CN110359128B - Fiber material, fiber gel, stretchable conductive composite fiber with superelasticity and frost resistance and preparation method thereof - Google Patents
Fiber material, fiber gel, stretchable conductive composite fiber with superelasticity and frost resistance and preparation method thereof Download PDFInfo
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- CN110359128B CN110359128B CN201810311223.8A CN201810311223A CN110359128B CN 110359128 B CN110359128 B CN 110359128B CN 201810311223 A CN201810311223 A CN 201810311223A CN 110359128 B CN110359128 B CN 110359128B
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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
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Abstract
The invention provides a fiber material which is polyacrylate fiber. The invention designs a polyacrylate fiber material which is formed by crosslinking without any crosslinking agent, is not crosslinked chemically, and is obtained by only physically crosslinking polyacrylate. Based on the hydrophobic layer, the core-sheath composite conductive hydrogel fiber with the core-shell structure and the hydrophobic layer on the surface is obtained. The composite conductive hydrogel fiber designed by the invention has excellent elasticity which can be stretched to ten times of the initial length, has good conductivity, and still has elasticity and conductivity at low temperature; the used materials are chemical raw materials for large-scale production, and are cheap and easy to obtain; the preparation method is simple, the raw materials are heated and dissolved in water and an organic solvent, and then are directly pulled at room temperature to obtain the fiber, and then the hydrophobic layer is covered on the surface of the fiber by a simple soaking method, so that the preparation method is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of conductive fiber materials, relates to a fiber material, a fiber gel, a composite fiber and preparation methods thereof, and particularly relates to a fiber material, a fiber gel, a stretchable conductive composite fiber with superelasticity and frost resistance and a preparation method thereof.
Background
The conductive fiber generally has a specific resistance of 10 in a standard state (20 ℃, 65% relative humidity)7The fibers having a length of not more than Ω · cm are classified into 4 types of conductive fibers, mainly metal fibers, carbon black fibers, conductive metal compound fibers, and conductive polymer fibers, based on the conductive component. Particularly, with the vigorous development of intelligent life concepts in recent years, the conductive fiber with stretchable performance is an important component for manufacturing wearable electronic devices, and as a functional material, the conductive fiber has very important application value in the fields of flexible electronic devices and intelligent wearable devices, and the demand is also increasing. At present, the main problem of stretchable conductive materials is how to make the conductive materials flexible and maintain good conductivity. There are two main applications of stretchable conductive materials: two-dimensional stretchable planar conductive material, one-dimensional stretchable conductive fibers. As the textile technology based on the fiber is very mature, the stretchable conductive fiber is easier to be applied to manufacturing wearable electronic equipment, and the application range is wider.
The key point of the stretchable conductive fiber lies in the design and preparation of the stretchable conductive material, and the existing methods for preparing the stretchable conductive fiber mainly comprise two methods: (1) compounding metal or carbon black material with elastic material such as rubber; (2) the conductive polymer is compounded with the flexible polymer. Although common metal and carbon materials (including carbon black, carbon nanotubes and the like) have good strength and excellent conductivity, the common metal and carbon materials are poor in elasticity, and conductive material filaments are wound on an elastic body so as to obtain stretchable conductive fibers. As disclosed in "Ag nanowire recycled and high purity tape conductive fibers for electric wires" by Lee S et al, silver nanowires and polystyrene-butadiene-styrene rubber are mixed and wet-spun to obtain SBS fibers containing silver nanowires, and then silver nanoparticles are formed on the surface and inside of the fibers by repeatedly absorbing and reducing a silver precursor solution, so that the conductivity of the finally obtained fibers is as high as 2450S/cm, but is reduced to 4.4% of the original conductivity when the fibers are stretched to 100%. The term "A high strain, fiber-shaped supercapacitors" as disclosed by Yang Z et al also refers to carbon nanotube-based composites. And compounding the orderly-arranged carbon nanotubes and the elastic fibers with the stretchable gel electrolyte to form the supercapacitor. The use of the carbon nano tube provides high conductivity, strength, stable mechanical property and thermal stability for the material; rubber gives the material tensile stability. After 100 stretches to 75%, the capacitance value is maintained at 18F/g. The fibers themselves are relatively coarse and the draw ratio is not high.
In addition, the conductive polymer and the flexible polymer can be compounded, so that the composite material has good conductivity and certain stretchability, but the preparation process is complex, the cost is high, the conductivity of the fiber is greatly reduced after the fiber is stretched, and the composite material of the conductive polymer and the flexible polymer has no frost resistance. As disclosed in Yao B et al, "ultra high-Conductivity polymers with argon Structures", a commercial suspension of PEDOT, PSS was placed in H2SO4And placing the mixture into a die and heating the mixture at 90 ℃ to obtain the conductive fiber. The final solids content was 0.78 wt%, toThe electric rate can reach 46S/m. If the sulfuric acid is changed into concentrated sulfuric acid, the solid content is increased to 4 wt%, and the conductivity can be as high as 880S/m. The fiber has certain elasticity in a water-containing state, and the strength of the fiber is greatly improved after the fiber is dried, but the stretchability can only reach 15%.
Therefore, how to design a stretchable conductive fiber, which solves the problems of the fiber, has the advantages of simple preparation process and low cost, and has become one of the focuses of common attention of many research and development enterprises and prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a fiber material, a fiber gel, a composite fiber and a preparation method thereof, and particularly to a stretchable conductive composite fiber with superelasticity and frost resistance.
The invention provides a fiber material which is polyacrylate fiber.
Preferably, the polyacrylate salt comprises an alkali metal salt of polyacrylic acid;
the diameter of the fiber material is 10 mu m-1 mm;
the weight average molecular weight of the polyacrylate is greater than or equal to 100 ten thousand Da.
Preferably, the polyacrylate comprises one or more of sodium polyacrylate, potassium polyacrylate and lithium polyacrylate;
the polyacrylate fiber is a polyacrylate physically crosslinked fiber.
The invention provides a fiber gel, which comprises the fiber material and a solution absorbed in the fiber material in any one of the technical schemes;
the mass fraction of the solution is 3-8%.
The invention provides a composite fiber, which comprises a fiber core and a hydrophobic layer compounded on the surface of the fiber core;
the fiber core is the fiber material or the fiber gel according to any one of the above technical aspects.
Preferably, the composite fiber is a sheath-core composite fiber;
the diameter of the fiber core is 10 mu m-1 mm;
the hydrophobic layer is a polyacrylate compound hydrophobic layer.
Preferably, the polyacrylate compound comprises one or more of polymethyl acrylate, polyethyl acrylate and polybutyl acrylate, or a copolymer of a plurality of polymethyl acrylate, polyethyl acrylate and polybutyl acrylate;
the thickness of the hydrophobic layer is 1-20 mu m;
the solution in the fiber gel comprises one or more of water, a saline solution and a small molecule organic solvent.
The invention also provides a preparation method of the composite fiber, which comprises the following steps:
1) mixing and dissolving polyacrylate in water and an organic solvent to obtain a mixed solution;
the organic solvent accounts for 10 to 40 percent of the mass fraction of the water and the organic solvent;
2) cooling the mixed solution obtained in the step, drawing or spinning, and standing to obtain polyacrylate fiber gel;
3) and (3) soaking the polyacrylate fiber gel in a polyacrylate compound solution to obtain the composite fiber.
Preferably, in the mixed solution, the mass fraction of the polyacrylate is 3% -6%;
the mixed solution also comprises alkali metal salt and/or ammonium salt;
the temperature for mixing and dissolving is 30-100 ℃;
the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone;
the standing time is 0.5-5 minutes;
the immersion time is 2-10 seconds.
Preferably, the alkali metal salt comprises one or more of a sulfate, chloride, phosphate, monohydrogen phosphate, and nitrate salt of an alkali metal;
the ammonium salt comprises one or more of sulfate, chloride, phosphate, monohydrogen phosphate and nitrate of ammonium;
in the mixed solution, the concentration of the alkali metal salt and/or the ammonium salt is 25-200 mM;
the mass fraction of the polyacrylate compound in the polyacrylate compound solution is 3-10%;
the solvent in the polyacrylate compound solution comprises one or more of ethyl acetate, chloroform, dichloromethane and acetone;
the number of immersion times may be one or more.
The invention provides a fiber material which is polyacrylate fiber. Compared with the prior art, the invention aims at the defects of more complicated preparation process, high cost, thicker fiber, lower fiber stretching rate and large reduction of the conductivity in the stretching process in the existing stretchable conductive fiber, and particularly has the defects of complicated preparation process, high cost, large reduction of the conductivity of the stretched fiber and no application defects of frost resistance and the like of the composite material of the conductive polymer and the flexible polymer. The present invention is based on the fact that it is believed that the conductive polymers, when used in the preparation of stretchable conductive materials, have a problem of dissolution due to their own large conjugated structure and long molecular chains, making them difficult to process. Further, in order to make it easy to process and have stretchability, a flexible polymer chain is introduced to prepare a gel, and a fibrous material is obtained by spinning or die forming, but there is still a problem that the stretchability is low and the strength is low.
The invention creatively designs a polyacrylate fiber material which is formed by crosslinking without any crosslinking agent, is not crosslinked chemically, and is obtained by only physically crosslinking polyacrylate. Based on the hydrophobic layer, the core-sheath composite conductive hydrogel fiber with the core-shell structure and the hydrophobic layer on the surface is obtained. The composite conductive hydrogel fiber designed by the invention has excellent elasticity which can be stretched to ten times of the initial length, has good conductivity, and still has elasticity and conductivity at low temperature; the used materials are chemical raw materials for large-scale production, and are cheap and easy to obtain. The preparation method is simple, the raw materials are heated and dissolved in water and an organic solvent, and then are directly pulled at room temperature to obtain the fiber, and then the hydrophobic layer is covered on the surface of the fiber by a simple soaking method, so that the preparation method is suitable for large-scale industrial production and is beneficial to industrial popularization and application.
The composite fiber and the preparation method thereof effectively solve the problems that the existing conductive fiber has low stretchability and is reduced along with the conductivity during stretching, overcome the defect that the conductive fiber is difficult to maintain elasticity and conductivity at low temperature, and simultaneously have no application problems of complex preparation method, complex steps, high cost, difficult large-scale preparation and the like.
The experimental result shows that the stretchable composite conductive hydrogel fiber prepared by the invention can be stretched to about ten times of the self-prepared composite conductive hydrogel fiber, has a waterproof function, good strength and conductivity, and extremely high damping capacity (71 +/-8%), exceeds the reported data of other existing fiber materials, and is higher than natural spider silk and artificially synthesized viscose fiber.
Drawings
FIG. 1 is a cross-sectional view of a PAAS fiber gel prepared in example 1 of the present invention after water removal;
FIG. 2 is a cross-sectional view of PMA-PAAS fibers prepared in example 1 of the present invention after water removal;
FIG. 3 is a graph showing the tensile profiles at 10, 100 and 1000mm/min for PMA-PAAS fibers prepared in example 1 of the present invention;
FIG. 4 is a graph of the damping capacity of PMA-PAAS fibers prepared in example 1 of the present invention after they have been drawn to 500%;
FIG. 5 is a graph of the damping capacity of PMA-PAAS fibers prepared in example 1 of the present invention after being drawn to 300%;
FIG. 6 is a photograph of a woven web of PASS fibers and PMA-PAAS fibers made in accordance with example 2 of the present invention tested under water drops;
FIG. 7 is a photograph of a strength test of PMA-PAAS fibers prepared in example 2 of the present invention in imitation of a woven spider web;
FIG. 8 is a graph showing the change in electrical resistance and conductivity at different draw ratios for PMA-PAAS fibers prepared in example 2 of the present invention;
FIG. 9 is a differential thermal scan of PMA-PAAS fibers prepared in example 3 of the present invention;
FIG. 10 is a photograph showing the mechanical properties of PMA-PAAS fibers prepared in example 3 of the present invention at-35 ℃;
FIG. 11 shows the conductivity of PMA-PAAS prepared in example 3 of the present invention at various temperatures.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs analytical purity or purity which is conventional in the field of membrane materials.
The invention provides a fiber material which is polyacrylate fiber.
The polyacrylate salt is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to the actual application, raw material conditions and product requirements, and the polyacrylate salt preferably includes alkali metal salts of polyacrylic acid, specifically may include one or more of sodium polyacrylate, potassium polyacrylate and lithium polyacrylate, more preferably sodium polyacrylate, potassium polyacrylate or lithium polyacrylate, and most preferably sodium polyacrylate.
The definition of the polyacrylate fiber is not particularly limited, and unlike the polyacrylate fiber known to those skilled in the art, the polyacrylate fiber of the present invention is chemically crosslinked with no crosslinking agent, and the polyacrylate fiber of the present invention is physically crosslinked with polyacrylate itself, and the structure of the polyacrylate fiber does not contain a crosslinking agent structure or segment, does not contain a structure or segment changed by chemical crosslinking, and does not contain other grafted structures or segments.
The molecular weight of the polyacrylate fiber is not particularly limited in the present invention, and may be the conventional molecular weight of polyacrylate known to those skilled in the art, and those skilled in the art can select and adjust the molecular weight according to the actual application, raw material condition and product requirement, and the weight average molecular weight of the polyacrylate of the present invention is preferably not less than 100 ten thousand Da, more preferably not less than 1000 ten thousand Da, and more preferably not less than 3000 ten thousand Da.
The invention has no special limitation on other parameters of the polyacrylate fiber, and the conventional parameters of the fiber known by the technicians in the field can be used, and the technicians in the field can select and adjust the parameters according to the actual application situation, the raw material situation and the product requirement, and the diameter of the fiber material in the invention is 10-1 mm, more preferably 50-500 μm, more preferably 100-400 μm, and more preferably 200-300 μm.
The invention provides a fiber gel, which comprises the fiber material and a solution absorbed in the fiber material in any one of the technical schemes; the mass fraction of the solution is 3-8%.
The selection, combination and preferred range of the fiber materials in the fiber gel in the invention can preferably correspond to the selection, combination and preferred range of the fiber materials in the invention, and are not described in detail herein.
The mass fraction of the solution of the present invention is not particularly limited, and those skilled in the art can select and adjust the solution according to the actual application situation, the raw material situation and the product requirement, and in order to further improve the performance of the final composite fiber and ensure the stability of the fiber material, the mass fraction of the solution of the present invention is preferably 3% to 8%, more preferably 4% to 7%, and more preferably 5% to 6%.
The fiber gel of the present invention is not particularly limited, and may be defined by the fiber gel known to those skilled in the art, and those skilled in the art can select and adjust the fiber gel according to the actual application, raw material condition and product requirement, and the fiber gel of the present invention includes polyacrylate fiber and solution absorbed in the polyacrylate fiber. The solution is not particularly limited in the present invention, and may be a conventional solution in fiber gel, which is well known to those skilled in the art, and may be hydrogel or other gel, and those skilled in the art can select and adjust the solution according to the actual application, raw material condition and product requirement, and the solution of the present invention preferably includes one or more of water, saline solution and small molecule organic solvent, more preferably water, saline solution or small molecule organic solvent, and more preferably a mixed solution of water and dimethyl sulfoxide.
The invention provides a composite fiber, which comprises a fiber core and a hydrophobic layer compounded on the surface of the fiber core;
the fiber core is the fiber material or the fiber gel according to any one of the above technical aspects.
The selection, combination and preferred range of the fiber material or the fiber gel in the composite fiber can correspond to the selection, combination and preferred range of the fiber material or the fiber gel, and are not described in detail herein.
The structure of the composite fiber is not particularly limited in the present invention, and may be the structure of such composite fiber known to those skilled in the art, and those skilled in the art can select and adjust the structure according to the actual application situation, the raw material situation and the product requirement, and the composite fiber of the present invention is preferably a sheath-core composite fiber, specifically, a fiber material or a fiber gel surface is covered with a hydrophobic layer, and viewed from the cross section, the composite fiber has a core-shell structure.
The structural parameters of the composite fiber are not particularly limited, and the structural parameters of the composite fiber known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual application, raw material conditions and product requirements, and the diameter of the fiber core is preferably 10 μm to 1mm, more preferably 50 μm to 500 μm, more preferably 100 μm to 400 μm, and more preferably 200 μm to 300 μm. The thickness of the hydrophobic layer is preferably 1-20 μm, more preferably 3-18 μm, more preferably 5-15 μm, and more preferably 8-12 μm.
The material of the hydrophobic layer is not particularly limited in the present invention, and the material of the hydrophobic layer of the composite fiber, which is well known to those skilled in the art, may be selected and adjusted by those skilled in the art according to the actual application, the raw material condition and the product requirement, and the hydrophobic layer of the present invention is preferably a hydrophobic layer of polyacrylate compound.
The polyacrylate compound preferably comprises one or more of polymethyl acrylate, polyethyl acrylate and polybutyl acrylate, or a copolymer of multiple of polymethyl acrylate, polyethyl acrylate and polybutyl acrylate, namely one or more of polymethyl acrylate, polyethyl acrylate and polybutyl acrylate, or a copolymer of two or three of polymethyl acrylate, polyethyl acrylate and polybutyl acrylate, and specifically can be a copolymer of multiple of polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polymethyl acrylate, polyethyl acrylate and polybutyl acrylate.
The invention also provides a preparation method of the composite fiber, which comprises the following steps:
1) mixing and dissolving polyacrylate in water and an organic solvent to obtain a mixed solution;
the organic solvent accounts for 10 to 40 percent of the mass fraction of the water and the organic solvent;
2) cooling the mixed solution obtained in the step, drawing or spinning, and standing to obtain polyacrylate fiber gel;
3) and (3) soaking the polyacrylate fiber gel in a polyacrylate compound solution to obtain the composite fiber.
In the preparation method of the composite fiber, the selection, combination and preferable range of the raw materials, preferably the selection, combination and preferable range corresponding to those in the composite fiber, the fiber material or the fiber gel, can correspond to those in the composite fiber, the fiber material or the fiber gel, and are not described in detail herein.
The invention firstly mixes and dissolves polyacrylate in water and organic solvent to obtain mixed solution.
The present invention dissolves a polyacrylate in a mixture of water and an organic solvent, particularly at a specific concentration. The organic solvent accounts for preferably 10-40% of the water and the organic solvent by mass, more preferably 15-35% of the water and the organic solvent by mass, more preferably 20-30% of the water and the organic solvent by mass, and particularly 15-22% of the water and the organic solvent by mass.
The adding amount of the water and the organic solvent is not particularly limited in the present invention, and may be a conventional adding amount well known to those skilled in the art, and those skilled in the art may select and adjust the adding amount according to the actual application situation, the raw material situation and the product requirement, and the mass fraction of the polyacrylate in the mixed solution of the present invention is preferably 3% to 6%, more preferably 3.5% to 5.5%, and more preferably 4% to 5%.
The selection of the organic solvent is not particularly limited in the present invention, and may be a conventional solvent well known to those skilled in the art, and those skilled in the art can select and adjust the solvent according to the actual application, raw material condition and product requirement, and the organic solvent of the present invention is preferably an organic solvent miscible with water, more preferably includes one or more of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone, and more preferably is dimethyl sulfoxide, N-dimethylformamide or N-methylpyrrolidone.
The temperature for mixing and dissolving is not particularly limited, and can be selected and adjusted by a person skilled in the art according to actual production conditions, raw material conditions and product requirements, and is preferably 30-100 ℃, more preferably 40-90 ℃, more preferably 50-80 ℃, and more preferably 60-70 ℃. The other conditions for mixing and dissolving are not particularly limited in the present invention, and those skilled in the art can select and adjust the conditions according to the actual production conditions, raw material conditions and product requirements.
In order to further improve the performance of the product and the controllability of the preparation process, the mixed solution preferably further comprises alkali metal salt and/or ammonium salt, i.e. the alkali metal salt and/or ammonium salt is preferably further added during the mixing and dissolving process, and more preferably the alkali metal salt or ammonium salt is further added during the gelling of the fiber and the diameter adjustment of the obtained fiber. The alkali metal salt or ammonium salt is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and is preferably one or more of alkali metal sulfate, chloride, phosphate, monohydrogen phosphate and nitrate, and more preferably alkali metal sulfate, chloride, phosphate, monohydrogen phosphate or nitrate. The ammonium salt of the present invention preferably comprises one or more of a sulfate, chloride, phosphate, monohydrogen phosphate and nitrate salt of ammonium, more preferably a sulfate, chloride, phosphate, monohydrogen phosphate or nitrate salt of ammonium.
The addition amount of the alkali metal salt and/or ammonium salt is not particularly limited in the present invention, and may be a conventional addition amount well known to those skilled in the art, and those skilled in the art may select and adjust the addition amount according to actual production conditions, raw material conditions, and product requirements, and the concentration of the alkali metal salt and/or ammonium salt in the mixed solution of the present invention is preferably 25 to 200mM (mmol/L), more preferably 25 to 100mM, more preferably 30 to 90mM, and more preferably 50 to 70 mM.
The mixed solution obtained in the step is cooled, and then is subjected to wire drawing or spinning, and then is stood to obtain polyacrylate fiber gel.
The specific process and parameters of the cooling are not particularly limited, and the conventional cooling process and parameters known by the skilled in the art can be used, and the skilled in the art can select and adjust the process according to the actual production condition, the raw material condition and the product requirement, and the cooling is preferably carried out to room temperature, and can be 10-40 ℃, or 15-35 ℃, or 20-30 ℃.
The drawing or spinning mode of the invention is not particularly limited, and the drawing or spinning mode can be a conventional fiber drawing mode known to those skilled in the art, and the person skilled in the art can select and adjust the drawing or spinning mode according to the actual application situation, the raw material situation and the product requirement, the drawing or spinning mode of the invention can be manual drawing or mechanical drawing, and the spinning mode can also be solution spinning.
The specific parameters of the standing are not particularly limited, and the conventional standing parameters well known to those skilled in the art can be used, and the persons skilled in the art can select and adjust the parameters according to the actual production situation, the raw material situation and the product requirement, and the standing time in the invention is preferably 0.5-5 minutes, more preferably 1-4.5 minutes, more preferably 1.5-4 minutes, and more preferably 2-3.5 minutes.
The invention finally soaks polyacrylate fiber gel in polyacrylate compound solution to obtain the composite fiber.
The specific parameters of the immersion are not particularly limited, and a conventional immersion process known by a person skilled in the art can be used, the person skilled in the art can select and adjust the immersion time according to the actual production situation, the raw material situation and the product requirement, and the immersion time is preferably 2-10 seconds, more preferably 3-9 seconds, more preferably 4-8 seconds, and more preferably 5-7 seconds. In order to further ensure the complete coating and the effective thickness of the hydrophobic layer, the number of immersion times can be one or more, more preferably multiple times, and specifically can be 2-5 times or 3-4 times.
The solvent of the polyacrylate compound solution of the present invention is not particularly limited, and may be selected and adjusted by those skilled in the art according to the practical application, raw material conditions and product requirements, and the solvent of the polyacrylate compound solution of the present invention is preferably a volatile organic solvent, more preferably one or more of ethyl acetate, chloroform, dichloromethane and acetone, and more preferably ethyl acetate, chloroform, dichloromethane or acetone.
The concentration of the polyacrylate compound solution in the present invention is not particularly limited, and may be a conventional concentration of such a solution known to those skilled in the art, and those skilled in the art may select and adjust the concentration according to the actual application, raw material conditions and product requirements, and the mass fraction of the polyacrylate compound in the polyacrylate compound solution in the present invention is preferably 3% to 10%, more preferably 4% to 9%, more preferably 5% to 8%, and more preferably 6% to 7%.
In order to further ensure the performance of the final product, complete and refine the process flow, the preparation method can specifically comprise the following steps:
(1) the polyacrylate salt is dissolved in water and an organic solvent, and is dissolved in a mixed solvent of the water and the organic solvent by stirring and heating at 80 ℃, wherein the ratio of the water to the organic solvent is very important and needs to be in a proper range. Sodium chloride with the concentration of 25-200 mM can be added into the solvent, the gelation of the fiber can be accelerated by increasing the NaCl concentration, and the diameter of the obtained fiber can be adjusted.
(2) The resulting mixed solution was cooled to room temperature, and then the polyacrylate fiber was drawn out directly and allowed to stand in the air to gel the fiber. (if dried, a polyacrylate fiber can be obtained)
(3) And dissolving the polyacrylate compound by using a solvent to obtain a polyacrylate compound solution with the mass fraction of 3-10%.
(4) Soaking the fiber gel obtained in the step (2) in a polyacrylate compound solution for a few seconds, taking out, volatilizing the solvent, and repeating the process for two to three times to obtain the stretchable composite conductive fiber.
More specifically, the method can be as follows:
(1) sodium Polyacrylate (PAAS) is dissolved in water and dimethyl sulfoxide (DMSO), and the mass fraction of the PAAS in the solution can be 3-6%. The PAAS is dissolved in a mixed solvent of water and DMSO at 80 ℃ by heating with stirring, and the ratio of water to DMSO is very important, and a suitable range is 10% to 40% by weight of DMSO, and most preferably 20% by weight of DMSO is used. Sodium chloride with the concentration of 25-200 mM can be added into the solvent, the gelation of the fiber can be accelerated by increasing the NaCl concentration, and the diameter of the obtained fiber can be adjusted, wherein the NaCl concentration is preferably 25-100 mM.
(2) And cooling the obtained PAAS solution to room temperature, directly pulling out the PAAS fiber, standing in the air for 1-2 minutes to gelatinize the fiber, and thus obtaining the PAAS fiber gel.
(3) Dissolving polymethyl acrylate (PMA) with ethyl acetate to obtain a PMA solution with the mass fraction of 3-10%.
(4) Soaking the PAAS fiber gel obtained in the step (2) in a PMA solution for a few seconds, taking out, volatilizing the solvent, and repeating the process for two to three times to obtain the PMA-PAAS stretchable composite conductive fiber.
The steps of the invention provide a fiber material, a fiber gel, a stretchable conductive composite fiber with super elasticity and frost resistance and a preparation method thereof. The invention designs a polyacrylate fiber material which is formed by crosslinking without any crosslinking agent, is not crosslinked chemically, and is obtained by only physically crosslinking polyacrylate. Based on the hydrophobic layer, the core-sheath composite conductive hydrogel fiber with the core-shell structure and the hydrophobic layer on the surface is obtained. The composite conductive hydrogel fiber designed by the invention has excellent elasticity which can be stretched to ten times of the initial length, has good conductivity, and still has elasticity and conductivity at low temperature; the used materials are chemical raw materials for large-scale production, and are cheap and easy to obtain. The preparation method is simple, the raw materials are heated and dissolved in water and an organic solvent, and then are directly pulled at room temperature to obtain the fiber, and then the hydrophobic layer is covered on the surface of the fiber by a simple soaking method, so that the preparation method is suitable for large-scale industrial production and is beneficial to industrial popularization and application.
Experimental results show that the stretchable composite conductive hydrogel fiber prepared by the invention has the advantages of 500-1500% of stretching rate, 3-6 MPa of strength, 0.1-2.5S/m of conductivity and waterproof function. And the fiber has extremely high damping capacity (71 +/-8 percent), exceeds the reported data of other existing fiber materials, and is higher than natural spider silks and synthetic viscose fibers.
For further illustration of the present invention, a fiber material, a fiber gel, a composite fiber and a method for preparing the same according to the present invention will be described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
(1) 200mg of PAAS particulate solid was dissolved in 4.8g of solvent containing 3.84g of water and 0.96g of DMSO and heated at 80 ℃ for 1 hour to give a homogeneous and transparent solution of 4 wt% PAAS solution.
(2) And cooling the obtained PAAS solution to room temperature, directly drawing out the PAAS fiber, and standing in the air for 1-2 minutes to gelatinize the fiber.
(3) 0.05g of PMA was dissolved in 1g of ethyl acetate to obtain a PMA solution having a mass fraction of 5%.
(4) Soaking the obtained PAAS fiber in PMA solution for several seconds, taking out, volatilizing the solvent, and repeating the process for two to three times to obtain the PMA-PAAS fiber.
The stretchable conductive composite fiber having superelasticity and freezing resistance prepared in example 1 of the present invention was characterized.
After freeze-drying the PAAS fiber gel and PMA-PAAS fiber distribution, the water was removed and the microscopic morphology was observed with a Scanning Electron Microscope (SEM).
Referring to fig. 1, fig. 1 is a cross-sectional view of a PAAS fiber gel prepared in example 1 of the present invention after water removal.
Referring to fig. 2, fig. 2 is a cross-sectional view of PMA-PAAS fibers prepared in example 1 of the present invention after water removal.
As can be seen from FIGS. 1 and 2, the cross-sectional views of the PAAS fiber show that the structure of the PAAS fiber is uniform and dense, and the PMA hydrophobic layer is well covered on the surface of the PAAS fiber to form a dense protective layer.
The stretchable conductive composite fiber having superelasticity and freezing resistance prepared in example 1 of the present invention was tested. Placing the sample on a universal testing machine, and testing mechanical properties including strength, elongation at break and conductivity change measurement along with the change of the elongation; and tested for water resistance in a non-stretched state as well as in a stretched state, frost resistance at low temperatures and conductive properties at different temperatures.
A section of the PMA-PAAS fiber prepared above, which had a diameter of about 100m and a length of 1cm, was taken, and its mechanical properties were measured by a tensile tester.
Referring to FIG. 3, FIG. 3 is a graph showing the tensile profiles at 10, 100 and 1000mm/min for PMA-PAAS fibers prepared in example 1 of the present invention.
As can be seen from FIG. 3, the PMA-PAAS fiber can be stretched to 1200% of its original length before breaking at a stretching rate of 100mm/min, can withstand a maximum stress of up to about 6MPa, and is a super-elastic material with good strength and toughness.
Referring to fig. 4, fig. 4 is a graph showing the damping capacity of the PMA-PAAS fiber prepared in example 1 of the present invention after stretching to 500%.
As can be seen from FIG. 4, the PMA-PAAS fiber prepared by the present invention has excellent damping capacity (71 + -8%), higher than that of natural spider silk and synthetic viscose fiber.
Referring to fig. 5, fig. 5 is a graph showing the damping capacity of the PMA-PAAS fiber prepared in example 1 of the present invention after being drawn to 300%.
As shown in FIG. 5, the PMA-PAAS fiber prepared by the present invention can recover rapidly after being stretched to 3 times of the original length, and has very good elasticity.
Example 2
(1) The particulate solid, in which 250mg of PAAS was dissolved, was dissolved in 4.8g of a solvent comprising 4.0g of water and 0.8g of DMSO and heated at 80 ℃ for 1 hour to give a homogeneous and transparent solution, 5 wt% PAAS solution.
(2) And cooling the obtained PAAS solution to room temperature, directly drawing out the PAAS fiber, and standing in the air for 1-2 minutes to gelatinize the fiber.
(3) 0.07g of PMA was dissolved in 1g of ethyl acetate to obtain a PMA solution having a mass fraction of 7%.
(4) The obtained PAAS fiber is soaked in PMA solution for a few seconds, taken out, the solvent is volatilized, and the process is repeated two to three times.
The application performance of the stretchable conductive composite fiber with super elasticity and frost resistance prepared in example 2 of the invention is tested.
The water resistance, frost resistance and conductivity of the PMA-PAAS fiber prepared by the invention are detected.
Referring to fig. 6, fig. 6 is a photograph of a woven web of PASS fibers and PMA-PAAS fibers made in example 2 of the present invention tested under water drop. Wherein i) is PAAS fiber and ii) is PMA-PAAS fiber.
As can be seen from fig. 6, the PAAS fibers were not water repellent, while the PMA-PAAS fibers were good in water repellency, indicating that the fibers had good water repellency after coating with the PMA hydrophobic layer.
Referring to FIG. 7, FIG. 7 is a photograph of a PMA-PAAS fiber produced in example 2 of the present invention, which simulates a woven spider web, and is subjected to a strength test.
As can be seen from FIG. 7, after the fibers are woven into a web, the fiber web can bear a weight about 900 times of its weight without being damaged due to the better strength of the fibers themselves.
Referring to fig. 8, fig. 8 is a graph showing the change in electrical resistance and conductivity at different draw ratios of the PMA-PAAS fibers prepared in example 2 of the present invention.
As can be seen from fig. 8, although the resistance was increased during the drawing, since the diameter and length of the fiber were changed by the drawing, the measured conductivity was stable after increasing, and the relative conductivity was changed to 3.2 times of the initial conductivity at a drawing rate of 300% to reach a maximum value.
Example 3
(1) 5.6mg NaCl was dissolved in 3.84g water to give a 25mM NaCl solution, which was mixed with 0.8g DMSO, and 200mg PAAS granular solid was added and heated at 80 ℃ for 1 hour to give a uniform and transparent solution as a 4 wt% PAAS solution.
(2) And cooling the obtained PAAS solution to room temperature, directly drawing out the PAAS fiber, and standing in the air for 1-2 minutes to gelatinize the fiber.
(3) 0.03g of PMA was dissolved in 1g of ethyl acetate to obtain a PMA solution having a mass fraction of 3%.
(4) The obtained PAAS fiber is soaked in PMA solution for a few seconds, taken out, the solvent is volatilized, and the process is repeated two to three times.
The application performance of the stretchable conductive composite fiber with super elasticity and frost resistance prepared in the embodiment 3 of the invention is tested.
The water resistance, frost resistance and conductivity of the PMA-PAAS fiber prepared by the invention are detected.
Referring to FIG. 9, FIG. 9 is a differential thermal scan of PMA-PAAS fibers prepared according to example 3 of the present invention.
As can be seen from FIG. 9, the PMA-PAAS fiber prepared by the invention has good frost resistance, the phase transition point of the PMA-PAAS fiber appears near-40 ℃, the moisture in the PMA-PAAS fiber freezes at-40 ℃, and the PMA-PAAS fiber maintains good elasticity at the temperature above-40 ℃.
Referring to FIG. 10, FIG. 10 is a photograph showing mechanical properties at-35 ℃ of PMA-PAAS fibers prepared in example 3 of the present invention.
As can be visually shown in FIG. 10, the PMA-PAAS fiber prepared by the invention has the anti-freezing property, maintains the elasticity of the fiber at the low temperature of-35 ℃, is recoverable, and has good elasticity, rebound resilience and bearing capacity.
Referring to FIG. 11, FIG. 11 is a graph showing the electrical conductivity of PMA-PAAS prepared in example 3 of the present invention at various temperatures.
As shown in FIG. 11, the PMA-PAAS fiber prepared by the present invention can maintain the conductive property at a low temperature of-35 ℃ as the conductive fiber.
While the present invention has been described in detail with respect to a fiber material, a fiber gel, a stretchable conductive composite fiber having superelasticity and freezing resistance, and a method for preparing the same, the principles and embodiments of the present invention are described herein using specific examples, which are provided only to help understand the method of the present invention and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any devices or systems, and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (8)
1. A composite fiber is characterized by comprising a fiber core and a hydrophobic layer compounded on the surface of the fiber core;
the fiber core is a fiber material and/or a fiber material gel;
the fiber material is polyacrylate fiber;
the polyacrylate comprises one or more of sodium polyacrylate, potassium polyacrylate and lithium polyacrylate;
the polyacrylate fiber is a fiber physically crosslinked by polyacrylate itself;
the fiber material gel comprises a fiber material and a solution absorbed in the fiber material;
the solution comprises one or more of water, a salt-containing aqueous solution and a small molecule organic solvent;
the hydrophobic layer is a polyacrylate compound hydrophobic layer;
the composite fiber is obtained by soaking a fiber core in a polyacrylate compound solution.
2. The composite fiber according to claim 1, wherein the fiber material has a diameter of 10 μm to 1 mm;
the weight average molecular weight of the polyacrylate is greater than or equal to 100 ten thousand Da.
3. The composite fiber according to claim 1, wherein the mass fraction of the solution is 3% to 8%.
4. The composite fiber according to claim 1, wherein the composite fiber is a sheath-core composite fiber;
the diameter of the fiber core is 10 mu m-1 mm.
5. The composite fiber of claim 1, wherein the polyacrylate compound comprises one or more of polymethyl acrylate, polyethyl acrylate, and polybutyl acrylate, or a copolymer of a plurality of polymethyl acrylate, polyethyl acrylate, and polybutyl acrylate;
the thickness of the hydrophobic layer is 1-20 mu m.
6. A method for preparing the composite fiber according to any one of claims 1 to 5, comprising the steps of:
1) mixing and dissolving polyacrylate in water and an organic solvent to obtain a mixed solution;
the mass fraction of the organic solvent in the water and the organic solvent is 10-40%;
2) cooling the mixed solution obtained in the step, drawing or spinning, and standing to obtain polyacrylate fiber gel;
3) and (3) soaking the polyacrylate fiber gel in a polyacrylate compound solution to obtain the composite fiber.
7. The preparation method according to claim 6, wherein the mass fraction of the polyacrylate in the mixed solution is 3% to 6%;
the mixed solution also comprises alkali metal salt and/or ammonium salt;
the temperature for mixing and dissolving is 30-100 ℃;
the organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone;
the standing time is 0.5-5 minutes;
the immersion time is 2-10 seconds.
8. The method according to claim 7, wherein the alkali metal salt comprises one or more of a sulfate, a chloride, a phosphate, a monohydrogen phosphate, and a nitrate of an alkali metal;
the ammonium salt comprises one or more of sulfate, chloride, phosphate, monohydrogen phosphate and nitrate of ammonium;
in the mixed solution, the concentration of the alkali metal salt and/or the ammonium salt is 25-200 mM;
the mass fraction of the polyacrylate compound in the polyacrylate compound solution is 3-10%;
the solvent in the polyacrylate compound solution comprises one or more of ethyl acetate, chloroform, dichloromethane and acetone;
the soaking times are one time or more.
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| CN113265721B (en) * | 2021-04-19 | 2022-02-08 | 浙江大学 | Fibrous dielectric elastomer driver and preparation method thereof |
| CN113089128B (en) * | 2021-04-20 | 2023-06-13 | 合肥学院 | Preparation method of polyacrylic acid/cellulose hydrogel fiber, prepared hydrogel fiber and application thereof |
| CN115595683A (en) * | 2021-07-08 | 2023-01-13 | 香港理工大学（Hk） | Composite conductive fiber and preparation method and application thereof |
| CN113818095B (en) * | 2021-08-27 | 2022-11-04 | 东华大学 | Wet spinning method capable of preparing degradable gelatin hydrogel fiber in large scale based on Hofmeister effect |
| CN114561718B (en) * | 2022-02-28 | 2023-06-16 | 中国科学技术大学 | Composite fiber material, preparation method thereof and high-stretchability fibrous supercapacitor |
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