation method of graphene as claimed in claim 1-polyvinyl alcohol function and service fiber, it is characterised in that described
The degree of polymerization of polyvinyl alcohol is 1750~2488, and alcoholysis degree is 80~99%.
10. the preparation method of graphene as claimed in claim 1-polyvinyl alcohol function and service fiber, it is characterised in that described
In coagulant liquid, the weight fraction of polyvinyl alcohol is 10~25%, and the dosage of graphene or Graphene derivative is PVA-based
The 0.1~10% of weight, the dosage of gel are the 0.1~5% of PVA-based weight.
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| CN109294131A (en) * | 2018-08-09 | 2019-02-01 | 东华大学 | A kind of polyvinyl alcohol/graphene conductive nanocomposite and its preparation and application |
| CN110563524A (en) * | 2019-10-17 | 2019-12-13 | 安徽省聚科石墨烯科技股份公司 | Polyvinyl alcohol/graphene coated controlled-release fertilizer |
| CN113896920A (en) * | 2021-11-05 | 2022-01-07 | 北京石墨烯技术研究院有限公司 | Antibacterial polyethylene film and preparation method and application thereof |
| CN115341307A (en) * | 2022-09-23 | 2022-11-15 | 内蒙古大学 | High-orientation-degree graphene oxide fiber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109294131A (en) * | 2018-08-09 | 2019-02-01 | 东华大学 | A kind of polyvinyl alcohol/graphene conductive nanocomposite and its preparation and application |
| CN109294131B (en) * | 2018-08-09 | 2021-03-19 | 东华大学 | Polyvinyl alcohol/graphene conductive nanocomposite and preparation and application thereof |
| CN110563524A (en) * | 2019-10-17 | 2019-12-13 | 安徽省聚科石墨烯科技股份公司 | Polyvinyl alcohol/graphene coated controlled-release fertilizer |
| CN113896920A (en) * | 2021-11-05 | 2022-01-07 | 北京石墨烯技术研究院有限公司 | Antibacterial polyethylene film and preparation method and application thereof |
| CN113896920B (en) * | 2021-11-05 | 2024-02-23 | 北京石墨烯技术研究院有限公司 | Antibacterial polyethylene film and preparation method and application thereof |
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