CN110359128A - A kind of fibrous material, fiber gel, stretchable electrically conductive composite fibre with super-elasticity and frost resistance and preparation method thereof - Google Patents
A kind of fibrous material, fiber gel, stretchable electrically conductive composite fibre with super-elasticity and frost resistance and preparation method thereof Download PDFInfo
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- CN110359128A CN110359128A CN201810311223.8A CN201810311223A CN110359128A CN 110359128 A CN110359128 A CN 110359128A CN 201810311223 A CN201810311223 A CN 201810311223A CN 110359128 A CN110359128 A CN 110359128A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
Abstract
The present invention provides a kind of fibrous material, the fibrous material is polyacrylate fiber.The present invention devises a kind of polyacrylate fibrous material, which does not use any cross-linking agents to be formed, and is fibrous material obtained from one kind is physical crosslinking only by polyacrylate not by chemical crosslinking.More based on this, a kind of core-skin type composite conducting aquagel fibre with nucleocapsid structure of the surface with hydrophobic layer has been obtained.The composite conducting aquagel fibre that the present invention designs has the excellent resilience for being stretchable to ten times of initial length, and has good electric conductivity, still has elasticity and electric conductivity at low temperature；Material therefor is the industrial chemicals of large-scale production, cheap and easy to get；And preparation method is simple, after raw material is dissolved by heating in water and organic solvent, directly draws at room temperature, fiber can be obtained, then cover hydrophobic layer in fiber surface by the method for simply immersing, is suitble to large-scale industrial production.
Description
Technical field
The present invention relates to conductive fiber material technical field, be related to a kind of fibrous material, fiber gel, composite fibre and its
Preparation method more particularly to a kind of fibrous material, fiber gel, stretchable conduction with super-elasticity and frost resistance compound fibre
Dimension and preparation method thereof.
Background technique
Conductive fiber typically refers under standard state (20 DEG C, 65% relative humidity), and specific resistance is 107Ω cm or less
Fiber, divide conductive fiber by conductive compositions and be broadly divided into 4 kinds: metallic fiber, carbon black series fiber, conductive metal chemical combination
Fibres and conducting polymer fiber type.Especially with flourishing for Intelligent life concept in recent years, there is tensility
The conductive fiber of energy is the important component for manufacturing wearable electronic device, functional material is used as, in flexible electronic device
Part, intelligent wearable device field have very important application value, and demand is also increasing.Currently, stretchable conduction material
The main problem of material is so that conductive material is had flexibility, and keep good electric conductivity.Stretchable conductive material mainly has
Two kinds of application forms: two-dimensional stretchable planar conductive material, one-dimensional stretchable conductive fiber.Due to the weaving based on fiber
Technology is highly developed, stretchable conductive fiber can be more easily applied for manufacture wearable electronic on, can application surface it is wider.
The key of stretchable conductive fiber is designing and preparing for stretchable conductive material, existing stretchable conduction
There are mainly two types of fiber producing processes: (1) metal or carbon black materials and rubber elastomeric material is compound；(2) by conductive polymer
Son is compound with flexible macromolecule.Common metal, carbon material (including carbon black, carbon nanotube etc.), although have preferable intensity,
Excellent electric conductivity, but lack flexibility, by conductive material filament wound on elastomer, to obtain stretchable conductive fine
Dimension, it is such as that metal or carbon black materials and rubber elastomeric material is compound, but preparation process is relatively complicated, at high cost and fiber
Relatively thick, usually more than several hundred microns, and fiber extensibility is lower, during stretching along with conductivity substantially under
Drop." the Ag nanowire reinforced highly stretchable conductive as disclosed in Lee S et al.
Fibers for wearable electronics " one the article pointed out, by silver nanowires and polystyrene-butadiene-benzene second
The mixing of alkene rubber bodies obtains the SBS fiber containing silver nanowires by wet spinning, passes through absorption repeatedly and reduction silver later
Precursor solution, in fiber surface and internal formation Nano silver grain, finally obtained fiber conductivity is up to 2450S/cm, but
When being stretched to 100%, conductivity is down to original 4.4%.Disclosed in Yang Z et al. " A highly stretchable,
The composite material based on carbon nanotube has been also indicated that in a fiber-shaped supercapacitor " text.By marshalling
Carbon nanotube and elastomer, stretchable gel electrolyte is compound, forms supercapacitor.Wherein due to carbon nanotube
Use provide high-conductivity, intensity and stable mechanical performance, thermal stability for material；Rubber has then given material to draw
Stretch stability.After 100 times are stretched to 75%, holding capacitor value is 18F/g.Fiber itself is relatively thick, and extensibility is not high.
Alternatively, it is also possible to conducting polymer is compound with flexible macromolecule, so that composite material is had satisfactory electrical conductivity and have
Standby certain tensility, but there is also preparation process complexity, higher costs, and the conductivity of fiber can be substantially after the stretch
Decline, and the composite material of this conducting polymer and flexible macromolecule does not have frost resistance.As disclosed in Yao B et al.
It, will in " Ultrahigh-Conductivity Polymer Hydrogels with Arbitrary Structures " text
Commercialized PEDOT:PSS suspension sets H2SO4In, it is put in 90 DEG C of heating in mold and obtains conductive fiber.Finally its solid content is
0.78wt%, conductivity is up to 46S/m.If changing sulfuric acid into the concentrated sulfuric acid, solid content is improved to 4wt%, conductivity can be high
Up to 880 S/m.There is certain elasticity, after drying fiber, intensity can be substantially increased, but stretchable rate is only under saturation state
15% can be reached.
Therefore, the fiber for how designing a kind of stretchable conduction, solves the problems, such as that above-mentioned fiber exists, and preparation process
Simply, at low cost, it has also become one of many R & D Enterprises and the common focus of attention of forward-looking researcher in field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of fibrous material, fiber gel, composite fibre
And preparation method thereof, the composite fibre of especially a kind of stretchable conduction with super-elasticity and frost resistance is prepared by the present invention
Conductive fiber has excellent resilience and good electric conductivity, and still has elasticity and electric conductivity at low temperature, while raw material is honest and clean
Valence is easy to get, and preparation method is simple, is suitble to large-scale industrial production, is conducive to industrialization promotion and application.
The present invention provides a kind of fibrous material, the fibrous material is polyacrylate fiber.
Preferably, the polyacrylate includes the alkali metal salt of polyacrylic acid；
The diameter of the fibrous material is 10 μm~1mm；
The weight average molecular weight of the polyacrylate is more than or equal to 1,000,000 Da.
Preferably, the polyacrylate include one of Sodium Polyacrylate, polyacrylic acid potassium and Lithium polyacrylate or
It is a variety of；
The polyacrylate fiber is the fiber of polyacrylate physical crosslinking.
The present invention provides a kind of fiber gels, including fibrous material described in above-mentioned technical proposal any one and absorption
Solution in the fibrous material；
The mass fraction of the solution is 3%~8%.
The present invention provides a kind of composite fibres, including fibre core and the hydrophobic layer for being compounded in the fiber wicking surface；
The fibre core is fibre described in fibrous material described in above-mentioned technical proposal any one or above-mentioned technical proposal
Tie up gel.
Preferably, the composite fibre is core-sheath compound fibre；
The diameter of the fibre core is 10 μm~1mm；
The hydrophobic layer is polyacrylacid ester compounds hydrophobic layer.
Preferably, the polyacrylacid ester compounds include polymethyl acrylate, polyethyl acrylate and polyacrylic acid
A variety of copolymer in one of butyl ester or a variety of or polymethyl acrylate, polyethyl acrylate and butyl polyacrylate；
The hydrophobic layer with a thickness of 1~20 μm；
Solution in the fiber gel includes one of water, the aqueous solution of saliferous and Small molecule organic solvents or more
Kind.
The present invention also provides a kind of preparation methods of composite fibre, comprising the following steps:
1) polyacrylate after mixed dissolution, is obtained into mixed solution in water and organic solvent；
It is 10%~40% that the organic solvent, which accounts for water and the mass fraction of organic solvent,；
2) after the mixed solution cooling obtained above-mentioned steps, wire drawing or spinning are carried out, then after standing, obtains polyacrylic acid
Salt fiber gel；
3) polyacrylate fiber gel is dipped in polyacrylacid ester compounds solution, obtains composite fibre.
Preferably, in the mixed solution, the mass fraction of the polyacrylate is 3%~6%；
It further include alkali metal salt and/or ammonium salt in the mixed solution；
The temperature of the mixed dissolution is 30~100 DEG C；
The organic solvent include one of dimethyl sulfoxide, N,N-dimethylformamide and N-Methyl pyrrolidone or
It is a variety of；
The time of the standing is 0.5~5 minute；
The time being dipped in is 2~10 seconds.
Preferably, the alkali metal salt includes sulfate, chloride, phosphate, dibasic alkaliine and the nitric acid of alkali metal
One of salt is a variety of；
The ammonium salt includes one of sulfate, chloride, phosphate, dibasic alkaliine and nitrate of ammonium root or more
Kind；
In the mixed solution, the concentration of the alkali metal salt and/or ammonium salt is 25~200mM；
The mass fraction of polyacrylacid ester compounds is 3%~10% in the polyacrylacid ester compounds solution；
Solvent in the polyacrylacid ester compounds solution includes in ethyl acetate, chloroform, methylene chloride and acetone
It is one or more；
The number being dipped in can be one or many.
The present invention provides a kind of fibrous material, the fibrous material is polyacrylate fiber.Compared with prior art,
The present invention is in existing stretchable conductive fiber, and it is relatively complicated that there are preparation processes, and at high cost and fiber is thicker, and
Fiber extensibility is lower, during stretching along with the defect of conductivity to decline to a great extent, especially conducting polymer with it is soft
Property the composite conducting materials such as macromolecule existing for preparation process it is complicated, it is at high cost, and the conductivity of fiber can be big after the stretch
Width decline, and the composite material of this conducting polymer and flexible macromolecule does not have many applied defects such as frost resistance.This
Invention is from the essence of its defect, it is believed that conducting polymer is when preparing stretchable conductive material, since their own is larger
Conjugated structure and longer strand so that dissolution become problem so that not easy to be processed.And in order to make it easier to process and have
Standby tensility is prepared into gel, is obtaining threadiness by spinning or with die forming so introducing flexible macromolecule chain
Material, but still there are stretchable rate is low, the lower problem of intensity.
The invention devises a kind of polyacrylate fibrous material, which does not use any crosslinking agent
It is cross-linked to form, is fibrous material obtained from one kind is physical crosslinking only by polyacrylate not by chemical crosslinking.More with
Based on this, a kind of core-skin type composite conducting aquagel fibre with nucleocapsid structure of the surface with hydrophobic layer has been obtained.This
The composite conducting aquagel fibre of design is invented, there is the excellent resilience for being stretchable to ten times of initial length, and have good
Good electric conductivity still has elasticity and electric conductivity at low temperature；Material therefor is the industrial chemicals of large-scale production, cheap easy
?.And preparation method is simple, after raw material is dissolved by heating in water and organic solvent, directly draws, can obtain at room temperature
Hydrophobic layer is covered in fiber surface to fiber, then by the method for simply immersing, is suitble to large-scale industrial production, is conducive to
Industrialization promotion and application.
The composite fibre and preparation method thereof that the present invention designs, effective solution existing conductive fiber stretchable rate are inadequate
Height, stretch when along with conductivity decline the problem of, more overcome conductive fiber be difficult to keep at low temperature elasticity and lead
The defect of electrical property, while there is not yet preparation method, complex steps are at high cost, are not easy the application problems such as large scale preparation.
The experimental results showed that stretchable composite conducting aquagel fibre prepared by the present invention, is stretchable to itself ten times
Left and right has water-proof function, and has good intensity and electric conductivity, and with high damping capacity (71 ±
It 8%), has been more than the report data of other existing fibrous materials, it is fine higher than the spider silk of nature and artificial synthesized viscose glue
Dimension.
Detailed description of the invention
Fig. 1 is the cross-sectional view after PAAS fiber gel water removal prepared by the embodiment of the present invention 1；
Fig. 2 is the cross-sectional view after PMA-PAAS fiber water removal prepared by the embodiment of the present invention 1；
Fig. 3 is stress strain curve of the PMA-PAAS fiber of the preparation of the embodiment of the present invention 1 at 10,100 and 1000 mm/min
Figure；
Fig. 4 is damping capacity curve of the PMA-PAAS fiber of the preparation of the embodiment of the present invention 1 after being stretched to 500%；
Fig. 5 is damping capacity curve of the PMA-PAAS fiber of the preparation of the embodiment of the present invention 1 after being stretched to 300%；
Fig. 6 be the embodiment of the present invention 2 prepare PASS fiber and PMA-PAAS fibrage web under water droplet into
The photo of row test；
Fig. 7 is the photograph for the cobweb progress strength test that PMA-PAAS fiber prepared by the embodiment of the present invention 2 imitates braiding
Piece；
Fig. 8 is resistance and conductivity variations of the PMA-PAAS fiber of the preparation of the embodiment of the present invention 2 under different stretch rate
Curve；
Fig. 9 is the differential heating scan figure of PMA-PAAS fiber prepared by the embodiment of the present invention 3；
Figure 10 is Mechanics Performance Testing photo of the PMA-PAAS fiber of the preparation of the embodiment of the present invention 3 at -35 DEG C；
Figure 11 is the conductivity of the PMA-PAAS of the preparation of the embodiment of the present invention 3 at different temperatures.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described below with reference to embodiment, but
It is it should be appreciated that these descriptions only require the invention patent to further illustrate the features and advantages of the present invention
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or field of membrane material
Conventional purity.
The present invention provides a kind of fibrous material, the fibrous material is polyacrylate fiber.
The polyacrylate is not particularly limited in the present invention, is with polyacrylate well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical situations, raw material condition and product requirement
The bright polyacrylate preferably includes the alkali metal salt of polyacrylic acid, can specifically include Sodium Polyacrylate, polyacrylic acid potassium
With one of Lithium polyacrylate or a variety of, more preferably Sodium Polyacrylate, polyacrylic acid potassium or Lithium polyacrylate, most preferably
Sodium Polyacrylate.
The definition of the polyacrylate fiber is not particularly limited in the present invention, gathers with well known to those skilled in the art
For acrylates fiber there may be difference, polyacrylate fiber of the present invention is the polypropylene after non-crosslinked dose of chemical crosslinking
Silicate fiber, polyacrylate fiber of the invention are the polyacrylate fibers after the crosslinking of polyacrylate own physical,
Crosslinking agent structure or segment are not contained in structure, without containing the structure or segment for generating variation due to chemical crosslinking, less yet
There are the structures or segment of other grafting.
The molecular weight of the polyacrylate fiber is not particularly limited in the present invention, with well known to those skilled in the art
The convenient molecular weight of polyacrylate, those skilled in the art can be according to practical situations, raw material condition and productions
Product require to be selected and adjusted, and the weight average molecular weight of polyacrylate of the present invention is preferably greater than or equal to 1,000,000 Da, more excellent
It is selected as being more than or equal to 10,000,000 Da, is more preferably greater than equal to 30,000,000 Da.
The other parameters of the polyacrylate fiber are not particularly limited in the present invention, known to those skilled in the art
Fiber conventional parameter, those skilled in the art can be according to practical situations, raw material condition and product requirement
It being selected and is adjusted, the diameter of fibrous material of the present invention is 10 μm~1mm, more preferably 50~500 μm, more preferably
100~400 μm, more preferably 200~300 μm.
The present invention provides a kind of fiber gels, including fibrous material described in above-mentioned technical proposal any one and absorption
Solution in the fibrous material；The mass fraction of the solution is 3%~8%.
Selection, combination and preferred scope of the present invention to the fibrous material in the fiber gel, preferably with aforementioned fiber
Selection, combination and preferred scope in material can correspond to, and this is no longer going to repeat them.
The mass fraction of solution of the present invention is not particularly limited, and those skilled in the art can be according to practical application feelings
Condition, raw material condition and product requirement are selected and are adjusted, and in order to further increase the performance of final composite fibre, are guaranteed fine
The stability of material is tieed up, the mass fraction of solution of the present invention is preferably 3%~8%, and more preferably 4%~7%, more preferably
It is 5%~6%.
The fiber gel is not particularly limited in the present invention, with the definition of fiber gel well known to those skilled in the art
, those skilled in the art can select and adjust according to practical situations, raw material condition and product requirement, this
Invent the solution that the fiber gel includes polyacrylate fiber He is adsorbed in the polyacrylate fiber.The present invention couple
The solution is not particularly limited, and can be water with the conventional soln in fiber gel well known to those skilled in the art
Gel, or other gels, those skilled in the art can be according to practical situations, raw material condition and product requirements
It is selected and is adjusted, solution of the present invention preferably includes one of water, the aqueous solution of saliferous and Small molecule organic solvents
Or it is a variety of, the more preferably aqueous solution or Small molecule organic solvents of water, saliferous, the mixing of more preferably water and dimethyl sulfoxide is molten
Liquid.
The present invention provides a kind of composite fibres, including fibre core and the hydrophobic layer for being compounded in the fiber wicking surface；
The fibre core is fibre described in fibrous material described in above-mentioned technical proposal any one or above-mentioned technical proposal
Tie up gel.
The present invention is to selection, combination and the preferred scope of fibrous material or fiber gel in the composite fibre, preferably
Can be corresponding with selection, combination and the preferred scope in aforementioned fiber materials or fiber gel, this is no longer going to repeat them.
The structure of the composite fibre is not particularly limited in the present invention, with well known to those skilled in the art such compound
The structure of fiber, those skilled in the art can select according to practical situations, raw material condition and product requirement
It selects and adjusts, composite fibre of the present invention is preferably core-sheath compound fibre, specially fibrous material or fiber gel surface
One layer of hydrophobic layer is covered, is the composite fibre with nucleocapsid structure from section.
The structural parameters of the composite fibre are not particularly limited in the present invention, with well known to those skilled in the art such
The structural parameters of composite fibre, those skilled in the art can want according to practical situations, raw material condition and product
It asks and is selected and adjusted, the diameter of fibre core of the present invention is preferably 10 μm~1mm, more preferably 50~500 μm, more excellent
It is selected as 100~400 μm, more preferably 200~300 μm.The thickness of hydrophobic layer of the present invention is preferably 1~20 μm, more excellent
It is selected as 3~18 μm, more preferably 5~15 μm, more preferably 8~12 μm.
The material of the hydrophobic layer is not particularly limited in the present invention, with such compound fibre well known to those skilled in the art
The hydrophobic layer material of dimension, those skilled in the art can according to practical situations, raw material condition and product requirement into
Row selection and adjustment, hydrophobic layer of the present invention is preferably the hydrophobic layer of polyacrylacid ester compounds.
Polyacrylacid ester compounds of the present invention preferably include polymethyl acrylate, polyethyl acrylate and polypropylene
A variety of copolymerization in one of acid butyl ester or a variety of or polymethyl acrylate, polyethyl acrylate and butyl polyacrylate
Object, it can be one of polymethyl acrylate, polyethyl acrylate and butyl polyacrylate or a variety of, or be polypropylene
Two or three of copolymer in sour methyl esters, polyethyl acrylate and butyl polyacrylate, be specifically as follows polymethyl acrylate,
A variety of copolymerization in polyethyl acrylate, butyl polyacrylate, polymethyl acrylate, polyethyl acrylate and butyl polyacrylate
Object.
The present invention also provides a kind of preparation methods of composite fibre, comprising the following steps:
1) polyacrylate after mixed dissolution, is obtained into mixed solution in water and organic solvent；
It is 10%~40% that the organic solvent, which accounts for water and the mass fraction of organic solvent,；
2) after the mixed solution cooling obtained above-mentioned steps, wire drawing or spinning are carried out, then after standing, obtains polyacrylic acid
Salt fiber gel；
3) polyacrylate fiber gel is dipped in polyacrylacid ester compounds solution, obtains composite fibre.
The present invention to selection, combination and the preferred scope of raw material in the preparation method of the composite fibre, preferably with it is aforementioned
Composite fibre, corresponding selection, combination and preferred scope can correspond in fibrous material or fiber gel, not another herein
One repeats.
Polyacrylate after mixed dissolution, is obtained mixed solution in water and organic solvent first by the present invention.
Especially in the mixed liquor of water and organic solvent under certain concentration, polyacrylate is dissolved by the present invention.This hair
It is preferably 10%~40% that the bright organic solvent, which accounts for water and the mass fraction of organic solvent, and more preferably 15%~35%, more
Preferably 20%~30%, it is specifically as follows 15%~22%.
The additional amount of the water and organic solvent is not particularly limited in the present invention, with well known to those skilled in the art normal
Additional amount is advised, those skilled in the art can select according to practical situations, raw material condition and product requirement
And adjustment, in mixed solution of the present invention, the mass fraction of the polyacrylate is preferably 3%~6%, more preferably
3.5%~5.5%, more preferably 4%~5%.
The selection of the organic solvent is not particularly limited in the present invention, with conventional this well known to those skilled in the art
Class solvent, those skilled in the art can be selected according to practical situations, raw material condition and product requirement and
Adjustment, organic solvent of the present invention is preferably organic solvent miscible with water, more specifically preferably includes dimethyl sulfoxide, N, N-
One of dimethylformamide and N-Methyl pyrrolidone are a variety of, more preferably dimethyl sulfoxide, N, N- dimethyl formyl
Amine or N-Methyl pyrrolidone.
The temperature of the mixed dissolution is not particularly limited in the present invention, and those skilled in the art can be according to actual production
Situation, raw material condition and product requirement are selected and are adjusted, and the temperature of mixed dissolution of the present invention is preferably 30~100
DEG C, more preferably 40~90 DEG C, more preferably 50~80 DEG C, more preferably 60~70 DEG C.The present invention is to the mixed dissolution
Other conditions are not particularly limited, and those skilled in the art can be according to practical condition, raw material condition and product requirement
It is selected and is adjusted.
The present invention is to further increase the controllability of the performance and preparation process of product, to control the gelation of fiber
With the diameter for adjusting gained fiber, it is also preferable to include alkali metal salt and/or ammonium salts, i.e. mixed dissolution process in the mixed solution
In be preferably additionally added alkali metal salt and/or ammonium salt, more preferably alkali metal salts or ammonium salt.The present invention is to the alkali metal salt or ammonium
Salt is not particularly limited, and with alkali metal salts or ammonium salt well known to those skilled in the art, those skilled in the art can root
It is selected and is adjusted according to practical condition, raw material condition and product requirement, the preferred alkali gold of alkali metal salt of the present invention
One of sulfate, chloride, phosphate, dibasic alkaliine and nitrate of category are a variety of, more preferably the sulphur of alkali metal
Hydrochlorate, chloride, phosphate, dibasic alkaliine or nitrate.Ammonium salt of the present invention preferably includes the sulfate of ammonium root, chlorination
One of object, phosphate, dibasic alkaliine and nitrate are a variety of, more preferably sulfate, chloride, the phosphoric acid of ammonium root
Salt, dibasic alkaliine or nitrate.
The additional amount of the alkali metal salt and/or ammonium salt is not particularly limited in the present invention, ripe with those skilled in the art
The amount of being routinely added to known, those skilled in the art can according to practical condition, raw material condition and product requirement into
Row selects and adjustment, and in mixed solution of the present invention, the concentration of the alkali metal salt and/or ammonium salt is preferably 25~200mM
(mmol/L), more preferably 25~100mM, more preferably 30~90mM, more preferably 50~70mM.
After then mixed solution cooling that the present invention obtains above-mentioned steps, wire drawing or spinning are carried out, then after standing, is obtained
Polyacrylate fiber gel.
The detailed process and parameter of the cooling is not particularly limited in the present invention, with well known to those skilled in the art normal
It advises temperature-fall period and parameter, those skilled in the art can be according to practical condition, raw material condition and product requirement
It is selected and is adjusted, it can be 10~40 DEG C, or be 15~35 DEG C that cooling of the present invention, which is preferably dropped to room temperature, can also
Think 20~30 DEG C.
The mode of the wire drawing or spinning is not particularly limited in the present invention, with well known to those skilled in the art conventional fine
The mode of the throwing of dimension, those skilled in the art can according to practical situations, raw material condition and product requirement into
Row selection and adjustment, wire drawing of the present invention can may be solution spray for the modes such as manual wire drawing or mechanical wire drawing, spinning
The modes such as silk.
The design parameter of the standing is not particularly limited in the present invention, with conventional standing well known to those skilled in the art
Parameter, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement
Whole, the time of standing of the present invention is preferably 0.5~5 minute, more preferably 1~4.5 minute, more preferably 1.5~4 points
Clock, more preferably 2~3.5 minutes.
Polyacrylate fiber gel is finally dipped in polyacrylacid ester compounds solution by the present invention, obtains compound fibre
Dimension.
The design parameter being dipped in is not particularly limited in the present invention, with conventional immersion well known to those skilled in the art
Process, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement
Whole, the time of the present invention being dipped in is preferably 2~10 seconds, more preferably 3~9 seconds, more preferably 4~8 seconds, more preferably 5
~7 seconds.The present invention is to be further ensured that hydrophobic layer completely coats and effective thickness, the number being dipped in can be primary or more
It is secondary, more preferably repeatedly, it is specifically as follows 2~5 times or 3~4 times.
The solvent selection of the polyacrylacid ester compounds solution is not particularly limited in the present invention, with art technology
Conventional such solvent known to personnel, those skilled in the art can according to practical situations, raw material condition and
Product requirement is selected and is adjusted, and the solvent of polyacrylacid ester compounds solution of the present invention is preferably volatile organic
Solvent more specifically preferably includes one of ethyl acetate, chloroform, methylene chloride and acetone or a variety of, more preferably acetic acid second
Ester, chloroform, methylene chloride or acetone.
The concentration of the polyacrylacid ester compounds solution is not particularly limited in the present invention, with those skilled in the art
The normal concentration of well known such solution, those skilled in the art can according to practical situations, raw material condition and
Product requirement is selected and is adjusted, polyacrylacid ester compounds in polyacrylacid ester compounds solution of the present invention
Mass fraction is preferably 3%~10%, and more preferably 4%~9%, more preferably 5%~8%, more preferably 6%~7%.
The present invention is to be further ensured that the performance of final products, complete and process for refining process, and above-mentioned preparation method can be with
Specially following steps:
(1) polyacrylate is dissolved in water and organic solvent, at 80 DEG C, agitating and heating make polyacrylate in water and
The in the mixed solvent of organic solvent dissolves, and the ratio of water and organic solvent is extremely important, needs in suitable range.In solvent
In can be added the sodium chloride between 25~200mM, gained fiber can be adjusted with the gelation of accelerating fibers by improving NaCl concentration
Diameter.
(2) gained mixed solution is cooled to room temperature, then directly traction pulls out polyacrylate fiber, quiet in air
It sets, makes fiber gel.(if being dried, polyacrylate fiber can be obtained)
(3) polyacrylacid ester compounds are dissolved with solvent, obtains polyacrylic acid of the mass fraction 3%~10%
Ester type compound solution.
(4) fiber gel that step (2) has obtained is impregnated several seconds in polyacrylacid ester compounds solution, is taken
Out, so that solvent is volatilized, repeat this process two to three times, obtain stretchable composite conducting fiber.
It more specifically can be with are as follows:
(1) Sodium Polyacrylate (PAAS) is dissolved in water and dimethyl sulfoxide (DMSO), the quality of PAAS in the solution point
Number can be 3%~6%.At 80 DEG C, agitating and heating dissolves PAAS in the in the mixed solvent of water and DMSO, water and DMSO's
Ratio is extremely important, and suitable range is DMSO wt%=10%~40%, most preferably can be DMSO wt%=20%.
The sodium chloride between 25~200mM can be added in a solvent, gained can be adjusted with the gelation of accelerating fibers by improving NaCl concentration
The diameter of fiber, preferably NaCl concentration are 25~100 mM.
(2) gained PAAS solution is cooled to room temperature, then directly traction pulls out PAAS fiber, stands 1~2 in air
Minute makes fiber gel, obtains PAAS fiber gel.
(3) polymethyl acrylate (PMA) is dissolved with ethyl acetate, the PMA for obtaining mass fraction 3%~10% is molten
Liquid.
(4) the PAAS fiber gel that step (2) has obtained is impregnated several seconds in PMA solution, takes out, waves solvent
Hair repeats this process two to three times, obtains the stretchable composite conducting fiber of PMA-PAAS.
Above-mentioned steps of the present invention provide a kind of fibrous material, fiber gel, stretchable with super-elasticity and frost resistance
Conductive composite fibre and preparation method thereof.The present invention devises a kind of polyacrylate fibrous material, which does not adopt
It is formed with any cross-linking agents, is obtained from one kind is physical crosslinking only by polyacrylate not by chemical crosslinking
Fibrous material.More based on this, a kind of core-skin type composite conducting with nucleocapsid structure of the surface with hydrophobic layer has been obtained
Aquagel fibre.The composite conducting aquagel fibre that the present invention designs has the excellent bullet for being stretchable to ten times of initial length
Property, and there is good electric conductivity, still have elasticity and electric conductivity at low temperature；Material therefor is the chemical industry of large-scale production
Raw material, it is cheap and easy to get.And preparation method is simple, after raw material is dissolved by heating in water and organic solvent, directly at room temperature
Traction can be obtained fiber, then cover hydrophobic layer in fiber surface by the method for simply immersing, be suitble to large-scale industry
Production, is conducive to industrialization promotion and application.
The experimental results showed that stretchable composite conducting aquagel fibre prepared by the present invention, extensibility is 500~
1500%, intensity is 3~6MPa, and conductivity is 0.1~2.5S/m, has water-proof function.And there is high damping capacity
(71 ± 8%) have been more than the report data of other existing fibrous materials, higher than the spider silk of nature and artificial synthesized viscous
Glue fiber.
In order to further illustrate the present invention, solidifying to a kind of fibrous material provided by the invention, fiber with reference to embodiments
Glue, composite fibre and preparation method thereof are described in detail, but it is to be understood that these embodiments are with the technology of the present invention side
Implemented under premised on case, the detailed implementation method and specific operation process are given, only to further illustrate this hair
Bright feature and advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following realities
Apply example.
Embodiment 1
(1) 200mg PAAS granular solids are dissolved in 4.8g solvent, 3.84g water and 0.96g is contained in solvent
DMSO is heated 1 hour at 80 DEG C, obtains the solution of homogeneous transparent, is the PAAS solution of 4wt%.
(2) gained PAAS solution is cooled to room temperature, then directly traction pulls out PAAS fiber, stands 1~2 in air
Minute makes fiber gel.
(3) PMA of 0.05g 1g ethyl acetate is dissolved, obtains PMA solution of the mass fraction 5%.
(4) obtained PAAS fiber is impregnated several seconds in PMA solution, takes out, solvent is made to volatilize, repeat this process
Two, to three times, obtain PMA-PAAS fiber.
Table is carried out to the composite fibre of the stretchable conduction with super-elasticity and frost resistance prepared by the embodiment of the present invention 1
Sign.
By PAAS fiber gel and the distribution of PMA-PAAS fiber after freeze-drying, moisture is removed, it is aobvious with scanning electron
Micro mirror (SEM) observes its microscopic appearance.
It is the cross-sectional view after PAAS fiber gel water removal prepared by the embodiment of the present invention 1 referring to Fig. 1, Fig. 1.
Referring to fig. 2, Fig. 2 is the cross-sectional view after PMA-PAAS fiber water removal prepared by the embodiment of the present invention 1.
By Fig. 1 and Fig. 2 it is found that the cross-sectional view of PAAS fiber shows PAAS fibre structure even compact, PMA hydrophobic layer is very
The good surface for being covered on PAAS forms one layer of fine and close protective layer.
The composite fibre of stretchable conduction with super-elasticity and frost resistance prepared by the embodiment of the present invention 1 is examined
It surveys.It is placed on universal testing machine, test mechanical performance, including intensity, elongation at break, the change conductivity of adjoint extensibility
Variation measurement；And the testing water-proof under unstretched condition and tensional state, frost resistance and different temperatures are tested under low temperature
Under conduction property.
The PMA-PAAS fiber of above-mentioned preparation is taken one section, diameter is about 100m, and long 1cm surveys it with cupping machine
Mechanical property.
Referring to the PMA-PAAS fiber that Fig. 3, Fig. 3 are the preparation of the embodiment of the present invention 1 under 10,100 and 1000mm/min
Stress strain curve figure.
From the figure 3, it may be seen that being that the 100mm/min PMA-PAAS fiber can be stretched to former length before fracturing in rate of extension
1200%, maximum stress can be born and be up to about 6MPa, be a kind of super-elasticity and the material with good strength and toughness.
Referring to fig. 4, Fig. 4 is damping capacity of the PMA-PAAS fiber of the preparation of the embodiment of the present invention 1 after being stretched to 500%
Curve.
As shown in Figure 4, PMA-PAAS fiber prepared by the present invention has fabulous damping capacity (71 ± 8%), is higher than certainly
The spider silk and artificial synthesized viscose rayon on right boundary.
Referring to damping capacity of the PMA-PAAS fiber that Fig. 5, Fig. 5 are the preparation of the embodiment of the present invention 1 after being stretched to 300%
Curve.
As shown in Figure 5, PMA-PAAS fiber prepared by the present invention can be replied quickly after being stretched to 3 times of former length,
With good elasticity.
Embodiment 2
(1) dissolution 250mg PAAS granular solids are dissolved in 4.8g solvent, 4.0g water and 0.8g is contained in solvent
DMSO is heated 1 hour at 80 DEG C, obtains the solution of homogeneous transparent, is 5wt%PAAS solution.
(2) gained PAAS solution is cooled to room temperature, then directly traction pulls out PAAS fiber, stands 1~2 in air
Minute makes fiber gel.
(3) PMA of 0.07g 1g ethyl acetate is dissolved, obtains PMA solution of the mass fraction 7%.
(4) obtained PAAS fiber is impregnated several seconds in PMA solution, takes out, solvent is made to volatilize, repeat this process
Two to three times.
The composite fibre of stretchable conduction with super-elasticity and frost resistance prepared by the embodiment of the present invention 2 is applied
Performance detection.
To the waterproofness of PMA-PAAS fiber prepared by the present invention, frost resistance and electric conductivity are detected.
Referring to Fig. 6, Fig. 6 is that the PASS fiber of the preparation of the embodiment of the present invention 2 and the web of PMA-PAAS fibrage exist
The photo tested under water droplet.Wherein i) it is PAAS fiber, ii) it is PMA-PAAS fiber.
It will be appreciated from fig. 6 that PAAS fiber is non-watertight, and PMA-PAAS fiber waterproof performance is good, shows hydrophobic in coating PMA
Make fiber that there is good waterproofness after layer.
It is that PMA-PAAS fiber prepared by the embodiment of the present invention 2 imitates the cobweb progress intensity of braiding referring to Fig. 7, Fig. 7
The photo of test.
As shown in Figure 7, after this fibrage networking, due to the preferable intensity of fiber itself, web can bear itself
The weight that about 900 times of weight is without being destroyed.
Referring to resistance and electricity of the PMA-PAAS fiber that Fig. 8, Fig. 8 are the preparation of the embodiment of the present invention 2 under different stretch rate
Conductance change curve.
As shown in Figure 8, although resistance constantly becomes larger during stretching, due to stretch result in fiber diameter and
Length is changed, thus measure stretching when conductivity show as first rising and tend to be steady afterwards, 300% phase of extensibility
It is initial 3.2 times to conductivity variation, reaches a maximum value.
Embodiment 3
(1) 5.6mg NaCl being dissolved in the water of 3.84g and obtaining 25mMNaCl solution, itself and 0.8g DMSO mixing add
Enter 200mg PAAS granular solids, heated 1 hour at 80 DEG C, obtain the solution of homogeneous transparent, is 4wt%PAAS solution.
(2) gained PAAS solution is cooled to room temperature, then directly traction pulls out PAAS fiber, stands 1~2 in air
Minute makes fiber gel.
(3) PMA of 0.03g 1g ethyl acetate is dissolved, obtains PMA solution of the mass fraction 3%.
(4) obtained PAAS fiber is impregnated several seconds in PMA solution, takes out, solvent is made to volatilize, repeat this process
Two to three times.
The composite fibre of stretchable conduction with super-elasticity and frost resistance prepared by the embodiment of the present invention 3 is applied
Performance detection.
To the waterproofness of PMA-PAAS fiber prepared by the present invention, frost resistance and electric conductivity are detected.
It is the differential heating scan figure of PMA-PAAS fiber prepared by the embodiment of the present invention 3 referring to Fig. 9, Fig. 9.
As shown in Figure 9, PMA-PAAS fiber prepared by the present invention has good frost resistance, and transformation temperature appears in -40
Near DEG C, moisture therein just freezes at -40 DEG C, all keeps good elasticity in -40 DEG C or more fibers.
It is surveyed referring to mechanical property of the PMA-PAAS fiber that Figure 10, Figure 10 are the preparation of the embodiment of the present invention 3 at -35 DEG C
Try photo.
It can intuitively be shown by Figure 10, the freeze proof property of PMA-PAAS fiber prepared by the present invention is protected at -35 DEG C of low temperature
The elasticity of itself is hold, reversibility has good elasticity, resilience and load-bearing capacity.
Referring to the conductivity of the PMA-PAAS that Figure 11, Figure 11 are the preparation of the embodiment of the present invention 3 at different temperatures.
As shown in Figure 11, PMA-PAAS fiber prepared by the present invention is as conductive fiber, in a low temperature of -35 DEG C still
It can keep conduction property.
It is led above to a kind of fibrous material provided by the invention, fiber gel, with super-elasticity and the stretchable of frost resistance
The composite fibre and preparation method thereof of electricity is described in detail, specific case used herein to the principle of the present invention and
Embodiment is expounded, and the above description of the embodiment is only used to help understand the method for the present invention and its core ideas,
Including best mode, and but also any person skilled in the art can practice the present invention, including manufacture and use are appointed
What device or system, and implement the method for any combination.It should be pointed out that for those skilled in the art,
Without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention, these improvement and modification
It falls into the protection scope of the claims in the present invention.The range of the invention patent protection is defined by the claims, and can wrap
Include those skilled in the art it is conceivable that other embodiments.If these other embodiments, which have, is not different from claim
The structural element of character express, or if they include wanting with the character express of claim without the equivalent structure of essence difference
Element, then these other embodiments should also be included in the scope of the claims.
Claims (10)
1. a kind of fibrous material, which is characterized in that the fibrous material is polyacrylate fiber.
2. fibrous material according to claim 1, which is characterized in that the polyacrylate includes the alkali gold of polyacrylic acid
Belong to salt；
The diameter of the fibrous material is 10 μm~1mm；
The weight average molecular weight of the polyacrylate is more than or equal to 1,000,000 Da.
3. fibrous material according to claim 1, which is characterized in that the polyacrylate includes Sodium Polyacrylate, gathers
One of potassium acrylate and Lithium polyacrylate are a variety of；
The polyacrylate fiber is the fiber of polyacrylate physical crosslinking.
4. a kind of fiber gel, which is characterized in that including fibrous material described in claims 1 to 3 any one and be adsorbed on
Solution in the fibrous material；
The mass fraction of the solution is 3%~8%.
5. a kind of composite fibre, which is characterized in that including fibre core and the hydrophobic layer for being compounded in the fiber wicking surface；
The fibre core is fibrous material or fiber gel as claimed in claim 4 described in claims 1 to 3 any one.
6. composite fibre according to claim 5, which is characterized in that the composite fibre is core-sheath compound fibre；
The diameter of the fibre core is 10 μm~1mm；
The hydrophobic layer is polyacrylacid ester compounds hydrophobic layer.
7. composite fibre according to claim 6, which is characterized in that the polyacrylacid ester compounds include polypropylene
One of sour methyl esters, polyethyl acrylate and butyl polyacrylate or a variety of or polymethyl acrylate, polyethyl acrylate
With copolymer a variety of in butyl polyacrylate；
The hydrophobic layer with a thickness of 1~20 μm；
Solution in the fiber gel includes one of water, the aqueous solution of saliferous and Small molecule organic solvents or a variety of.
8. a kind of preparation method of composite fibre, which comprises the following steps:
1) polyacrylate after mixed dissolution, is obtained into mixed solution in water and organic solvent；
It is 10%~40% that the organic solvent, which accounts for water and the mass fraction of organic solvent,；
2) after the mixed solution cooling obtained above-mentioned steps, wire drawing or spinning are carried out, then after standing, obtains polyacrylate fibre
Tie up gel；
3) polyacrylate fiber gel is dipped in polyacrylacid ester compounds solution, obtains composite fibre.
9. preparation method according to claim 8, which is characterized in that in the mixed solution, the polyacrylate
Mass fraction is 3%~6%；
It further include alkali metal salt and/or ammonium salt in the mixed solution；
The temperature of the mixed dissolution is 30~100 DEG C；
The organic solvent includes one of dimethyl sulfoxide, N,N-dimethylformamide and N-Methyl pyrrolidone or more
Kind；
The time of the standing is 0.5~5 minute；
The time being dipped in is 2~10 seconds.
10. preparation method according to claim 9, which is characterized in that the alkali metal salt include alkali metal sulfate,
One of chloride, phosphate, dibasic alkaliine and nitrate are a variety of；
The ammonium salt includes one of sulfate, chloride, phosphate, dibasic alkaliine and nitrate of ammonium root or a variety of；
In the mixed solution, the concentration of the alkali metal salt and/or ammonium salt is 25~200mM；
The mass fraction of polyacrylacid ester compounds is 3%~10% in the polyacrylacid ester compounds solution；
Solvent in the polyacrylacid ester compounds solution includes one in ethyl acetate, chloroform, methylene chloride and acetone
Kind is a variety of；
The number being dipped in can be one or many.
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| CN113024717A (en) * | 2021-03-08 | 2021-06-25 | 南开大学 | Preparation method of polyelectrolyte hydrogel fiber with opposite charges |
| CN113089128A (en) * | 2021-04-20 | 2021-07-09 | 合肥学院 | Preparation method of polyacrylic acid/cellulose hydrogel fiber, prepared hydrogel fiber and application thereof |
| CN113265721A (en) * | 2021-04-19 | 2021-08-17 | 浙江大学 | Fibrous dielectric elastomer driver and preparation method thereof |
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| CN114561718A (en) * | 2022-02-28 | 2022-05-31 | 中国科学技术大学 | Composite fiber material, preparation method thereof and high-stretchability fibrous supercapacitor |
| CN115595683A (en) * | 2021-07-08 | 2023-01-13 | 香港理工大学（Hk） | Composite conductive fiber and preparation method and application thereof |
| CN115887990A (en) * | 2022-10-27 | 2023-04-04 | 中国人民解放军92228部队 | Human body emergency heat protection method |
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| CN115887990A (en) * | 2022-10-27 | 2023-04-04 | 中国人民解放军92228部队 | Human body emergency heat protection method |
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