WO2018166477A1 - 一种改性纤维制品、制备方法及其用途 - Google Patents

一种改性纤维制品、制备方法及其用途 Download PDF

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Publication number
WO2018166477A1
WO2018166477A1 PCT/CN2018/079035 CN2018079035W WO2018166477A1 WO 2018166477 A1 WO2018166477 A1 WO 2018166477A1 CN 2018079035 W CN2018079035 W CN 2018079035W WO 2018166477 A1 WO2018166477 A1 WO 2018166477A1
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Prior art keywords
graphene
fiber
modified
temperature
based substance
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PCT/CN2018/079035
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English (en)
French (fr)
Inventor
张金柱
王文平
张安
刘顶
Original Assignee
山东圣泉新材料股份有限公司
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Priority claimed from CN201710153992.5A external-priority patent/CN106930099A/zh
Priority claimed from CN201710153981.7A external-priority patent/CN106930098A/zh
Priority claimed from CN201710153028.2A external-priority patent/CN106930096B/zh
Priority claimed from CN201710153200.4A external-priority patent/CN106930097A/zh
Priority claimed from CN201710197196.1A external-priority patent/CN106948171B/zh
Priority claimed from CN201710196817.4A external-priority patent/CN106948170B/zh
Priority claimed from CN201710443946.9A external-priority patent/CN107245878A/zh
Priority claimed from CN201710443948.8A external-priority patent/CN107254774A/zh
Priority claimed from CN201710443947.3A external-priority patent/CN107245879A/zh
Priority to DE112018001356.1T priority Critical patent/DE112018001356T5/de
Priority to KR1020197030234A priority patent/KR20190125480A/ko
Priority to JP2019572277A priority patent/JP6852200B2/ja
Application filed by 山东圣泉新材料股份有限公司 filed Critical 山东圣泉新材料股份有限公司
Publication of WO2018166477A1 publication Critical patent/WO2018166477A1/zh

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Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • 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
    • D06M11/58—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 nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/63—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 nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form

Definitions

  • the invention belongs to the field of preparation of fiber products, in particular to a modified fiber product, a preparation method and the use thereof, in particular to an electrically conductive modified fiber product, a preparation method and the use thereof.
  • Conductive fibers are generally referred to in standard environments (temperature 20 ° C, humidity 65%) and specific resistances below 10 7 ⁇ cm. Its development process generally includes four stages: metal fiber, carbon fiber and composite conductive fiber containing carbon black composite polymer, conductive fiber containing metal salt, conductive polymer conductive fiber.
  • metal fiber carbon fiber and composite conductive fiber containing carbon black composite polymer
  • conductive fiber containing metal salt conductive polymer conductive fiber.
  • the conductive fiber has been greatly developed, there are certain problems.
  • the fabric made of the metal conductive fiber and the metal-plated conductive fiber has a rough handle and poor comfort, and the conductive polymer process is complicated and the pollution is serious.
  • the composite of the fibrous product graphene prepared by the coating or simple impregnation process is not strong enough, and the additional function is lost after washing many times. Therefore, the development of new methods for preparing conductive fibers is of great significance and practical application prospects.
  • Graphene is a two-dimensional material of honeycomb structure composed of single-layer sp2 hybrid carbon atoms. It has many excellent properties (high strength, high thermal conductivity, high electrical conductivity, high light weight), and also has a large ⁇ conjugate system. . Since its discovery in 2004, graphene has become a research hotspot in the scientific community. While studying the physicochemical properties of graphene, the graphene-related composite materials are endless. In the prior art, graphene is combined with textile fibers, and it is desired to obtain functional fiber fibers having conductivity and far-infrared, and further secure the adhesion of graphene, so that the function is not greatly increased by the number of times of washing. attenuation.
  • It is an object of the present invention to provide a modified fiber product comprising a modified fiber, a graphene-like substance present inside the modified fiber, and a graphene-based substance also present outside the modified fiber.
  • the invention can improve the firmness of the graphene-based material on the fiber by simultaneously providing the graphene-based substance inside and outside the fiber, and at the same time, improve the uniformity of the graphene in the radial direction of the fiber, and increase the compounding amount of the graphene.
  • the electrical conductivity of the fiber is improved, and the solidity of the graphene-based composite on the fiber is improved.
  • the graphene-based substance existing outside the modified fiber is more than the graphene-based substance existing inside the modified fiber.
  • the modified fiber has a large amount of graphene-like substances on the outside, and can be overlapped on the outside of the modified fiber to better improve the conductivity of the modified fiber product.
  • the fibers are obtained by aggregating macromolecular materials, and the macromolecules are regularly arranged neatly and stably to have a high degree of geometric regularity and become a crystalline structure or a crystalline state.
  • the regular arrangement of the fiber macromolecules becomes a crystallization zone; in the crystallization zone, the macromolecular segments are arranged neatly, the structure is tight, the gaps and pores are less, and the intermolecular binding force is strong.
  • the irregularly arranged regions of the fiber macromolecules are amorphous regions. In the amorphous regions, the macromolecular segments are disorderly arranged, irregular, loose in structure, and have many gaps and holes, and the mutual bonding force is small.
  • the total mass of graphenes in the modified fibrous article does not exceed 0.5 to 3 wt% of the total mass of the fibrous product, such as 0.6 wt%, 0.7 wt%, 0.9 wt%, 1 wt%, 1.6 wt%, 1.8 wt% %, 2.4 wt%, 2.6 wt%, 2.7 wt%, 2.9 wt%, and the like.
  • the content of graphenes should not be too much, and too much may lead to a decrease in fiber strength and waste of resources.
  • the graphene-based substance has a particle diameter of ⁇ 20 ⁇ m, for example, 0.2 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 12 ⁇ m, 14 ⁇ m. , 16 ⁇ m, 18 ⁇ m, 19 ⁇ m, and the like.
  • the graphene-based substance has a graphene-like substance having a particle diameter of less than 1 ⁇ m (for example, 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, etc.) mainly present in the
  • the inside of the modified fiber has a particle diameter of 1 to 20 ⁇ m (for example, 0.05 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m).
  • a graphene-like substance of 19 ⁇ m or the like is mainly present outside the modified fiber.
  • the "main” means most, to some extent, 80% by weight or more, or 90% by weight or more, or 95% by weight or more.
  • the inside of the modified fiber includes a crystal region of the modified fiber, an amorphous region, and a gap between the crystalline region and the amorphous region.
  • gaps, voids, and voids of the present invention may be replaced with each other to represent voids inside the fibers.
  • a graphene-like substance is present in the inner crystallized region of the modified fiber, and a graphene-based substance is present outside the modified fiber.
  • the graphene-based substance comprises any one or a mixture of at least two of graphene, biomass graphene, graphene oxide, and graphene derivatives, preferably graphene and/or biomass graphene.
  • the graphene derivative comprises any one or a combination of at least two of element-doped graphene or functionalized graphene.
  • the graphene-based substance existing outside the modified fiber has a particle diameter of 2 to 10 ⁇ m.
  • the modified fiber product of the present invention contains a modified fiber, a graphene-like substance is present in the inner crystallized region of the modified fiber, and a graphene-based substance is also present outside the modified fiber.
  • the present invention by distributing graphene-like substances having different particle diameters inside and outside the fiber, it is possible to simultaneously improve the adhesion fastness of the graphene-based substance to the fiber while improving the uniformity of distribution in the fiber radial direction.
  • the graphene-like substance of 1 to 20 ⁇ m is present on the outside of the fiber in a coating or laminating manner, and on the one hand, it can ensure the solid presence of the internal graphene-like substance, and on the other hand, the graphene-like substance can be improved.
  • the contact between the particles of matter increases the effect of conductivity.
  • the graphene-like substance having a particle diameter of less than 1 ⁇ m is present in at least one of a crystalline region, an amorphous region, and a gap between the crystalline region and the amorphous region inside the modified fiber.
  • a graphene-like substance is present in the crystallization zone inside the modified fiber, and preferably, the crystallization zone inside the modified fiber has a graphene-like substance having a particle diameter of less than 1 ⁇ m.
  • a crystalline region, an amorphous region, and a gap between the crystalline region and the amorphous region are present in the modified fiber;
  • the specific resistance of the modified fiber in the modified fiber product is ⁇ 1 ⁇ 10 5 ⁇ cm, for example, 1 ⁇ 10 4 ⁇ . ⁇ cm, 4 ⁇ 10 4 ⁇ cm, 7 ⁇ 10 4 ⁇ cm, 9 ⁇ 10 4 ⁇ cm, 1 ⁇ 10 3 ⁇ cm, 5 ⁇ 10 3 ⁇ cm, 8 ⁇ 10 3 ⁇ cm , 1 ⁇ 10 2 ⁇ cm, 1 ⁇ 10 ⁇ cm, and the like.
  • the graphene-based substance is graphene and/or biomass graphene
  • its specific resistance is ⁇ 1 ⁇ 10 5 ⁇ cm, for example, 1 ⁇ 10 4 ⁇ cm, 4 ⁇ 10 4 ⁇ cm, 7 ⁇ 10 4 ⁇ cm, 9 ⁇ 10 4 ⁇ cm, 1 ⁇ 10 3 ⁇ cm, 5 ⁇ 10 3 ⁇ cm, 8 ⁇ 10 3 ⁇ cm, 1 ⁇ 10 2 ⁇ cm, 1 ⁇ 10 ⁇ cm, and the like.
  • the far-infrared normal emissivity of the fiber product after washing 50 times is not less than 0.85, for example, not less than 0.87. Not less than 0.88, not less than 0.90.
  • the modified fiber product is not specifically limited.
  • the modified fibrous article comprises any one or a combination of at least two of modified fibers, yarns comprising modified fibers, and fabrics comprising modified fibers.
  • the fiber product may be a fiber, which may be a yarn or a fabric; that is, a fiber impregnated graphene solution, which may be a yarn impregnated graphene solution, or a fabric impregnated graphene solution.
  • the modified fiber comprises modified polyester fiber, modified nylon fiber, modified spandex fiber, modified aramid fiber, modified acrylic fiber, modified PVA fiber, and modified regenerated cellulose fiber.
  • the yarn comprising the modified fiber is obtained by monofilament, blending or blending with the unmodified fiber.
  • the fabric comprising modified fibers is made of the modified fibers, the yarns comprising modified fibers.
  • the modified fiber product contains nanocellulose.
  • the addition of an appropriate amount of nanocellulose can increase the entanglement of the graphene-like substance on the fiber, and the entanglement of the nanocellulose can increase the strength of the modified fiber product.
  • the modified fiber of the modified fiber product is compounded with nanocellulose.
  • the nanocellulose is entangled inside and/or outside the modified fiber.
  • the nanocellulose has a high aspect ratio and a small diameter, and the external graphene-like substance is bound or overlapped with the internal crystal region of the fiber or the graphene of the fiber, so that the external graphene-like substance is not easily peeled off.
  • a second object of the present invention is to provide a process for producing a modified fibrous article according to one of the objects, which comprises immersing an unmodified fibrous product in a graphene-based dispersion, followed by cooling and drying. , obtaining the treated fibrous product;
  • the temperature range of the impregnation is at a high elastic temperature of the fibrous material in the unmodified fibrous article.
  • the unmodified fibrous product is immersed in a high elastic temperature graphene-like material dispersion of the fibrous material of the fibrous product, wherein the high elastic state means that the material is between the glass transition temperature and the viscous flow temperature, Reaching the glass transition temperature of the material can increase the motion of the macromolecules in the fiber, so that the crystallization zone is converted to the non-crystalline region, so that the voids in the amorphous region become larger, so that the inter-matrix region between the crystalline region and the amorphous region is The voids become large; at the same time, particles of the graphene-like substance dispersed in the graphene-based dispersion enter the void; the impregnated fibers are then cooled, so that the graphene entering the void during the impregnation is fixed inside the fiber
  • the particle size is larger, the graphene-like substance which is blocked outside the void may be coated, laminated, or even partially enter the inside of the fiber, and partially exist outside the fiber
  • the interior of the fiber and the exterior of the fiber of the present invention are well-known concepts in the art, and it can also be understood that the macromolecules constituting the fiber aggregate in space to form a supramolecular structure, and the inside of the macromolecule is crystallized.
  • the region, the amorphous region, and the region of the crystalline region and the amorphous region; and the outer side formed by the aggregation of the macromolecule is regarded as the outer portion of the fiber.
  • the impregnation temperature should be below the viscous flow (viscous flow) temperature of all fibrous materials, and the impregnation temperature should be higher than the fiber having the lowest glass transition temperature therein.
  • the material has a low glass transition temperature above.
  • the high elastic temperature of the present invention refers to the lowest temperature when the fiber material reaches a high elastic state; the glass transition temperature refers to the lowest temperature when the fiber material reaches a glass state; the viscous flow temperature refers to the fiber The material reaches the lowest temperature of the viscous flow state.
  • the impregnation temperature is at least 5 ° C higher than the glass transition temperature of the fibrous material in the unmodified fibrous article.
  • a range of 5 ° C higher than the glass transition temperature of the fiber material is more favorable for the creep of the fiber molecules, the voids are opened more rapidly, and the graphene-like substance enters the voids for a shorter period of time.
  • the modified fibrous article comprises any one or a combination of at least two of the modified fiber, the yarn comprising the modified fiber, and the fabric comprising the modified fiber.
  • the fiber product may be a fiber, which may be a yarn or a fabric; that is, a fiber impregnated graphene solution, which may be a yarn impregnated graphene solution, or a fabric impregnated graphene solution.
  • the modified fiber comprises modified polyester fiber, modified nylon fiber, modified spandex fiber, modified aramid fiber, modified acrylic fiber, modified PVA fiber, and modified regenerated cellulose fiber.
  • the fiber is a polyester fiber, a nylon fiber or an acrylic fiber;
  • the temperature of the impregnation is 80 to 120 ° C;
  • the temperature of the impregnation is 45 to 80 ° C;
  • the temperature of the impregnation is 80 to 100 °C.
  • the yarn containing the modified fiber is obtained by single-spinning the modified fiber or blended with the unmodified fiber.
  • the fabric comprising modified fibers is made of the modified fibers, the yarns comprising modified fibers.
  • the graphene-based substance comprises any one or a mixture of at least two of graphene, biomass graphene, graphene oxide, and graphene derivatives, preferably graphene, biomass graphene, and/or graphite oxide. Alkene.
  • the graphene oxide comprises graphene oxidized by a TEMPO system.
  • the graphene oxidized by the TEMPO system can insert an oxidizing functional group into the graphene, improve the uniformity of dispersion of graphene oxide in the dispersion, reduce the agglomeration of graphene in the graphene dispersion, and improve the utilization of graphene.
  • the graphene derivative comprises any one or a combination of at least two of element-doped graphene or functionalized graphene.
  • the concentration of the graphene-based substance dispersion is 0.1 to 5 wt%, preferably 0.3 to 2 wt%, such as 0.3%, 0.5%, 0.8%, 0.9%, 1.3%, 1.6%, 1.8%, 1.9%, 1.5%, 3%, 3.6%, 4%, 4.5%, etc.
  • the graphene-based substance in the graphene-based substance dispersion has a particle diameter of not more than 20 ⁇ m, preferably 100 nm to 10 ⁇ m, further preferably 200 nm to 5 ⁇ m; for example, 30 nm, 150 nm, 190 nm, 230 nm, 260 nm, 290 nm, 330 nm, 460 nm, 590 nm, 630 nm, 760 nm, 890 nm, 930 nm, 1 ⁇ m, 3 ⁇ m, 8 ⁇ m, 11 ⁇ m, 13 ⁇ m, 18 ⁇ m, and the like.
  • the immersion time is 15 to 120 min, such as 16 min, 19 min, 23 min, 26 min, 32 min, 55 min, 66 min, 73 min, 78 min, 85 min, 88 min, 95 min, and the like.
  • the immersing of the unmodified fiber product in the graphene-based material dispersion is performed in two steps, and specifically includes the following steps:
  • the impregnation of the unmodified fibrous product in the graphene-based material dispersion having a particle diameter of less than 1 ⁇ m enables the graphene-like substance having a particle diameter of less than 1 ⁇ m to enter the inside of the fiber (for example, an amorphous region or a crystalline region and a non-crystalline region).
  • the step (A1) since the size of the voids in the fiber is limited, the step (A1) only uses the graphene-like material having a particle diameter of less than 1 ⁇ m to modify the fiber product. It is well known that the smaller the particle size of the graphene, the less likely it is to disperse.
  • the fiber product is modified by using a graphene-like material having a particle diameter of 1 to 20 ⁇ m, so that a large-sized graphene-based material having a particle diameter of more than 1 ⁇ m can be coated and laminated on the outside of the fiber, and more It is advantageous for graphene to form a conductive network outside the fiber, partially blocking the opening of the void filled with the graphene-like substance within 1 ⁇ m, and also functioning to close the internal void of the fiber, thereby increasing the robustness of the graphene-like substance in the fiber.
  • the at least first impregnation temperature range is at a high elastic temperature of the fibrous material in the unmodified fibrous article.
  • the impregnation temperature range of the first impregnation and the second impregnation is in a high elastic temperature of the fibrous material in the unmodified fibrous product and the second impregnation temperature is lower than the first impregnation temperature.
  • the first impregnation and/or second impregnation temperature is at least 5 ° C higher than the glass transition temperature of the fibrous material in the unmodified fibrous article.
  • the high elastic temperature of the fiber material in the unmodified fiber product can increase the movement of macromolecules in the fiber, so that the crystallization zone is converted to the non-crystalline zone, so that the void of the amorphous zone becomes larger, so that crystallization
  • the interstices between the macromolecules in the region between the region and the amorphous region become larger; thus, the graphene-like substances entering the inside of the fiber are increased.
  • part of the graphene can enter the crystallization region at a low temperature, and is firmly present in the crystallization region at a low temperature. Inside the fiber, the firmness of the graphene-like substance in the fiber is improved.
  • the invention can set the secondary impregnation temperature to be lower than the primary impregnation temperature, to avoid the graphene-like substance running out of the fiber, but the secondary graphene can be better fixed by the secondary impregnation and outside the fiber.
  • a protective layer is formed.
  • the times of the first impregnation and the second impregnation are each independently selected from 15 to 120 min, such as 16 min, 19 min, 23 min, 26 min, 32 min, 55 min, 66 min, 73 min, 78 min, 85 min, 88 min, 95 min. Wait.
  • the first immersed graphene-based substance has a particle diameter of 0.1 to 1 ⁇ m, for example, 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, or the like. Preferably, it is 0.2 to 0.5 ⁇ m.
  • the second impregnated graphene-like substance has a particle diameter of 2 to 10 ⁇ m, for example, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, etc., preferably 5 to 10 ⁇ m;
  • the concentration of the graphene-based substance is 0.5 to 5 wt%, for example, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.1 wt%. 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, and the like.
  • the concentration of the graphene-based substance is 0.5 to 7 wt%, for example, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.1. Wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt% , 6.5 wt%, etc.
  • the graphene oxide itself is inferior in conductivity, and in order to ensure the conductivity of the graphene-modified fiber product, the present invention can carry out a reduction treatment on the modified fiber product in which graphene oxide is compounded.
  • the graphene-based substance includes graphene oxide
  • a reduction treatment is performed before and/or after cooling.
  • the method of the reduction treatment comprises a reducing agent reduction method and/or a heating reduction method.
  • the reducing agent reduction method comprises adding a reducing agent for reduction.
  • the reducing agent is added in an amount of 10 to 200% by weight, preferably 50 to 100% by weight based on the graphene-based substance.
  • the reducing agent comprises any one or a combination of at least two of ascorbic acid, hydrazine hydrate, glucose, ethylenediamine, sodium citrate, L-cysteine, hydroiodic acid or sodium borohydride.
  • the heat reduction method comprises heating in a non-oxidizing atmosphere for reduction.
  • the step of heating and reducing comprises: heating and reducing in a high pressure reaction vessel by introducing a protective atmosphere and/or a reducing atmosphere; the temperature of the heating reduction is ⁇ 200 ° C, and the pressure is ⁇ 1.6 MPa.
  • nanocellulose is added to the graphene-based material dispersion.
  • the nanocellulose has a diameter of not more than 10 nm, an aspect ratio of not less than 10, and an aspect ratio of 20, 30, 50, 100 or the like.
  • the concentration of the nanocellulose in the dispersion is 2 wt% or less, preferably 1 wt% or less, more preferably 0.5 wt% or less.
  • the nanocellulose itself is linear, and it can be wound around the outer periphery of the fiber. This winding method can increase the strength of the fiber and improve the firmness of the graphene outside the fiber; on the other hand, one end of the nanocellulose can be inserted. In the graphene sheet layer, the amount of the graphene-based substance adhered to the fiber is increased. However, nanocellulose itself is not electrically conductive, and excessive nanocellulose causes a decrease in electrical conductivity.
  • the unmodified fibers of the present invention may be nascent fibers or commercially available commercially available fibers.
  • the unmodified fibers are nascent fibers.
  • the nascent fibers of the present invention are obtained by polymer spinning.
  • the polymer comprises any one or a combination of at least two of polyester, polyamide, polyacrylonitrile, polypropylene, polyurethane, polyvinyl acetal and polyvinyl chloride.
  • the spinning comprises any one or a combination of at least two of electrospinning, melt spinning, wet solution spinning, dry solution spinning.
  • the nascent fibers of the present invention refer to fibers which are extruded from a spinning orifice and which are solidified in a spinning field. It should be apparent to those skilled in the art that the present invention can provide a method for preparing a composite fiber which is a fiber formed by curing a polymer extruded from a spinneret, and the obtained fiber can continue the subsequent process steps, such as Coating silicone oil, etc.
  • the third object of the present invention is to provide a method for preparing a modified fiber product, which comprises: immersing an unmodified fiber product in a graphene-based material dispersion, and extracting and heating to a high elastic temperature of the fiber material. And the composite treatment is carried out at a constant temperature, and then cooled and dried to obtain a modified fiber product.
  • the unmodified fibrous product is immersed in a graphene-based material dispersion, for example, immersing the fibrous product in a graphene-based material dispersion at a normal temperature, and the graphene-based substance can be adsorbed on the outer side of the fibrous product.
  • a graphene-based material dispersion for example, immersing the fibrous product in a graphene-based material dispersion at a normal temperature
  • the graphene-based substance can be adsorbed on the outer side of the fibrous product.
  • Removing the fibrous product adsorbed with the graphene substance and heating it to a high elastic temperature of the fiber material the voids inside the fiber are increased, and the existing voids become large, and the graphene substance adsorbed on the outside of the fiber moves to the In the voids, after cooling, the voids inside the fibers are reduced, and the purpose of solidifying the graphene-based substances inside the fibers is achieved.
  • the interior of the fiber and the exterior of the fiber of the present invention are well-known concepts in the art, and it can also be understood that the macromolecules constituting the fiber aggregate in space to form a supramolecular structure, and the inside of the macromolecule is crystallized.
  • the region, the amorphous region, and the region of the crystalline region and the amorphous region; and the outer side formed by the aggregation of the macromolecule is regarded as the outer portion of the fiber.
  • the treatment temperature is more than 5 ° C above the glass transition temperature of the fibrous material in the unmodified fibrous article. More than 5 ° C higher than the glass transition temperature of the fiber material is conducive to the creep of the fiber molecules, the gap is opened more rapidly, and the time for the graphene to enter the void is shorter.
  • the concentration of the graphene-based substance dispersion is 0.1 to 5 wt%, preferably 0.3 to 2 wt%, such as 0.3%, 0.5%, 0.8%, 0.9%, 1.3%, 1.6%, 1.8%, 1.9%, 1.5%, 3%, 3.6%, 4%, 4.5%, etc., preferably 0.3 to 2% by weight.
  • the graphene-based substance in the graphene-based substance dispersion has a particle diameter of not more than 20 ⁇ m; preferably 100 nm to 10 ⁇ m, further preferably 200 nm to 5 ⁇ m; for example, 30 nm, 150 nm, 190 nm, 230 nm, 260 nm, 290 nm 330 nm, 460 nm, 590 nm, 630 nm, 760 nm, 890 nm, 930 nm, 1 ⁇ m, 3 ⁇ m, 8 ⁇ m, 11 ⁇ m, 13 ⁇ m, 18 ⁇ m, and the like.
  • the immersion time of the unmodified fiber product in the graphene-based material dispersion is not specifically limited, and may be, for example, 5 to 30 minutes, for example, 6 minutes, 9 minutes, 13 minutes, 16 minutes, 22 minutes, 25 minutes, 26min, 28min, etc.
  • the temperature is raised to the high elastic temperature of the fiber material, and the process of the composite treatment at a constant temperature is carried out without solvent.
  • the ambient temperature can be used for heating, such as a hot air heating lamp, such as a greenhouse or an oven heating.
  • the manner of raising the temperature is hot air heating.
  • the time for the composite treatment after the fiber product impregnated with the graphene-based material is heated to the high elastic temperature of the fiber material is not particularly limited, and may be, for example, 15 to 120 minutes; for example, 16 minutes, 19 minutes, 23 minutes, 26 minutes, 32 minutes, 55 min, 66 min, 73 min, 78 min, 85 min, 88 min, 95 min, and the like.
  • nanocellulose is added to the graphene-based material dispersion.
  • nanocellulose can increase the entanglement of the graphene-based substance on the fiber, and the entanglement of the nanocellulose can increase the strength of the conjugate fiber.
  • the nanocellulose has a diameter of not more than 10 nm, such as 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, etc., and an aspect ratio of not less than 10, such as 11, 12, 13, 14, 15, 18, 20, 30, 50, 100, etc.; the invention binds the outer graphene substance to the inner crystal region of the fiber or the graphene substance inside the fiber through the high aspect ratio and the small diameter of the nano cellulose. Or lap joints, making the external graphene-like substances difficult to fall off.
  • the concentration of the nanocellulose in the dispersion is 2 wt% or less, such as 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt. %, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, etc., preferably 1 wt% or less, still more preferably 0.5 wt% or less .
  • the nanocellulose itself is linear, and it can be wound around the outer periphery of the fiber. This winding method can increase the strength of the fiber and improve the firmness of the graphene outside the fiber; on the other hand, one end of the nanocellulose can be inserted. In the graphene sheet layer, the amount of the graphene-based substance adhered to the fiber is increased. However, nanocellulose itself is not electrically conductive, and excessive nanocellulose causes a decrease in electrical conductivity.
  • the graphene-based substance comprises any one or a mixture of at least two of graphene, biomass graphene, graphene oxide, and graphene derivatives, preferably graphene and/or biomass graphene.
  • the graphene materials referred to in the present invention include graphene, biomass graphene, graphene oxide, graphene derivatives, which can be prepared by different processes or prepared from different raw materials, for example, mechanical stripping method, redox method. Biomass graphene prepared by carbonization and atomic rearrangement using biomass as a resource.
  • the graphene material (or graphene-based substance) of the present invention refers in principle to different types of graphene which can be prepared by those skilled in the art.
  • the graphene derivative comprises any one or a combination of at least two of element-doped graphene or functionalized graphene.
  • the graphene oxide itself is inferior in conductivity, and in order to ensure the conductivity of the fiber composited by the graphene oxide, the present invention can carry out a reduction treatment on the modified fiber product in which graphene oxide is compounded.
  • the graphene-based substance is graphene oxide
  • a reduction treatment is performed before and/or after cooling.
  • the method of the reduction treatment comprises a reducing agent reduction method and/or a heating reduction method.
  • the reducing agent reduction method comprises adding a reducing agent for reduction.
  • the reducing agent is added in an amount of 10 to 200% by weight, preferably 50 to 100% by weight based on the graphene-based substance.
  • the reducing agent comprises any one or a combination of at least two of ascorbic acid, hydrazine hydrate, glucose, ethylenediamine, sodium citrate, L-cysteine, hydroiodic acid or sodium borohydride.
  • the heat reduction method comprises heating in a non-oxidizing atmosphere for reduction.
  • the step of heating and reducing comprises: heating and reducing in a high pressure reaction vessel by introducing a protective atmosphere and/or a reducing atmosphere; the temperature of the heating reduction is ⁇ 200 ° C, and the pressure is ⁇ 1.6 MPa.
  • the modified fiber product is not specifically limited.
  • the fibrous product comprises any one or a combination of at least two of fiber strands, yarns and fabrics;
  • the fibers of the fibrous article may be any fiber known to those skilled in the art, and exemplary fibers include polyester fibers, nylon fibers, spandex fibers, aramid fibers, acrylic fibers, PVA fibers, regenerated cellulose. fiber.
  • the high-elastic temperature referred to in the invention "injecting the fibrous product into the dispersion of the graphene-based material and heating it up to the high elastic temperature of the fibrous material" to the high elastic temperature of the fibrous material generally means that the blended yarn or fabric is relatively large.
  • the high elastic temperature of a fibrous material is relatively large.
  • the yarn may be a yarn made in any manner known to those skilled in the art, for example, by any unmodified fiber that can be obtained, separately spun, blended, or modified by treatment as previously described.
  • the fibers are mono-spun, blended, or blended from the unmodified fibers and the modified fibers. It should be clear that in order to ensure the electrical conductivity of the fibrous product, in general all fibrous materials in the fibrous product should contain graphene materials.
  • the fabric may be a fabric made in any manner known to those skilled in the art, for example, any one or at least 2 of the modified fiber, the modified yarn, the unmodified fiber, and the unmodified yarn.
  • Kind of textiles are obtained. It should be clear that in order to ensure the electrical conductivity of the fiber product, in general, most of the fiber products should be fiber materials modified by graphene materials.
  • the method for preparing the modified fibrous article comprises the following steps:
  • the particle size of the graphene-based substance in the dispersion is less than 1 ⁇ m (for example, 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, etc.);
  • the particle size of the graphene-based substance in the second graphene-based material dispersion is 1 to 20 ⁇ m (for example, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 11 ⁇ m, 12 ⁇ m) , 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, etc.).
  • the step (A1) only uses the graphene-like material having a particle size of ⁇ 1 ⁇ m to modify the fiber product. It is well known that the smaller the particle size of the graphene, the less likely it is to be dispersed, and the easier it is to agglomerate, so it is often selected. The low concentration of the graphene solution also saves the amount of graphene, and reduces the probability of blocking the voids by the large-sized graphene materials, and increases the adhesion of graphene.
  • the fiber product is modified and composited by using a graphene-like material having a particle diameter of 1 to 20 ⁇ m, so that the large-sized graphene-based substance is present on the outside of the fiber in a coating and laminating manner, which is more advantageous for the graphite.
  • the olefin forms a conductive network outside the fiber, and can also function to close the internal voids of the fiber, and can increase the robustness of the graphene-like substance in the fiber.
  • the second composite treatment temperature is lower than the first composite treatment temperature.
  • the unmodified fiber product is immersed in a graphene-based material dispersion having a particle diameter of less than 1 ⁇ m, and after being taken out, the temperature is raised to a high elastic temperature of the fiber material, so that the graphene-based substance having a particle diameter of less than 1 ⁇ m can enter the fiber of the fiber product.
  • the invention sets the second composite processing temperature to be lower than the first composite processing temperature, avoids the graphene-like substance running out of the fiber, and the second composite treatment can better fix the graphene-like substance inside the fiber and A protective layer is formed on the outside of the fiber.
  • the first composite treatment temperature and/or the second composite treatment temperature is more than 5 ° C higher than the glass transition temperature of the fibrous material in the fibrous article.
  • the immersion temperature is at a high elastic temperature of the fiber material of the fiber product, which can increase the movement of the macromolecule in the fiber, so that the crystallization zone is converted to the non-crystalline zone, so that the void of the amorphous zone becomes larger, so that the crystallization zone and the amorphous zone
  • the interstices between the macromolecules in the region become larger; thus, the graphene-like substances entering the inside of the fibers are increased.
  • part of the graphene can enter the crystallization region at a low temperature, and is firmly present inside the fibers. Improve the firmness of graphene in the fiber.
  • the high elastic temperature of the present invention refers to the lowest temperature when the fiber material reaches a high elastic state; the glass transition temperature refers to the lowest temperature when the fiber material reaches a glass state; the viscous flow temperature refers to the fiber The material reaches the lowest temperature of the viscous flow state.
  • the time of the combined treatment of the first composite treatment and the second composite treatment is independently 15 to 120 minutes, for example, 16 minutes, 19 minutes, 23 minutes, 26 minutes, 32 minutes, 55 minutes, 66 minutes, 73 minutes, 78 minutes. , 85min, 88min, 95min, etc.
  • the graphene-based substance has a particle diameter of 0.1 to 1 ⁇ m, for example, 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, and 0.8. Mm, 0.9 ⁇ m, etc., and does not include 1 ⁇ m, preferably 0.2 to 0.5 ⁇ m.
  • the graphene-based material has a particle diameter of 2 to 10 ⁇ m, for example, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, or the like, preferably 5 to 10 ⁇ m.
  • the concentration of the graphene-based substance is 0.5 to 5 wt%, for example, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.1 wt%, 1.2 wt. %, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, and the like.
  • the concentration of the graphene-based substance is 0.5 to 7 wt%, for example, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.1 wt%, 1.2 wt%. %, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 6.5 wt%, etc. .
  • the unmodified fiber of the present invention may be a virgin fiber or a commercially available fiber.
  • the unmodified fiber is a commercially available fiber. That is to say, the preparation method of the modified fiber product can also be regarded as a post-treatment method of a commercially available commercial fiber.
  • a fourth object of the present invention is to provide a composite yarn comprising the modified fiber according to one of the objects;
  • the composite yarn is blended with a modified fiber of one of the purposes and a fiber containing no graphene.
  • a fifth object of the present invention is to provide a composite fabric comprising the modified fiber according to any one of the objects, or the composite yarn according to the fourth aspect.
  • the composite fabric is obtained by interlacing a modified fiber according to one of the objectives with a fiber containing no graphene-based material, or a composite yarn of the fourth object and a yarn containing no graphene-based material. Lines are interwoven.
  • a sixth object of the present invention is to provide a use of a modified fibrous article for the preparation of home textiles, underwear, protective clothing, warm clothing, and socks, according to one of the objects.
  • the present invention has the following beneficial effects:
  • the present invention simultaneously attaches or fills graphene inside and outside the fiber, thereby increasing the uniformity and firmness of the presence of graphene;
  • the present invention improves the electrical conductivity of the fiber by adding graphene and/or biomass graphene; the addition of graphene oxide and/or biomass graphene further enhances the far-infrared performance of the fiber;
  • the preparation method provided by the invention can effectively fill the inside of the fiber with graphene, and simultaneously coat the graphene-like substance on the outside of the fiber, and uniformly deposit the graphene on the fiber by impregnating the graphene solution with the fiber product.
  • a modified fiber, the specific steps include:
  • Performance test The obtained modified fiber is tested according to GB/T 14342-2015; then the modified fiber is washed 50 times, and the modified fiber after washing is further carried out according to GB/T 14342-2015. Detection.
  • Table 1 shows the process conditions of Examples 1 to 9 and the test results of the obtained modified fibers.
  • a modified fiber is different from the seventh embodiment in that the first graphene dispersion in the step (2) is simultaneously dispersed with nanocellulose (length to diameter ratio of 80 to 120, diameter: 10 nm or less), the nanocellulose.
  • the concentration in the dispersion was 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%.
  • Example 7 The same performance test method as in Example 7 was employed, and the test results are shown in Table 2.
  • a modified fiber is different from the third embodiment in that both the first and second graphene dispersions are replaced with a graphene oxide dispersion, and a reduction step is performed, specifically: taking the second impregnation in step 2)
  • the impregnated fiber is placed in a hydrazine hydrate reducing solution for reduction treatment, and then dried to obtain a modified fiber.
  • the same performance test method as in Example 3 was employed, and the test results are shown in Table 2.
  • a modified fiber differs from Example 3 in that all of the first and second graphene dispersions are replaced with a biomass graphene dispersion.
  • a modified fiber, the specific steps include:
  • polyester fiber was impregnated with the graphene dispersion at 95 ° C for 30 min, and then taken out and dried to obtain a modified fiber.
  • Example 3 The fibers of Example 3 were replaced with a siro-spun yarn (Example 17), and a knitted fabric (Example 18).
  • Table 2 shows the test results of the modified fiber products obtained in Examples 10 to 18.
  • Example 10 1 ⁇ 10 3 1 ⁇ 10 3
  • Example 11 1 ⁇ 10 3 1 ⁇ 10 3
  • Example 12 1 ⁇ 10 3 2 ⁇ 10 3
  • Example 13 8 ⁇ 10 3 9 ⁇ 10 3
  • Example 14 3 ⁇ 10 3 8 ⁇ 10 3
  • Example 15 2 ⁇ 10 3 5 ⁇ 10 3
  • Example 16 6 ⁇ 10 4 1 ⁇ 10 5
  • Example 17 3 ⁇ 10 2 6 ⁇ 10 2
  • Example 18 2 ⁇ 10 2 6 ⁇ 10 2
  • the yarn of Example 17 can be knitted into a fabric, and the surface resistivity is measured by GB12703.4-2010.
  • the surface resistivity of the non-washed surface is 2 ⁇ 10 2 ⁇ , and the surface resistivity of washing 50 times is 7 ⁇ . 10 2 ⁇ ;
  • the surface resistivity of the fabric of Example 18 was measured by GB 12703.4-2010, the surface resistivity of the non-washed surface was 2 ⁇ 10 2 ⁇ , and the surface resistivity of washing 50 times was 6 ⁇ 10 2 ⁇ .
  • a modified fiber is modified by in-situ composite method, and the specific steps are as follows:
  • the graphene composite PET masterbatch is directly used for melt spinning after drum drying at 110 ° C for 24 hours.
  • the spinning filament is cooled by water mist, the cooling temperature is 40 ° C, the drying temperature is 35 ° C, and the melt spinning is performed.
  • the silk is obtained by modifying the polyester fiber.
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance of the water-washing was 1 ⁇ 10 13 ⁇ cm.
  • a modified fiber is modified by means of normal temperature impregnation, and the specific steps are as follows:
  • polyester fiber was impregnated with the graphene dispersion at 25 ° C for 30 min, and then taken out and dried to obtain a modified fiber.
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance without washing was 1 ⁇ 10 4 ⁇ cm, and the specific resistance after washing 20 times was 1 ⁇ 10 10 ⁇ cm.
  • a composite fiber, the specific steps include:
  • Performance test The obtained modified fiber is tested according to GB/T 14342-2015; then the modified fiber is washed 50 times, and the modified fiber after washing is further carried out according to GB/T 14342-2015. Detection.
  • Table 3 shows the process conditions of Examples 1a to 9a and the test results of the obtained composite fibers.
  • Table 3 Process conditions and test results for preparing nascent fibers of Examples 1a to 9a
  • a composite fiber is different from the embodiment 7a in that the first graphene dispersion in the step (2) simultaneously disperses nanocellulose (length to diameter ratio of 80 to 120, diameter: 10 nm or less), and the nanocellulose is The concentration in the dispersion was 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%.
  • Example 7a The same performance test method as in Example 7a was employed, and the test results are shown in Table 4.
  • a composite fiber which differs from Embodiment 3a in that both the first and second graphene dispersions are replaced with a graphene oxide dispersion, and a reduction step is performed, specifically: in step (3) from the second graphene
  • the fiber taken out in the dispersion is placed in a hydrazine hydrate reducing solution for reduction treatment, and then dried to obtain a composite fiber.
  • the same performance test method as in Example 3a was used, and the test results are shown in Table 4.
  • a composite fiber differs from Example 3a in that all of the first graphene dispersion and the second graphene dispersion are replaced with a biomass graphene dispersion.
  • Example 3a The same performance test method as in Example 3a was used, and the test results are shown in Table 4.
  • a composite fiber, the specific steps include:
  • a molten polymer PET polyethylene terephthalate obtained by melt spinning to obtain nascent fibers
  • polyester fiber was impregnated with the graphene dispersion at 95 ° C for 30 min, and then taken out and dried to obtain a composite fiber.
  • Example 3a The same performance test method as in Example 3a was used, and the test results are shown in Table 4.
  • a composite fiber differs from Example 3a in that the immersion temperature is normal temperature.
  • Example 3a The same performance test method as in Example 3a was used, and the test results are shown in Table 4.
  • Table 4 shows the test results of the conjugate fibers obtained in Examples 10a to 17a.
  • Example 11a 3 ⁇ 10 2 3 ⁇ 10 2
  • Example 12a 3 ⁇ 10 2 4 ⁇ 10 2
  • Example 13a 4 ⁇ 10 3 5 ⁇ 10 3
  • Example 14a 2 ⁇ 10 2 7 ⁇ 10 2
  • Example 15a 4 ⁇ 10 2 8 ⁇ 10 2
  • Example 16a 2 ⁇ 10 4 6 ⁇ 10 4
  • Example 17a 2 ⁇ 10 3 1 ⁇ 10 5
  • a composite fiber is modified by in-situ composite method, and the specific steps are as follows:
  • the graphene composite PET masterbatch is directly used for melt spinning after drum drying at 110 ° C for 24 hours.
  • the spinning filament is cooled by water mist, the cooling temperature is 40 ° C, the drying temperature is 35 ° C, and the melt spinning is performed.
  • the silk is obtained by modifying the polyester fiber.
  • the specific resistance (GB/T 14342-2015) was measured, and the specific resistance of the non-washing was 1 ⁇ 10 13 ⁇ cm.
  • a composite fiber which differs from the embodiment 16a in that the virgin fiber of the step (1) is replaced by the polyester POY product provided by Zhejiang Hengguan Chemical Fiber Co., Ltd.
  • the specific resistance (GB/T 14342-2015) was measured, and the specific resistance of the non-washing was 5 ⁇ 10 6 ⁇ cm, and the specific resistance after washing 50 times was 1 ⁇ 10 10 ⁇ .
  • a composite fiber, the specific steps include:
  • a molten polymer PET polyethylene terephthalate obtained by melt spinning to obtain nascent fibers
  • polyester fiber was impregnated with the graphene dispersion at room temperature for 30 minutes, and then taken out and dried to obtain a composite fiber.
  • the specific resistance (GB/T 14342-2015) was measured, and the specific resistance of the non-washing was 3 ⁇ 10 5 ⁇ cm, and the specific resistance after washing 50 times was 1 ⁇ 10 7 ⁇ .
  • a modified fiber, the specific steps include:
  • Performance test The obtained modified fiber is tested according to GB/T 14342-2015; then the modified fiber is washed 50 times, and the modified fiber after washing is further carried out according to GB/T 14342-2015. Detection.
  • Table 5 shows the process conditions of Examples 1b to 9b and the test results of the obtained composite fibers.
  • a modified fiber is different from the embodiment 7b in that the first graphene dispersion in the step (2) simultaneously disperses nanocellulose (length to diameter ratio of 80 to 120, diameter: 10 nm or less), the nanocellulose The concentration in the dispersion was 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%.
  • Example 7b The same performance test method as in Example 7b was employed, and the test results are shown in Table 6.
  • a modified fiber is different from the embodiment 3b in that both the first and second graphene dispersions are replaced with a graphene oxide dispersion, and a reduction step is performed, specifically: the second modification in the step (3) After the fiber is placed in a hydrazine hydrate reducing solution for reduction treatment, the step (4) is carried out to obtain a modified fiber product.
  • the same performance test method as in Example 3b was used, and the test results are shown in Table 6.
  • a modified fiber differs from Example 3b in that all of the first graphene dispersion and the second graphene dispersion are replaced with a biomass graphene dispersion.
  • a modified fiber, the specific steps include:
  • polyester fiber was impregnated with the graphene dispersion at room temperature for 10 min, and then taken out, placed in air at 95 ° C for 30 min, and then cooled and dried to obtain a modified fiber.
  • Example 3b The fibers of Example 3b were replaced with a siro-spun spun yarn (Example 17b) and a knitted fabric (Example 18b).
  • Table 6 shows the test results of the modified fiber products obtained in Examples 10b to 18b.
  • Example 10b 1.0 ⁇ 10 3 1.0 ⁇ 10 3
  • Example 11b 1.0 ⁇ 10 3 1.0 ⁇ 10 3
  • Example 12b 1.0 ⁇ 10 3 2.0 ⁇ 10 3
  • Example 13b 7.0 ⁇ 10 3
  • Example 14b 3.0 ⁇ 10 3 7.0 ⁇ 10 3
  • Example 15b 2.0 ⁇ 10 3 4.8 ⁇ 10 3
  • Example 16b 5.8 ⁇ 10 4 1.0 ⁇ 10 5
  • the yarn of Example 17b can be knitted into a fabric, and the surface resistivity is measured by GB12703.4-2010.
  • the surface resistivity of the non-washed surface is 2 ⁇ 10 2 ⁇ , and the surface resistivity of the water washing 50 times is 7 ⁇ . 10 2 ⁇ ;
  • the surface resistivity of the fabric of Example 18b was measured by GB12703.4-2010, the surface resistivity of the non-washed surface was 2 ⁇ 10 2 ⁇ , and the surface resistivity of washing 50 times was 6 ⁇ 10 2 ⁇ .
  • a modified fiber is modified by in-situ composite method, and the specific steps are as follows:
  • the graphene composite PET masterbatch is directly used for melt spinning after drum drying at 110 ° C for 24 hours.
  • the spinning filament is cooled by water mist, the cooling temperature is 40 ° C, the drying temperature is 35 ° C, and the melt spinning is performed.
  • the silk is obtained by modifying the polyester fiber.
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance of the water-washing was 1 ⁇ 10 13 ⁇ cm.
  • a modified fiber is modified by means of normal temperature impregnation, and the specific steps are as follows:
  • polyester fiber was impregnated with the graphene dispersion at 25 ° C for 30 min, and then taken out and dried to obtain a modified fiber.
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance without washing was 1 ⁇ 10 4 ⁇ cm, and the specific resistance after washing 20 times was 1 ⁇ 10 10 ⁇ cm.
  • a modified polyester fiber the specific steps include:
  • the modified polyester fiber obtained shall be tested according to GB/T 14342-2015 for the modified polyester fiber; then the modified polyester fiber shall be washed 50 times and continue to be modified according to GB/T 14342-2015 after washing. Polyester fiber is tested.
  • Table 7 shows the test conditions of Examples 1c to 7c and the test results of the obtained modified polyester fibers.
  • a modified polyester fiber is different from the embodiment 3c in that the first graphene dispersion in the step (2) simultaneously disperses nanocellulose (length to diameter ratio of 80 to 120, diameter: 10 nm or less), the nanofiber
  • the concentration of the prime in the dispersion was 0.1 wt% (Example 8c), 0.5 wt% (Example 9c), 1 wt% (Example 10c), 2 wt% (Example 11c).
  • a modified polyester fiber is different from the embodiment 3c in that both the first and second graphene dispersions are replaced with a graphene oxide dispersion, and a reduction step is performed, specifically: removing the second impregnation in step 2)
  • the sub-impregnated polyester fiber is placed in a hydrazine hydrate reducing solution for reduction treatment, and then dried to obtain a modified polyester fiber.
  • the same performance test method as in Example 3c was used, and the test results are shown in Table 8.
  • a modified polyester fiber differs from Example 3c in that all of the first and second graphene dispersions are replaced with a biomass graphene dispersion.
  • a modified polyester fiber the specific steps include:
  • polyester fiber was impregnated with the graphene dispersion at 95 ° C for 30 min, and then taken out and dried to obtain a modified polyester fiber.
  • Example 3c The fibers of Example 3c were replaced with a siro-spun yarn (Example 15c), and a knitted fabric (Example 16c).
  • Table 8 shows the test results of the modified polyester fiber products obtained in Examples 8c to 16c.
  • Example 8c 1 ⁇ 10 2 1 ⁇ 10 2 Example 9c 1 ⁇ 10 2 1 ⁇ 10 2
  • Example 10c 1 ⁇ 10 2 2 ⁇ 10 2 Example 11c 8 ⁇ 10 3 9 ⁇ 10 3
  • Example 12c 3 ⁇ 10 2 8 ⁇ 10 2 Example 13c 2 ⁇ 10 2 5 ⁇ 10 2
  • Example 14c 6 ⁇ 10 4 1 ⁇ 10 5
  • the yarn of Example 15c can be knitted into a fabric, and the surface resistivity is measured by GB12703.4-2010.
  • the surface resistivity of the non-washed surface is 2 ⁇ 10 2 ⁇ , and the surface resistivity of washing 50 times is 7 ⁇ . 10 2 ⁇ ;
  • the surface resistivity of the fabric of Example 16c was measured by GB12703.4-2010, the surface resistivity of the non-washed surface was 2 ⁇ 10 2 ⁇ , and the surface resistivity of washing 50 times was 6 ⁇ 10 2 ⁇ .
  • a modified polyester fiber is modified by in-situ composite method, and the specific steps are as follows:
  • the graphene composite PET masterbatch is directly used for melt spinning after drum drying at 110 ° C for 24 hours.
  • the spinning filament is cooled by water mist, the cooling temperature is 40 ° C, the drying temperature is 35 ° C, and the melt spinning is performed.
  • the silk is obtained by modifying the polyester fiber.
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance of the water-washing was 1 ⁇ 10 13 ⁇ cm.
  • a modified polyester fiber is modified by means of normal temperature impregnation, and the specific steps are as follows:
  • polyester fiber was impregnated with the graphene dispersion at 25 ° C for 30 min, and then taken out and dried to obtain a modified fiber.
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance without washing was 1 ⁇ 10 4 ⁇ cm, and the specific resistance after washing 20 times was 1 ⁇ 10 10 ⁇ cm.
  • a modified nylon fiber the specific steps include:
  • Table 9 shows the process conditions of Examples 1d to 8d and the test results of the obtained modified nylon fibers.
  • a modified fiber is different from the embodiment 3d in that the first graphene dispersion in the step (2) simultaneously disperses nanocellulose (length to diameter ratio of 80 to 120, diameter: 10 nm or less), the nanocellulose The concentration in the dispersion was 0.1 wt% (Example 9d), 0.5 wt% (Example 10d), 1 wt% (Example 11d), 2 wt% (Example 12d).
  • Example 3d The same performance test method as in Example 3d was employed, and the test results are shown in Table 10.
  • a modified nylon fiber which differs from Example 3d in that both the first and second graphene dispersions are replaced with a graphene oxide dispersion, and a reduction step is performed, specifically: removing the second impregnation in step 2) After the secondary impregnated nylon fiber is placed in a hydrazine hydrate reducing solution for reduction treatment, it is dried to obtain a modified nylon fiber.
  • the same performance test method as in Example 3d was employed, and the test results are shown in Table 10.
  • a modified nylon fiber differs from Example 3d in that all of the first and second graphene dispersions are replaced with a biomass graphene dispersion.
  • Example 3d The same performance test method as in Example 3d was employed, and the test results are shown in Table 10.
  • a modified nylon fiber the specific steps include:
  • Example 4d The same performance test method as in Example 4d was employed, and the test results are shown in Table 10.
  • Example 3d The nylon fibers of Example 3d were replaced with a siro-spun yarn (Example 16d), and a knitted fabric (Example 17d).
  • Table 10 shows the test results of the modified fiber products obtained in Examples 9d to 17d.
  • the yarn of Example 16d can be knitted into a fabric, and the surface resistivity is measured by GB12703.4-2010.
  • the surface resistivity of the non-washed surface is 2 ⁇ 10 2 ⁇ , and the surface resistivity of washing 50 times is 7 ⁇ . 10 2 ⁇ ;
  • the surface resistivity of the fabric of Example 17d was measured by GB 12703.4-2010, the surface resistivity of the non-washed surface was 2 ⁇ 10 2 ⁇ , and the surface resistivity of washing 50 times was 6 ⁇ 10 2 ⁇ .
  • a modified nylon fiber the specific steps are:
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance of the water-washing was 1 ⁇ 10 13 ⁇ cm.
  • a modified nylon fiber is modified by means of normal temperature impregnation, and the specific steps are as follows:
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance without washing was 1 ⁇ 10 4 ⁇ cm, and the specific resistance after washing 20 times was 1 ⁇ 10 10 ⁇ cm.
  • a modified acrylic fiber, the specific steps include:
  • Performance test The obtained modified fiber is tested according to GB/T 14342-2015; then the modified fiber is washed 50 times, and the modified fiber after washing is further carried out according to GB/T 14342-2015. Detection.
  • Table 11 shows the process conditions of Examples 1e to 8e and the test results of the obtained modified fibers.
  • Table 11 Process conditions for preparing modified fibers of Examples 1e to 8e and test results of the modified fibers
  • a modified fiber is different from the embodiment 3e in that the first graphene dispersion in the step (2) simultaneously disperses nanocellulose (length to diameter ratio of 80 to 120, diameter: 10 nm or less), the nanocellulose The concentration in the dispersion was 0.1 wt% (Example 9e), 0.5 wt% (Example 10e), 1 wt% (Example 11e), 2 wt% (Example 12e).
  • a modified fiber which differs from Example 3e in that both the first and second graphene dispersions are replaced with a graphene oxide dispersion, and a reduction step is carried out, specifically: taking the second impregnation in step 2)
  • the impregnated fiber is placed in a hydrazine hydrate reducing solution for reduction treatment, and then dried to obtain a modified fiber.
  • the same performance test method as in Example 3e was employed, and the test results are shown in Table 12.
  • a modified fiber differs from Example 3e in that all of the first and second graphene dispersions are replaced with a biomass graphene dispersion.
  • a modified fiber, the specific steps include:
  • polyester fiber was impregnated with the graphene dispersion at 95 ° C for 30 min, and then taken out and dried to obtain a modified fiber.
  • Example 3e The fibers of Example 3e were replaced with a siro-spun yarn (Example 16e), and a knitted fabric (Example 17e).
  • Table 12 shows the test results of the modified fiber products obtained in Examples 9e to 17e.
  • Example 12e 8 ⁇ 10 3 9 ⁇ 10 3
  • Example 16e can be knitted into a fabric, and the surface resistivity is measured by GB12703.4-2010.
  • the surface resistivity of the non-washed surface is 2 ⁇ 10 2 ⁇ , and the surface resistivity of washing 50 times is 7 ⁇ . 10 2 ⁇ ; surface resistivity Example 17e using GB12703.4-2010 detecting fabric, the surface resistance of not washing with water was 2 ⁇ 10 2 ⁇ , washed 50 times the surface resistivity was 6 ⁇ 10 2 ⁇ .
  • a modified acrylic fiber fiber the specific steps are:
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance of the water-washing was 1 ⁇ 10 13 ⁇ cm.
  • a modified acrylic fiber is modified by means of normal temperature impregnation, and the specific steps are as follows:
  • the obtained fiber was examined in accordance with GB/T 14342-2015, and the specific resistance without washing was 1 ⁇ 10 4 ⁇ cm, and the specific resistance after washing 20 times was 1 ⁇ 10 10 ⁇ cm.
  • the present invention illustrates the process of the present invention by the above-described embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the materials selected for the present invention, and the addition of the auxiliary ingredients, the selection of the specific means, etc., are all within the scope of the present invention.

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Abstract

本发明涉及一种改性纤维制品，所述改性纤维制品含有改性纤维，所述改性纤维内部存在石墨烯类物质，所述改性纤维外部也存在石墨烯类物质。所述方法包括将未改性的纤维制品在石墨烯类物质分散液中浸渍，在浸渍的同时或者在浸渍后进行升温处理，之后经过冷却、干燥，得到处理后的纤维制品；其中，所述处理的温度范围处于未改性的纤维制品中纤维材料的高弹态温度。本发明同时在纤维内部和外部附着或填加石墨烯，增加了石墨烯存在的均匀性，提高了纤维的导电性能；本发明提供的制备方法能够有效的将石墨烯填加至纤维内部，同时在纤维外部包覆石墨烯类物质，实现石墨烯在纤维的均匀分布。

Description

一种改性纤维制品、制备方法及其用途 技术领域
本发明属于纤维制品制备领域，具体涉及一种改性纤维制品、制备方法及其用途，特别涉及一种导电的改性纤维制品、制备方法及其用途。
背景技术
导电纤维的研制始于20世纪60年代，导电纤维通常是指在标准环境下(温度20℃，湿度65％)，比电阻低于10 7Ω·cm。其发展历程大致包括4个阶段：金属纤维、碳纤维及含碳黑复合聚合物的复合型导电纤维，含有金属盐的导电纤维，导电高聚物导电纤维。虽然导电纤维得到了长足的发展，但也存在着一定的问题，如由金属导电纤维和镀金属导电纤维制成的织物手感粗糙，舒适性较差，导电聚合物工艺较复杂，污染严重。再者，通过涂覆或者简单的浸渍工艺制备的纤维制品石墨烯的复合牢固度不够强，洗涤多次后便失去附加的功能。因此，开发新的制备导电纤维的新方法具有重要意义和实际应用前景。
石墨烯是一种由单层sp2杂化碳原子组成的蜂窝状结构的二维材料，具有许多优异的性能(高强、高导热、高导电、高轻质)，同时也拥有大π共轭体系。自从2004年被发现起，石墨烯就成为了科学界的一大研究热点。在对石墨烯的物理化学性质进行研究的同时，与石墨烯相关的复合材料层出不穷。现有技术将石墨烯与纺织纤维复合，期望能够获得具有导电性和远红外等功能性纤维性纤维的同时，进一步保障石墨烯的附着牢固度，使其功能不因水洗次数的增多而大幅度衰减。
本领域需要开发一种改性纤维制品，其与石墨烯类材料复合，能够改进所述纤维制品的导电性或远红外等性能，同时保证是石墨烯的附着牢固度。
发明内容
本发明的目的在于提供一种改性纤维制品，所述改性纤维制品含有改性纤维，所述改性纤维内部存在石墨烯类物质，所述改性纤维外部也存在石墨烯类物质。
本发明通过在纤维内部和外部同时设置石墨烯类物质，能够提高石墨烯类物质在纤维上的牢固性，同时提高石墨烯在纤维径向的分部均匀性，增加了石墨烯的复合量，提高了纤维的导电性能，提高了石墨烯类物质在纤维上复合的牢固性。
优选地，本发明所述改性纤维中，存在于所述改性纤维外部的石墨烯类物质比存在于改性纤维内部的石墨烯类物质多。所述改性纤维外部具有较多的石墨烯类物质，在改性纤维的外部能够搭接在一起，更好的提高所述改性纤维制品的导电性。
纤维是有大分子材料聚集得到的，大分子有规律的相互整齐稳定的排列成具有高度的几何规整性，成为结晶结构或结晶态。纤维大分子有规律的整齐排列的区域成为结晶区；在结晶区大分子链段排列规整，结构紧密，缝隙和孔洞较少，分子间结合力强。纤维大分子无规律地紊乱排列的区域为非结晶区，在非结晶区，大分子链段排列混乱，无规则，结构松散，有较多的缝隙和孔洞，相互结合力小。
优选地，所述改性纤维制品中石墨烯类物质总质量不超过纤维制品总质量的0.5～3wt％，例如0.6wt％、0.7wt％、0.9wt％、1wt％、1.6wt％、1.8wt％、2.4wt％、2.6wt％、2.7wt％、2.9wt％等。石墨烯类物质含量不宜过多，过多容易导致纤维强度降低，资源浪费。
在本发明中，优选地，所述石墨烯类物质的粒径≤20μm，例如0.2μm、0.5μm、1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、12μm、14μm、16μm、18μm、19μm等。所述石墨烯类物质，粒径小于1μm(例如0.1μm、0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm等)的石墨烯类物质主要存在于所述改性纤维内部，粒径为1～20μm(例如0.05μm、1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm等)的石墨烯类物质主要存在于所述改性纤维的外部。
所述“主要”意指大部分，在某种程度上可以理解为80wt％以上，或90wt％以上，或95wt％以上。
在本发明中，所述改性纤维内部包括改性纤维的结晶区、非结晶区、以及结晶区与非结晶区之间的间隙。
本发明所述间隙、空隙、孔洞可以相互替换，代表纤维内部的空隙。
优选地，所述改性纤维内部结晶区存在石墨烯类物质，同时所述改性纤维外部存在石墨烯类物质。
优选地，所述石墨烯类物质包括石墨烯、生物质石墨烯、氧化石墨烯、石 墨烯衍生物的任意1种或至少2种的混合，优选石墨烯和/或生物质石墨烯。
优选地，所述石墨烯衍生物包括元素掺杂石墨烯或官能团化石墨烯物中的任意1种或至少2种的组合。
优选地，所述改性纤维外部存在的石墨烯类物质的粒径为2～10μm。
在一个具体实施方式中，本发明所述改性纤维制品含有改性纤维，所述改性纤维内部结晶区存在石墨烯类物质，所述改性纤维外部也存在石墨烯类物质。
本发明通过在纤维内部和外部分布不同粒径的石墨烯类物质，能够同时提高石墨烯类物质在纤维上的附着牢固度，同时提高在纤维径向的分布均匀性。1～20μm的石墨烯类物质以包覆、贴合的方式存在于所述纤维的外部，一方面能够起到保证内部石墨烯类物质牢固存在的作用，另一方面还起到提高石墨烯类物质颗粒之间的接触，增加导电性的作用。
优选地，所述粒径小于1μm的石墨烯类物质存在于所述改性纤维内部的结晶区、非结晶区、以及结晶区与非结晶区之间的间隙中的至少1处。
优选地，所述改性纤维内部的结晶区存在石墨烯类物质，优选所述改性纤维内部的结晶区存在粒径小于1μm的石墨烯类物质。
优选地，所述改性纤维内部的结晶区、非结晶区、以及结晶区与非结晶区之间的间隙均存在石墨烯类物质；
优选地，当所述石墨烯类物质为石墨烯和/或生物质石墨烯时，所述改性纤维制品中改性纤维的比电阻≤1×10 5Ω·cm，例如1×10 4Ω·cm、4×10 4Ω·cm、7×10 4Ω·cm、9×10 4Ω·cm、1×10 3Ω·cm、5×10 3Ω·cm、8×10 3Ω·cm、1×10 2Ω·cm、1×10Ω·cm等。
优选地，当所述石墨烯类物质为石墨烯和/或生物质石墨烯时，所述改性纤维制品中改性纤维水洗50次之后，其比电阻≤1×10 5Ω·cm，例如1×10 4Ω·cm、4×10 4Ω·cm、7×10 4Ω·cm、9×10 4Ω·cm、1×10 3Ω·cm、5×10 3Ω·cm、8×10 3Ω·cm、1×10 2Ω·cm、1×10Ω·cm等。
优选地，当所述石墨烯类物质为氧化石墨烯和/或生物质石墨烯时，所述纤维制品水洗50次之后，其远红外法向发射率不低于0.85，例如不低于0.87，不低于0.88，不低于0.90。
在本发明所述的技术方案中，对所述改性纤维制品没有具体限定。优选 地，所述改性纤维制品包括改性纤维、包含改性纤维的纱线和包含改性纤维的织物中的任意1种或至少2种的组合。进一步说，纤维制品可以是纤维，可以是纱线，也可以是面料；即可以是纤维浸渍石墨烯溶液，可以是纱线浸渍石墨烯溶液，可以是面料浸渍石墨烯溶液。
优选地，所述改性纤维包括改性涤纶纤维、改性锦纶纤维、改性氨纶纤维、改性芳纶纤维、改性腈纶纤维、改性PVA纤维、改性再生纤维素纤维。
优选地，所述包含改性纤维的纱线由所述改性纤维单纺，混纺或与未改性纤维混纺得到。
优选地，所述包含改性纤维的织物由所述改性纤维，所述包含改性纤维的纱线制成。
为了进一步提高所述改性纤维制品的强度和石墨烯类物质的牢固性，所述的改性纤维制品中含有纳米纤维素。适量的纳米纤维素的加入能够提高将石墨烯类物质缠绕在所述纤维上，且纳米纤维素的缠绕能够提高所述改性纤维制品的强度。
优选地，所述改性纤维制品的改性纤维中复合有纳米纤维素。
优选地，所述纳米纤维素缠绕在所述改性纤维的内部和/或外部。具体指，纳米纤维素通过高的长径比和小的直径，将外部石墨烯类物质与纤维内部结晶区或纤维内部石墨烯类物质进行捆绑或者搭接，使得外部石墨烯类物质不易脱落。
本发明目的之二是提供一种如目的之一所述的改性纤维制品的制备方法，所述方法包括将未改性的纤维制品在石墨烯类物质分散液中浸渍，之后经过冷却、干燥，得到处理后的纤维制品；
其中，所述浸渍的温度范围处于未改性的纤维制品中纤维材料的高弹态温度。
将未改性的纤维制品浸渍在所述纤维制品的纤维材料的高弹态温度的石墨烯类物质分散液中，其中高弹态是指材料处于玻璃化转变温度和黏流态温度之间，到达材料的玻璃化转变温度能够提高所述纤维中大分子的运动，使得结晶区向非结晶区转化，使得非结晶区的空隙变大，使得结晶区与非结晶区之间区域的大分子间的空隙变大；同时分散在石墨烯类分散液中的石墨烯类物质的颗粒进入所述的空隙；随后浸渍过的纤维冷却，使得浸渍过程中进入所述空隙的 石墨烯被固定在纤维内部，而因为粒径较大被挡在空隙外部的石墨烯类物质会以包覆、贴合，甚至会以部分进入纤维内部，部分位于纤维外部的形式存在。
本领域技术人员应该明了，本发明所述的纤维内部和纤维外部是本领域公知的概念，也可以理解成组成纤维的大分子在空间聚集形成超分子结构，所述大分子聚集的内部存在结晶区、非结晶区、以及结晶区和非结晶区间的区域；而大分子聚集完毕形成的外侧看做纤维的外部。
当纤维制品包括2种或以上的纤维材料时，所述浸渍温度应当在所有纤维材料的黏流态(粘流态)温度以下，且所述浸渍温度应当高于其中玻璃化转变温度最低的纤维材料的低玻璃化转变温度以上。
本发明所述高弹态温度指所述纤维材料达到高弹态时的最低温度；所述玻璃化温度指所述纤维材料达到玻璃态时的最低温度；所述粘流态温度指所述纤维材料达到粘流态的最低温度。
优选地，所述浸渍温度至少比未改性的纤维制品中纤维材料的玻璃化转变温度高5℃。比纤维材料的玻璃化转变温度高5℃的范围更有利于纤维分子的蠕动，空隙张开的更迅速，石墨烯类物质进入空隙的时间更短。
优选地，所述改性纤维制品包括改性纤维、包含改性纤维的纱线和包含改性纤维的织物中的任意1种或至少2种的组合。进一步说，纤维制品可以是纤维，可以是纱线，也可以是面料；即可以是纤维浸渍石墨烯溶液，可以是纱线浸渍石墨烯溶液，可以是面料浸渍石墨烯溶液。
优选地，所述改性纤维包括改性涤纶纤维、改性锦纶纤维、改性氨纶纤维、改性芳纶纤维、改性腈纶纤维、改性PVA纤维、改性再生纤维素纤维。进一步优选地，所述纤维是涤纶纤维、锦纶纤维或腈纶纤维；
优选地，当所述纤维是涤纶纤维时，所述浸渍的温度为80～120℃；
优选地，当所述纤维是锦纶纤维时，所述浸渍的温度为45～80℃；
优选地，当所述纤维是锦纶纤维时，所述浸渍的温度为80～100℃。
优选地，所述包含改性纤维的纱线由所述改性纤维单纺，或与未改性纤维混纺得到。
优选地，所述包含改性纤维的织物由所述改性纤维，所述包含改性纤维的纱线制成。
优选地，所述石墨烯类物质包括石墨烯、生物质石墨烯、氧化石墨烯、石 墨烯衍生物的任意1种或至少2种的混合，优选石墨烯、生物质石墨烯和/或氧化石墨烯。
优选地，所述氧化石墨烯包括TEMPO体系氧化的石墨烯。
TEMPO体系氧化的石墨烯能够将氧化性官能团插入石墨烯内部，提高氧化石墨烯在分散液中的分散均匀性，减少石墨烯分散液中石墨烯的团聚，提高石墨烯的利用率。
优选地，所述石墨烯衍生物包括元素掺杂石墨烯或官能团化石墨烯物中的任意1种或至少2种的组合。
优选地，所述石墨烯类物质分散液的浓度为0.1～5wt％，优选0.3～2wt％，例如0.3％、0.5％、0.8％、0.9％、1.3％、1.6％、1.8％、1.9％、1.5％、3％、3.6％、4％、4.5％等。
优选地，所述石墨烯类物质分散液中的石墨烯类物质的粒径为不大于20μm，优选为100nm～10μm，进一步优选200nm～5μm；例如30nm、150nm、190nm、230nm、260nm、290nm、330nm、460nm、590nm、630nm、760nm、890nm、930nm、1μm、3μm、8μm、11μm、13μm、18μm等。
优选地，所述浸渍时间为15～120min，例如16min、19min、23min、26min、32min、55min、66min、73min、78min、85min、88min、95min等。
作为可选技术方案，所述将未改性的纤维制品在石墨烯类物质分散液中浸渍分两步进行，具体包括如下步骤：
(A1)将未改性纤维制品浸渍至第一石墨烯类物质分散液中，进行第一次浸渍，得到第一浸渍纤维制品；所述第一石墨烯类物质分散液中石墨烯类物质的粒径小于1μm；
(A2)将第一浸渍纤维制品浸渍至第二石墨烯类物质分散液中，进行第二次浸渍，得到第二浸渍纤维制品；所述第二石墨烯类物质分散液中石墨烯类物质的粒径为1～20μm。
将未改性的纤维制品浸渍在粒径小于1μm的石墨烯类物质分散液中，能够使得粒径小于1μm的石墨烯类物质进入所述纤维的内部(如非结晶区、或结晶区与非结晶区的空隙)，由于纤维内部空隙的大小有限，步骤(A1)只采用粒径小于1μm的石墨烯类物质对纤维制品进行改性，众所周知，石墨烯粒径越小越不容易分散，越容易团聚，因此往往选择低浓度的石墨烯溶液，这样还节省 了石墨烯的用量，且减少了大粒径石墨烯类物质堵塞空隙的概率，提高了石墨烯的附着量。
步骤(A2)采用粒径为1～20μm的石墨烯类物质对纤维制品进行改性，能够使大于1μm的大粒径石墨烯类物质以包覆、贴合的方式存在于纤维外部，更有利于石墨烯在纤维外部形成导电网络，部分能够堵塞填充有1μm以内的石墨烯类物质的空隙的洞口，还能够起到封闭纤维内部空隙的作用，能够增加石墨烯类物质在纤维中的牢固性。
优选地，所述至少第一次浸渍温度范围处于未改性的纤维制品中纤维材料的高弹态温度。
优选地，所述第一次浸渍和第二次浸渍的浸渍温度范围均处于未改性的纤维制品中纤维材料的高弹态温度且第二次浸渍温度低于第一次浸渍温度。
优选地，所述第一次浸渍和/或第二次浸渍温度比未改性的纤维制品中纤维材料的玻璃化转变温度至少高5℃。
所述浸渍温度处于未改性的纤维制品中纤维材料的高弹态温度能够提高所述纤维中大分子的运动，使得结晶区向非结晶区转化，使得非结晶区的空隙变大，使得结晶区与非结晶区之间区域的大分子间的空隙变大；从而使得进入纤维内部的石墨烯类物质增多，另一方面，降温后，部分石墨烯能够进入低温下的结晶区，牢固存在于所述纤维内部，提高石墨烯类物质在纤维中的牢固度。本发明可以将所述二次浸渍温度设置为低于一次浸渍温度，避免纤维内部石墨烯类物质跑出，但是通过二次浸渍也能更好的将纤维内部石墨烯类物质固定并在纤维外部形成保护层。
优选地，所述第一次浸渍、第二次浸渍的时间均各自独立地选自15～120min，例如16min、19min、23min、26min、32min、55min、66min、73min、78min、85min、88min、95min等。
优选地，所述第一次浸渍的石墨烯类物质的粒径为0.1～1μm，例如0.1μm、0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm等，优选0.2～0.5μm。
优选地，所述第二次浸渍的石墨烯类物质的粒径为2～10μm，例如3μm、4μm、5μm、6μm、7μm、8μm、9μm等，优选5～10μm；
优选地，所述粒径小于1μm的石墨烯类物质分散液中，石墨烯类物质的浓 度为0.5～5wt％，例如0.6wt％、0.7wt％、0.8wt％、0.9wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％、2.5wt％、3wt％、4wt％、5wt％等。
优选地，所述粒径为1～20μm的石墨烯类物质分散液中，石墨烯类物质的浓度为0.5～7wt％，例如0.6wt％、0.7wt％、0.8wt％、0.9wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％、2.5wt％、3wt％、4wt％、5wt％、6wt％、6.5wt％等。
氧化石墨烯本身导电性较差，为了保证通过氧化石墨烯改性的纤维制品的导电性，本发明可以对复合有氧化石墨烯的改性纤维制品进行还原处理。
优选地，当所述石墨烯类物质包括氧化石墨烯时，在冷却之前和/或之后进行还原处理。
优选地，所述还原处理的方法包括还原剂还原法和/或加热还原法。
优选地，所述还原剂还原法包括加入还原剂进行还原。
优选地，所述还原剂的加入量为石墨烯类物质的10～200wt％，优选50～100wt％。
优选地，所述还原剂包括抗坏血酸、水合肼、葡萄糖、乙二胺、柠檬酸钠、L-半胱氨酸、氢碘酸或硼氢化钠中的任意1种或至少2种的组合。
优选地，所述加热还原法包括在非氧化性气氛中，加热进行还原。
优选地，所述加热还原法步骤包括：在高压反应釜中，通入保护性气氛和/或还原性气氛，加热还原；所述加热还原的温度≤200℃，压力≤1.6MPa。
优选地，所述石墨烯类物质分散液中添加有纳米纤维素。
优选地，所述纳米纤维素的直径不大于10nm，长径比不小于10，长径比可以为20，30，50，100等。
优选地，所述纳米纤维素在分散液中的浓度为2wt％以下，优选1wt％以下，再优选0.5wt％以下。
纳米纤维素本身呈线状，其可以再纤维外部沿外周缠绕，这种缠绕方式能够提高纤维的强度，且能够提高石墨烯在纤维外部的牢固度；另一个方面，纳米纤维素的一端能够插入石墨烯片层中，提高石墨烯类物质在纤维上的附着量。但是纳米纤维素本身不导电，过多的纳米纤维素会引起导电性能的下降。
本发明所述的未改性的纤维可以是初生纤维也可以是市售可得的商品化纤 维，优选地，所述未改性的纤维是初生纤维。
优选地，本发明所述初生纤维通过聚合物纺丝得到。
优选地，所述聚合物包括聚酯、聚酰胺、聚丙烯腈、聚丙烯、聚氨酯、聚乙烯醇缩醛和聚氯乙烯中的任意1种或至少2种的组合。
优选地，所述纺丝包括静电纺丝、熔体纺丝、湿法溶液纺丝、干法溶液纺丝中的任意1种或至少2种的组合。
优选地，本发明所述初生纤维指从喷丝孔挤出的聚合物细流在纺丝场中固化成形的纤维。本领域技术人员应该明了，本发明提供的可以是一种复合纤维的制备方法，其是对从喷丝空挤出的聚合物固化形成的纤维，得到的纤维能够继续进行后续的工艺步骤，如涂覆硅油等。
本发明目的之三在于提供一种改性纤维制品的制备方法，所述方法包括：将未改性的纤维制品在石墨烯类物质分散液中浸渍，取出后升温至纤维材料的高弹态温度，并恒温进行复合处理，之后经过冷却、干燥，得到改性纤维制品。
本发明将未改性的纤维制品浸渍在石墨烯类物质分散液中，比如在常温下将纤维制品浸渍在石墨烯类物质分散液中，能够将石墨烯类物质吸附在所述纤维制品的外侧，取出吸附了石墨烯类物质的纤维制品，并升温至纤维材料的高弹态温度，纤维内部的空隙增多，已有空隙变大，已经吸附在纤维外部的石墨烯类物质会运动至所述空隙中，之后冷却，纤维内部的空隙减小，实现石墨烯类物质固化在纤维内部的目的。
本领域技术人员应该明了，本发明所述的纤维内部和纤维外部是本领域公知的概念，也可以理解成组成纤维的大分子在空间聚集形成超分子结构，所述大分子聚集的内部存在结晶区、非结晶区、以及结晶区和非结晶区间的区域；而大分子聚集完毕形成的外侧看做纤维的外部。
优选地，所述处理温度比未改性的纤维制品中纤维材料的玻璃化转变温度高5℃以上。比纤维材料的玻璃化转变温度高5℃以上有利于纤维分子的蠕动，空隙张开的更迅速，石墨烯类物质进入空隙的时间更短。
优选地，所述石墨烯类物质分散液的浓度为0.1～5wt％，优选0.3～2wt％，例如0.3％、0.5％、0.8％、0.9％、1.3％、1.6％、1.8％、1.9％、1.5％、3％、3.6％、4％、4.5％等，优选0.3～2wt％。
优选地，所述石墨烯类物质分散液中的石墨烯类物质的粒径为不大于20μ m；优选为100nm～10μm，进一步优选200nm～5μm；例如30nm、150nm、190nm、230nm、260nm、290nm、330nm、460nm、590nm、630nm、760nm、890nm、930nm、1μm、3μm、8μm、11μm、13μm、18μm等。
对于未改性的纤维制品在所述石墨烯类物质分散液中的浸渍时间，本发明不做具体限定，示例性的可以是5～30min，例如6min、9min、13min、16min、22min、25min、26min、28min等。
升温至纤维材料的高弹态温度，恒温进行复合处理的过程在无溶剂作用下进行，例如可以利用环境温度进行加热，如热空气加热灯，示例性的如暖房、烘箱加热等。
优选地，所述升温的方式为热空气加热。
对于浸渍石墨烯类物质的纤维制品取出后升温至纤维材料的高弹温度恒温进行复合处理的时间不做具体限定，示例性的可以是15～120min；例如16min、19min、23min、26min、32min、55min、66min、73min、78min、85min、88min、95min等。
优选地，所述石墨烯类物质分散液中添加有纳米纤维素。
适量的纳米纤维素的加入能够提高将石墨烯类物质缠绕在所述纤维上，且纳米纤维素的缠绕能够提高所述复合纤维的强度。
优选地，所述纳米纤维素的直径不大于10nm，例如1nm、2nm、3nm、4nm、5nm、6nm、7nm、8nm、9nm等，长径比不小于10，例如11、12、13、14、15、18、20、30、50、100等；本发明通过纳米纤维素通过高的长径比和小的直径，将外部石墨烯类物质与纤维内部结晶区或纤维内部石墨烯类物质进行捆绑或者搭接，使得外部石墨烯类物质不易脱落。
优选地，所述纳米纤维素在分散液中的浓度为2wt％以下，例如0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％等，优选1wt％以下，再优选0.5wt％以下。
纳米纤维素本身呈线状，其可以再纤维外部沿外周缠绕，这种缠绕方式能够提高纤维的强度，且能够提高石墨烯在纤维外部的牢固度；另一个方面，纳米纤维素的一端能够插入石墨烯片层中，提高石墨烯类物质在纤维上的附着量。但是纳米纤维素本身不导电，过多的纳米纤维素会引起导电性能的下降。
优选地，所述石墨烯类物质包括石墨烯、生物质石墨烯、氧化石墨烯、石墨烯衍生物的任意1种或至少2种的混合，优选石墨烯和/或生物质石墨烯。
本发明所指的石墨烯材料包括石墨烯、生物质石墨烯、氧化石墨烯、石墨烯衍生物，他们是可以通过不同工艺制备，或者不同的原材料制备得到，例如，机械剥离法、氧化还原法、以生物质为资源经过炭化和原子重排制备的生物质石墨烯等。本发明所述的石墨烯材料(或石墨烯类物质)原则上指本领域技术人员能够制备得到的不同类型的石墨烯。
优选地，所述石墨烯衍生物包括元素掺杂石墨烯或官能团化石墨烯物中的任意1种或至少2种的组合。
氧化石墨烯本身导电性较差，为了保证通过氧化石墨烯复合的纤维的导电性，本发明可以对复合有氧化石墨烯的改性纤维制品进行还原处理。
当所述石墨烯类物质为氧化石墨烯时，在冷却之前和/或之后进行还原处理。
优选地，所述还原处理的方法包括还原剂还原法和/或加热还原法。
优选地，所述还原剂还原法包括加入还原剂进行还原。
优选地，所述还原剂的加入量为石墨烯类物质的10～200wt％，优选50～100wt％。
优选地，所述还原剂包括抗坏血酸、水合肼、葡萄糖、乙二胺、柠檬酸钠、L-半胱氨酸、氢碘酸或硼氢化钠中的任意1种或至少2种的组合。
优选地，所述加热还原法包括在非氧化性气氛中，加热进行还原。
优选地，所述加热还原法步骤包括：在高压反应釜中，通入保护性气氛和/或还原性气氛，加热还原；所述加热还原的温度≤200℃，压力≤1.6MPa。
在本发明所述的技术方案中，对所述改性纤维制品没有具体限定。优选地，所述纤维制品包括纤维原丝、纱线和织物中的任意1种或至少2种的组合；
优选地，所述纤维制品的纤维可以是本领域技术人员能够获知的任何纤维，示例性的所述纤维包括涤纶纤维、锦纶纤维、氨纶纤维、芳纶纤维、腈纶纤维、PVA纤维、再生纤维素纤维。
本领域人员应该清楚，对于纱线和织物存在混纺的情况，例如涤纶和再生纤维素纤维的混纺，锦纶、腈纶和尼龙的混纺等；由于各种纤维材料的高弹态温度区间不同，所以本发明“将纤维制品浸渍石墨烯类物质分散液，取出后升 温至纤维材料的高弹态温度”中所指的升温至纤维材料的高弹态温度一般是指混纺纱线或织物中占比较大的一种纤维材料的高弹态温度。
所述纱线可以是本领域技术人员能够获知的任何方式制成的纱线，例如由任何能够获得的未改性纤维单纺、混纺，或者由经过如前所述的方式进行处理的改性纤维进行单纺、混纺，或者由所述未改性纤维与改性纤维混纺得到。应该明确的是，为了保证纤维制品的导电性，一般情况下纤维制品中所有的纤维材料都应该含有石墨烯材料。
所述织物可以是本领域技术人员能够获知的任何方式制成的织物，例如由所述改性纤维、改性纱线、未改性纤维、未改性纱线中的任意1种或至少2种进行纺织得到。应该明确的是，为了保证纤维制品的导电性，一般情况下纤维制品中绝大多数都应为经过石墨烯材料改性的纤维材料。
优选地，所述改性的纤维制品的制备方法包括如下步骤：
(A1)将未改性的纤维制品浸渍至第一石墨烯类物质分散液中，取出后升温至高弹态温度，在处理温度下恒温进行第一次复合处理；所述第一石墨烯类物质分散液中石墨烯类物质的粒径小于1μm(例如0.1μm、0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm等)；
(A2)将第一次复合处理后的纤维制品浸渍至第二石墨烯类物质分散液中，取出后升温至第二处理温度后，恒温进行第二次复合处理，之后经过冷却、干燥，得到改性纤维制品；所述第二石墨烯类物质分散液中石墨烯类物质的粒径为1～20μm(例如1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm等)。
由于纤维内部空隙的大小有限，步骤(A1)只采用粒径＜1μm的石墨烯类物质对纤维制品进行改性，众所周知，石墨烯粒径越小越不容易分散，越容易团聚，因此往往选择低浓度的石墨烯溶液，这样还节省了石墨烯的用量，且减少了大粒径石墨烯类物质堵塞空隙的概率，提高了石墨烯的附着量。步骤(A2)采用粒径为1～20μm的石墨烯类物质对纤维制品进行改性复合，能够使大粒径石墨烯类物质以包覆、贴合的方式存在于纤维外部，更有利于石墨烯在纤维外部形成导电网络，还能够起到封闭纤维内部空隙的作用，能够增加石墨烯类物质在纤维中的牢固性。
优选地，所述第二次复合处理温度比第一次复合处理温度低。
将未改性的纤维制品浸渍在粒径小于1μm的石墨烯类物质分散液中，取出后升温至纤维材料的高弹态温度，能够使得粒径小于1μm的石墨烯类物质进入纤维制品的纤维内部(如非结晶区、或结晶区与非结晶区的空隙)，之后浸渍粒径为1～20μm的石墨烯类物质分散液，取出至第二处理温度，能够使大于1μm的石墨烯颗粒包覆或贴合在纤维外部，部分能够堵塞填充有1μm以内的石墨烯类物质的空隙的洞口，提高石墨烯类物质的牢固度。本发明将所述第二次复合处理温度设置为低于第一次复合处理温度，避免纤维内部石墨烯类物质跑出，通过第二复合处理能更好的将纤维内部石墨烯类物质固定并在纤维外部形成保护层。
优选地，所述第一次复合处理温度和/或第二次复合处理温度比纤维制品中纤维材料的玻璃化转变温度高5℃以上。
所述浸渍温度处于纤维制品纤维材料的高弹态温度能够提高所述纤维中大分子的运动，使得结晶区向非结晶区转化，使得非结晶区的空隙变大，使得结晶区与非结晶区之间区域的大分子间的空隙变大；从而使得进入纤维内部的石墨烯类物质增多，另一方面，降温后，部分石墨烯能够进入低温下的结晶区，牢固存在于所述纤维内部，提高石墨烯类物质在纤维中的牢固度。
本发明所述高弹态温度指所述纤维材料达到高弹态时的最低温度；所述玻璃化温度指所述纤维材料达到玻璃态时的最低温度；所述粘流态温度指所述纤维材料达到粘流态的最低温度。
优选地，所述第一次复合处理和第二次复合处理的恒温进行复合处理的时间均各自独立地为15～120min，例如16min、19min、23min、26min、32min、55min、66min、73min、78min、85min、88min、95min等。
优选地，所述第一石墨烯类物质分散液中，石墨烯类物质的粒径为0.1～1μm，例如0.1μm、0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm等，且不包括1微米，优选0.2～0.5μm。
优选地，所述第二石墨烯类物质分散液中，石墨烯类物质的粒径为2～10μm，例如3μm、4μm、5μm、6μm、7μm、8μm、9μm等，优选5～10μm。
优选地，所述第一石墨烯类物质分散液中，石墨烯类物质的浓度为0.5～5wt％，例如0.6wt％、0.7wt％、0.8wt％、0.9wt％、1.1wt％、1.2wt％、 1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％、2.5wt％、3wt％、4wt％、5wt％等。
优选地，所述第二石墨烯类物质分散液中，石墨烯类物质的浓度为0.5～7wt％，例如0.6wt％、0.7wt％、0.8wt％、0.9wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％、2.5wt％、3wt％、4wt％、5wt％、6wt％、6.5wt％等。
本发明所述未改性的纤维可以是初生纤维也可以是市售可得的商品化纤维，优选地，所述未改性的纤维是市售可得的商品化纤维。也就是说，所述改性纤维制品的制备方法也可以看作是市售可得的商品化纤维的后处理方法。
本发明目的之四是提供一种复合纱线，所述复合纱线包括如目的之一所述的改性纤维；
优选地，所述复合纱线由目的之一所述的改性纤维与不含石墨烯类物质的纤维混纺而成。
本发明目的之五是提供一种复合织物，所述复合织物包括如目的之一所述的改性纤维，或包括如目的之四所述的复合纱线。
优选地，所述复合织物由目的之一所述的改性纤维与不含石墨烯类物质的纤维交织而成，或者由目的之四所述的复合纱线与不含石墨烯类物质的纱线交织而成。
本发明目的之六是提供一种如目的之一所述改性纤维制品的用途，所述改性纤维制品用于制备家纺、内衣、防护服、保暖衣、袜子。
与现有技术相比，本发明具有如下有益效果：
(1)本发明同时在纤维内部和外部附着或填加石墨烯，增加了石墨烯存在的均匀性和牢固性；
(2)本发明通过添加石墨烯和/或生物质石墨烯提高了纤维的导电性能；添加氧化石墨烯和/或生物质石墨烯进一步增强了纤维的远红外性能；
(3)本发明提供的制备方法能够有效的将石墨烯填加至纤维内部，同时在纤维外部包覆石墨烯类物质，通过纤维制品浸渍石墨烯溶液实现石墨烯在纤维上的均匀分布。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1～9
一种改性纤维，具体步骤包括：
(1)配制第一石墨烯分散液，所述第一石墨烯分散液中石墨烯的粒径在0.1～1μm之间；配制第二石墨烯分散液，所述第二石墨烯分散液中石墨烯的粒径在1～2μm之间；
(2)将纤维在第一温度浸渍第一石墨烯分散液，之后取出浸渍有第一石墨烯的纤维，并将其继续浸渍在第二石墨烯分散液中浸渍30min，之后取出，干燥，得到改性纤维。
性能测试：将得到的改性纤维按照GB/T 14342-2015对得到的改性纤维进行检测；之后将改性纤维水洗50次，继续按照GB/T 14342-2015对水洗后的改性纤维进行检测。
表1给出了实施例1～9的工艺条件和得到的改性纤维的测试结果。
表1：实施例1～9制备改性纤维的工艺条件和所述改性纤维的测试结果
Figure PCTCN2018079035-appb-000001
实施例10～13
一种改性纤维，与实施例7的区别在于，步骤(2)所述第一石墨烯分散液 中同时分散纳米纤维素(长径比80～120，直径10nm以下)，所述纳米纤维素在分散液中的浓度为0.1wt％、0.5wt％、1wt％、2wt％。
采用与实施例7相同的性能测试方法，测试结果见表2。
实施例14
一种改性纤维，与实施例3的区别在于，将第一和第二石墨烯分散液都替换为氧化石墨烯分散液，且进行还原步骤，具体为：在步骤2)取出浸渍第二次浸渍完的纤维后放入水合肼还原液中进行还原处理后，干燥，得到改性纤维。采用与实施例3相同的性能测试方法，测试结果见表2。
实施例15
一种改性纤维，与实施例3的区别在于，将第一和第二石墨烯分散液全部替换为生物质石墨烯分散液。
采用与实施例3相同的性能测试方法，测试结果见表2。
此外，本实施例纤维的远红外法向发射率(测试方法FZ/T64010-2000)达到0.9。
实施例16
一种改性纤维，具体步骤包括：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(2)将涤纶纤维在95℃浸渍石墨烯分散液30min，之后取出，烘干，得到改性纤维。
采用与实施例4相同的性能测试方法，测试结果见表2。
实施例17-18
将实施例3中的纤维替换为赛络紧密纺纺成的纱线(实施例17)，和针织面料(实施例18)。
表2给出了实施例10～18得到的改性纤维制品的测试结果。
表2：实施例10～18改性纤维制品的测试结果
实施例 不水洗比电阻，Ω·cm 水洗50次后的比电阻，Ω·cm
实施例10 1×10 3 1×10 3
实施例11 1×10 3 1×10 3
实施例12 1×10 3 2×10 3
实施例13 8×10 3 9×10 3
实施例14 3×10 3 8×10 3
实施例15 2×10 3 5×10 3
实施例16 6×10 4 1×10 5
实施例17 3×10 2 6×10 2
实施例18 2×10 2 6×10 2
表2中，可以将实施例17纱线针织成面料，采用GB12703.4-2010进行检测表面电阻率，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为7×10 2Ω；实施例18面料的表面电阻率采用GB12703.4-2010进行检测，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为6×10 2Ω。
对比例1
一种改性纤维，采用原位复合的方式对纤维本体进行改性，具体步骤为：
(1)将200g石墨烯与8.52kgPTA、3.5L乙二醇投料混匀，球磨处理20min后直接引入到打浆釜打浆30min，按照利用三釜PET聚合工艺进行反应，进行聚合反应，聚合反应完毕得到熔体；
(2)熔体在40℃冷却水，0.5m/s牵伸速度条件下出料，直接造粒得到石墨烯复合PET母粒；
(3)将石墨烯复合PET母粒在110℃下，转鼓干燥24h后，直接用于熔融纺丝，纺丝出丝采用水雾冷却，冷却温度40℃，烘干温度35℃，熔融纺丝得到改性涤纶纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 13Ω·cm。
对比例2
一种改性纤维，采用常温浸渍的方式进行改性，具体步骤为：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(2)将涤纶纤维在25℃浸渍石墨烯分散液30min，之后取出，烘干，得到改性纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 4Ω·cm，水洗20次后的比电阻为1×10 10Ω·cm。
实施例1a～9a
一种复合纤维，具体步骤包括：
(1)熔融聚合物，经过熔融纺丝得到初生纤维；
(2)配制第一石墨烯分散液，所述第一石墨烯分散液中石墨烯的粒径在0.1～1μm之间；配制第二石墨烯分散液，所述第二石墨烯分散液中石墨烯的粒径在1～2μm之间；
(3)将步骤(1)的初生纤维在第一温度浸渍第一石墨烯分散液，之后取出浸渍有第一石墨烯的纤维，并将其继续浸渍在第二石墨烯分散液中浸渍30min，之后取出，干燥，得到复合纤维。
性能测试：将得到的改性纤维按照GB/T 14342-2015对得到的改性纤维进行检测；之后将改性纤维水洗50次，继续按照GB/T 14342-2015对水洗后的改性纤维进行检测。
表3给出了实施例1a～9a的工艺条件和得到的复合纤维的测试结果。
表3：实施例1a～9a制备初生纤维的工艺条件和测试结果
Figure PCTCN2018079035-appb-000002
实施例10a～13a
一种复合纤维，与实施例7a的区别在于，步骤(2)所述第一石墨烯分散 液中同时分散纳米纤维素(长径比80～120，直径10nm以下)，所述纳米纤维素在分散液中的浓度为0.1wt％、0.5wt％、1wt％、2wt％。
采用与实施例7a相同的性能测试方法，测试结果见表4。
实施例14a
一种复合纤维，与实施例3a的区别在于，将第一和第二石墨烯分散液都替换为氧化石墨烯分散液，且进行还原步骤，具体为：在步骤(3)从第二石墨烯分散液中取出的纤维后放入水合肼还原液中进行还原处理后，干燥，得到复合纤维。采用与实施例3a相同的性能测试方法，测试结果见表4。
实施例15a
一种复合纤维，与实施例3a的区别在于，将第一石墨烯分散液和第二石墨烯分散液全部替换为生物质石墨烯分散液。
采用与实施例3a相同的性能测试方法，测试结果见表4。
此外，本实施例纤维的远红外法向发射率(测试方法FZ/T64010-2000)达到0.91。
实施例16a
一种复合纤维，具体步骤包括：
(1)熔融聚合物PET(聚对苯二甲酸乙二醇酯)，经过熔融纺丝得到初生纤维；
(2)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(3)将涤纶纤维在95℃浸渍石墨烯分散液30min，之后取出，烘干，得到复合纤维。
采用与实施例3a相同的性能测试方法，测试结果见表4。
实施例17a
一种复合纤维，与实施例3a的区别点在于所述浸渍温度为常温。
采用与实施例3a相同的性能测试方法，测试结果见表4。
表4给出了实施例10a～17a得到的复合纤维的测试结果。
表4：实施例10a～17a复合纤维的测试结果
实施例 不水洗比电阻，Ω·cm 水洗50次后的比电阻，Ω·cm
实施例10a 2×10 3 1×10 3
实施例11a 3×10 2 3×10 2
实施例12a 3×10 2 4×10 2
实施例13a 4×10 3 5×10 3
实施例14a 2×10 2 7×10 2
实施例15a 4×10 2 8×10 2
实施例16a 2×10 4 6×10 4
实施例17a 2×10 3 1×10 5
对比例1a
一种复合纤维，采用原位复合的方式对纤维本体进行改性，具体步骤为：
(1)将200g石墨烯与8.52kgPTA(对苯二甲酸)、3.5L乙二醇投料混匀，球磨处理20min后直接引入到打浆釜打浆30min，按照利用三釜PET聚合工艺进行反应，进行聚合反应，聚合反应完毕得到熔体；
(2)熔体在40℃冷却水，0.5m/s牵伸速度条件下出料，直接造粒得到石墨烯复合PET母粒；
(3)将石墨烯复合PET母粒在110℃下，转鼓干燥24h后，直接用于熔融纺丝，纺丝出丝采用水雾冷却，冷却温度40℃，烘干温度35℃，熔融纺丝得到改性涤纶纤维。
测其比电阻(GB/T 14342-2015)，其不水洗的比电阻为1×10 13Ω·cm。
对比例2a
一种复合纤维，与实施例16a的区别点在于将步骤(1)的初生纤维替换为浙江恒冠化纤有限公司提供的涤纶POY成品。
测其比电阻(GB/T 14342-2015)，其不水洗的比电阻为5×10 6Ω·cm，水洗50次后的比电阻为1×10 10Ω。
对比例3a
一种复合纤维，具体步骤包括：
(1)熔融聚合物PET(聚对苯二甲酸乙二醇酯)，经过熔融纺丝得到初生纤维；
(2)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(3)将涤纶纤维在常温下浸渍石墨烯分散液30min，之后取出，烘干，得到复合纤维。
测其比电阻(GB/T 14342-2015)，其不水洗的比电阻为3×10 5Ω·cm，水洗50次后的比电阻为1×10 7Ω。
实施例1b～9b
一种改性纤维，具体步骤包括：
(1)配制第一石墨烯分散液，所述第一石墨烯分散液中石墨烯的粒径在0.1～1μm之间；配制第二石墨烯分散液，所述第二石墨烯分散液中石墨烯的粒径在1～2μm之间；
(2)将纤维在常温浸渍第一石墨烯分散液，之后取出浸渍有第一石墨烯的纤维，升温至第一温度，恒温进行第一后处理，得到第一改性纤维；
(3)将第一改性纤维在常温浸渍第二石墨烯分散液，之后取出浸渍有第二石墨烯的纤维，升温至第二温度，恒温30min进行第二后处理，得到第二改性纤维；
(4)将第二改性纤维冷却、干燥，得到改性纤维产品。
性能测试：将得到的改性纤维按照GB/T 14342-2015对得到的改性纤维进行检测；之后将改性纤维水洗50次，继续按照GB/T 14342-2015对水洗后的改性纤维进行检测。
表5给出了实施例1b～9b的工艺条件和得到的复合纤维的测试结果。
表5：实施例1b～9b制备改性纤维制品的工艺条件和测试结果
Figure PCTCN2018079035-appb-000003
Figure PCTCN2018079035-appb-000004
实施例10b～13b
一种改性纤维，与实施例7b的区别在于，步骤(2)所述第一石墨烯分散液中同时分散纳米纤维素(长径比80～120，直径10nm以下)，所述纳米纤维素在分散液中的浓度为0.1wt％、0.5wt％、1wt％、2wt％。
采用与实施例7b相同的性能测试方法，测试结果见表6。
实施例14b
一种改性纤维，与实施例3b的区别在于，将第一和第二石墨烯分散液都替换为氧化石墨烯分散液，且进行还原步骤，具体为：在步骤(3)第二改性纤维放入水合肼还原液中进行还原处理后，进行步骤(4)得到改性纤维产品。采用与实施例3b相同的性能测试方法，测试结果见表6。
实施例15b
一种改性纤维，与实施例3b的区别在于，将第一石墨烯分散液和第二石墨烯分散液全部替换为生物质石墨烯分散液。
采用与实施例3b相同的性能测试方法，测试结果见表6。
此外，本实施例纤维的远红外法向发射率(测试方法FZ/T64010-2000)达到0.9。
实施例16b
一种改性纤维，具体步骤包括：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(2)将涤纶纤维在室温下浸渍石墨烯分散液10min，之后取出，置于95℃的空气中30min，之后冷却、烘干，得到改性纤维。
采用与实施例3b相同的性能测试方法，测试结果见表6。
实施例17b-18b
将实施例3b中的纤维替换为赛络紧密纺纺成纱线(实施例17b)和针织面料(实施例18b)。
表6给出了实施例10b～18b得到的改性纤维制品的测试结果。
表6：实施例10b～18b改性纤维制品的测试结果
实施例 不水洗比电阻，Ω·cm 水洗50次后的比电阻，Ω·cm
实施例10b 1.0×10 3 1.0×10 3
实施例11b 1.0×10 3 1.0×10 3
实施例12b 1.0×10 3 2.0×10 3
实施例13b 7.0×10 3 8.0×10 3
实施例14b 3.0×10 3 7.0×10 3
实施例15b 2.0×10 3 4.8×10 3
实施例16b 5.8×10 4 1.0×10 5
实施例17b 3.0×10 2 5.7×10 2
实施例18b 2.0×10 2 6.2×10 2
表6中，可以将实施例17b纱线针织成面料，采用GB12703.4-2010进行检测表面电阻率，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为7×10 2Ω；实施例18b面料的表面电阻率采用GB12703.4-2010进行检测，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为6×10 2Ω。
对比例1b
一种改性纤维，采用原位复合的方式对纤维本体进行改性，具体步骤为：
(1)将200g石墨烯与8.52kgPTA、3.5L乙二醇投料混匀，球磨处理20min后直接引入到打浆釜打浆30min，按照利用三釜PET聚合工艺进行反应，进行聚合反应，聚合反应完毕得到熔体；
(2)熔体在40℃冷却水，0.5m/s牵伸速度条件下出料，直接造粒得到石墨烯复合PET母粒；
(3)将石墨烯复合PET母粒在110℃下，转鼓干燥24h后，直接用于熔融纺丝，纺丝出丝采用水雾冷却，冷却温度40℃，烘干温度35℃，熔融纺丝得到改性涤纶纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 13Ω·cm。
对比例2b
一种改性纤维，采用常温浸渍的方式进行改性，具体步骤为：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(2)将涤纶纤维在25℃浸渍石墨烯分散液30min，之后取出，烘干，得到改性纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 4Ω·cm，水洗20次后的比电阻为1×10 10Ω·cm。
实施例1c～7c
一种改性涤纶纤维，具体步骤包括：
(1)配制第一石墨烯分散液，所述第一石墨烯分散液中石墨烯的粒径小于1μm；配制第二石墨烯分散液，所述第二石墨烯分散液中石墨烯的粒径在1～2μm之间；
(2)将涤纶纤维在第一温度浸渍第一石墨烯分散液，之后取出浸渍有第一石墨烯的涤纶纤维，并将其继续浸渍在第二石墨烯分散液中浸渍30min，之后取出，干燥，得到改性涤纶纤维。
性能测试：将得到的改性涤纶纤维按照GB/T 14342-2015对得到的改性涤纶纤维进行检测；之后将改性涤纶纤维水洗50次，继续按照GB/T 14342-2015对水洗后的改性涤纶纤维进行检测。
表7给出了实施例1c～7c的工艺条件和得到的改性涤纶纤维的测试结果。
表7：实施例1c～7c制备改性涤纶纤维的工艺条件和测试结果
Figure PCTCN2018079035-appb-000005
通过表7可以看出，当实施例6c第一浸渍温度低于第二浸渍温度时，由于二次浸渍时纤维高分子运动比第一次浸渍剧烈，导致第一次浸渍在纤维内部的石墨烯溢出，同时阻碍第二次浸渍效果，使得比电阻升高；当实施例7c第一浸渍液中石墨烯粒径大于第二浸渍液的石墨烯粒径时，使得纤维内部石墨烯含量较低，外部含量较高，内外之间没有形成较强的作用力，导致水洗次数增多石墨烯脱落较为明显。
实施例8c～11c
一种改性涤纶纤维，与实施例3c的区别在于，步骤(2)所述第一石墨烯分散液中同时分散纳米纤维素(长径比80～120，直径10nm以下)，所述纳米纤维素在分散液中的浓度为0.1wt％(实施例8c)、0.5wt％(实施例9c)、1wt％(实施例10c)、2wt％(实施例11c)。
采用与实施例3c相同的性能测试方法，测试结果见表8。
实施例12c
一种改性涤纶纤维，与实施例3c的区别在于，将第一和第二石墨烯分散液都替换为氧化石墨烯分散液，且进行还原步骤，具体为：在步骤2)取出浸渍第二次浸渍完的涤纶纤维后放入水合肼还原液中进行还原处理后，干燥，得到改性涤纶纤维。采用与实施例3c相同的性能测试方法，测试结果见表8。
实施例13c
一种改性涤纶纤维，与实施例3c的区别在于，将第一和第二石墨烯分散液全部替换为生物质石墨烯分散液。
采用与实施例3c相同的性能测试方法，测试结果见表8。
此外，本实施例改性涤纶纤维的远红外法向发射率(测试方法FZ/T64010-2000)达到0.9。
实施例14c
一种改性涤纶纤维，具体步骤包括：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(2)将涤纶纤维在95℃浸渍石墨烯分散液30min，之后取出，烘干，得到改性涤纶纤维。
采用与实施例3c相同的性能测试方法，测试结果见表8。
实施例15c-16c
将实施例3c中的纤维替换为赛络紧密纺纺成的纱线(实施例15c)，和针织面料(实施例16c)。
表8给出了实施例8c～16c得到的改性涤纶纤维制品的测试结果。
表8：实施例8c～16c改性涤纶纤维制品的测试结果
实施例 不水洗比电阻，Ω·cm 水洗50次后的比电阻，Ω·cm
实施例8c 1×10 2 1×10 2
实施例9c 1×10 2 1×10 2
实施例10c 1×10 2 2×10 2
实施例11c 8×10 3 9×10 3
实施例12c 3×10 2 8×10 2
实施例13c 2×10 2 5×10 2
实施例14c 6×10 4 1×10 5
实施例15c 3×10 2 6×10 2
实施例16c 2×10 2 6×10 2
表8中，可以将实施例15c纱线针织成面料，采用GB12703.4-2010进行检测表面电阻率，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为7×10 2Ω；实施例16c面料的表面电阻率采用GB12703.4-2010进行检测，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为6×10 2Ω。
对比例1c
一种改性涤纶纤维，采用原位复合的方式对涤纶纤维本体进行改性，具体步骤为：
(1)将200g石墨烯与8.52kgPTA、3.5L乙二醇投料混匀，球磨处理20min后直接引入到打浆釜打浆30min，按照利用三釜PET聚合工艺进行反应，进行聚合反应，聚合反应完毕得到熔体；
(2)熔体在40℃冷却水，0.5m/s牵伸速度条件下出料，直接造粒得到石墨烯复合PET母粒；
(3)将石墨烯复合PET母粒在110℃下，转鼓干燥24h后，直接用于熔融纺丝，纺丝出丝采用水雾冷却，冷却温度40℃，烘干温度35℃，熔融纺丝得到改性涤纶纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 13Ω·cm。
对比例2c
一种改性涤纶纤维，采用常温浸渍的方式进行改性，具体步骤为：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(2)将涤纶纤维在25℃浸渍石墨烯分散液30min，之后取出，烘干，得到改性纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 4Ω·cm，水洗20次后的比电阻为1×10 10Ω·cm。
实施例1d～8d
一种改性锦纶纤维，具体步骤包括：
(1)配制第一石墨烯分散液，所述第一石墨烯分散液中石墨烯的粒径小于1μm；配制第二石墨烯分散液，所述第二石墨烯分散液中石墨烯的粒径在1～2μm之间；
(2)将锦纶纤维在第一温度浸渍第一石墨烯分散液，之后取出浸渍有第一石墨烯的锦纶纤维，并将其继续浸渍在第二石墨烯分散液中浸渍30min，之后取出，干燥，得到改性锦纶纤维。
性能测试：将得到的改性锦纶纤维按照GB/T 14342-2015对得到的改性锦纶纤维进行检测；之后将改性锦纶纤维水洗50次，继续按照GB/T 14342-2015对水洗后的改性锦纶纤维进行检测。
表9给出了实施例1d～8d的工艺条件和得到的改性锦纶纤维的测试结果。
表9：实施例1d～8d制备改性锦纶纤维的工艺条件和测试结果
Figure PCTCN2018079035-appb-000006
Figure PCTCN2018079035-appb-000007
通过表9可以看出，当实施例7d第一浸渍温度低于第二浸渍温度时，由于二次浸渍时纤维高分子运动比第一次浸渍剧烈，导致第一次浸渍在纤维内部的石墨烯溢出，同时阻碍第二次浸渍效果，使得比电阻升高；当实施例8d第一浸渍液中石墨烯粒径大于第二浸渍液的石墨烯粒径时，使得纤维内部石墨烯含量较低，外部含量较高，内外之间没有形成较强的作用力，导致水洗次数增多石墨烯脱落较为明显。
实施例9d～12d
一种改性纤维，与实施例3d的区别在于，步骤(2)所述第一石墨烯分散液中同时分散纳米纤维素(长径比80～120，直径10nm以下)，所述纳米纤维素在分散液中的浓度为0.1wt％(实施例9d)、0.5wt％(实施例10d)、1wt％(实施例11d)、2wt％(实施例12d)。
采用与实施例3d相同的性能测试方法，测试结果见表10。
实施例13d
一种改性锦纶纤维，与实施例3d的区别在于，将第一和第二石墨烯分散液都替换为氧化石墨烯分散液，且进行还原步骤，具体为：在步骤2)取出浸渍第二次浸渍完的锦纶纤维后放入水合肼还原液中进行还原处理后，干燥，得到改性锦纶纤维。采用与实施例3d相同的性能测试方法，测试结果见表10。
实施例14d
一种改性锦纶纤维，与实施例3d的区别在于，将第一和第二石墨烯分散液全部替换为生物质石墨烯分散液。
采用与实施例3d相同的性能测试方法，测试结果见表10。
此外，本实施例改性锦纶纤维的远红外法向发射率(测试方法FZ/T64010-2000)达到0.9。
实施例15d
一种改性锦纶纤维，具体步骤包括：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm 之间；
(2)将锦纶纤维在95℃浸渍石墨烯分散液30min，之后取出，烘干，得到改性纤维。
采用与实施例4d相同的性能测试方法，测试结果见表10。
实施例16d～17d
将实施例3d中的锦纶纤维替换为赛络紧密纺纺成的纱线(实施例16d)，和针织面料(实施例17d)。
表10给出了实施例9d～17d得到的改性纤维制品的测试结果。
表10：实施例9d～17d改性纤维制品的测试结果
实施例 不水洗比电阻，Ω·cm 水洗50次后的比电阻，Ω·cm
实施例9d 1×10 2 1×10 2
实施例10d 1×10 2 1×10 2
实施例11d 1×10 2 2×10 2
实施例12d 8×10 3 9×10 3
实施例13d 3×10 2 8×10 2
实施例14d 2×10 2 5×10 2
实施例15d 6×10 4 1×10 5
实施例16d 3×10 2 6×10 2
实施例17d 2×10 2 6×10 2
表10中，可以将实施例16d纱线针织成面料，采用GB12703.4-2010进行检测表面电阻率，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为7×10 2Ω；实施例17d面料的表面电阻率采用GB12703.4-2010进行检测，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为6×10 2Ω。
对比例1d
一种改性锦纶纤维，具体步骤为：
(1)将200g石墨烯与2kg锦纶切片熔融造粒得到石墨烯复合PA母粒；
(2)将上述石墨烯复合PA母粒与13kg锦纶切片混合后，熔融纺丝得到改性锦纶纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 13Ω·cm。
对比例2d
一种改性锦纶纤维，采用常温浸渍的方式进行改性，具体步骤为：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(2)将锦纶纤维在25℃浸渍石墨烯分散液30min，之后取出，烘干，得到改性锦纶纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 4Ω·cm，水洗20次后的比电阻为1×10 10Ω·cm。
实施例1e～8e
一种改性腈纶纤维，具体步骤包括：
(1)配制第一石墨烯分散液，所述第一石墨烯分散液中石墨烯的粒径小于1μm；配制第二石墨烯分散液，所述第二石墨烯分散液中石墨烯的粒径在1～2μm之间；
(2)将纤维在第一温度浸渍第一石墨烯分散液，之后取出浸渍有第一石墨烯的腈纶纤维，并将其继续浸渍在第二石墨烯分散液中浸渍30min，之后取出，干燥，得到腈纶改性纤维。
性能测试：将得到的改性纤维按照GB/T 14342-2015对得到的改性纤维进行检测；之后将改性纤维水洗50次，继续按照GB/T 14342-2015对水洗后的改性纤维进行检测。
表11给出了实施例1e～8e的工艺条件和得到的改性纤维的测试结果。
表11：实施例1e～8e制备改性纤维的工艺条件和所述改性纤维的测试结果
Figure PCTCN2018079035-appb-000008
Figure PCTCN2018079035-appb-000009
通过表11可以看出，当实施例7e第一浸渍温度低于第二浸渍温度时，由于二次浸渍时纤维高分子运动比第一次浸渍剧烈，导致第一次浸渍在纤维内部的石墨烯溢出，同时阻碍第二次浸渍效果，使得比电阻升高；当实施例8e第一浸渍液中石墨烯粒径大于第二浸渍液的石墨烯粒径时，使得纤维内部石墨烯含量较低，外部含量较高，内外之间没有形成较强的作用力，导致水洗次数增多石墨烯脱落较为明显。
实施例9e～12e
一种改性纤维，与实施例3e的区别在于，步骤(2)所述第一石墨烯分散液中同时分散纳米纤维素(长径比80～120，直径10nm以下)，所述纳米纤维素在分散液中的浓度为0.1wt％(实施例9e)、0.5wt％(实施例10e)、1wt％(实施例11e)、2wt％(实施例12e)。
采用与实施例3e相同的性能测试方法，测试结果见表12。
实施例13e
一种改性纤维，与实施例3e的区别在于，将第一和第二石墨烯分散液都替换为氧化石墨烯分散液，且进行还原步骤，具体为：在步骤2)取出浸渍第二次浸渍完的纤维后放入水合肼还原液中进行还原处理后，干燥，得到改性纤维。采用与实施例3e相同的性能测试方法，测试结果见表12。
实施例14e
一种改性纤维，与实施例3e的区别在于，将第一和第二石墨烯分散液全部替换为生物质石墨烯分散液。
采用与实施例3e相同的性能测试方法，测试结果见表12。
此外，本实施例纤维的远红外法向发射率(测试方法FZ/T64010-2000)达到0.9。
实施例15e
一种改性纤维，具体步骤包括：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(2)将涤纶纤维在95℃浸渍石墨烯分散液30min，之后取出，烘干，得到改性纤维。
采用与实施例4e相同的性能测试方法，测试结果见表12。
实施例16e-17e
将实施例3e中的纤维替换为赛络紧密纺纺成的纱线(实施例16e)，和针织面料(实施例17e)。
表12给出了实施例9e～17e得到的改性纤维制品的测试结果。
表12：实施例9e～17e改性纤维制品的测试结果
实施例 不水洗比电阻，Ω·cm 水洗50次后的比电阻，Ω·cm
实施例9e 1×10 2 1×10 2
实施例10e 1×10 2 1×10 2
实施例11e 1×10 2 2×10 2
实施例12e 8×10 3 9×10 3
实施例13e 3×10 2 8×10 2
实施例14e 2×10 2 5×10 2
实施例15e 7×10 4 2×10 5
实施例16e 4×10 2 6×10 2
实施例17e 2×10 2 5×10 2
表12中，可以将实施例16e纱线针织成面料，采用GB12703.4-2010进行检测表面电阻率，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为7×10 2Ω；实施例17e面料的表面电阻率采用GB12703.4-2010进行检测，不水洗的表面电阻率为2×10 2Ω，水洗50次的表面电阻率为6×10 2Ω。
对比例1e
一种改性腈纶纤维，具体步骤为：
(1)将200g石墨烯与2kg腈纶切片熔融造粒，得到石墨烯复合腈纶母粒；
(2)将上述石墨烯复合腈纶母粒与13kg腈纶切片混合后，熔融纺丝得到改性腈纶纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 13Ω·cm。
对比例2e
一种改性腈纶纤维，采用常温浸渍的方式进行改性，具体步骤为：
(1)配制石墨烯分散液，所述石墨烯分散液中石墨烯的粒径在0.1～3μm之间；
(2)将腈纶纤维在25℃浸渍石墨烯分散液30min，之后取出，烘干，得到 改性腈纶纤维。
按照GB/T 14342-2015对得到的纤维进行检测，其不水洗的比电阻为1×10 4Ω·cm，水洗20次后的比电阻为1×10 10Ω·cm。
申请人声明，本发明通过上述实施例来说明本发明的工艺方法，但本发明并不局限于上述工艺步骤，即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (26)

  1. 一种改性纤维制品，其中，所述改性纤维制品含有改性纤维，所述改性纤维内部存在石墨烯类物质，所述改性纤维外部也存在石墨烯类物质。
  2. 如权利要求1所述的纤维制品，其中，存在于所述改性纤维外部的石墨烯类物质比存在于改性纤维内部的石墨烯类物质多。
  3. 如权利要求1所述的纤维制品，其中所述改性纤维制品中石墨烯类物质总质量为纤维制品总质量的0.5～3wt％。
  4. 如权利要求1～3之一所述的纤维制品，其中所述石墨烯类物质的粒径≤20μm，粒径小于1μm的石墨烯类物质主要存在于所述改性纤维内部，粒径为1～20μm的石墨烯类物质主要存在于所述改性纤维的外部；
    优选地，所述改性纤维外部存在的石墨烯类物质的粒径为2～10μm。
  5. 如权利要求1～4之一所述的纤维制品，其中所述改性纤维内部包括改性纤维的结晶区、非结晶区、以及结晶区与非结晶区之间的间隙，粒径小于1μm的石墨烯类物质存在于所述改性纤维内部的结晶区、非结晶区、以及结晶区与非结晶区之间的间隙中的至少1处；
    优选地，所述改性纤维内部结晶区存在石墨烯类物质，同时所述改性纤维外部存在石墨烯类物质，优选所述改性纤维内部的结晶区存在粒径小于1μm的石墨烯类物质；
    优选地，所述改性纤维内部的结晶区、非结晶区、以及结晶区与非结晶区之间的间隙均存在石墨烯类物质。
  6. 如权利要求1～5之一所述的纤维制品，其中所述石墨烯类物质包括石墨烯、生物质石墨烯、氧化石墨烯、石墨烯衍生物的任意1种或至少2种的混合，优选石墨烯和/或生物质石墨烯；
    优选地，所述石墨烯衍生物包括元素掺杂石墨烯或官能团化石墨烯物中的任意1种或至少2种的组合。
  7. 如权利要求1～6之一所述的改性纤维制品，其中，当所述石墨烯类物 质为石墨烯和/或生物质石墨烯时，所述改性纤维制品中改性纤维的比电阻≤1×10 5Ω·cm；
    优选地，当所述石墨烯类物质为石墨烯和/或生物质石墨烯时，所述改性纤维制品中改性纤维水洗50次之后，其比电阻≤1×10 5Ω·cm。
  8. 如权利要求1～7之一所述的改性纤维制品，其中，所述改性纤维制品包括改性纤维、包含改性纤维的纱线和包含改性纤维的织物中的任意1种或至少2种的组合；
    优选地，所述改性纤维包括改性涤纶纤维、改性锦纶纤维、改性氨纶纤维、改性芳纶纤维、改性腈纶纤维、改性PVA纤维、改性再生纤维素纤维；进一步优选地，所述改性纤维是改性涤纶纤维、改性锦纶纤维或改性腈纶纤维；
    优选地，所述包含改性纤维的纱线由所述改性纤维单纺，混纺或与未改性纤维混纺得到；
    优选地，所述包含改性纤维的织物由所述改性纤维，所述包含改性纤维的纱线制成。
  9. 如权利要求1～8之一所述的改性纤维制品，其中，所述改性纤维制品的改性纤维中复合有纳米纤维素；
    优选地，所述纳米纤维素缠绕在所述改性纤维的内部和/或外部。
  10. 一种如权利要求1～9之一所述的改性纤维制品的制备方法，其中，所述方法包括将未改性的纤维制品在石墨烯类物质分散液中浸渍，之后经过冷却、干燥，得到处理后的纤维制品；
    其中，所述浸渍的温度范围处于未改性的纤维制品中纤维材料的高弹态温度。
  11. 如权利要求10所述的制备方法，其中所述浸渍温度至少比未改性的纤维制品中纤维材料的玻璃化转变温度高5℃。
  12. 如权利要求10所述的制备方法，其中，所述石墨烯类物质分散液的浓度为0.1～5wt％，优选0.3～2wt％；
    优选地，所述石墨烯类物质分散液中的石墨烯类物质的粒径为不大于20μm；优选为100nm～10μm，进一步优选200nm～5um；
    优选地，所述浸渍时间为15～120min。
  13. 如权利要求10～12之一所述的制备方法，其中，将所述未改性的纤维制品在石墨烯类物质分散液中浸渍分两步进行，具体包括如下步骤：
    (A1)将未改性纤维制品浸渍至第一石墨烯类物质分散液中，进行第一次浸渍，得到第一浸渍纤维制品；所述第一石墨烯类物质分散液中石墨烯类物质的粒径小于1μm；
    (A2)将第一浸渍纤维制品浸渍至第二石墨烯类物质分散液中，进行第二次浸渍，得到第二浸渍纤维制品；所述第二石墨烯类物质分散液中石墨烯类物质的粒径为1～20μm。
  14. 如权利要求13所述的制备方法，其特征在于，所述第一次浸渍和第二次浸渍至少所述第一次浸渍温度范围处于未改性的纤维制品中纤维材料的高弹态温度；
    进一步优选地，所述第一次浸渍和第二次浸渍的浸渍温度范围均处于未改性的纤维制品中纤维材料的高弹态温度，且第二次浸渍温度小于第一次浸渍温度；
    优选地，所述第一次浸渍和/或第二次浸渍温度比未改性的纤维制品中纤维材料的玻璃化转变温度至少高5℃；
    优选地，所述第一次浸渍、第二次浸渍的时间均各自独立地选自15～120min；
    优选地，所述第一次浸渍的石墨烯类物质的粒径为0.1～1μm，且不包括1微米，优选0.2～0.5μm；
    优选地，所述第二次浸渍的石墨烯类物质的粒径为2～10μm，优选5～10μm；
    优选地，所述粒径小于1μm的石墨烯类物质分散液中，石墨烯类物质的浓 度为0.5～5wt％；
    优选地，所述粒径为1～20μm的石墨烯类物质分散液中，石墨烯类物质的浓度为0.5～7wt％。
  15. 如权利要求10～14之一所述的制备方法，其中所述纤维包括涤纶纤维、锦纶纤维、氨纶纤维、芳纶纤维、腈纶纤维、PVA纤维、聚乙烯醇缩丁醛纤维或再生纤维素纤维；进一步优选地，所述纤维是涤纶纤维、锦纶纤维或腈纶纤维；
    优选地，当所述纤维是涤纶纤维时，所述浸渍的温度为80～120℃；
    优选地，当所述纤维是锦纶纤维时，所述浸渍的温度为45～80℃；
    优选地，当所述纤维是锦纶纤维时，所述浸渍的温度为80～100℃。
  16. 如权利要求10～15之一所述的制备方法，其中所述未改性的纤维制品是通过聚合物纺丝得到的初生纤维。
  17. 如权利要求16所述的制备方法，其中，所述纺丝包括静电纺丝、熔体纺丝、湿法溶液纺丝、干法溶液纺丝中的任意1种或至少2种的组合。
  18. 一种如权利要求1～9之一所述的改性纤维制品的制备方法，所述方法包括：将未改性的纤维制品在石墨烯类物质分散液中浸渍，取出后升温至纤维材料的高弹态温度，并恒温进行复合处理，之后经过冷却、干燥，得到改性纤维制品。
  19. 如权利要求18所述的制备方法，其中，所述处理温度比纤维制品中纤维材料的玻璃化转变温度高5℃以上；
    优选地，所述石墨烯类物质分散液的浓度为0.1～5wt％，优选0.3～2wt％；
    优选地，所述石墨烯类物质分散液中的石墨烯类物质的粒径为不大于20μm；优选为100nm～10μm，进一步优选200nm～5μm；
    优选地，所述升温的方式为热空气加热；
    优选地，所述恒温进行复合处理的时间为15～120min。
  20. 如权利要求18或19所述的制备方法，其中，所述纤维制品包括纤维 原丝、纱线和织物中的任意1种或至少2种的组合；
    优选地，所述纤维包括涤纶纤维、锦纶纤维、氨纶纤维、芳纶纤维、腈纶纤维、PVA纤维、再生纤维素纤维。
  21. 如权利要求18～20之一所述的制备方法，其中，所述制备方法包括如下步骤：
    (A1)将纤维制品浸渍至第一石墨烯类物质分散液中，取出后升温至高弹态温度，在处理温度下恒温进行第一次复合处理；所述第一石墨烯类物质分散液中石墨烯类物质的粒径小于1μm；
    (A2)将第一次复合处理后的纤维制品浸渍至第二石墨烯类物质分散液中，取出后升温至第二处理温度后，恒温进行第二次复合处理，之后经过冷却、干燥，得到改性纤维制品；所述第二石墨烯类物质分散液中石墨烯类物质的粒径为1～20μm。
  22. 如权利要求21所述的制备方法，其中，所述第二次复合处理温度比第一次复合处理温度低；
    优选地，所述第一次复合处理温度和/或第二次复合处理温度比纤维制品中纤维材料的玻璃化转变温度高5℃以上；
    优选地，所述第一次复合处理和第二次复合处理的恒温进行复合处理的时间均各自独立地为15～120min；
    优选地，所述第一石墨烯类物质分散液中，石墨烯类物质的粒径为0.1～1μm，且不包括1微米，优选0.2～0.5μm；
    优选地，所述第二石墨烯类物质分散液中，石墨烯类物质的粒径为2～10μm，优选5～10μm；
    优选地，所述第一石墨烯类物质分散液中，石墨烯类物质的浓度为0.5～5wt％；
    优选地，所述第二石墨烯类物质分散液中，石墨烯类物质的浓度为0.5～7wt％。
  23. 如权利要求10～22之一所述的制备方法，其中，所述石墨烯类物质包括石墨烯、生物质石墨烯、氧化石墨烯、石墨烯衍生物的任意1种或至少2种的混合，优选石墨烯和/或生物质石墨烯；
    优选地，所述石墨烯衍生物包括元素掺杂石墨烯或官能团化石墨烯物中的任意1种或至少2种的组合。
  24. 如权利要求23所述的制备方法，其中当所述石墨烯类物质包括氧化石墨烯时，在冷却之前和/或之后进行还原处理；
    优选地，所述还原处理的方法包括还原剂还原法和/或加热还原法；
    优选地，所述还原剂还原法包括加入还原剂进行还原；
    优选地，所述还原剂的加入量为石墨烯类物质的10～200wt％，优选50～100wt％；
    优选地，所述还原剂包括抗坏血酸、水合肼、葡萄糖、乙二胺、柠檬酸钠、L-半胱氨酸、氢碘酸或硼氢化钠中的任意1种或至少2种的组合；
    优选地，所述加热还原法包括在非氧化性气氛中，加热进行还原；
    优选地，所述加热还原法步骤包括：在高压反应釜中，通入保护性气氛和/或还原性气氛，加热还原；所述加热还原的温度≤200℃，压力≤1.6MPa。
  25. 如权利要求10～22之一所述的制备方法，其中，所述石墨烯类物质分散液中添加有纳米纤维素；
    优选地，所述纳米纤维素的直径不大于10nm，长径比不小于10；
    优选地，所述纳米纤维素在分散液中的浓度为2wt％以下，优选1wt％以下，再优选0.5wt％以下。
  26. 一种如权利要求1～9之一所述改性纤维制品的用途，其特征在于，所述改性纤维制品用于制备家纺、内衣、防护服、保暖衣、袜子。
PCT/CN2018/079035 2017-03-15 2018-03-14 一种改性纤维制品、制备方法及其用途 WO2018166477A1 (zh)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110373892A (zh) * 2019-07-02 2019-10-25 天津工业大学 一种石墨烯改性兔毛纤维及其制备方法
WO2020064961A1 (en) * 2018-09-27 2020-04-02 Sanko Tekstil Isletmeleri San. Ve Tic. A.S. A process for providing a textile with electrical conductivity properties
CN111137881A (zh) * 2019-12-27 2020-05-12 北京光华纺织集团有限公司 硅氧烷改性氧化石墨烯、氨纶纺丝油剂及其制备方法
CN111519436A (zh) * 2020-03-24 2020-08-11 合肥克拉伦斯科技有限公司 一种添加有石墨烯的服装面料生产工艺
CN111629457A (zh) * 2020-06-08 2020-09-04 北京石墨烯研究院有限公司 发热膜及其制备方法
CN111996611A (zh) * 2020-09-03 2020-11-27 涂一淼 抗静电剂及其制备方法
CN113062006A (zh) * 2021-04-02 2021-07-02 邵阳阳光发品有限公司 一种环保型复合纺织材料及其制备方法
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CN116791229A (zh) * 2022-03-14 2023-09-22 北京石墨烯研究院 高性能石墨烯改性芳纶纤维及其制备方法

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102877286A (zh) * 2012-11-05 2013-01-16 东华大学 一种导电复合纤维及其制备方法
CN103556452A (zh) * 2013-10-30 2014-02-05 苏州龙杰特种纤维股份有限公司 一种具有弹性的导电复合纤维及其制备方法
CN104328653A (zh) * 2014-10-11 2015-02-04 江南大学 一种氧化石墨烯衍生物用于纺织品多功能整理的方法
CN105484016A (zh) * 2015-12-28 2016-04-13 宁国市龙晟柔性储能材料科技有限公司 一种石墨烯复合导电纤维的制备方法
CN106930099A (zh) * 2017-03-15 2017-07-07 山东圣泉新材料股份有限公司 一种复合纤维、制备方法及其用途
CN106930096A (zh) * 2017-03-15 2017-07-07 山东圣泉新材料股份有限公司 一种改性纤维制品、制备方法及其用途
CN106930098A (zh) * 2017-03-15 2017-07-07 山东圣泉新材料股份有限公司 一种复合纤维、制备方法及其用途
CN106930097A (zh) * 2017-03-15 2017-07-07 山东圣泉新材料股份有限公司 一种改性纤维制品、制备方法及其用途
CN106948171A (zh) * 2017-03-29 2017-07-14 山东圣泉新材料股份有限公司 一种纤维制品的后处理方法、得到的改性纤维制品及其用途
CN106948170A (zh) * 2017-03-29 2017-07-14 山东圣泉新材料股份有限公司 一种纤维制品的后处理方法、得到的改性纤维制品及其用途
CN107245879A (zh) * 2017-06-13 2017-10-13 山东圣泉新材料股份有限公司 一种改性涤纶纤维制品、制备方法及其用途
CN107245878A (zh) * 2017-06-13 2017-10-13 山东圣泉新材料股份有限公司 一种改性腈纶纤维制品、制备方法及其用途
CN107254774A (zh) * 2017-06-13 2017-10-17 山东圣泉新材料股份有限公司 一种改性锦纶纤维制品、制备方法及其用途

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101233818B1 (ko) * 2011-06-07 2013-02-18 단국대학교 산학협력단 그래핀이 처리된 섬유의 제조 방법
CN102912471B (zh) * 2011-08-04 2015-06-10 中国石油化工集团公司 小溶程70℃水溶性聚乙烯醇纤维及其制备方法
US9862840B2 (en) * 2014-09-17 2018-01-09 National University Corporation Nagoya University Conducting composition and method for producing the same
KR101630699B1 (ko) * 2015-05-13 2016-06-15 (주)탑나노시스 전도성 코팅액 조성물, 및 상기 전도성 코팅액을 포함한 전도성 원단 및 원사
CN104831389B (zh) * 2015-05-22 2017-04-19 济南圣泉集团股份有限公司 一种多功能粘胶纤维及其制备方法
EP3411882A4 (en) * 2016-02-03 2019-11-13 Imagine Intelligent Materials Limited GEOTEXTIL WITH CONDUCTIVE CHARACTERISTICS
CN105860143A (zh) * 2016-05-14 2016-08-17 上海大学 一种柔性纳米纤维素-石墨烯复合膜及其制备方法
CN106245441B (zh) * 2016-07-29 2018-04-27 佛山市高明区诚睿基科技有限公司 一种石墨烯改性复合玻璃纤维在玻璃纤维过滤纸的应用

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102877286A (zh) * 2012-11-05 2013-01-16 东华大学 一种导电复合纤维及其制备方法
CN103556452A (zh) * 2013-10-30 2014-02-05 苏州龙杰特种纤维股份有限公司 一种具有弹性的导电复合纤维及其制备方法
CN104328653A (zh) * 2014-10-11 2015-02-04 江南大学 一种氧化石墨烯衍生物用于纺织品多功能整理的方法
CN105484016A (zh) * 2015-12-28 2016-04-13 宁国市龙晟柔性储能材料科技有限公司 一种石墨烯复合导电纤维的制备方法
CN106930099A (zh) * 2017-03-15 2017-07-07 山东圣泉新材料股份有限公司 一种复合纤维、制备方法及其用途
CN106930096A (zh) * 2017-03-15 2017-07-07 山东圣泉新材料股份有限公司 一种改性纤维制品、制备方法及其用途
CN106930098A (zh) * 2017-03-15 2017-07-07 山东圣泉新材料股份有限公司 一种复合纤维、制备方法及其用途
CN106930097A (zh) * 2017-03-15 2017-07-07 山东圣泉新材料股份有限公司 一种改性纤维制品、制备方法及其用途
CN106948171A (zh) * 2017-03-29 2017-07-14 山东圣泉新材料股份有限公司 一种纤维制品的后处理方法、得到的改性纤维制品及其用途
CN106948170A (zh) * 2017-03-29 2017-07-14 山东圣泉新材料股份有限公司 一种纤维制品的后处理方法、得到的改性纤维制品及其用途
CN107245879A (zh) * 2017-06-13 2017-10-13 山东圣泉新材料股份有限公司 一种改性涤纶纤维制品、制备方法及其用途
CN107245878A (zh) * 2017-06-13 2017-10-13 山东圣泉新材料股份有限公司 一种改性腈纶纤维制品、制备方法及其用途
CN107254774A (zh) * 2017-06-13 2017-10-17 山东圣泉新材料股份有限公司 一种改性锦纶纤维制品、制备方法及其用途

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JP7529202B2 (ja) 2018-09-27 2024-08-06 サンコ テキスタイル イスレットメレリ サン ベ ティク エーエス 導電特性を有する繊維製品を提供するためのプロセスと導電性複合繊維製品
JP2022512564A (ja) * 2018-09-27 2022-02-07 サンコ テキスタイル イスレットメレリ サン ベ ティク エーエス 導電特性を有する繊維製品を提供するためのプロセスと導電性複合繊維製品
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CN111519436A (zh) * 2020-03-24 2020-08-11 合肥克拉伦斯科技有限公司 一种添加有石墨烯的服装面料生产工艺
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