WO2014069853A1 - Aramid fiber product with excellent conductivity and method of manufacturing the same - Google Patents

Aramid fiber product with excellent conductivity and method of manufacturing the same Download PDF

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Publication number
WO2014069853A1
WO2014069853A1 PCT/KR2013/009624 KR2013009624W WO2014069853A1 WO 2014069853 A1 WO2014069853 A1 WO 2014069853A1 KR 2013009624 W KR2013009624 W KR 2013009624W WO 2014069853 A1 WO2014069853 A1 WO 2014069853A1
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aramid fiber
adhesive
fiber material
graphene sheet
aramid
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PCT/KR2013/009624
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French (fr)
Inventor
Jae Young Lee
Sang Ouk Kim
Je Moon Yun
Kyung Eun Lee
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Kolon Industries, Inc.
Korea Advenced Institute Of Science And Technology
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Publication of WO2014069853A1 publication Critical patent/WO2014069853A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/1845—Aromatic mono- or polycarboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides

Definitions

  • the present invention relates to a conductive aramid fiber product and a method of manufacturing the same, and more particularly, to a conductive aramid fiber material provided by adhering a graphene sheet to a surface of an aramid fiber material using a biological adhesive, without a decrease in mechanical properties such as strength, as well as a method of manufacturing the same.
  • an aromatic polyamide fiber commonly called 'aramid fiber' is manufactured by preparing an aromatic polyamide polymer through polymerization of aromatic diamine and aromatic diacid chloride in a polymerization solvent, dissolving the aromatic polyamide polymer in a concentrated sulfuric acid solvent to form a spin dope, spinning the spin dope through a spinneret, and coagulating a spun product to form filaments.
  • Such an aramid fiber includes a para-aramid fiber having a structure of benzene rings straightly linked together through amide groups (CONH), and a meta-aramid fiber without the structure described above.
  • the para-aramid fiber has excellent properties such as a high strength, high elasticity, low shrinkage, etc.
  • the para-aramid fiber has such a high strength that it is possible to lift up an automobile with a weight of about 2 tons using a very fine thread having a thickness of about 5 mm, therefore, has been employed in bullet-proofing applications and for a variety of other uses in high-technology industries in relation to space and aeronautics.
  • Korean Patent Laid-Open Publication No. 10-2012-0028998 discloses a method of applying and adhering a conductive polymer solution to a surface of an aramid fiber material.
  • a conventional method has caused a decrease in flexibility of a conductive polymer, which in turn, leads to a shorting of the conductive polymer coating due to bending of the aramid fiber material, thus entailing reduction of electrical conductivity and mechanical properties such as strength.
  • an object of the present invention is to provide a conductive aramid fiber material having excellent electrical conductivity and mechanical properties such as strength since a conductive material adhered to the aramid fiber material does not undergo shorting caused by bending the aramid fiber material, as well as a method of manufacturing the same.
  • the present invention may enable strong adhesion of a graphene sheet having excellent flexibility to the aramid fiber material using a biological adhesive with excellent amphoteric adhesion, thereby effectively preventing shorting of the adhered graphene sheet even during bending of the aramid fiber material.
  • the present invention does not involve shorting caused by bending an aramid fiber material thanks to flexibility of the graphene sheet adhered to the aramid fiber material, thereby maintaining mechanical properties such as strength while remarkably improving an electrical conductivity thereof.
  • the graphene sheet having flexibility is securely adhered to the surface of the aramid fiber material, thereby more effectively preventing shorting due to bending of the aramid fiber material.
  • a method of manufacturing a conductive aramid fiber material according to the present invention includes adhering a graphene sheet to a surface of an aramid fiber material using a biological adhesive (also referred to as a 'bio-adhesive').
  • a biological adhesive also referred to as a 'bio-adhesive'
  • the graphene sheet refers to a sheet made of a material having a two-dimensional planar structure wherein carbon atoms are linked in a hexagonal form like a honeycomb, and may include a graphene oxide sheet as well as a pure graphene sheet.
  • a method of coating the surface of the aramid fiber material with an adhesive solution containing a bio-adhesive, a graphene sheet and a solvent may be executed.
  • a method of coating the surface of the aramid fiber material with a bio-adhesive, and then, with a solution containing a graphene sheet may be executed.
  • the graphene sheet used herein may include not only a pure graphene sheet but also a graphene oxide sheet.
  • the graphene sheet has excellent flexibility and is homogeneously dispersed in a solvent and adhesive solution.
  • the aramid fiber material may include an aramid fiber, a woven fabric of aramid fibers, a knitted fabric of aramid fibers, or the like.
  • a content of the graphene sheet in the adhesive solution preferably ranges from 0.01 to 10 parts by weight ('wt. part') relative to 100 wt. parts of a solvent contained in the adhesive solution.
  • a content of the bio-adhesive in the adhesive solution preferably ranges from 0.01 to 10 wt. parts relative to 100 wt. parts of the solvent. When the content of the bio-adhesive is less than 0.01 wt. part, adhesiveness is decreased. When the content of the bio-adhesive exceeds 10 wt. parts, the electrical conductivity may be deteriorated.
  • the bio-adhesive has such a chemical structure that two catechol groups (-OH) and one amine group (NH 2 ) are introduced into benzene, and may include an adhesive component extracted from animal tissues, an adhesive component extracted from plants, or any synthetic adhesive component thereof.
  • bio-adhesive may include dopamine, tyrosine, dihydroxyphenylalanine, norepinephrine, epinephrine, normetanephrine, 3,4-dihydroxyphenylacetic acid, or the like.
  • the bio-adhesive may have amphoteric adhesion to express favorable adhesion to both the aramid fiber material and the graphene sheet
  • dopamine is represented by the following formula and has favorable adhesion to both the aramid fiber material and the graphene sheet by ⁇ - ⁇ interaction of benzene, and hydrogen bond and coordinate bond between oxygen and nitrogen.
  • the conductive aramid fiber material produced according to the manufacturing method of the present invention as described above may have an excellent electrical conductivity of 10 2 to 10 7 ⁇ /cm 2 , and not cause shorting due to bending of the conductive aramid fiber material, thus not leading to a decrease in mechanical properties such as strength.
  • An organic solvent used herein may include amide organic solvents, urea solvents, or a mixture thereof.
  • Particular examples of the organic solvent may include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), hexamethyl phosphoamide (HMPA), N,N,N′,N′-tetramethylurea (TMU), N,N-dimethylformamide (DMF), or a mixture thereof.
  • An inorganic salt may be added to increase a degree of polymerization of the aramid polymer and may include, for example, halogenated alkali-metal salts or halogenated alkali-earth metal salts such as CaCl 2 , LiCl, NaCl, KCl, LiBr and KBr, or the like.
  • the inorganic salts may be added alone or in combination of two or more thereof.
  • a degree of polymerization of the aramid polymer may also increase.
  • excess of inorganic salt is added, the inorganic salt may partially remain without being dissolved. Accordingly, it is preferable that a content of the inorganic salt is within a range of 10 wt.% or less to a total weight of the polymerization solvent.
  • aromatic diamine may include, para-phenylenediamine, 4,4′-diaminobiphenyl, 2,6-naphthalenediamine, 1,5-naphthalenediamine or 4,4′-diaminobenzanilide, however, not be particularly limited thereto.
  • Polymerization of aromatic diamine and aromatic diacid halide generates heat when conducted at a high rate. If a polymerization rate is high, a difference in degrees of polymerization between finally formed polymers may be enlarged. More particularly, since the polymerization does not simultaneously progress throughout the mixed solution, a polymer under polymerization earlier may rapidly react during the polymerization to form a long molecular chain while a polymer under polymerization later cannot help forming a shorter molecular chain than the polymer under polymerization earlier. If the polymerization rate is higher, such a difference in the length of chain may be more considerably enlarged. As such, when such a difference in degrees of polymerization between finally formed polymers is enlarged, a deviation in physical properties may also increase to hence make it difficult to achieve desired characteristics.
  • aromatic diacid halide may include terephthaloyl dichloride, 4,4′-benzoyl dichloride, 2,6-naphthalene dicarboxylic acid dichloride, 1,5-naphthalene dicarboxylic acid dichloride, or the like, however, not be particularly limited thereto.
  • the aromatic diacid halide reacts with the aromatic diamine in a molar ratio of 1:1, these compounds, that is, the aromatic diamine and aromatic diacid halide may be added with the same molar ratio.
  • an amount of each of the aromatic diamine and diacid halide may be adjusted such that a concentration of a final polymer in the whole polymerization solution reaches a range of 5 to 20 wt.%.
  • a concentration of a final polymer in the whole polymerization solution reaches a range of 5 to 20 wt.%.
  • the aromatic diamine and diacid halide are added to make the concentration of the final polymer to be less than 5 wt.%, a polymerization rate is decreased and the reaction should be executed for a long time, hence reducing economic feasibility.
  • the aromatic diamine and diacid halide are added to make the concentration of the final polymer to exceed 20 wt.%, polymerization is not actively proceeded, hence not improving an inherent viscosity of the polymer.
  • aramid polymer formed by the polymerization may include poly(para-phenylene terephthalamide: PPD-T), poly(4,4′-benzanilide terephthalamide), poly(para-phenylene-4,4′-biphenylene-dicarboxylic acid amide) or poly(para-phenylene-2,6-naphthalene dicarboxylic acid amide).
  • the acid generated during polymerization is preferably neutralized by adding an inorganic alkaline compound or organic alkaline compound during or after the polymerization.
  • an aramid polymer-containing solution does not have good flowability. Therefore, in order to improve the flowability, it is preferable to add water to an aromatic polyamide solution to prepare a slurry, and then execute subsequent processes.
  • the aromatic polyamide solution may be provided with water as well as an alkaline compound and subjected to a neutralization process.
  • the inorganic alkaline compound used herein may be selected from a group consisting of carbonates of alkali-metals and alkali-earth metals, hydrogenates of alkali-earth metals, hydroxides of alkali-earth metals, or oxides of alkali-earth metals, such as NaOH, Li 2 CO 3 , CaCO 3 , LiH, CaH 2 , LiOH, Ca(OH) 2 , Li 2 O or CaO.
  • the aramid polymer is ground, the polymerization solvent is removed, and the remaining product is dehydrated and dried, thus completing preparation of a final aramid polymer.
  • the aramid polymer prepared as described above is added to a sulfuric acid solution and dissolved to form a spin dope.
  • the sulfuric acid solution used herein may be a concentrated sulfuric acid solvent having a concentration of 97 to 100% and, instead of concentrated sulfuric acid, chlorosulfuric acid or fluorosulfuric acid may be used.
  • the spin dope may sequentially pass through an air gap and a coagulation bath, so as to be coagulated.
  • an aramid fiber is prepared in a filament form by drying and winding the coagulated dope.
  • an adhesive solution containing a bio-adhesive such as dopamine extracted from mussels, a graphene sheet and a solvent may be applied and adhered to the surface of the aramid fiber or the surface of a fabric or knitted material made of the aramid fiber, thus producing a conductive aramid fiber material.
  • the conductive aramid fiber material produced according to the present invention may have such a structure that the graphene sheet is adhered to the surface of the aramid fiber material by the bio-adhesive.
  • a content of the graphene sheet adhered to the aramid fiber material by the bio-adhesive ranges from 0.01 to 10 wt.% relative to a total weight of the conductive aramid fiber material.
  • the bio-adhesive used herein has such a chemical structure that two catechol groups (-OH) and one amine group (-NH 2 ) are introduced into benzene.
  • the aramid fiber material may include an aramid fiber, aramid fabric or aramid knitted material.
  • the prepared aramid polymer was added to a sulfuric acid solution having a concentration of 99% and dissolved therein to form a spin dope.
  • the spin dope was passed through an air gap and a coagulation bath in sequential order to be coagulated, followed by drying and winding, thus resulting in an aramid fiber.
  • an aramid fabric was formed.
  • the treated fabric was dried to form a conductive aramid fabric.
  • an adhesive solution including: (i) 10 wt.% of dopamine (a natural adhesive) extracted from mussels; (ii) 5 wt.% of graphene sheet; and (iii) 85 wt.% of organic solvent, the treated fabric was dried to form a conductive aramid fabric.
  • the prepared aramid polymer was added to a sulfuric acid solution having a concentration of 99% and dissolved therein to form a spin dope.
  • the spin dope was passed through an air gap and a coagulation bath in sequential order to be coagulated, followed by drying and winding, thus resulting in an aramid fiber. Subsequently, using the prepared aramid fiber, an aramid fabric was formed.
  • a conductive aramid fabric was formed by applying an adhesive solution including: (i) 10 wt.% of dopamine (a natural adhesive) extracted from mussels; (ii) 7 wt.% of graphene sheet; and (iii) 83 wt.% of organic solvent to the surface of the prepared aramid fabric through knife coating method, then, drying the same.
  • an adhesive solution including: (i) 10 wt.% of dopamine (a natural adhesive) extracted from mussels; (ii) 7 wt.% of graphene sheet; and (iii) 83 wt.% of organic solvent to the surface of the prepared aramid fabric through knife coating method, then, drying the same.
  • the prepared aramid polymer was added to a sulfuric acid solution having a concentration of 99% and dissolved therein to form a spin dope.
  • the spin dope was passed through an air gap and a coagulation bath in sequential order to be coagulated, followed by drying and winding, thus resulting in an aramid fiber.
  • an adhesive solution including 7 wt.% of graphene sheet and 93 wt.% of organic solvent was applied to the surface of the coated aramid fiber through knife coating method, followed by drying the same to prepare a conductive aramid fiber (in a filament form). After this, the prepared conductive aramid fiber was subjected to weaving to form a conductive aramid fabric.
  • the prepared aramid polymer was dissolved in a sulfuric acid solution having a concentration of 99% to form a spin dope.
  • the prepared aramid fabric was dipped in a processing solution including: (i) 30 wt.% of poly(diallyldimethylammonium chloride: Catalog No. 52237-6, manufactured by Aldrich Chemical Company, United States); and (ii) 70 wt.% of desalted water, and dried to form a conductive aramid fabric.
  • a processing solution including: (i) 30 wt.% of poly(diallyldimethylammonium chloride: Catalog No. 52237-6, manufactured by Aldrich Chemical Company, United States); and (ii) 70 wt.% of desalted water, and dried to form a conductive aramid fabric.
  • the strength of the conductive aramid fiber and the electrical conductivity of the aramid fabric were measured by the following methods.
  • the strength of the aramid fiber was obtained by pulling the aramid fiber having a length of 25 cm in an Instron tester (Instron Engineering Corp., Canton, Massachusetts) until the aramid fiber was broken.
  • a tensile velocity was 300 mm/min and a primary load was defined by fiber fineness ⁇ 1/30 g.
  • the conductive aramid fiber material produced according to the present invention may be effectively used in materials for industrial protective clothing and heat-tech garments that require electrostatic-protection effects.

Abstract

A conductive aramid fiber material of the present invention is provided by adhering a graphene sheet to a surface of an aramid fiber material using a biological adhesive. According to one embodiment of the present invention, the surface of the aramid fiber material is coated with an adhesive solution containing a bio-adhesive, a graphene sheet and a solvent. The present invention does not involve shorting caused by bending an aramid fiber material thanks to flexibility of the graphene sheet adhered to the aramid fiber material, thereby maintaining mechanical properties such as strength while remarkably improving an electrical conductivity thereof. Further, because of excellent amphoteric adhesion of a biological adhesive, the graphene sheet having flexibility is securely adhered to the surface of the aramid fiber material, thereby more effectively preventing shorting due to bending of the aramid fiber material.

Description

ARAMID FIBER PRODUCT WITH EXCELLENT CONDUCTIVITY AND METHOD OF MANUFACTURING THE SAME
The present invention relates to a conductive aramid fiber product and a method of manufacturing the same, and more particularly, to a conductive aramid fiber material provided by adhering a graphene sheet to a surface of an aramid fiber material using a biological adhesive, without a decrease in mechanical properties such as strength, as well as a method of manufacturing the same.
In general, an aromatic polyamide fiber commonly called 'aramid fiber' is manufactured by preparing an aromatic polyamide polymer through polymerization of aromatic diamine and aromatic diacid chloride in a polymerization solvent, dissolving the aromatic polyamide polymer in a concentrated sulfuric acid solvent to form a spin dope, spinning the spin dope through a spinneret, and coagulating a spun product to form filaments.
Such an aramid fiber includes a para-aramid fiber having a structure of benzene rings straightly linked together through amide groups (CONH), and a meta-aramid fiber without the structure described above. The para-aramid fiber has excellent properties such as a high strength, high elasticity, low shrinkage, etc. In particular, the para-aramid fiber has such a high strength that it is possible to lift up an automobile with a weight of about 2 tons using a very fine thread having a thickness of about 5 mm, therefore, has been employed in bullet-proofing applications and for a variety of other uses in high-technology industries in relation to space and aeronautics.
Meanwhile, with regard to specific applications, there is a need for aramid fibers having favorable electrical conductivity as well as more excellent mechanical properties.
As one of conventional technologies to endow conductive properties to an aramid fiber material, Korean Patent Laid-Open Publication No. 10-2012-0028998 discloses a method of applying and adhering a conductive polymer solution to a surface of an aramid fiber material. However, such a conventional method has caused a decrease in flexibility of a conductive polymer, which in turn, leads to a shorting of the conductive polymer coating due to bending of the aramid fiber material, thus entailing reduction of electrical conductivity and mechanical properties such as strength.
Accordingly, an object of the present invention is to provide a conductive aramid fiber material having excellent electrical conductivity and mechanical properties such as strength since a conductive material adhered to the aramid fiber material does not undergo shorting caused by bending the aramid fiber material, as well as a method of manufacturing the same.
In order to achieve the above object, the present invention may enable strong adhesion of a graphene sheet having excellent flexibility to the aramid fiber material using a biological adhesive with excellent amphoteric adhesion, thereby effectively preventing shorting of the adhered graphene sheet even during bending of the aramid fiber material.
The present invention does not involve shorting caused by bending an aramid fiber material thanks to flexibility of the graphene sheet adhered to the aramid fiber material, thereby maintaining mechanical properties such as strength while remarkably improving an electrical conductivity thereof.
Further, because of excellent amphoteric adhesion of a biological adhesive, the graphene sheet having flexibility is securely adhered to the surface of the aramid fiber material, thereby more effectively preventing shorting due to bending of the aramid fiber material.
Hereinafter, the present invention will be described in more detail.
A method of manufacturing a conductive aramid fiber material according to the present invention includes adhering a graphene sheet to a surface of an aramid fiber material using a biological adhesive (also referred to as a 'bio-adhesive').
The graphene sheet refers to a sheet made of a material having a two-dimensional planar structure wherein carbon atoms are linked in a hexagonal form like a honeycomb, and may include a graphene oxide sheet as well as a pure graphene sheet.
According to one embodiment of the present invention, a method of coating the surface of the aramid fiber material with an adhesive solution containing a bio-adhesive, a graphene sheet and a solvent may be executed.
According to another embodiment of the present invention, a method of coating the surface of the aramid fiber material with a bio-adhesive, and then, with a solution containing a graphene sheet may be executed.
The graphene sheet used herein may include not only a pure graphene sheet but also a graphene oxide sheet.
When using the graphene oxide sheet, it should be subjected to reduction reaction to become a graphene sheet.
The graphene sheet has excellent flexibility and is homogeneously dispersed in a solvent and adhesive solution.
The aramid fiber material may include an aramid fiber, a woven fabric of aramid fibers, a knitted fabric of aramid fibers, or the like.
A content of the graphene sheet in the adhesive solution preferably ranges from 0.01 to 10 parts by weight ('wt. part') relative to 100 wt. parts of a solvent contained in the adhesive solution.
When the content of the graphene sheet is less than 0.01 wt. part, an electrical conductivity is not sufficiently improved. On the other hand, when the content of the graphene sheet exceeds 10 wt. parts, dispersibility is decreased due to phase separation of the graphene sheet, thus possibly causing uneven surface coating of the aramid fiber material.
A content of the bio-adhesive in the adhesive solution preferably ranges from 0.01 to 10 wt. parts relative to 100 wt. parts of the solvent. When the content of the bio-adhesive is less than 0.01 wt. part, adhesiveness is decreased. When the content of the bio-adhesive exceeds 10 wt. parts, the electrical conductivity may be deteriorated.
The bio-adhesive has such a chemical structure that two catechol groups (-OH) and one amine group (NH2) are introduced into benzene, and may include an adhesive component extracted from animal tissues, an adhesive component extracted from plants, or any synthetic adhesive component thereof.
Particular examples of the bio-adhesive may include dopamine, tyrosine, dihydroxyphenylalanine, norepinephrine, epinephrine, normetanephrine, 3,4-dihydroxyphenylacetic acid, or the like.
The bio-adhesive may have amphoteric adhesion to express favorable adhesion to both the aramid fiber material and the graphene sheet
As an example of the bio-adhesive, dopamine is represented by the following formula and has favorable adhesion to both the aramid fiber material and the graphene sheet by Π-Π interaction of benzene, and hydrogen bond and coordinate bond between oxygen and nitrogen.
[Formula]
Figure PCTKR2013009624-appb-I000001
The conductive aramid fiber material produced according to the manufacturing method of the present invention as described above may have an excellent electrical conductivity of 102 to 107 Ω/cm2, and not cause shorting due to bending of the conductive aramid fiber material, thus not leading to a decrease in mechanical properties such as strength.
Preferred embodiments of the present invention will be described in more detail. First, after dissolving aromatic diamine in a polymerization solvent to prepare a mixed solution, a predetermined amount of aromatic diacid halide is added to the mixed solution and pre-polymerization is executed. Following this, a residual quantity of aromatic diacid halide is further added to the mixed solution while agitating it at 0 to 30 ℃ to polymerize the same, thus forming an aramid polymer.
An organic solvent used herein may include amide organic solvents, urea solvents, or a mixture thereof. Particular examples of the organic solvent may include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), hexamethyl phosphoamide (HMPA), N,N,N′,N′-tetramethylurea (TMU), N,N-dimethylformamide (DMF), or a mixture thereof.
An inorganic salt may be added to increase a degree of polymerization of the aramid polymer and may include, for example, halogenated alkali-metal salts or halogenated alkali-earth metal salts such as CaCl2, LiCl, NaCl, KCl, LiBr and KBr, or the like. The inorganic salts may be added alone or in combination of two or more thereof. As an added amount of the inorganic salt increases, a degree of polymerization of the aramid polymer may also increase. However, when excess of inorganic salt is added, the inorganic salt may partially remain without being dissolved. Accordingly, it is preferable that a content of the inorganic salt is within a range of 10 wt.% or less to a total weight of the polymerization solvent.
Particular examples of aromatic diamine may include, para-phenylenediamine, 4,4′-diaminobiphenyl, 2,6-naphthalenediamine, 1,5-naphthalenediamine or 4,4′-diaminobenzanilide, however, not be particularly limited thereto.
Polymerization of aromatic diamine and aromatic diacid halide generates heat when conducted at a high rate. If a polymerization rate is high, a difference in degrees of polymerization between finally formed polymers may be enlarged. More particularly, since the polymerization does not simultaneously progress throughout the mixed solution, a polymer under polymerization earlier may rapidly react during the polymerization to form a long molecular chain while a polymer under polymerization later cannot help forming a shorter molecular chain than the polymer under polymerization earlier. If the polymerization rate is higher, such a difference in the length of chain may be more considerably enlarged. As such, when such a difference in degrees of polymerization between finally formed polymers is enlarged, a deviation in physical properties may also increase to hence make it difficult to achieve desired characteristics.
Accordingly, it is preferable to minimize a difference in degrees of polymerization between finally formed polymers by primarily preparing individual polymers having a molecular chain in a predetermined length through a pre-polymerization, and then, executing the polymerization thereof.
Particular examples of aromatic diacid halide may include terephthaloyl dichloride, 4,4′-benzoyl dichloride, 2,6-naphthalene dicarboxylic acid dichloride, 1,5-naphthalene dicarboxylic acid dichloride, or the like, however, not be particularly limited thereto.
With regard to preparation of the aramid polymer, since the aromatic diacid halide reacts with the aromatic diamine in a molar ratio of 1:1, these compounds, that is, the aromatic diamine and aromatic diacid halide may be added with the same molar ratio.
After completing the above polymerization, an amount of each of the aromatic diamine and diacid halide may be adjusted such that a concentration of a final polymer in the whole polymerization solution reaches a range of 5 to 20 wt.%. When the aromatic diamine and diacid halide are added to make the concentration of the final polymer to be less than 5 wt.%, a polymerization rate is decreased and the reaction should be executed for a long time, hence reducing economic feasibility. On the other hand, when the aromatic diamine and diacid halide are added to make the concentration of the final polymer to exceed 20 wt.%, polymerization is not actively proceeded, hence not improving an inherent viscosity of the polymer.
Particular examples of the aramid polymer formed by the polymerization may include poly(para-phenylene terephthalamide: PPD-T), poly(4,4′-benzanilide terephthalamide), poly(para-phenylene-4,4′-biphenylene-dicarboxylic acid amide) or poly(para-phenylene-2,6-naphthalene dicarboxylic acid amide).
Meanwhile, acid such as hydrochloric acid is generated during the polymerization and such acid may cause problems, i.e., corrosion of a polymerization apparatus. Therefore, the acid generated during polymerization is preferably neutralized by adding an inorganic alkaline compound or organic alkaline compound during or after the polymerization.
In this case, since the aramid polymer formed by the polymerization is present in a bread crumb type form, an aramid polymer-containing solution does not have good flowability. Therefore, in order to improve the flowability, it is preferable to add water to an aromatic polyamide solution to prepare a slurry, and then execute subsequent processes. For this purpose, the aromatic polyamide solution may be provided with water as well as an alkaline compound and subjected to a neutralization process.
The inorganic alkaline compound used herein may be selected from a group consisting of carbonates of alkali-metals and alkali-earth metals, hydrogenates of alkali-earth metals, hydroxides of alkali-earth metals, or oxides of alkali-earth metals, such as NaOH, Li2CO3, CaCO3, LiH, CaH2, LiOH, Ca(OH)2, Li2O or CaO.
After completing the neutralization process, the aramid polymer is ground, the polymerization solvent is removed, and the remaining product is dehydrated and dried, thus completing preparation of a final aramid polymer.
Next, the aramid polymer prepared as described above is added to a sulfuric acid solution and dissolved to form a spin dope.
The sulfuric acid solution used herein may be a concentrated sulfuric acid solvent having a concentration of 97 to 100% and, instead of concentrated sulfuric acid, chlorosulfuric acid or fluorosulfuric acid may be used.
Then, after passing the prepared spin dope through a spinneret, the spin dope may sequentially pass through an air gap and a coagulation bath, so as to be coagulated. Subsequently, an aramid fiber is prepared in a filament form by drying and winding the coagulated dope.
Next, an adhesive solution containing a bio-adhesive such as dopamine extracted from mussels, a graphene sheet and a solvent may be applied and adhered to the surface of the aramid fiber or the surface of a fabric or knitted material made of the aramid fiber, thus producing a conductive aramid fiber material.
The conductive aramid fiber material produced according to the present invention may have such a structure that the graphene sheet is adhered to the surface of the aramid fiber material by the bio-adhesive.
In this regard, it is preferable that a content of the graphene sheet adhered to the aramid fiber material by the bio-adhesive ranges from 0.01 to 10 wt.% relative to a total weight of the conductive aramid fiber material.
Preferably, the bio-adhesive used herein has such a chemical structure that two catechol groups (-OH) and one amine group (-NH2) are introduced into benzene.
The aramid fiber material may include an aramid fiber, aramid fabric or aramid knitted material.
Hereinafter, the present invention will be more clearly understood by the following examples and comparative examples. However, these examples are proposed for concretely explaining the present invention, while not limiting the scope of the present invention to be protected.
Example 1
After adding CaCl2 to N-methyl-2-pyrrolidone (NMP) to prepare a polymerization solvent, para-phenylenediamine was dissolved in the polymerization solvent to prepare a mixed solution. Then, para-phenylenediamine and terephthaloyl dichloride in the same molar ratio were added to the mixed solution in twice while agitating the mixed solution to form a poly(para-phenylene terephthalamide) polymer. After this, acid was neutralized by adding water and NaOH to the polymerization solution containing the above polymer, followed by grinding the polymer. Subsequently, the polymerization solvent contained in the polymer was extracted using water, and dehydrating and drying were conducted to finally prepare an aramid polymer.
Next, the prepared aramid polymer was added to a sulfuric acid solution having a concentration of 99% and dissolved therein to form a spin dope.
Following this, after spinning the formed spin dope through a spinneret, the spin dope was passed through an air gap and a coagulation bath in sequential order to be coagulated, followed by drying and winding, thus resulting in an aramid fiber.
Using the prepared aramid fiber, an aramid fabric was formed.
Next, after dipping the formed aramid fabric in an adhesive solution including: (i) 10 wt.% of dopamine (a natural adhesive) extracted from mussels; (ii) 5 wt.% of graphene sheet; and (iii) 85 wt.% of organic solvent, the treated fabric was dried to form a conductive aramid fabric.
Results of measuring an electrical conductivity of the formed conductive aramid fabric and a strength of the prepared aramid fiber are shown in Table 1 below.
Example 2
After adding CaCl2 to N-methyl-2-pyrrolidone (NMP) to prepare a polymerization solvent, para-phenylenediamine was dissolved in the polymerization solvent to prepare a mixed solution. Then, para-phenylenediamine and terephthaloyl dichloride in the same molar ratio were added to the mixed solution in twice while agitating the mixed solution to form a poly(para-phenylene terephthalamide) polymer. After this, acid was neutralized by adding water and NaOH to the polymerization solution containing the above polymer, followed by grinding the polymer. Subsequently, the polymerization solvent contained in the polymer was extracted using water, and dehydrating and drying were conducted to finally prepare an aramid polymer.
Next, the prepared aramid polymer was added to a sulfuric acid solution having a concentration of 99% and dissolved therein to form a spin dope.
Following this, after spinning the formed spin dope through a spinneret, the spin dope was passed through an air gap and a coagulation bath in sequential order to be coagulated, followed by drying and winding, thus resulting in an aramid fiber. Subsequently, using the prepared aramid fiber, an aramid fabric was formed.
Next, a conductive aramid fabric was formed by applying an adhesive solution including: (i) 10 wt.% of dopamine (a natural adhesive) extracted from mussels; (ii) 7 wt.% of graphene sheet; and (iii) 83 wt.% of organic solvent to the surface of the prepared aramid fabric through knife coating method, then, drying the same.
Results of measuring an electrical conductivity of the formed conductive aramid fabric and a strength of the prepared aramid fiber are shown in Table 1 below.
Example 3
After adding CaCl2 to N-methyl-2-pyrrolidone (NMP) to prepare a polymerization solvent, para-phenylenediamine was dissolved in the polymerization solvent to prepare a mixed solution. Then, para-phenylenediamine and terephthaloyl dichloride in the same molar ratio were added to the mixed solution in twice while agitating the mixed solution to form a poly(para-phenylene terephthalamide) polymer. After this, acid was neutralized by adding water and NaOH to the polymerization solution containing the above polymer, followed by grinding the polymer. Subsequently, the polymerization solvent contained in the polymer was extracted using water, and dehydrating and drying were conducted to finally prepare an aramid polymer.
Next, the prepared aramid polymer was added to a sulfuric acid solution having a concentration of 99% and dissolved therein to form a spin dope.
Following this, after spinning the formed spin dope through a spinneret, the spin dope was passed through an air gap and a coagulation bath in sequential order to be coagulated, followed by drying and winding, thus resulting in an aramid fiber.
Next, after firstly coating the surface of the prepared aramid fiber (in a filament form) with dopamine (a natural adhesive) extracted from mussels, an adhesive solution including 7 wt.% of graphene sheet and 93 wt.% of organic solvent was applied to the surface of the coated aramid fiber through knife coating method, followed by drying the same to prepare a conductive aramid fiber (in a filament form). After this, the prepared conductive aramid fiber was subjected to weaving to form a conductive aramid fabric.
Results of measuring an electrical conductivity of the formed conductive aramid fabric and a strength of the prepared aramid fiber are shown in Table 1 below.
Comparative Example 1
After adding CaCl2 to N-methyl-2-pyrrolidone (NMP) to prepare a polymerization solvent, para-phenylenediamine was dissolved in the polymerization solvent to prepare a mixed solution. Then, para-phenylenediamine and terephthaloyl dichloride in the same molar ratio were added to the mixed solution in twice while agitating the mixed solution to form a poly(para-phenylene terephthalamide) polymer. After this, acid was neutralized by adding water and NaOH to the polymerization solution containing the above polymer, followed by grinding the polymer. Subsequently, the polymerization solvent contained in the polymer was extracted using water, and dehydrating and drying were conducted to finally prepare an aramid polymer.
The prepared aramid polymer was dissolved in a sulfuric acid solution having a concentration of 99% to form a spin dope.
Then, after spinning the formed spin dope through a spinneret and passing the same through an air gap, a coagulating solution was injected to the spin dope while passing the spin dope through the spinning tube, followed by drying the same to prepare an aramid fiber.
Next, the prepared aramid fabric was dipped in a processing solution including: (i) 30 wt.% of poly(diallyldimethylammonium chloride: Catalog No. 52237-6, manufactured by Aldrich Chemical Company, United States); and (ii) 70 wt.% of desalted water, and dried to form a conductive aramid fabric.
Results of measuring an electrical conductivity of the formed conductive aramid fabric and a strength of the prepared aramid fiber are shown in Table 1 below.
Table 1 Evaluation results of physical properties
Section Electrical conductivity (Ω/cm2) Strength (g/d)
Example 1 105 25
Example 2 106 24
Example 3 105 24
Comparative Example 1 104 21
The strength of the conductive aramid fiber and the electrical conductivity of the aramid fabric were measured by the following methods.
Strength (g/d)
According to ASTM D 885 test procedures, the strength of aramid fiber was measured.
More particularly, the strength of the aramid fiber was obtained by pulling the aramid fiber having a length of 25 cm in an Instron tester (Instron Engineering Corp., Canton, Massachusetts) until the aramid fiber was broken. Herein, a tensile velocity was 300 mm/min and a primary load was defined by fiber fineness × 1/30 g.
After testing five samples, a mean value of measured results of these samples was determined as the strength.
Electrical conductivity (Ω/cm 2 )
After placing an aramid fabric having a size of 1 cm (width) × 1 cm (length) on a glass plate to prepare a sample, the sample was placed on a 4-point probe device and a surface resistance of the sample was measured using an electrical resistance tester (Model 3244, manufactured by Hioki Co. Ltd.).
The conductive aramid fiber material produced according to the present invention may be effectively used in materials for industrial protective clothing and heat-tech garments that require electrostatic-protection effects.

Claims (16)

  1. A method of manufacturing a conductive aramid fiber material, comprising:
    adhering a graphene sheet to a surface of the aramid fiber material using a bio-adhesive.
  2. The method according to claim 1, wherein the surface of the aramid fiber material is coated with an adhesive solution containing a bio-adhesive, a graphene sheet and a solvent.
  3. The method according to claim 1, wherein, after firstly coating the surface of the aramid fiber material with a bio-adhesive, a solution containing a solvent and a graphene sheet is applied to the bio-adhesive coated on the aramid fiber material.
  4. The method according to claim 1, 2 or 3, wherein the aramid fiber material is one selected from an aramid fiber, aramid woven fabric and aramid knitted fabric.
  5. The method according to claim 2, wherein the graphene sheet is homogeneously dispersed in the adhesive solution.
  6. The method according to claim 3, wherein the graphene sheet is homogeneously dispersed in the solution containing the solvent and the graphene sheet.
  7. The method according to claim 2, wherein a content of the graphene sheet in the adhesive solution ranges from 0.01 to 10 wt. parts relative to 100 wt. parts of the solvent in the adhesive solution.
  8. The method according to claim 2, wherein a content of the bio-adhesive in the adhesive solution ranges from 0.01 to 10 wt. parts relative to 100 wt. parts of the solvent in the adhesive solution.
  9. The method according to claim 1, wherein the bio-adhesive has such a chemical structure that two catechol groups (-OH) and one amine group (-NH2) are introduced into benzene.
  10. The method according to claim 1, wherein the bio-adhesive is one selected from an adhesive component extracted from animal tissues, an adhesive component extracted from plants, and a synthetic adhesive component thereof.
  11. The method according to claim 1, wherein the bio-adhesive is one selected from dopamine, tyrosine, dihydroxyphenylalanine, norepinephrine, epinephrine, normetanephrine and 3,4-dihydroxyphenylacetic acid.
  12. The method according to claim 1, wherein the graphene sheet is obtained by a reduction reaction of a graphene oxide sheet.
  13. A conductive aramid fiber material, comprising:
    a graphene sheet adhered to a surface of an aramid fiber material by a bio-adhesive.
  14. The conductive aramid fiber material according to claim 13, wherein a content of the graphene sheet ranges from 0.01 to 10 wt.%.
  15. The conductive aramid fiber material according to claim 13, wherein the bio-adhesive has such a chemical structure that two catechol groups (-OH) and one amine group (-NH2)areintroducedintobenzene.
  16. The conductive aramid fiber material according to claim 13, wherein the aramid fiber material is one selected from an aramid fiber, aramid woven fabric and aramid knitted fabric.
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CN105821663A (en) * 2016-05-10 2016-08-03 北京创新爱尚家科技股份有限公司 Conductive graphene fiber and production method and system
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CN106544867A (en) * 2016-10-09 2017-03-29 苏州大学 Coloured flame-retardant polyester-cotton fabric and preparation method thereof
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CN108085767A (en) * 2017-12-30 2018-05-29 杭州高烯科技有限公司 A kind of preparation method of multifunction polyacrylonitrile-graphene oxide composite fibre
CN109898328A (en) * 2019-03-14 2019-06-18 赵鑫飚 A kind of modification of aramid fiber and its processing technology

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