WO2020037549A1 - 一种芳纶纤维远红外发射纸及其制备方法 - Google Patents

一种芳纶纤维远红外发射纸及其制备方法 Download PDF

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Publication number
WO2020037549A1
WO2020037549A1 PCT/CN2018/101733 CN2018101733W WO2020037549A1 WO 2020037549 A1 WO2020037549 A1 WO 2020037549A1 CN 2018101733 W CN2018101733 W CN 2018101733W WO 2020037549 A1 WO2020037549 A1 WO 2020037549A1
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Prior art keywords
aramid
para
paper
treatment
far
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PCT/CN2018/101733
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English (en)
French (fr)
Inventor
孙晓刚
郑典模
蔡满园
聂艳艳
陈珑
潘鹤政
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江西克莱威纳米碳材料有限公司
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Priority to JP2019536980A priority Critical patent/JP6910447B2/ja
Priority to US16/481,337 priority patent/US11131064B2/en
Priority to EP18930922.2A priority patent/EP3663464A4/en
Priority to PCT/CN2018/101733 priority patent/WO2020037549A1/zh
Publication of WO2020037549A1 publication Critical patent/WO2020037549A1/zh

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • D21D1/02—Methods of beating; Beaters of the Hollander type
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F13/00—Making discontinuous sheets of paper, pulpboard or cardboard, or of wet web, for fibreboard production
    • D21F13/10—Making discontinuous sheets of paper, pulpboard or cardboard, or of wet web, for fibreboard production using board presses
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D21H15/06—Long fibres, i.e. fibres exceeding the upper length limit of conventional paper-making fibres; Filaments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/26—Ethers thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes

Definitions

  • the invention relates to the technical field of far-infrared emitting materials, in particular to an aramid fiber far-infrared emitting paper and a preparation method thereof.
  • Far infrared is a type of light wave located in the infrared wavelength range. Its wavelength is in the range of 3 to 100 ⁇ m and is often not noticed. However, far infrared has a very important role in living organisms. After the human body absorbs far infrared, its temperature rises. Capillary blood vessels are dilated and blood circulation is active to enhance the body's metabolism and body movement. The excellent performance of far infrared makes it more and more widely used in life sciences and biomedical fields.
  • Carbon nanotubes as a new type of far-infrared radiation source, have good physical and chemical properties, and the proportion of far-infrared rays that can be emitted is as high as 90% or more. It is an ideal material for emitting far-infrared rays.
  • carbon nanotubes are usually coated on a finished film (such as a plastic film). The formed carbon nanotube layer and the finished film are simply laminated and composited. Two materials There will be a large energy loss in the composite area, and the characteristics of the material itself cannot be fully exerted. Therefore, the far-infrared emissivity of the composite material obtained by this method is low, which severely restricts its further application.
  • the object of the present invention is to provide an aramid fiber far-infrared emitting paper and a preparation method thereof.
  • the aramid fiber far-infrared emitting paper prepared by the method provided by the present invention has excellent far-infrared emitting performance and excellent mechanical properties. .
  • the invention provides a method for preparing aramid fiber far-infrared emitting paper, including the following steps:
  • the para-aramid chopped fibers are mixed with a dissolving agent and water for a dissolution treatment, the obtained fibers are washed and subjected to a low-temperature plasma surface treatment, and the obtained fibers are mixed with a dispersant and water for ultrasonic treatment and Beating treatment to obtain para-aramid chopped fiber slurry;
  • the aramid fiber slurry in the step (1) is mixed with the carbon nanotube dispersion liquid and the paper strength enhancer in the step (2), and then the shearing treatment is performed, and the obtained mixed slurry is coated on a substrate.
  • the substrate is peeled off after curing, and the resulting cured film is hot-pressed to obtain aramid fiber far-infrared emitting paper;
  • the steps (1) and (2) are not limited in time sequence.
  • the mass ratio of the para-aramid chopped fibers and para-aramid pulp fibers in step (1) to the carbon nanotubes in step (2) is (0.5-1.5): (0.5-1.5): (0.5 to 8).
  • the length of the para-aramid chopped fibers in the step (1) is 3 to 5 mm.
  • the length of the para-aramid pulp fiber in the step (1) is 1.2 to 1.8 mm.
  • the pressure of the surface treatment in the step (1) is 75 to 85 Pa, the power is 75 to 85 W, and the time is 2.5 to 3.5 min.
  • the disintegrating agent in the step (1) includes sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, polyethylene oxide or polyvinyl alcohol.
  • the dispersant in the step (1) comprises polyethylene oxide.
  • the dispersant in the step (2) includes sodium dodecyl sulfate, polyvinylpyrrolidone or sodium dodecylbenzenesulfonate.
  • the carbon nanotubes in the step (2) are whisker-shaped multi-walled carbon nanotubes.
  • the carbon nanotubes have a length of 2 to 5 ⁇ m and a diameter of 30 to 150 nm.
  • the paper strength enhancer in the step (3) comprises an anionic polyacrylamide or carboxymethyl cellulose.
  • the coating amount of the mixed slurry on one side of the substrate in the step (3) is 0.2 to 2 mL / cm 2 .
  • the curing temperature in the step (3) is 60 to 80 ° C., and the time is 22 to 26 h.
  • the temperature of the hot press forming in the step (3) is 250-350 ° C, and the linear pressure is 120-150KN / m.
  • the invention provides aramid fiber far-infrared emitting paper prepared by the preparation method described in any one of the above technical solutions, and is prepared from raw materials including para-aramid chopped fibers, para-aramid pulp fibers, and carbon nanotubes.
  • the para-aramid chopped fibers and para-aramid pulp fibers form a paper with pores and channels, and the carbon nanotubes are embedded in the structural pores and channels of the paper.
  • the thickness of the aramid fiber far-infrared emitting paper is 0.25 to 0.35 mm.
  • the invention provides a method for preparing aramid fiber far-infrared emitting paper.
  • Para-aramid chopped fibers are mixed with a dissolving agent and water to perform a disintegration treatment.
  • the obtained fibers are washed and subjected to a surface treatment with a low-temperature plasma.
  • the obtained fiber is mixed with a dispersant and water and then subjected to ultrasonic treatment and beating treatment in order to obtain a para-aramid chopped fiber slurry;
  • the para-aramid pulp fiber is mixed with a dispersant and water and then subjected to ultrasonic treatment and beating treatment in order.
  • para-aramid pulp fiber slurry To obtain para-aramid pulp fiber slurry; mixing the para-aramid chopped fiber slurry with para-aramid pulp fiber slurry and subjecting it to shear treatment to obtain aramid fiber slurry; carbon After the nanotubes are mixed with the dispersant and ethanol, they are sequentially subjected to ultrasonic treatment and shearing treatment to obtain a carbon nanotube dispersion; the aramid fiber slurry is mixed with the carbon nanotube dispersion and a paper strength enhancer, and then sheared. Cutting treatment, coating the obtained mixed slurry on one side of the substrate, peeling off the substrate after curing, and hot-pressing the obtained cured film to obtain aramid fiber far-infrared emitting paper.
  • the para-aramid chopped fibers and para-aramid pulp fibers as paper-based functional materials, have excellent characteristics of high specific strength and large specific stiffness; at the same time, para-aramid chopped fibers and Para-aramid pulp fibers can form a paper with pores and channels, and the carbon nanotubes are embedded in the structural pores and channels of the paper. Therefore, the aramid fiber far-infrared emitting paper has better molding quality and composite properties, and can be used for heating cushions such as high-speed rail, aircraft, and cars.
  • the far-infrared wavelength emitted by the aramid fiber far-infrared emitting paper provided by the present invention is 4-20 ⁇ m, the main frequency band is about 10 ⁇ m, and the far-infrared conversion efficiency is as high as 99%; at the same time, its tensile strength is 0.12 ⁇ 0.18KN / mm 2 , and can be bent and folded. It shows that the aramid fiber far-infrared emitting paper provided by the present invention has excellent far-infrared emitting performance and mechanical properties.
  • the preparation method provided by the present invention has simple operation and is convenient for large-scale production.
  • the invention provides a method for preparing aramid fiber far-infrared emitting paper, including the following steps:
  • the para-aramid chopped fibers are mixed with a dissolving agent and water for a dissolution treatment, the obtained fibers are washed and subjected to a low-temperature plasma surface treatment, and the obtained fibers are mixed with a dispersant and water for ultrasonic treatment and Beating treatment to obtain para-aramid chopped fiber slurry;
  • the aramid fiber slurry in the step (1) is mixed with the carbon nanotube dispersion liquid and the paper strength enhancer in the step (2), and then the shearing treatment is performed, and the obtained mixed slurry is coated on a substrate.
  • the substrate is peeled off after curing, and the resulting cured film is hot-pressed to obtain aramid fiber far-infrared emitting paper;
  • the steps (1) and (2) are not limited in time sequence.
  • para-aramid chopped fibers are mixed with a dissolving agent and water, and then subjected to a dissolving treatment.
  • the obtained fibers are washed with a low-temperature plasma for surface treatment, and the obtained fibers are mixed with a dispersant and water and then subjected to ultrasonic treatment and beating in order. Processing to obtain para-aramid chopped fiber slurry.
  • the length of the para-aramid chopped fiber is preferably 3 to 5 mm.
  • the source of the para-aramid chopped fiber is not particularly limited, and commercial products well known to those skilled in the art may be used.
  • the degrading agent preferably includes sodium dodecylbenzenesulfonate (SDBS), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO) or polyvinyl alcohol (PVA), more preferably sodium dodecylbenzenesulfonate.
  • SDBS sodium dodecylbenzenesulfonate
  • PVP polyvinylpyrrolidone
  • PEO polyethylene oxide
  • PVA polyvinyl alcohol
  • the mass ratio of the degrading agent, para-aramid chopped fiber and water is preferably (0.009 to 0.011): 1: (50 to 150), and more preferably 0.01: 1: 100.
  • the present invention has no particular limitation on the deblocking process, and the technical solution of the deblocking process well known to those skilled in the art may be adopted.
  • the washing is preferably water washing.
  • the present invention does not specifically limit the specific operation method of the washing, and it is only necessary to adopt a washing technical solution well known to those skilled in the art.
  • the invention uses washing to remove impurities on the surface of the para-aramid chopped fiber.
  • the pressure of the surface treatment is preferably 75 to 85 Pa, more preferably 80 Pa; the power is preferably 75 to 85 W, more preferably 80 W; the time is preferably 2.5 to 3.5 min, and more preferably 3 min.
  • the invention uses low-temperature plasma to perform surface treatment to further remove minute impurities on the surface of the para-aramid chopped fiber.
  • the dispersant is not particularly limited, and a dispersant well known to those skilled in the art may be used, such as polyethylene oxide.
  • the mass ratio of the dispersant, para-aramid chopped fibers and water is preferably (0.009 to 0.011): 1: (50 to 150), and more preferably 0.01: 1: 100.
  • the sonication time is preferably 20 to 30 minutes; the power of the sonication is not particularly limited in the present invention, and a power well known to those skilled in the art may be used.
  • the beating treatment is not particularly limited, and it is only necessary to adopt a technical solution of beating treatment that is well known to those skilled in the art; in the present invention, the beating treatment time is preferably 5 to 10 minutes; the beating during the beating process The degree is preferably 40 to 50 ° SR, and more preferably 45 ° SR.
  • para-aramid chopped fibers are uniformly dispersed in water by ultrasonic treatment under the action of the dispersant, and para-aramid chopped fiber slurry is obtained through beating treatment.
  • para-aramid pulp fibers are mixed with a dispersant and water, and then subjected to ultrasonic treatment and beating treatment in order to obtain para-aramid pulp fiber slurry.
  • the length of the para-aramid pulp fiber is preferably 1.2 to 1.8 mm.
  • the source of the para-aramid pulp fiber is not particularly limited, and commercial products well known to those skilled in the art may be used.
  • the dispersant is not particularly limited, and a dispersant well known to those skilled in the art may be used; specifically, such as polyethylene oxide.
  • the mass ratio of the dispersant, para-aramid pulp fiber, and water is preferably (0.009 to 0.011): 1: (50 to 150), and more preferably 0.01: 1: 100.
  • the sonication time is preferably 20 to 30 minutes; the power of the sonication is not particularly limited in the present invention, and a power well known to those skilled in the art may be used.
  • the beating treatment is not particularly limited, and it is only necessary to adopt a technical solution of beating treatment that is well known to those skilled in the art; in the present invention, the beating treatment time is preferably 5 to 10 minutes; the beating during the beating process The degree is preferably 40 to 50 ° SR, and more preferably 45 ° SR.
  • para-aramid pulp fibers are uniformly dispersed in water by ultrasonic treatment under the action of the dispersant, and para-aramid pulp fiber slurry is obtained through beating treatment.
  • the present invention mixes the para-aramid chopped fiber pulp with para-aramid pulp fiber pulp and cuts Cutting treatment to obtain aramid fiber slurry.
  • the rotation speed of the shearing treatment is preferably 1800 to 2200 r / min, more preferably 2000 r / min; the time is preferably 30 to 60 min, and more preferably 40 to 50 min.
  • carbon nanotubes are mixed with a dispersant and ethanol and then subjected to ultrasonic treatment and shear treatment in order to obtain a carbon nanotube dispersion.
  • the carbon nanotubes are preferably whisker-shaped multi-walled carbon nanotubes.
  • the length of the carbon nanotube is preferably 2 to 5 ⁇ m, and the diameter is preferably 30 to 150 nm.
  • the carbon nanotubes are preferably in accordance with the literature (Sun, X, G, Qi, Z, W, Chen, L, et al. Industrial Science of Whisker Carbon Carbon Nanotubes [C] // Materials Science Science Forum.
  • the dispersant is not particularly limited, and a dispersant well known to those skilled in the art may be used.
  • the dispersant preferably includes sodium dodecyl sulfate (SDS), polyvinylpyrrolidone (PVP ), Sodium dodecylbenzenesulfonate (SDBS).
  • the mass ratio of the carbon nanotubes, the dispersant, and the ethanol is preferably 1: (0.05 to 0.1): (50 to 150).
  • the sonication time is preferably 10 to 30 minutes, and more preferably 20 minutes.
  • the power of the sonication is not particularly limited in the present invention, and a power well known to those skilled in the art may be used.
  • the rotation speed of the shearing treatment is preferably 1800 to 2200 r / min, more preferably 2000 r / min; the time is preferably 10 to 30 min, and more preferably 20 min.
  • the present invention uniformly disperses carbon nanotubes in ethanol through ultrasonic treatment and shearing treatment.
  • the present invention mixes the aramid fiber slurry with the carbon nanotube dispersion liquid and a paper strength enhancer, and then performs a shearing treatment to apply the obtained mixed slurry to On one side of the substrate, the substrate is peeled after curing, and the obtained cured film is hot-pressed to obtain aramid fiber far-infrared emitting paper.
  • the mass ratio of the para-aramid chopped fibers, para-aramid pulp fibers, and carbon nanotubes is preferably (0.5 to 1.5): (0.5 to 1.5): (0.5 To 8), more preferably 1: 1: (1 to 4), and most preferably 1: 1: 2.
  • the paper strength enhancer preferably includes an anionic polyacrylamide or carboxymethyl cellulose.
  • the mass of the paper strength enhancer is preferably 0.8 to 1.2%, more preferably 1%, of the total mass of the para-aramid chopped fibers and para-aramid pulp fibers.
  • the mixing of the aramid fiber slurry with the carbon nanotube dispersion liquid and the paper strength enhancer is preferably performed in a stainless steel fluid mixer.
  • the rotation speed of the shearing treatment is preferably 1800 to 2200 r / min, more preferably 2000 r / min; the time is preferably 30 to 60 min, and more preferably 40 to 50 min.
  • the substrate is not particularly limited in the present invention, and a substrate well known to those skilled in the art may be used; in the embodiment of the present invention, a cellulose substrate is specifically used.
  • the size of the substrate is not particularly limited in the present invention, and the size of the substrate may be selected according to actual needs; in the embodiment of the present invention, the size of the substrate is specifically A4 paper size, that is, 210mm ⁇ 297mm.
  • the substrate mainly functions as a substrate, can withstand pressure and high temperature, and is suitable for peeling and separating.
  • the present invention has no particular limitation on the coating, and it is sufficient to adopt a coating technical solution well known to those skilled in the art.
  • the coating amount of the mixed slurry on one side of the substrate is preferably 0.2 to 2 mL / cm 2 , and more preferably 0.8 to 1.3 mL / cm 2 .
  • the curing temperature is preferably 60 to 80 ° C, and the time is preferably 22 to 26 hours.
  • the curing enables preliminary drying of the mixed slurry coated on one side of the substrate to form a cured film on one side of the substrate; and enables the para-aramid chopped fibers and The meta-aramid pulp fibers initially form a grid structure so that carbon nanotubes are filled in the grid structure.
  • the temperature of the hot press molding is preferably 250 to 350 ° C, and the linear pressure is preferably 120 to 150 KN / m.
  • the hot-press molding can further press the carbon nanotubes into the porous network formed by the aramid fiber slurry to realize the carbon nanotubes and para-aramid chopped fibers and para-aramid pulp Fiber composite.
  • the present invention provides aramid fiber far-infrared emitting paper prepared by the preparation method described in the above technical solution, and is prepared from raw materials including para-aramid chopped fibers, para-aramid pulp fibers, and carbon nanotubes.
  • Para-aramid chopped fibers and para-aramid pulp fibers form a paper with pores and channels, and the carbon nanotubes are embedded in the structural pores and channels of the paper.
  • the thickness of the aramid fiber far-infrared emitting paper is preferably 0.25 to 0.35 mm, and more preferably 0.3 mm.
  • a stainless steel fluid mixer was used to mix the aramid fiber slurry and the carbon nanotube dispersion with anionic polyacrylamide (addition amount is 1% of the total mass of para-aramid chopped fibers and para-aramid pulp fibers ) After mixing, perform a shear treatment at 2000 r / min for 30 min, and apply the obtained mixed slurry to a single side of a cellulose substrate (size: 210 mm ⁇ 297 mm) by means of slit extrusion coating. After vacuum drying for 24 hours at °C, the cellulose substrate was peeled off, and the obtained cured film was hot-pressed by a roller hot press under the conditions of a temperature of 250 ° C. and a linear pressure of 150 KN / m to obtain a far-infrared fiber. Emission paper with a thickness of 0.3mm.
  • a grating and a detector were used to test the far-infrared emission performance of the aramid fiber far-infrared emitting paper prepared in this embodiment.
  • the results show that the far-infrared wavelength emitted by the aramid fiber far-infrared emitting paper is 4-20 ⁇ m, and the main frequency band is 10 ⁇ m Left and right, and the far infrared conversion efficiency is as high as 99%. It shows that the aramid fiber far-infrared emitting paper provided by the present invention has good far-infrared emitting performance.
  • the tensile strength at the crease is about 0.13KN / mm 2
  • the tensile strength at the crease is 0.15KN / mm 2 . It shows that the aramid fiber far-infrared emitting paper provided by the present invention has good mechanical properties.
  • 2g para-aramid chopped fiber (length: 3 ⁇ 5mm) was mixed with 0.02g sodium dodecylbenzenesulfonate and 200mL water and then subjected to disintegration treatment.
  • the obtained fiber was washed with water under the conditions of a pressure of 80Pa and a power of 80W. Surface treatment with low-temperature plasma for 3 min.
  • the obtained fiber was mixed with 0.02 g of polyethylene oxide and 200 mL of water and then subjected to ultrasonic treatment for 30 min. Then, the pulp was treated for 5 min.
  • the degree of beating was controlled to 45 ° SR to obtain para-aramid chopped fibers.
  • a stainless steel fluid mixer was used to mix the aramid fiber slurry and the carbon nanotube dispersion with anionic polyacrylamide (addition amount is 1% of the total mass of para-aramid chopped fibers and para-aramid pulp fibers ) After mixing, shear treatment was performed at 2000 r / min for 60 min, and the obtained mixed slurry was applied to one side of a cellulose substrate (size 210 mm ⁇ 297 mm) by means of slit extrusion coating, at 80 After vacuum drying for 24 hours at °C, the cellulose substrate was peeled off, and the obtained cured film was hot-pressed by a roller hot press under the conditions of a temperature of 350 ° C. and a linear pressure of 120 KN / m to obtain a far-infrared fiber. Emission paper with a thickness of 0.3mm.
  • a grating and a detector were used to test the far-infrared emission performance of the aramid fiber far-infrared emitting paper prepared in this embodiment.
  • the results show that the far-infrared wavelength emitted by the aramid fiber far-infrared emitting paper is 4-20 ⁇ m, and the main frequency band is 10 ⁇ m Left and right, and the far infrared conversion efficiency is as high as 99%. It shows that the aramid fiber far-infrared emitting paper provided by the present invention has good far-infrared emitting performance.
  • the aramid fiber far-infrared emitting paper per square millimeter of cross-sectional area can withstand a weight of 17 kg without Will break.
  • the aramid fiber far-infrared emitting paper prepared in this embodiment can be bent freely, and the bending angle is 0 to 180 °; the aramid fiber far-red emitting paper has no obvious creases after being folded in half, and after strength testing, the folded There is a small difference between the tensile strength at the crease and the tensile strength at the uncrease.
  • the tensile strength at the crease is about 0.16KN / mm 2
  • the tensile strength at the crease is 0.17KN / mm 2 .
  • 1g para-aramid chopped fiber (length: 3 ⁇ 5mm) was mixed with 0.01g sodium dodecylbenzenesulfonate and 100mL of water, and then subjected to disintegration treatment.
  • the obtained fiber was washed under water at a pressure of 80Pa and a power of 80W. Surface treatment with low-temperature plasma for 3 min.
  • the obtained fiber was mixed with 0.01 g of polyethylene oxide and 100 mL of water and then subjected to ultrasonic treatment for 30 min. Then, it was beaten for 10 min. The beating degree was controlled to 50 ° SR to obtain para-aramid chopped Fiber slurry
  • whisker-shaped multi-walled carbon nanotubes (length of 2 to 5 ⁇ m, diameter of 30 to 150 nm) were mixed with 0.2 g of sodium lauryl sulfate and 400 g of ethanol, followed by sonication for 30 min, and finally at 2000 r
  • the carbon nanotube dispersion was obtained by performing a shearing treatment for 30 min under a condition of 1 / min;
  • a stainless steel fluid mixer was used to mix the aramid fiber slurry and the carbon nanotube dispersion with anionic polyacrylamide (addition amount is 1% of the total mass of para-aramid chopped fibers and para-aramid pulp fibers ) After mixing, perform a shear treatment at 2000 r / min for 30 min, and apply the obtained mixed slurry to a single side of a cellulose substrate (size: 210 mm ⁇ 297 mm) by means of slit extrusion coating. After vacuum drying at °C for 24 hours, the cellulose substrate was peeled off, and the obtained cured film was hot-pressed by a roller hot press at a temperature of 350 ° C. and a linear pressure of 150 KN / m to obtain a far-infrared fiber. Emission paper with a thickness of 0.3mm.
  • a grating and a detector were used to test the far-infrared emission performance of the aramid fiber far-infrared emitting paper prepared in this embodiment.
  • the results show that the far-infrared wavelength emitted by the aramid fiber far-infrared emitting paper is 4-20 ⁇ m, and the main frequency band is 10 ⁇ m Left and right, and the far infrared conversion efficiency is as high as 99%. It shows that the aramid fiber far-infrared emitting paper provided by the present invention has good far-infrared emitting performance.
  • the aramid fiber far-infrared emitting paper per square millimeter of cross-sectional area can withstand a weight of 13 kg without Will break.
  • the aramid fiber far-infrared emitting paper prepared in this embodiment can be bent freely, and the bending angle is 0 to 180 °; the aramid fiber far-red emitting paper has no obvious creases after being folded in half, and after strength testing, the folded There is a small difference between the tensile strength at the crease and the tensile strength at the uncrease.
  • the tensile strength at the crease is about 0.1 KN / mm 2
  • the tensile strength at the uncrease is 0.13 KN / mm 2 .

Abstract

一种芳纶纤维远红外发射纸及其制备方法。采用对位芳纶短切纤维和对位芳纶浆粕纤维作为纸基功能材料，具有比强度高、比刚度大的优异特性；同时，对位芳纶短切纤维和对位芳纶浆粕纤维能够形成具有孔隙和孔道的纸状物，碳纳米管嵌在所述纸状物的结构孔隙和孔道里，因此，其拥有更好的成型质量和复合性能。该芳纶纤维远红外发射纸发射出的远红外波长在4～20μm，主频段为10μm左右，且远红外转换效率高达99％；其抗拉强度为0.12～0.18KN/mm 2，且可弯曲和折叠。

Description

一种芳纶纤维远红外发射纸及其制备方法 技术领域
本发明涉及远红外发射材料技术领域，具体涉及一种芳纶纤维远红外发射纸及其制备方法。
背景技术
远红外线是一种位于位于红外线波长范围内的光波，其波长在3～100μm范围内，往往不被人察觉，然而远红外线对于生命体却有相当重要的作用，人体吸收远红外线后，体温上升、毛细血管扩张、血液循环活跃，以此来增强人体的新陈代谢与机体的运转。远红外线所具备的优异的性能使得其在生命科学以及生物医疗领域的应用愈发的广泛。目前仅有少量的能够发射出远红线外的装置，但是由于用于发射远红外线的材料本性的限制，这些装置所发出的远红外线中杂波较多，远红外线发射率较低。
碳纳米管作为远红外线辐射源的一种新型材料，其在具有良好物理化学性能的同时，能够发射出的远红外线的比例高达90％以上，是一种理想的发射远红外线的材料。目前，碳纳米管应用于发射远红外线通常是将碳纳米管涂覆于成品薄膜(如塑料薄膜)之上，形成的碳纳米管层与成品薄膜之间仅是简单的层叠复合，两种材料之间复合处会产生较大能量缺失，不能完全发挥出材料本身的特性。因此，采用这种方法得到的复合材料的远红外线发射率较低，严重制约了其进一步应用。
发明内容
本发明的目的在于提供一种芳纶纤维远红外发射纸及其制备方法，采用本发明提供的方法制备得到的芳纶纤维远红外发射纸具有优异的远红外线发射性能，同时具有优异的机械性能。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种芳纶纤维远红外发射纸的制备方法，包括以下步骤：
(1)将对位芳纶短切纤维与疏解剂和水混合后进行疏解处理，将所得纤维洗涤后用低温等离子体进行表面处理，将所得纤维与分散剂和水混 合后依次进行超声处理和打浆处理，得到对位芳纶短切纤维浆料；
将对位芳纶浆粕纤维与分散剂和水混合后依次进行超声处理和打浆处理，得到对位芳纶浆粕纤维浆料；
将所述对位芳纶短切纤维浆料和对位芳纶浆粕纤维浆料混合后进行剪切处理，得到芳纶纤维浆料；
(2)将碳纳米管与分散剂和乙醇混合后依次进行超声处理和剪切处理，得到碳纳米管分散液；
(3)将所述步骤(1)中芳纶纤维浆料与所述步骤(2)中碳纳米管分散液和纸力增强剂混合后进行剪切处理，将所得混合浆料涂覆到基材的单面，经固化后剥离基材，将所得固化膜进行热压成型，得到芳纶纤维远红外发射纸；
所述步骤(1)和步骤(2)无时间顺序限定。
优选地，所述步骤(1)中对位芳纶短切纤维和对位芳纶浆粕纤维与步骤(2)中碳纳米管的质量比为(0.5～1.5)：(0.5～1.5)：(0.5～8)。
优选地，所述步骤(1)中对位芳纶短切纤维的长度为3～5mm。
优选地，所述步骤(1)中对位芳纶浆粕纤维的长度为1.2～1.8mm。
优选地，所述步骤(1)中表面处理的压力为75～85Pa，功率为75～85W，时间为2.5～3.5min。
优选地，所述步骤(1)中疏解剂包括十二烷基苯磺酸钠、聚乙烯吡咯烷酮、聚环氧乙烷或聚乙烯醇。
优选地，所述步骤(1)中分散剂包括聚氧化乙烯。
优选地，所述步骤(2)中分散剂包括十二烷基硫酸钠、聚乙烯吡咯烷酮或十二烷基苯磺酸钠。
优选地，所述步骤(2)中碳纳米管为晶须状的多壁碳纳米管。
优选地，所述碳纳米管的长度为2～5μm，直径为30～150nm。
优选地，所述步骤(3)中纸力增强剂包括阴离子聚丙烯酰胺或羧甲基纤维素。
优选地，所述步骤(3)中混合浆料在基材单面的涂覆量为0.2～2mL/cm 2。
优选地，所述步骤(3)中固化的温度为60～80℃，时间为22～26h。
优选地，所述步骤(3)中热压成型的温度为250～350℃，线压力为120～150KN/m。
本发明提供了上述技术方案任一项所述制备方法制备得到的芳纶纤维远红外发射纸，由包括对位芳纶短切纤维、对位芳纶浆粕纤维和碳纳米管的原料制备得到，所述对位芳纶短切纤维和对位芳纶浆粕纤维形成具有孔隙和孔道的纸状物，所述碳纳米管嵌在所述纸状物的结构孔隙和孔道里。
优选地，所述芳纶纤维远红外发射纸的厚度为0.25～0.35mm。
本发明提供了一种芳纶纤维远红外发射纸的制备方法，将对位芳纶短切纤维与疏解剂和水混合后进行疏解处理，将所得纤维洗涤后用低温等离子体进行表面处理，将所得纤维与分散剂和水混合后依次进行超声处理和打浆处理，得到对位芳纶短切纤维浆料；将对位芳纶浆粕纤维与分散剂和水混合后依次进行超声处理和打浆处理，得到对位芳纶浆粕纤维浆料；将所述对位芳纶短切纤维浆料和对位芳纶浆粕纤维浆料混合后进行剪切处理，得到芳纶纤维浆料；将碳纳米管与分散剂和乙醇混合后依次进行超声处理和剪切处理，得到碳纳米管分散液；将所述芳纶纤维浆料与所述碳纳米管分散液和纸力增强剂混合后进行剪切处理，将所得混合浆料涂覆到基材的单面，经固化后剥离基材，将所得固化膜进行热压成型，得到芳纶纤维远红外发射纸。在本发明中，所述对位芳纶短切纤维和对位芳纶浆粕纤维作为纸基功能材料，具有比强度高、比刚度大的优异特性；同时，对位芳纶短切纤维和对位芳纶浆粕纤维能够形成具有孔隙和孔道的纸状物，所述碳纳米管嵌在所述纸状物的结构孔隙和孔道里。因此，所述芳纶纤维远红外发射纸拥有更好的成型质量和复合性能，可以用于高铁、飞机、轿车等加热坐垫。实施例的结果表明，本发明提供的芳纶纤维远红外发射纸发射出的远红外波长在4～20μm，主频段在10μm左右，且远红外转换效率高达99％；同时，其抗拉强度为0.12～0.18KN/mm 2，且可弯曲和折叠。说明本发明提供的芳纶纤维远红外发射纸具有优异的远红外线发射性能和机械性能。
此外，本发明提供的制备方法操作简单，便于规模化生产。
具体实施方式
本发明提供了一种芳纶纤维远红外发射纸的制备方法，包括以下步骤：
(1)将对位芳纶短切纤维与疏解剂和水混合后进行疏解处理，将所得纤维洗涤后用低温等离子体进行表面处理，将所得纤维与分散剂和水混合后依次进行超声处理和打浆处理，得到对位芳纶短切纤维浆料；
将对位芳纶浆粕纤维与分散剂和水混合后依次进行超声处理和打浆处理，得到对位芳纶浆粕纤维浆料；
将所述对位芳纶短切纤维浆料和对位芳纶浆粕纤维浆料混合后进行剪切处理，得到芳纶纤维浆料；
(2)将碳纳米管与分散剂和乙醇混合后依次进行超声处理和剪切处理，得到碳纳米管分散液；
(3)将所述步骤(1)中芳纶纤维浆料与所述步骤(2)中碳纳米管分散液和纸力增强剂混合后进行剪切处理，将所得混合浆料涂覆到基材的单面，经固化后剥离基材，将所得固化膜进行热压成型，得到芳纶纤维远红外发射纸；
所述步骤(1)和步骤(2)无时间顺序限定。
本发明将对位芳纶短切纤维与疏解剂和水混合后进行疏解处理，将所得纤维洗涤后用低温等离子体进行表面处理，将所得纤维与分散剂和水混合后依次进行超声处理和打浆处理，得到对位芳纶短切纤维浆料。在本发明中，所述对位芳纶短切纤维的长度优选为3～5mm。本发明对于所述对位芳纶短切纤维的来源没有特殊的限定，采用本领域技术人员熟知的市售商品即可。
本发明对于所述疏解剂没有特殊的限定，采用本领域技术人员熟知的疏解剂即可；在本发明中，所述疏解剂优选包括十二烷基苯磺酸钠(SDBS)、聚乙烯吡咯烷酮(PVP)、聚环氧乙烷(PEO)或聚乙烯醇(PVA)，更优选为十二烷基苯磺酸钠。在本发明中，所述疏解剂、对位芳纶短切纤维和水的质量比优选为(0.009～0.011)：1：(50～150)，更优选为0.01：1：100。本发明对于所述疏解处理没有特殊的限定，采用本领域技术人员熟知的疏解处理的技术方案即可。
在本发明中，所述洗涤优选为水洗。本发明对于所述洗涤的具体操作 方法没有特殊的限定，采用本领域技术人员熟知的洗涤的技术方案即可。本发明利用洗涤去除所述对位芳纶短切纤维表面的杂质。
在本发明中，所述表面处理的压力优选为75～85Pa，更优选为80Pa；功率优选为75～85W，更优选为80W；时间优选为2.5～3.5min，更优选为3min。本发明利用低温等离子体进行表面处理进一步去除所述对位芳纶短切纤维表面的微小杂质。
本发明对于所述分散剂没有特殊的限定，采用本领域技术人员熟知的分散剂即可，具体如聚氧化乙烯。在本发明中，所述分散剂、对位芳纶短切纤维和水的质量比优选为(0.009～0.011)：1：(50～150)，更优选为0.01：1：100。在本发明中，所述超声处理的时间优选为20～30min；本发明对于所述超声处理的功率没有特殊的限定，采用本领域技术人员熟知的功率即可。本发明对于所述打浆处理没有特殊的限定，采用本领域技术人员熟知的打浆处理的技术方案即可；在本发明中，所述打浆处理的时间优选为5～10min；所述打浆过程中打浆度优选为40～50°SR，更优选为45°SR。本发明在所述分散剂作用下通过超声处理使对位芳纶短切纤维均匀的分散在水中，进而通过打浆处理得到对位芳纶短切纤维浆料。
本发明将对位芳纶浆粕纤维与分散剂和水混合后依次进行超声处理和打浆处理，得到对位芳纶浆粕纤维浆料。在本发明中，所述对位芳纶浆粕纤维的长度优选为1.2～1.8mm。本发明对于所述对位芳纶浆粕纤维的来源没有特殊的限定，采用本领域技术人员熟知的市售商品即可。本发明对于所述分散剂没有特殊的限定，采用本领域技术人员熟知的分散剂即可；具体如聚氧化乙烯。在本发明中，所述分散剂、对位芳纶浆粕纤维与水的质量比优选为(0.009～0.011)：1：(50～150)，更优选为0.01：1：100。在本发明中，所述超声处理的时间优选为20～30min；本发明对于所述超声处理的功率没有特殊的限定，采用本领域技术人员熟知的功率即可。本发明对于所述打浆处理没有特殊的限定，采用本领域技术人员熟知的打浆处理的技术方案即可；在本发明中，所述打浆处理的时间优选为5～10min；所述打浆过程中打浆度优选为40～50°SR，更优选为45°SR。本发明在所述分散剂作用下通过超声处理使对位芳纶浆粕纤维均匀的分散在水中，进而通过打浆处理得到对位芳纶浆粕纤维浆料。
得到对位芳纶短切纤维浆料和对位芳纶浆粕纤维浆料后，本发明将所述对位芳纶短切纤维浆料和对位芳纶浆粕纤维浆料混合后进行剪切处理，得到芳纶纤维浆料。在本发明中，所述剪切处理的转速优选为1800～2200r/min，更优选为2000r/min；时间优选为30～60min，更优选为40～50min。
本发明将碳纳米管与分散剂和乙醇混合后依次进行超声处理和剪切处理，得到碳纳米管分散液。在本发明中，所述碳纳米管优选为晶须状的多壁碳纳米管。在本发明中，所述碳纳米管的长度优选为2～5μm，直径优选为30～150nm。在本发明中，所述碳纳米管优选按照文献(Sun X G,Qiu Z W,Chen L,et al.Industrial synthesis of Whisker carbon nanotubes[C]//Materials Science Forum.Trans Tech Publications Ltd.,2016,852:514)公开的方法制备得到；按照此方法制备得到的为直线型高纯度高结晶度碳纳米管。本发明对于所述分散剂没有特殊的限定，采用本领域技术人员熟知的分散剂即可；在本发明中，所述分散剂优选包括十二烷基硫酸钠(SDS)、聚乙烯吡咯烷酮(PVP)、十二烷基苯磺酸钠(SDBS)。在本发明中，所述碳纳米管、分散剂和乙醇的质量比优选为1：(0.05～0.1)：(50～150)。在本发明中，所述超声处理的时间优选为10～30min，更优选为20min；本发明对于所述超声处理的功率没有特殊的限定，采用本领域技术人员熟知的功率即可。在本发明中，所述剪切处理的转速优选为1800～2200r/min，更优选为2000r/min；时间优选为10～30min，更优选为20min。本发明在所述分散剂作用下通过超声处理和剪切处理使碳纳米管均匀的分散在乙醇中。
得到芳纶纤维浆料与碳纳米管分散液后，本发明将所述芳纶纤维浆料与碳纳米管分散液和纸力增强剂混合后进行剪切处理，将所得混合浆料涂覆到基材的单面，经固化后剥离基材，将所得固化膜进行热压成型，得到芳纶纤维远红外发射纸。在本发明中，在本发明中，所述对位芳纶短切纤维、对位芳纶浆粕纤维与碳纳米管的质量比优选为(0.5～1.5)：(0.5～1.5)：(0.5～8)，更优选为1：1：(1～4)，最优选为1：1：2。在本发明中，所述纸力增强剂优选包括阴离子聚丙烯酰胺或羧甲基纤维素。在本发明中，所述纸力增强剂的质量优选为对位芳纶短切纤维和对位芳纶浆粕纤维 总质量的0.8～1.2％，更优选为1％。在本发明中，所述芳纶纤维浆料与碳纳米管分散液和纸力增强剂的混合优选在不锈钢流体混合机中进行。在本发明中，所述剪切处理的转速优选为1800～2200r/min，更优选为2000r/min；时间优选为30～60min，更优选为40～50min。
本发明对于所述基材没有特殊的限定，采用本领域技术人员熟知的基材即可；在本发明的实施例中，具体采用纤维素基材。本发明对于所述基材的尺寸大小没有特殊的限定，根据实际需要选择所述基材的尺寸大小即可；在本发明的实施例中，所述基材的尺寸具体为A4纸大小，即210mm×297mm。在本发明中，所述基材主要起基底作用，能够承受压力与高温，且适合剥离分开。
本发明对于所述涂覆没有特殊的限定，采用本领域技术人员熟知的涂覆的技术方案即可，本发明优选通过狭缝挤压涂布的方式将所述混合浆料均匀地涂覆到基材的单面。在本发明中，所述混合浆料在基材单面的涂覆量优选为0.2～2mL/cm 2，更优选为0.8～1.3mL/cm 2。
在本发明中，所述固化的温度优选为60～80℃，时间优选为22～26h。在本发明中，所述固化能够使涂覆在基材单面的混合浆料初步干燥，在基材的单面形成固化膜；且使所述固化膜中对位芳纶短切纤维和对位芳纶浆粕纤维初步形成网格结构，使碳纳米管填充在所述网格结构中。
在本发明中，所述热压成型的温度优选为250～350℃，线压力优选为120～150KN/m。在本发明中，所述热压成型能够进一步将碳纳米管压入由芳纶纤维浆料形成的多孔网络之中，实现碳纳米管与对位芳纶短切纤维和对位芳纶浆粕纤维的复合。
本发明提供了上述技术方案所述制备方法制备得到的芳纶纤维远红外发射纸，由包括对位芳纶短切纤维、对位芳纶浆粕纤维和碳纳米管的原料制备得到，所述对位芳纶短切纤维和对位芳纶浆粕纤维形成具有孔隙和孔道的纸状物，所述碳纳米管嵌在所述纸状物的结构孔隙和孔道里。在本发明中，所述芳纶纤维远红外发射纸的厚度优选为0.25～0.35mm，更优选为0.3mm。
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全 部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将1g对位芳纶短切纤维(长度为3～5mm)与0.01g十二烷基苯磺酸钠和100mL水混合后进行疏解处理，将所得纤维水洗后在压力80Pa、功率80W的条件下用低温等离子体进行表面处理3min，将所得纤维与0.01g聚氧化乙烯和100mL水混合后进行超声处理20min，然后进行打浆处理10min，控制打浆度为40°SR，得到对位芳纶短切纤维浆料；
将1g对位芳纶浆粕纤维(长度为1.2～1.8mm)与0.01g聚氧化乙烯和100mL水混合后进行超声处理20min，然后进行打浆处理10min，控制打浆度为40°SR，得到对位芳纶浆粕纤维浆料；
将所述对位芳纶短切纤维浆料和对位芳纶浆粕纤维浆料混合后在2000r/min条件下进行剪切处理30min，得到芳纶纤维浆料；
将2g晶须状的多壁碳纳米管(长度为2～5μm，直径为30～150nm)与0.1g十二烷基硫酸钠和200g乙醇混合后进行搅拌，之后进行超声处理10min，最后在2000r/min条件下进行剪切处理10min，得到碳纳米管分散液；
采用不锈钢流体混合机将所述芳纶纤维浆料和所述碳纳米管分散液与阴离子聚丙烯酰胺(添加量为对位芳纶短切纤维和对位芳纶浆粕纤维总质量的1％)混合后在2000r/min条件下进行剪切处理30min，通过狭缝挤压涂布的方式将所得混合浆料涂布到纤维素基材(尺寸大小为210mm×297mm)的单面，在60℃条件下进行真空干燥24h后剥离纤维素基材，在温度为250℃、线压力为150KN/m的条件下，将所得固化膜经辊式热压机热压成型，得到芳纶纤维远红外发射纸，厚度为0.3mm。
使用光栅和探测器测试本实施例制备的芳纶纤维远红外发射纸的远红外线发射性能，结果显示所述芳纶纤维远红外发射纸发射出的远红外波长在4～20μm，主频段为10μm左右，且远红外转换效率高达99％。说明本发明提供的芳纶纤维远红外发射纸具有良好的远红外线发射性能。
在本实施例制备的芳纶纤维远红外发射纸的下方吊挂砝码，以测试其强度，结果发现每平方毫米截面积的所述芳纶纤维远红外发射纸可以承受 15kg的砝码且不会破碎。同时，本实施例制备的芳纶纤维远红外发射纸可随意弯曲，弯曲角度为0～180°；将所述芳纶纤维远红发射纸对折后未见明显折痕，且经强度测试，折痕处的抗拉强度和未折痕处的抗拉强度相差较小，折痕处的抗拉强度约为0.13KN/mm 2，未折痕处的抗拉强度为0.15KN/mm 2。说明本发明提供的芳纶纤维远红外发射纸具有良好的机械性能。
实施例2
将2g对位芳纶短切纤维(长度为3～5mm)与0.02g十二烷基苯磺酸钠和200mL水混合后进行疏解处理，将所得纤维水洗后在压力80Pa、功率80W的条件下用低温等离子体进行表面处理3min，将所得纤维与0.02g聚氧化乙烯和200mL水混合后进行超声处理30min，然后进行打浆处理5min，控制打浆度为45°SR，得到对位芳纶短切纤维浆料；
将2g对位芳纶浆粕纤维(长度为1.2～1.8mm)与0.01g聚氧化乙烯和200mL水混合后进行超声处理30min，然后进行打浆处理5min，控制打浆度为45°SR，得到对位芳纶浆粕纤维浆料；
将所述对位芳纶短切纤维浆料和对位芳纶浆粕纤维浆料混合后在2000r/min条件下进行剪切处理60min，得到芳纶纤维浆料；
将2g晶须状的多壁碳纳米管(长度为2～5μm，直径为30～150nm)与0.15g十二烷基硫酸钠和150g乙醇混合后进行搅拌，之后进行超声处理20min，最后在2000r/min条件下进行剪切处理20min，得到碳纳米管分散液；
采用不锈钢流体混合机将所述芳纶纤维浆料和所述碳纳米管分散液与阴离子聚丙烯酰胺(添加量为对位芳纶短切纤维和对位芳纶浆粕纤维总质量的1％)混合后在2000r/min条件下进行剪切处理60min，通过狭缝挤压涂布的方式将所得混合浆料涂布到纤维素基材(尺寸大小为210mm×297mm)的单面，在80℃条件下进行真空干燥24h后剥离纤维素基材，在温度为350℃、线压力为120KN/m的条件下，将所得固化膜经辊式热压机热压成型，得到芳纶纤维远红外发射纸，厚度为0.3mm。
使用光栅和探测器测试本实施例制备的芳纶纤维远红外发射纸的远红外线发射性能，结果显示所述芳纶纤维远红外发射纸发射出的远红外波 长在4～20μm，主频段为10μm左右，且远红外转换效率高达99％。说明本发明提供的芳纶纤维远红外发射纸具有良好的远红外线发射性能。
在本实施例制备的芳纶纤维远红外发射纸的下方吊挂砝码，以测试其强度，结果发现每平方毫米截面积的所述芳纶纤维远红外发射纸可以承受17kg的砝码且不会破碎。同时，本实施例制备的芳纶纤维远红外发射纸可随意弯曲，弯曲角度为0～180°；将所述芳纶纤维远红发射纸对折后未见明显折痕，且经强度测试，折痕处的抗拉强度和未折痕处的抗拉强度相差较小，折痕处的抗拉强度约为0.16KN/mm 2，未折痕处的抗拉强度为0.17KN/mm 2。
实施例3
将1g对位芳纶短切纤维(长度为3～5mm)与0.01g十二烷基苯磺酸钠和100mL水混合后进行疏解处理，将所得纤维水洗后在压力80Pa、功率80W的条件下用低温等离子体进行表面处理3min，将所得纤维与0.01g聚氧化乙烯和100mL水混合后进行进行超声处理30min，然后进行打浆处理10min，控制打浆度为50°SR，得到对位芳纶短切纤维浆料；
将1g对位芳纶浆粕纤维(长度为1.2～1.8mm)与0.01g十二烷基硫酸钠和100mL水混合后进行超声处理30min，然后进行打浆处理10min，控制打浆度为50°SR，得到对位芳纶浆粕纤维浆料；
将所述对位芳纶短切纤维浆料和对位芳纶浆粕纤维浆料混合后在2000r/min条件下进行剪切处理30min，得到芳纶纤维浆料；
将4g晶须状的多壁碳纳米管(长度为2～5μm，直径为30～150nm)与0.2g十二烷基硫酸钠和400g乙醇混合后进行搅拌，之后进行超声处理30min，最后在2000r/min条件下进行剪切处理30min，得到碳纳米管分散液；
采用不锈钢流体混合机将所述芳纶纤维浆料和所述碳纳米管分散液与阴离子聚丙烯酰胺(添加量为对位芳纶短切纤维和对位芳纶浆粕纤维总质量的1％)混合后在2000r/min条件下进行剪切处理30min，通过狭缝挤压涂布的方式将所得混合浆料涂布到纤维素基材(尺寸大小为210mm×297mm)的单面，在60℃条件下进行真空干燥24h后剥离纤维素基材，在温度为350℃、线压力为150KN/m的条件下，将所得固化膜经辊式热 压机热压成型，得到芳纶纤维远红外发射纸，厚度为0.3mm。
使用光栅和探测器测试本实施例制备的芳纶纤维远红外发射纸的远红外线发射性能，结果显示所述芳纶纤维远红外发射纸发射出的远红外波长在4～20μm，主频段为10μm左右，且远红外转换效率高达99％。说明本发明提供的芳纶纤维远红外发射纸具有良好的远红外线发射性能。
在本实施例制备的芳纶纤维远红外发射纸的下方吊挂砝码，以测试其强度，结果发现每平方毫米截面积的所述芳纶纤维远红外发射纸可以承受13kg的砝码且不会破碎。同时，本实施例制备的芳纶纤维远红外发射纸可随意弯曲，弯曲角度为0～180°；将所述芳纶纤维远红发射纸对折后未见明显折痕，且经强度测试，折痕处的抗拉强度和未折痕处的抗拉强度相差较小，折痕处的抗拉强度约为0.1KN/mm 2，未折痕处的抗拉强度为0.13KN/mm 2。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (16)

  1. 一种芳纶纤维远红外发射纸的制备方法，包括以下步骤：
    (1)将对位芳纶短切纤维与疏解剂和水混合后进行疏解处理，将所得纤维洗涤后用低温等离子体进行表面处理，将所得纤维与分散剂和水混合后依次进行超声处理和打浆处理，得到对位芳纶短切纤维浆料；
    将对位芳纶浆粕纤维与分散剂和水混合后依次进行超声处理和打浆处理，得到对位芳纶浆粕纤维浆料；
    将所述对位芳纶短切纤维浆料和对位芳纶浆粕纤维浆料混合后进行剪切处理，得到芳纶纤维浆料；
    (2)将碳纳米管与分散剂和乙醇混合后依次进行超声处理和剪切处理，得到碳纳米管分散液；
    (3)将所述步骤(1)中芳纶纤维浆料与所述步骤(2)中碳纳米管分散液和纸力增强剂混合后进行剪切处理，将所得混合浆料涂覆到基材的单面，经固化后剥离基材，将所得固化膜进行热压成型，得到芳纶纤维远红外发射纸；
    所述步骤(1)和步骤(2)无时间顺序限定。
  2. 根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中对位芳纶短切纤维和对位芳纶浆粕纤维与步骤(2)中碳纳米管的质量比为(0.5～1.5)：(0.5～1.5)：(0.5～8)。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述步骤(1)中对位芳纶短切纤维的长度为3～5mm。
  4. 根据权利要求1或2所述的制备方法，其特征在于，所述步骤(1)中对位芳纶浆粕纤维的长度为1.2～1.8mm。
  5. 根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中表面处理的压力为75～85Pa，功率为75～85W，时间为2.5～3.5min。
  6. 根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中疏解剂包括十二烷基苯磺酸钠、聚乙烯吡咯烷酮、聚环氧乙烷或聚乙烯醇。
  7. 根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中分散剂包括聚氧化乙烯。
  8. 根据权利要求1所述的制备方法，其特征在于，所述步骤(2)中分散剂包括十二烷基硫酸钠、聚乙烯吡咯烷酮、十二烷基苯磺酸钠。
  9. 根据权利要求1或2所述的制备方法，其特征在于，所述步骤(2)中碳纳米管为晶须状的多壁碳纳米管。
  10. 根据权利要求9所述的制备方法，其特征在于，所述碳纳米管的长度为2～5μm，直径为30～150nm。
  11. 根据权利要求1所述的制备方法，其特征在于，所述步骤(3)中纸力增强剂包括阴离子聚丙烯酰胺或羧甲基纤维素。
  12. 根据权利要求1所述的制备方法，其特征在于，所述步骤(3)中混合浆料在基材单面的涂覆量为0.2～2mL/cm 2。
  13. 根据权利要求1所述的制备方法，其特征在于，所述步骤(3)中固化的温度为60～80℃，时间为22～26h。
  14. 根据权利要求1所述的制备方法，其特征在于，所述步骤(3)中热压成型的温度为250～350℃，线压力120～150KN/m。
  15. 权利要求1～14任一项所述制备方法制备得到的芳纶纤维远红外发射纸，由包括对位芳纶短切纤维、对位芳纶浆粕纤维和碳纳米管的原料制备得到，所述对位芳纶短切纤维和对位芳纶浆粕纤维形成具有孔隙和孔道的纸状物，所述碳纳米管嵌在所述纸状物的结构孔隙和孔道里。
  16. 根据权利要求15所述的芳纶纤维远红外发射纸，其特征在于，所述芳纶纤维远红外发射纸的厚度为0.25～0.35mm。
PCT/CN2018/101733 2018-08-22 2018-08-22 一种芳纶纤维远红外发射纸及其制备方法 WO2020037549A1 (zh)

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