WO2017084542A1 - Fibre de cellulose régénérée fonctionnelle, procédé de préparation pour celle-ci, et application de celle-ci - Google Patents

Fibre de cellulose régénérée fonctionnelle, procédé de préparation pour celle-ci, et application de celle-ci Download PDF

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Publication number
WO2017084542A1
WO2017084542A1 PCT/CN2016/105641 CN2016105641W WO2017084542A1 WO 2017084542 A1 WO2017084542 A1 WO 2017084542A1 CN 2016105641 W CN2016105641 W CN 2016105641W WO 2017084542 A1 WO2017084542 A1 WO 2017084542A1
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Prior art keywords
carbon
regenerated cellulose
cellulose fiber
oxygen element
composite
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PCT/CN2016/105641
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English (en)
Chinese (zh)
Inventor
唐一林
张金柱
王双成
许日鹏
刘顶
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济南圣泉集团股份有限公司
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Priority claimed from CN201510819312.XA external-priority patent/CN105504341B/zh
Priority claimed from CN201510817208.7A external-priority patent/CN105506765B/zh
Priority claimed from CN201510849113.3A external-priority patent/CN105525377B/zh
Application filed by 济南圣泉集团股份有限公司 filed Critical 济南圣泉集团股份有限公司
Priority to JP2018526241A priority Critical patent/JP6663991B2/ja
Priority to US15/777,636 priority patent/US11306416B2/en
Priority to KR1020187016652A priority patent/KR102033268B1/ko
Publication of WO2017084542A1 publication Critical patent/WO2017084542A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D10B2101/122—Nanocarbons
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D10B2201/24—Viscose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
    • D21H5/14—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of cellulose fibres only
    • D21H5/148—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of cellulose fibres only viscose

Definitions

  • the invention relates to a regenerated cellulose fiber, in particular to a functional regenerated cellulose fiber and a preparation process and application thereof.
  • Regenerated cellulose fiber refers to a chemical fiber which is chemically prepared from a natural polymer and which is chemically composed of the original polymer. At the same time, the cellulose-based regenerated fiber made of cellulose can be used.
  • the development of regenerated cellulose fibers can be generally divided into three stages, forming three generations of products.
  • the first generation was an ordinary viscose fiber that was introduced in the early 20th century to solve the cotton shortage.
  • the second generation is a high-moisture modulus viscose fiber that has been industrially produced in the 1950s. Its main products include tiger kapok developed in Japan (later named Polynosic) and the modified high-moisture modulus fiber HWM developed by the United States and blue. Modal fiber produced by the company in the late 1980s using a new process. Since the late 1960s, due to the rapid development of synthetic fiber production technology, abundant raw materials and low cost, synthetic fibers have greatly impacted the market position of regenerated cellulose fibers.
  • viscose fiber is currently used as a kind of textile fiber. It is made from natural cellulose as raw material, and is made into soluble cellulose xanthate through alkalization, aging, sulfonation and other processes. The acid ester is redissolved in a dilute alkali solution to make a viscose, which is made by wet spinning.
  • the viscose fiber is mainly made of natural cellulose such as cotton linters, corn cob, wood or bamboo, and is cooked and bleached. After a series of treatment processes, the pulp slurry with high purity of cellulose is prepared, and then impregnated, pressed, crushed, aged, and yellow. Prepared by chemical, dissolution, mixing, filtration, defoaming, filtration, spinning, post-treatment, drying, packaging and other sections.
  • the technical problem to be solved by the present invention is to provide a functional regenerated cellulose fiber and a preparation process and application thereof, and the functional regenerated cellulose fiber provided by the present invention, that is, a functional viscose fiber, not only has a comparative Good far infrared performance, but also can produce high antibacterial and antibacterial properties.
  • the present invention provides a functional regenerated cellulose fiber comprising a graphene structure and a non-carbon non-oxygen element
  • the non-carbon non-oxygen element includes Fe, Si, and Al elements
  • the Fe, Si and Al elements constitute from 0.018 wt% to 0.8 wt% of the regenerated cellulose fibers.
  • the material containing a graphene structure and a non-carbon non-oxygen element is introduced in the form of a composite containing carbon nanostructures.
  • the carbon nanostructure-containing composite contains graphene, amorphous carbon and non-carbon non-oxygen elements;
  • the non-carbon non-oxygen element includes Fe, Si, and Al elements
  • the non-carbon non-oxygen element content is from 0.5 wt% to 6 wt% of the carbon nanostructure-containing composite.
  • the carbon element content of the carbon nanostructure-containing composite is ⁇ 80% by weight.
  • the non-carbon non-oxygen element comprises from 0.3% by weight to 5% by weight, preferably from 1.5% by weight to 5% by weight, of the carbon nanostructure-containing composite.
  • the non-carbon non-oxygen element is adsorbed on the surface or inside of the carbon nanostructure in the form of any one or more of a simple substance, an oxide or a carbide.
  • the preparation method of the carbon nanostructure-containing composite includes the following steps:
  • the heating rate in the steps (3) and (4) is from 14 ° C / min to 18 ° C / min.
  • the biomass carbon source is one or more of lignocellulose, cellulose and lignin.
  • the method for preparing the carbon nanostructure-containing composite comprises the following steps:
  • the precursor In the protective atmosphere, the precursor is kept at 280-350 °C for 1.5-2.5 h, then the temperature is programmed to 950-1200 °C, and the heat is maintained for 3 ⁇ 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 15-20 °C. /min;
  • the biomass carbon source and the catalyst mass ratio is 1: 0.1 ⁇ 10, preferably 1: 0.5 ⁇ 5, further preferably 1:1 ⁇ 3;
  • the catalyst is selected from the group consisting of a manganese compound, an iron-containing compound, a cobalt-containing compound, and a nickel-containing compound, or a combination of at least two; preferably, the iron-containing compound is selected from the group consisting of a halogen compound of iron, Any one or a combination of at least two of iron cyanide and ferric acid salt; preferably, the cobalt-containing compound is selected from any one or at least two of a cobalt halogen compound and a cobalt acid salt.
  • the nickel-containing compound is selected from any one or a combination of at least two of a nickel chloride salt and a nickel-containing acid salt; preferably, the catalyst is selected from the group consisting of iron chloride and ferrous chloride. , ferric nitrate, ferrous nitrate, iron sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium ferric acid, potassium chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, Any one or a combination of at least two of nickel nitrate, nickel sulfate, and nickel acetate.
  • the temperature at which the agitation is subjected to the catalytic treatment is 150 to 200 ° C, and the time is ⁇ 4 h, preferably 4 to 14 h; preferably, the moisture content in the precursor is 10 wt% or less; preferably, the precursor is heated to 280 ⁇
  • the heating rate at 350 ° C is 3 to 5 ° C / min; preferably, the protective atmosphere is any one of nitrogen, helium, and argon, or a combination of at least two, preferably nitrogen; preferably, the crude product
  • the washing is sequential pickling and water washing; the pickling preferably uses hydrochloric acid at a concentration of 3 to 6 wt%, further preferably hydrochloric acid at a concentration of 5 wt%; the water washing preferably uses deionized water and/or distilled water; preferably, The washing The temperature is 55 to 65 ° C, preferably 60 ° C.
  • the biomass carbon source is cellulose and/or lignin, preferably cellulose, further preferably porous cellulose;
  • the porous cellulose is obtained by the following method:
  • the biomass resource is subjected to acid hydrolysis to obtain lignocellulose, and then subjected to porous treatment to obtain porous cellulose; optionally, the porous cellulose is used after being bleached;
  • the biomass resource is selected from any one or a combination of at least two of plant and/or agricultural and forestry waste; preferably any one or a combination of at least two of agricultural forest waste; preferably, said The agricultural and forestry waste is selected from the group consisting of corn cob, corn cob, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalks and reeds, or a combination of at least two, preferably corn cob.
  • the method for preparing the carbon nanostructure-containing composite comprises the following steps:
  • the corn cob is subjected to acid hydrolysis to obtain lignocellulose, and then subjected to porosification to obtain porous cellulose, and the porous cellulose is bleached and used;
  • step (1') porous cellulose and the catalyst at a mass ratio of 1:0.5 to 1.5, stirring at 150 to 200 ° C for catalytic treatment for 4 hours or more, and drying to a precursor having a moisture content of less than 10% by weight to obtain a precursor body;
  • the precursor is heated to 280-350 ° C at a rate of 3 ⁇ 5 ° C / min, and kept for 2 h, then the temperature is programmed to 950 ⁇ 1050 ° C, and the heat is maintained for 3 ⁇ 4 h to obtain a crude product;
  • the heating rate is 15-20 ° C / min;
  • the carbon nanostructure-containing composite prepared by the above method is also a case containing biomass graphene.
  • the carbon nanostructure-containing composite may be any one or a combination of at least two of substance 1, substance 2, substance 3 or substance 4 having the properties described in Table a:
  • IG/ID is the peak height ratio of the G peak and the D peak in the Raman spectrum.
  • the peak height ratio of the G peak and the D peak in the carbon-containing nanostructure composite of the present invention is preferably ⁇ 2.0, further preferably ⁇ 3.0, particularly preferably ⁇ 5.0.
  • the peak height ratio of the G peak and the D peak in the carbon-containing nanostructure composite of the present invention is ⁇ 30, for example, 27, 25, 20, 18, 15, 12, 10, 8, 7, and the like.
  • the performance index of the carbon nanostructure-containing composites listed in Table a refers to the index of the powder of the carbon nanostructure-containing composite, if the carbon nanostructure-containing composite is For the slurry, the above index is an index of the powder before the preparation of the slurry.
  • the carbon nanostructure-containing composite powder has the following properties in addition to the performance index described in Table a:
  • Black powder uniform fineness, no obvious large particles, water content ⁇ 3.0%, particle size D90 ⁇ 10.0 ⁇ m, pH 5.0-8.0, apparent density 0.2-0.4g/cm 3 .
  • the carbon nanostructure-containing composite is a slurry, which is a product in which a carbon nanostructure-containing composite is dispersed in a solvent
  • the carbon-containing nanostructure may be provided in addition to the performance index described in Table a.
  • the composite slurry also has the following properties:
  • the solid content is 1.0 to 10.0%, the particle size D50 is 0.7 um, the pH is 8.0 to 10.0, the zeta potential is ⁇ -10 mV, and the viscosity is 5.0 to 8.0 mPa ⁇ s.
  • the mass of the carbon nanostructure-containing composite is from 0.1% by weight to 10% by weight based on the mass of the functional regenerated cellulose fiber.
  • the graphene structure has a thickness of 100 nm or less.
  • the graphene structure is a combination of one or more of a six-membered ring-shaped honeycomb sheet structure having a layer number of 1 to 10 layers of carbon.
  • the Fe, Si and Al elements comprise from 0.1% by weight to 0.7% by weight of the regenerated cellulose fibers.
  • the non-carbon non-oxygen element comprises from 0.03 wt% to 1 wt% of the regenerated cellulose fiber.
  • the graphene structure has a thickness of 100 nm or less.
  • the graphene structure is a six-membered ring-shaped honeycomb layer structure having a layer of 1 to 10 layers of carbon. a combination of one or more of them.
  • the non-carbon non-oxygen element further comprises one or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S, and Co.
  • the non-carbon non-oxygen element accounts for 0.1% by weight to 1% by weight of the regenerated cellulose fiber.
  • the invention also provides a preparation method of functional regenerated cellulose fibers, comprising the steps of: pulp impregnation, pressing, pulverizing, aging, yellowing, dissolving, ripening, filtering and defoaming steps;
  • the graphene structure and the non-carbon non-oxygen element are introduced in the step following the yellowing step.
  • the graphene structure and the non-carbon non-oxygen element are added in the form of a composite of carbon nanostructures.
  • the invention also provides a method for functionally regenerating cellulose fibers, comprising the steps of: dissolving cellulose pulp with NMMO (N-methylmorpholine-N-oxide) solution, introducing graphene structure and non-carbon A material of a non-oxygen element is obtained as a spinning dope, and a regenerated cellulose fiber is prepared using the spinning dope.
  • NMMO N-methylmorpholine-N-oxide
  • the material containing a graphene structure and a non-carbon non-oxygen element comprises a composite of carbon nanostructures.
  • the present invention also provides an article comprising the functional regenerated cellulose fiber as described above, or a regenerated cellulose fiber prepared by the preparation method as described above.
  • the articles include civilian clothing, home textiles, ultraviolet protective fabrics or special protective clothing for industrial use.
  • the home textile comprises a towel, a bath towel, a bed sheet, a quilt cover.
  • the present invention has the following beneficial effects:
  • the functional regenerated cellulose fiber provided by the present invention introduces a material containing a graphene structure and a non-carbon non-oxygen element into a conventional regenerated cellulose fiber through a graphene structure, Fe, Si, and Al.
  • the combination of the elements makes the regenerated cellulose fiber provided by the invention have far-infrared properties and antibacterial and bacteriostatic properties, and can have a high far-infrared effect and a bacteriostatic effect by controlling a specific addition ratio.
  • the experimental results show that the regenerated cellulose fiber provided by the invention has a far infrared performance of up to 0.93 and a bacteriostatic performance of up to 99%.
  • Figure 1 is a flow chart of the filament process of viscose fiber.
  • All the raw materials of the present invention are not particularly limited in their source, are purchased on the market or according to the field. It can be prepared by a conventional method well known to the skilled person.
  • the purity of all the raw materials of the present invention is not particularly limited, and the present invention preferably uses analytically pure.
  • the present invention provides a functional regenerated cellulose fiber comprising a graphene structure and a non-carbon non-oxygen element; the non-carbon non-oxygen element comprising Fe, Si and Al elements; the Fe, Si and Al elements occupying the
  • the regenerated cellulose fibers are from 0.018 wt% to 0.8 wt%.
  • the Fe, Si and Al elements of the present invention preferably comprise from 0.010% by weight to 0.8% by weight of the regenerated cellulose fibers, more preferably from 0.1% by weight to 0.7% by weight, still more preferably from 0.2% by weight to 0.7% by weight, most It is preferably from 0.3% by weight to 0.5% by weight, and may be 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.45% by weight, 0.7% by weight, 0.72% by weight, 0.78% by weight or the like.
  • the non-carbon non-oxygen non-hydrogen element of the present invention accounts for the mass fraction of the regenerated cellulose fiber, and refers to the content of the non-carbon non-oxygen non-hydrogen element in the regenerated cellulose fiber, that is, the content of the element in the fiber. .
  • the post-spinning process is not included as a result of the process conditions, such as silicone oil coating of the filaments.
  • the non-carbon non-oxygen element accounts for 0.03 wt% to 1 wt% of the regenerated cellulose fiber.
  • the non-carbon non-oxygen element of the present invention preferably accounts for 0.03 wt% to 1 wt%, more preferably 0.1 wt% to 0.8 wt%, more preferably 0.2 wt% to 0.7 wt%, most preferably 0.3 wt% to 0.5 wt% may be 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.45 wt%, 0.7 wt%, 0.82 wt%, 0.93 wt%, and the like.
  • the above non-carbon non-oxygen element in the present invention accounts for the mass fraction of the regenerated cellulose fiber, and refers to the content of the non-carbon non-oxygen element in the regenerated cellulose fiber, that is, the content of the element in the mixture.
  • the non-carbon non-oxygen element of the present invention preferably comprises a non-carbon non-oxygen non-hydrogen element, and the non-carbon non-oxygen element referred to in the present invention refers especially to mineral elements, and the reference to non-carbon non-oxygen elements is for the purpose of increasing the citation basis. It is known to those skilled in the art that in the regenerated cellulose fiber, a certain amount of hydrogen element is contained, and the proportion of the non-carbon non-oxygen element in the regenerated cellulose fiber is not limited to 0.03 wt% to 1 wt%, and may also be Appropriate amplification, for example, to 0.03 to 5 wt%, and the like.
  • the graphene structure of the present invention is not particularly limited, and may be defined by those skilled in the art.
  • the graphene structure of the present invention refers to a combination of various structures containing a single-layer graphene structure or a multilayer graphene structure. More preferably, it is a combination of a single-layer graphene and a graphene of different layers; the graphene structure of the present invention is more preferably a six-membered ring-shaped honeycomb sheet structure having a layer of 1 to 10 layers of carbon. Any combination of one or more is more preferably a combination of any one or more of a single layer, a double layer or a 3 to 10 layer structure.
  • a six-membered ring-shaped honeycomb sheet structure having a number of layers of more than 10 layers and a thickness of less than 100 nm is called a graphene nanosheet layer, and the number of layers prepared by using biomass as a carbon source is more than 10 layers, and the thickness is
  • biomass graphene The six-membered ring-shaped honeycomb sheet structure in which the number of layers prepared by the carbon source is 1 to 10 layers of carbon is called biomass graphene.
  • the graphene structure of the present invention preferably exhibits a combination of any one or more of a warp, curl, and folded conformation on the microscopic appearance of the six-membered ring-shaped honeycomb sheet structure of the carbon.
  • the microscopic morphology of the sheet structure in the composite can be typically obtained by electron microscopic observation, which may be a transmission electron microscope or a scanning electron microscope.
  • the graphene structure of the present invention preferably has a thickness of 100 nm or less, more preferably 50 nm or less, and most preferably 20 nm or less.
  • the non-carbon non-oxygen element preferably further comprises one or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co, and more It is preferably a plurality of P, Ca, Na, Ni, Mn, K, Mg, Cr, S, and Co; the non-carbon non-oxygen element exists in the form of a combination of any one or more of a simple substance and a compound. .
  • the ratio of the non-carbon non-oxygen element to the regenerated cellulose fiber is preferably 0.1% by weight to 1% by weight in the regenerated cellulose fiber. It is preferably 0.2% by weight to 0.8% by weight, more preferably 0.3% by weight to 0.7% by weight, most preferably 0.4% by weight to 0.5% by weight.
  • the non-carbon non-oxygen element comprises a combination of P, Ca and Na, a combination of Ni, Mn, K and Co, a combination of Mg, Cr, S and Mn, A combination of P, Ca, Na, Ni, Mn, K, and Cr, a combination of P, Ca, Na, Ni, Mn, K, Mg, Cr, S, and Co.
  • the content of the non-carbon non-oxygen element in the regenerated cellulose fiber may be, for example, 0.21 wt%, 0.24 wt%, 0.27 wt%, 0.29 wt%, 0.33 wt%, 0.36 wt%, 0.38 wt%, 0.45 wt%, 0.48 wt%, and the like.
  • the present invention is not particularly limited as to how the graphene structure and the substance containing the non-carbon non-oxygen element are introduced into the regenerated cellulose fiber, and the method of introduction is well known to those skilled in the art, and the present invention is to improve the functionality of the regenerated cellulose fiber.
  • Properties preferably the graphene structure and a substance containing a non-carbon non-oxygen element are introduced in the form of a composite of carbon nanostructures.
  • the substance containing a non-carbon non-oxygen element of the present invention is preferably a nano-scale material of the above elements, more preferably one or more of a nano-scale elemental substance, a nano-scale oxide, and a nano-scale inorganic compound.
  • the mass of the carbon nanostructure-containing composite of the present invention is preferably from 0.1% by weight to 10% by weight, more preferably from 1% by weight to 8% by weight, most preferably from 3% by weight to 5% by weight, based on the mass of the regenerated cellulose fiber;
  • the content of the carbon element is preferably 80% by weight or more, more preferably 85% by weight to 97% by weight, most preferably 90% by weight to 95% by weight; in the carbon nanostructure-containing composite
  • the content of the non-carbon non-oxygen element is preferably from 0.5 wt% to 6 wt%, more preferably from 1 wt% to 5 wt%, most preferably from 2 wt% to 4 wt%; the carbon nanostructure-containing composite is in Raman spectrum
  • the peak height ratio of the lower carbon element G peak to the D peak is preferably from 1 to 20, and more preferably from 3 to 20.
  • the graphene structure preferably has a thickness of 100 nm.
  • the following six-membered ring-shaped honeycomb sheet structure of carbon is preferably a six-membered ring-shaped honeycomb sheet structure having carbon having a thickness of 20 nm or less, and more preferably a six-membered ring-shaped honeycomb sheet layer having a layer of one to ten layers of carbon.
  • any one or a combination of at least two of the structures is preferably any one of a single layer, a double layer or a 3 to 10 layer structure or a combination of at least two; preferably, a six member of carbon in the composite
  • the ring-shaped honeycomb sheet structure microscopically exhibits any one or a combination of at least two of a warp, curl, and folded conformation.
  • the carbon nanostructure-containing composite of the present invention preferably contains a graphene structure and amorphous carbon; the non-carbon non-oxygen element is preferably in the form of a combination of any one or a combination of a simple substance, an oxide and a carbide. Adsorbed on the surface or inside of carbon nanostructures.
  • the shaped carbon also contains two-dimensional graphite layer or three-dimensional graphite crystallites, and there are a large number of irregular bonds on the edge of the crystallite. In addition to containing a large amount of sp2 carbon, it also contains a lot of sp3 carbon.
  • amorphous carbon is a molecular layer of a graphite layer structure which is substantially parallel to each other and randomly stacked together, and may be simply referred to as a disordered layer structure. Interlayers or fragments are bonded by a diamond-structured tetrahedral bonding carbon atom.
  • the material introduced into the graphene structure is not activated or modified during the introduction of the graphene structure.
  • the preparation method of the carbon nanostructure-containing composite of the present invention is not particularly limited.
  • the carbon nanostructure-containing composite contains graphene, amorphous carbon and a non-carbon non-oxygen element; the carbon nanostructure-containing composite species, the non-carbon non-oxygen elements including Fe, Si and Al elements
  • the non-carbon non-oxygen element content is from 0.5 wt% to 6 wt% of the carbon nanostructure-containing composite.
  • the carbon element content in the carbon nanostructure-containing composite is preferably ⁇ 80 wt%, such as 82 wt%, 86 wt%, 89 wt%, 91 wt%, 94 wt%, 97 wt%, 99 wt%, etc., preferably 85 to 97 wt%, further preferably 90 to 95% by weight.
  • the non-carbon non-oxygen element comprises from 0.3% by weight to 5% by weight, preferably from 0.5% to 5% by weight, further preferably from 1.5% by weight to 5% by weight, of the carbon nanostructure-containing composite.
  • the non-carbon non-oxygen element comprises 0.7 wt%, 1.1 wt%, 1.3 wt%, 1.6 wt%, 2 wt%, 2.8 wt% of the carbon nanostructure-containing composite, 3.5 wt%, 4.2 wt%, 5.3 wt% or 5.8 wt%.
  • the non-carbon non-oxygen element is adsorbed on the surface or inside of the carbon nanostructure in the form of any one or more of a simple substance, an oxide or a carbide.
  • the preparation method of the carbon nanostructure-containing composite of the present invention is not particularly limited, and a method of preparing a similar composite well known to those skilled in the art may be used.
  • the method for preparing the carbon nanostructure-containing composite includes the following steps (recorded as method 1):
  • the heating rate in the steps (3) and (4) is from 14 ° C / min to 18 ° C / min.
  • the carbon source is preferably a biomass carbon source, and the biomass resource is selected from any one or a combination of at least two of plant and/or agricultural and forestry waste; preferably any of softwood, hardwood, forestwood, and agricultural and forestry waste. 1 or a combination of at least 2; the agricultural and forestry waste is preferably selected from the group consisting of corn cob, corn cob, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalks, husks, and reeds. Any one or a combination of at least two, preferably a corn cob.
  • the biomass carbon source is selected from lignocellulose, cellulose and/or lignin, more preferably cellulose and/or lignin, more preferably cellulose, and further preferably porous cellulose.
  • the material introduced into the graphene structure is not activated or modified during the introduction of the graphene structure.
  • the biomass carbon source and the catalyst have a mass ratio of 1:0.1 to 10, such as 1:0.2, 1:0.5, 1:0.8, 1:1.1, 1:1.5, 1:2, 1:3, 1:4. 1,5, 1:6, 1:7, 1:8, 1:9, etc., preferably 1:0.5 to 5, further preferably 1:1 to 3.
  • the catalyst is selected from the group consisting of a manganese compound, an iron-containing compound, a cobalt-containing compound, and a nickel-containing compound, or a combination of at least two;
  • the iron-containing compound is selected from the group consisting of iron halogen compounds, iron cyanide a combination of any one or at least two of a compound and a ferrite;
  • the cobalt-containing compound is selected from any one or a combination of at least two of a cobalt compound and a cobalt salt;
  • the compound is selected from any one or a combination of at least two of a nickel chloride salt and a nickel-containing acid salt;
  • the catalyst is selected from the group consisting of iron chloride, ferrous chloride, iron nitrate, ferrous nitrate, Ferric sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium ferric acid sulphate, cobalt chloride, cobalt nitrate, cobalt
  • the catalyst is selected from the group consisting of a combination of ferric chloride and ferric nitrate, a combination of ferrous nitrate, ferric sulfate and cobalt chloride, a combination of cobalt acetate, nickel chloride and nickel sulfate, potassium ferricyanide, ferrous iron A combination of potassium cyanide, potassium ferric acid tricarboxylate and ferrous nitrate, a combination of cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate.
  • the temperature at which the stirring is subjected to the catalytic treatment in the step (1) is 150 to 200 ° C, the time is ⁇ 4 h, preferably 4 to 14 h; the moisture content in the precursor is preferably 10 wt% or less; the step (2)
  • the heating rate of the precursor to 280-350 ° C is preferably 3 to 5 ° C / min;
  • the protective atmosphere is any one of nitrogen, helium and argon or a combination of at least two, preferably nitrogen;
  • the crude washing is sequential pickling and water washing;
  • the pickling preferably uses hydrochloric acid at a concentration of 3 to 6 wt%, further preferably hydrochloric acid at a concentration of 5 wt%;
  • the water washing preferably uses deionized water and/or Distilled water; the temperature of the washing is 55 to 65 ° C, preferably 60 ° C.
  • the above preparation steps of the present invention may further preferably be:
  • the precursor is then held at 140-180 ° C for 1.5-2.5 h in a protective atmosphere to provide a first intermediate; in some embodiments of the invention, the temperature is 142 ° C, 148 ° C, 155 °C, 1600 ° C, 172 ° C or 178 ° C; the holding time is 1.6h, 1.8h, 2h, 2.2h or 2.4h.
  • the temperature is programmed to 350-450 ° C, and the temperature is maintained for 3 to 4 hours to obtain a second intermediate; in some specific embodiments of the invention, the temperature is 360 ° C, 370 ° C, 380 ° C, 390 ° C, 410 ° C, 420 ° C, 430 ° C or 440 ° C; the incubation time is 3.1h, 3.3h, 3.5h, 3.8h or 3.9h.
  • the temperature is further raised to 1100 to 1300 ° C, and the temperature is maintained for 2 to 4 hours to obtain a third intermediate, that is, a crude product; in some specific embodiments of the present invention, the temperature is 1130 ° C, 1170 ° C, 1210 ° C or 1280 ° C.
  • the time is 2.2h, 2.4h, 2.6h, 2.8h, 3.0h, 3.2h, 3.4h, 3.6h or 3.8h.
  • the programmed temperature ramp rate is from 14 ° C/min to 18 ° C/min. In some embodiments of the invention, the ramp rate is 15 ° C/min, 16 ° C/min or 17 ° C/min.
  • the third intermediate i.e., the crude product
  • alkali alkali
  • pickled alkali
  • washed with water to obtain a complex
  • the biomass carbon source is preferably one or more of lignocellulose, cellulose and lignin, more preferably lignocellulose, cellulose or lignin.
  • the mass ratio of the biomass carbon source to the catalyst is 1: (0.5 to 5), preferably 1: (1 to 3); in some embodiments of the invention, the ratio is 1: 0.5, 1:1 or 1:3.
  • the catalyst is selected from any one or a combination of at least two of a halogen compound of manganese, an iron-containing compound, a cobalt-containing compound, and a nickel-containing compound.
  • the iron-containing compound is selected from any one or a combination of at least two of a halogen compound of iron, a cyanide of iron, and a ferrite.
  • the ferrite-containing salt is a salt of an organic acid containing an iron element or a salt of an inorganic acid containing an iron element.
  • the halogen compound of iron may be ferric chloride and/or iron bromide.
  • the cobalt-containing compound is selected from any one or a combination of at least two of a halogen compound of cobalt and a cobalt-containing acid salt.
  • the cobalt-containing acid salt is a salt of an organic acid containing a cobalt element or a cobalt-containing element Acidic salt.
  • the cobalt halogen compound may be cobalt chloride and/or cobalt bromide.
  • the nickel-containing compound is selected from any one or a combination of at least two of a nickel chloride salt and a nickel-containing acid salt.
  • the nickel-containing acid salt is a salt of an organic acid containing a nickel element or a salt of a mineral acid containing a nickel element.
  • the halogen compound of nickel may be nickel chloride and/or nickel bromide.
  • the catalyst is selected from the group consisting of ferric chloride, ferrous chloride, iron nitrate, ferrous nitrate, iron sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium ferric acid trihydrate, and chlorine. Any one or a combination of at least two of cobalt, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, and nickel acetate.
  • Typical, but non-limiting examples of combinations of catalysts according to the invention are combinations of ferrous chloride and ferric sulfate, combinations of potassium ferricyanide and potassium trioxalate, cobalt chloride, cobalt nitrate and ferric chloride.
  • the temperature at which the agitation is subjected to catalytic treatment is from 150 ° C to 200 ° C, for example, 160 ° C, 170 ° C, 180 ° C, 190 ° C, etc., time ⁇ 4 h, preferably 4 h to 14 h, in some embodiments of the present invention, The time is 4.2h, 7h, 9h, 12h, 16h, 19h, 23h.
  • the moisture content in the precursor is 10 wt% or less.
  • the moisture content is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 10 wt%, and the like.
  • the protective atmosphere is any one or a combination of at least two of nitrogen, helium and argon, preferably nitrogen.
  • the pickling uses a hydrochloric acid aqueous solution having a concentration of 3 wt% to 6 wt%, further preferably a hydrochloric acid aqueous solution having a concentration of 5 wt%;
  • the water washing preferably uses deionized water and/or distilled water; and the alkali washing uses a concentration of 5 wt%.
  • a % to 15% by weight aqueous sodium hydroxide solution is further preferably an aqueous sodium hydroxide solution having a concentration of 10% by weight.
  • the washing temperature is 55 to 65 ° C, for example, 56 ° C, 57 ° C, 58 ° C, 60 ° C, 63 ° C, etc., preferably 60 ° C.
  • the biomass carbon source is cellulose and/or lignin, preferably cellulose, further preferably porous cellulose.
  • porous cellulose of the present invention can be obtained by the prior art.
  • Typical, but non-limiting, prior art methods for obtaining porous cellulose include, for example, the preparation of porous cellulose by the method disclosed in Patent Publication No. CN104016341A, and the preparation of fibers by the method disclosed in CN103898782A. Prime.
  • the porous cellulose is obtained by the following method:
  • the biomass resource is selected from any one or a combination of at least two of plants and/or agricultural and forestry wastes; preferably one or a combination of at least two of agricultural and forestry wastes.
  • the agricultural and forestry waste is selected from the group consisting of corn cob, corn cob, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalks and reeds, or a combination of at least two.
  • a corn cob is preferred.
  • Typical but non-limiting examples of combinations of biomass resources according to the present invention include combinations of corn cobs and corn cobs, combinations of bagasse, sorghum and wood chips, combinations of beet pulp, bagasse and corn cobs, high stalks, beet pulp Combination with xylose residue, etc.
  • the carbon nanostructure-containing composite of the present invention can also be prepared by various methods as follows:
  • the method for preparing the carbon nanostructure-containing composite comprises the following steps (referred to as method 2):
  • the precursor In the protective atmosphere, the precursor is kept at 280-350 °C for 1.5-2.5 h, then the temperature is programmed to 950-1200 °C, and the heat is maintained for 3 ⁇ 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 15-20 °C. /min;
  • the biomass carbon source and the catalyst mass ratio is 1: 0.1 ⁇ 10, preferably 1: 0.5 ⁇ 5, further preferably 1:1 ⁇ 3;
  • the catalyst is selected from the group consisting of a manganese compound, an iron-containing compound, a cobalt-containing compound, and a nickel-containing compound, or a combination of at least two; preferably, the iron-containing compound is selected from the group consisting of a halogen compound of iron, Any one or a combination of at least two of iron cyanide and ferric acid salt; preferably, the cobalt-containing compound is selected from any one or at least two of a cobalt halogen compound and a cobalt acid salt.
  • the nickel-containing compound is selected from any one or a combination of at least two of a nickel chloride salt and a nickel-containing acid salt; preferably, the catalyst is selected from the group consisting of iron chloride and ferrous chloride. , ferric nitrate, ferrous nitrate, iron sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium ferric acid, potassium chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, Any one or a combination of at least two of nickel nitrate, nickel sulfate, and nickel acetate.
  • the temperature at which the agitation is subjected to the catalytic treatment is 150 to 200 ° C, and the time is ⁇ 4 h, preferably 4 to 14 h; preferably, the moisture content in the precursor is 10 wt% or less; preferably, the precursor is heated to 280 ⁇
  • the heating rate at 350 ° C is 3 to 5 ° C / min; preferably, the protective atmosphere is any one of nitrogen, helium, and argon, or a combination of at least two, preferably nitrogen; preferably, the crude product
  • the washing is a pickling and water washing which are sequentially performed; the pickling is preferably carried out using a hydrochloric acid having a concentration of 3 to 6 wt%, more preferably concentrated.
  • the degree is 5 wt% hydrochloric acid; the water washing preferably uses deionized water and/or distilled water; preferably, the washing temperature is 55 to 65 ° C, preferably 60 ° C.
  • the biomass carbon source is cellulose and/or lignin, preferably cellulose, further preferably porous cellulose;
  • the porous cellulose is obtained by the following method:
  • the biomass resource is subjected to acid hydrolysis to obtain lignocellulose, and then subjected to porous treatment to obtain porous cellulose; optionally, the porous cellulose is used after being bleached;
  • the biomass resource is selected from any one or a combination of at least two of plant and/or agricultural and forestry waste; preferably any one or a combination of at least two of agricultural forest waste; preferably, said The agricultural and forestry waste is selected from the group consisting of corn cob, corn cob, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalks and reeds, or a combination of at least two, preferably corn cob.
  • the method for preparing the carbon nanostructure-containing composite comprises the following steps (referred to as method 3):
  • the corn cob is subjected to acid hydrolysis to obtain lignocellulose, and then subjected to porosification to obtain porous cellulose, and the porous cellulose is bleached and used;
  • step (1') porous cellulose and the catalyst at a mass ratio of 1:0.5 to 1.5, stirring at 150 to 200 ° C for catalytic treatment for 4 hours or more, and drying to a precursor having a moisture content of less than 10% by weight to obtain a precursor body;
  • the precursor is heated to 280-350 ° C at a rate of 3 ⁇ 5 ° C / min, and kept for 2 h, then the temperature is programmed to 950 ⁇ 1050 ° C, and the heat is maintained for 3 ⁇ 4 h to obtain a crude product;
  • the heating rate is 15-20 ° C / min;
  • the carbon nanostructure-containing composite prepared by the above methods also belongs to a case containing biomass graphene.
  • the carbon nanostructure-containing composite composite prepared by the above preparation method also belongs to a case containing biomass graphene.
  • the carbon nanostructure-containing composite of the present invention can also be prepared by various methods as follows:
  • Method 4 Using activated carbon resources to prepare activated carbon by existing processes, because the types and contents of trace elements in different plants are very different, so the content of non-carbon non-oxygen elements is controlled by later pickling, washing, etc. On the basis of this, graphene is introduced so that the non-carbon non-oxygen element accounts for 0.5% by weight to 6% by weight of the composite.
  • Method 5 commercially available lignin, carbonized at a high temperature under an inert gas or subjected to incomplete graphitization reaction, and then added graphene, and later introduced nano-P, Si, Ca, Al, Na, Fe, Ni, Mn, A combination of any three or more of K, Mg, Cr, S or Co and the content thereof is controlled to be 0.5 wt% to 6 wt%.
  • Method 6 For some organic wastes, such as phenolic resin foam sheets, after carbonization, graphene is introduced, and late introduction of nano P, Si, Ca, Al, Na, Fe, Ni, Mn, K, Mg, Cr, S or The combination of any three or more elements in Co and the content thereof is controlled to be 0.5 wt% to 6 wt%.
  • Method 7 Adding activated carbon and graphene to the nano-graphite, and introducing any three or more elements of nano P, Si, Ca, Al, Na, Fe, Ni, Mn, K, Mg, Cr, S or Co later. Combine and control the content to be 0.5 wt% to 6 wt%.
  • the carbon-containing nanostructure composite to be protected by the present invention is not limited to the above preparation method.
  • the products of the carbon-containing nanostructure composites to be protected by the above method have far-infrared properties and antibacterial properties which are superior to the methods 4 to 7 obtained by the methods 1 to 3, but all of which can be used in the preparation of downstream products.
  • the carbon nanostructure-containing composite can be dispersed uniformly in the functional regenerated cellulose fiber by activation or modification treatment, and has certain effects, especially methods 1 to 3.
  • the invention introduces a graphene structure and a substance containing a non-carbon non-oxygen element by means of a carbon-containing nanostructure composite, and in the introduction process, without pre-treatment of the introduced substance, such as activation, modification, etc., Regenerated cellulose is effectively combined to provide an additional enhanced far-infrared and bacteriostatic effect.
  • the method for determining the non-carbon non-oxygen element in the present invention is not limited, and any method known in the art or a new assay method can be used in the present invention; the present invention provides a method for determining the content of two non-carbon non-oxygen elements, Preferably, the first method for determining the content of the non-carbon non-oxygen element is used for the measurement, and the first method for determining the content of the non-carbon non-oxygen element is used in the embodiment of the present invention.
  • the infrared detection data of the carbon-containing nanostructure composite is based on: GBT 7286.1-1987 "Metal Test method for full normal emissivity of non-metallic materials;
  • the bacteriostatic detection data of the carbon-containing nanostructure composite is based on: GB/T20944.3-2008 test method, taking Staphylococcus aureus as an example.
  • the invention provides a preparation method of functional regenerated cellulose fibers, comprising the steps of: pulp impregnation, pressing, pulverizing, aging, yellowing, dissolving, ripening, filtering and defoaming steps;
  • the material containing a graphene structure and a non-carbon non-oxygen element is introduced after the yellowing step.
  • the graphene structure of the present invention is preferably introduced in the form of a mixture, preferably comprising a non-graphene structural component, such as an amorphous carbon component.
  • a non-graphene structural component such as an amorphous carbon component.
  • the graphene structure and the non-carbon non-oxygen element are added in the form of a composite of carbon nanostructures.
  • the substance containing a graphene structure and a non-carbon non-oxygen element is more preferably introduced in the dissolution step, and more preferably it is previously dispersed in a dilute alkali solution for dissolving the cellulose xanthate.
  • the carbon nanostructure-containing composite may be any one or a combination of at least two of substance 1, substance 2, substance 3 or substance 4 having the properties described in Table a:
  • IG/ID is the peak height ratio of the G peak and the D peak in the Raman spectrum.
  • the performance index of the carbon nanostructure-containing composites listed in Table a refers to the index of the powder of the carbon nanostructure-containing composite, if the carbon nanostructure-containing composite is For the slurry, the above index is an index of the powder before the preparation of the slurry.
  • the carbon nanostructure-containing composite powder has the following properties in addition to the performance index described in Table a:
  • Black powder uniform fineness, no obvious large particles, water content ⁇ 3.0%, particle size D90 ⁇ 10.0 ⁇ m, pH 5.0-8.0, apparent density 0.2-0.4g/cm 3 .
  • the carbon nanostructure-containing composite is a slurry, which is a product in which a carbon nanostructure-containing composite is dispersed in a solvent
  • the carbon-containing nanostructure may be provided in addition to the performance index described in Table a.
  • the composite slurry also has the following properties:
  • the solid content is 1.0 to 10.0%, the particle size D50 is 0.7 um, the pH is 8.0 to 10.0, the zeta potential is ⁇ -10 mV, and the viscosity is 5.0 to 8.0 mPa ⁇ s.
  • the invention provides a method for functionally regenerating cellulose fibers, comprising the steps of: dissolving a cellulose pulp with a NMMO solution, introducing a material containing a graphene structure and a non-carbon non-oxygen element to obtain a spinning dope, using the spinning Regenerated cellulose fibers were prepared from silk stocks.
  • the regenerated cellulose fiber production process is a spinning process using N-methylmorpholine-N-oxide (NMMO) solvent.
  • NMMO N-methylmorpholine-N-oxide
  • the specific method is to directly mix cellulose pulp with N-methylmorpholine-N-oxide (NMMO), add additives (such as CaCl 2 ) and antioxidants (such as PG) to prevent oxidative decomposition of fibers during dissolution. And adjust the viscosity of the solution and improve the properties of the fiber. Control the moisture content to less than 133% to achieve the best insolubility.
  • the solution Dissolved at 85-125 ° C, a higher concentration of the solution, the solution is filtered, defoamed, wet or dry spinning at 88-125 ° C, solidified in low temperature water soluble or water / NMMO system, pulled Fiber, by washing, washing, oil removal, drying and solvent recovery.
  • a substance containing a graphene structure and a non-carbon non-oxygen element is introduced into the cellulose pulp.
  • the present invention provides an article characterized by comprising the functional regenerated cellulose fiber according to any one of the above aspects, or the regenerated cellulose fiber prepared by the preparation method according to any one of the above aspects;
  • the article preferably includes a civilian garment, a home textile, an ultraviolet protective fabric or a special protective garment for industrial use.
  • the functional regenerated cellulose fiber provided by the invention, the preparation process and the application article thereof, the graphene structure and the non-carbon non-oxygen element are introduced into the traditional regenerated cellulose fiber, and the graphene structure, the combination of Fe, Si and Al elements are adopted.
  • the regenerated cellulose fiber provided by the present invention has far-infrared properties and antibacterial and bacteriostatic properties, and can have a high far-infrared effect and a bacteriostatic effect by controlling a specific addition ratio.
  • the present invention introduces a material containing a graphene structure and a non-carbon non-oxygen element by means of a carbon-containing nanostructure composite, and does not require pretreatment of the introduced substance, such as activation, modification, etc., during the introduction process. It can be effectively combined with regenerated cellulose, resulting in an additional enhanced far-infrared effect and bacteriostatic effect.
  • the invention relates to one of the methods for determining the non-carbon non-oxygen non-hydrogen element content of the functional fiber:
  • the influence elements mainly include silicone oil, etc.
  • the removal method is boiled and washed many times.
  • the method for determining the non-carbon non-oxygen non-hydrogen element of the present invention is not limited, and any method known in the art or new assay method can be used in the present invention; the present invention provides two non-carbon non-oxygen non-hydrogen element contents.
  • the measurement method is preferably "the first non-carbon non-oxygen non-hydrogen element content determination method", and the "first non-carbon non-oxygen non-hydrogen element content measurement method" is used in the embodiment of the present invention.
  • the non-carbon non-oxygen element according to the present invention is an element which is inside the fiber and cannot be removed by simple washing.
  • the invention detects the far infrared performance and the antibacterial performance of the functional fiber, and the detection standards are as follows:
  • the infrared detection data is based on: the National Textile Products Quality Supervision and Inspection Center, in accordance with the FZ/T64010-2000 inspection method for inspection;
  • Antibacterial test data based on: National Textile Products Quality Supervision and Inspection Center, in accordance with GB/T20944.3-2008 test method.
  • the experimental results show that the regenerated cellulose fiber provided by the invention has a far infrared performance of up to 0.93 and a bacteriostatic performance of up to 99%.
  • a composite of carbon nanostructures obtained by the following method:
  • the precursor is heated to 170 ° C at a rate of 3 ° C / min, kept for 2 h, then programmed to 400 ° C, held for 3 h, then heated to 1200 ° C, after 3 h of heat to obtain a crude product;
  • the heating rate of the heating is 15 ° C / min;
  • the carbon nanostructure-containing composite prepared in Example 1 was subjected to Raman spectroscopy, and the results showed that the height ratio of the peak of the G peak and the peak of the D peak was 3;
  • the first non-carbon non-oxygen content determination method was used to detect that the carbon-containing nanostructure-containing composite mainly contained P, Si, Ca, Al, Fe, and Mg elements, and the content was 3.2 wt%.
  • Example 1 The corncob cellulose of Example 1 was replaced with reed cellulose.
  • the carbon nanostructure-containing composite prepared in Example 2 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 4.8;
  • the first non-carbon non-oxygen element content measurement method was used to detect that the carbon-containing nanostructure-containing composite mainly contained Si, Ca, Al, Fe, Mg, and S elements in an amount of 2.5 wt%.
  • Example 1 The corncob cellulose of Example 1 was replaced with poplar cellulose.
  • the carbon nanostructure-containing composite prepared in Example 3 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 4.6;
  • the first non-carbon non-oxygen element content determination method was used to detect that the carbon-containing nanostructure-containing composite mainly contained P, Si, Al, Na, Fe, and Ni elements in an amount of 3.5% by weight.
  • Example 1 The corncob cellulose of Example 1 was replaced with corncob lignin.
  • the carbon nanostructure-containing composite prepared in Example 4 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 2.8;
  • the first non-carbon non-oxygen content determination method was used to detect that the carbon-containing nanostructured composite mainly contained P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, and K elements, and the content was 2.7 wt. %.
  • the mixture is stirred and washed with an equal amount of 30% hydrochloric acid, and the carbon particles are collected by filtration, and then added to an equal volume of water, boiled and washed until no ammonium chloride is washed, heated and evaporated, stirred and stir-fried. Discard the water, dry, pulverize, and pass through a 120 mesh sieve to obtain activated carbon.
  • nano material containing P, Si, Ca, Al, Fe, Mg is added, and the content is 3.5 wt%
  • the specific materials are nano phosphorus pentoxide, nano silicon powder, nano calcium carbonate, Nano-aluminum oxide, nano-iron, nano-magnesium powder, to obtain a composite of carbon-containing nanostructures.
  • the lignin is carbonized in a carbonization furnace, carbonized at 400 ° C for 3 hours, thoroughly stirred once every 30 minutes, the furnace temperature is reduced to below 100 ° C before stirring, and then heated to 2200 ° C in an argon atmosphere. After graphitization for 2h, the material is cooled, and then washed with 30%, 12% and 3% ammonium chloride solution, and then stirred and washed with an equal amount of 30% hydrochloric acid, dried, pulverized and passed through a 120 mesh sieve to obtain graphite and Activated carbon mixed carbon material. On this basis, graphene was introduced, and a nano material containing P, Si, Ca, Al, Fe, Mg was added, and the content was 3.3 wt%. Specifically, it is nanometer phosphorus pentoxide, nano silica, nano calcium carbonate, nano aluminum powder, nano iron, nano magnesium carbonate, and a composite containing carbon nanostructures is obtained.
  • Activated carbon and graphene are added to the nanometer graphite, and the nano material containing P, Si, Ca, Al, Fe, Mg is added, and the content is 3.3 wt%, specifically nano phosphorus pentoxide, nano silicon powder, nano aluminum powder, Nano-iron, nano-magnesium powder, to obtain a composite of carbon-containing nanostructures.
  • the lignocellulose is immersed in acidic sulfite for 1 h to obtain porous cellulose; wherein the acid is sulfuric acid and the sulfite is magnesium sulfite, the mass of the sulfuric acid is 4% of the mass of the lignocellulose, and the liquid solid
  • the ratio is 2:1; it is ready for use after preparation (this step can be borrowed from the patent document with the publication number CN104016341A).
  • Example 9 The carbon nanostructure-containing composite prepared in Example 9 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 6.8;
  • the first non-carbon non-oxygen content determination method was used to detect that the carbon-containing nanostructured composite mainly contained P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, and K elements, and the content was 3.5 wt. %.
  • step (2) is:
  • the porous cellulose obtained in the step (1) of Example 9 and the chlorination were mixed at a mass ratio of 1:5, and the mixture was stirred at 180 ° C for catalytic treatment for 5 hours, and dried to a moisture content of the precursor of 6 wt% to obtain a precursor; a protective atmosphere;
  • the precursor was heated to 300 ° C at a rate of 4 ° C / min, kept for 3 h, then programmed to 1000 ° C, and kept for 4 h to obtain a crude product; the temperature rising rate of the programmed temperature was 17 ° C / min; at 60 ° C, the crude product After pickling with a concentration of 5 wt% hydrochloric acid, the mixture was washed with water to obtain a carbon nanostructure-containing composite.
  • the carbon nanostructure-containing composite prepared in Example 10 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 15;
  • the first non-carbon non-oxygen element content determination method was used to detect that the carbon-containing nanostructure-containing composite mainly contained P, Si, Ca, Al, Na, Fe, Mg, Mn, and S elements, and the content was 5.7 wt%.
  • the treated wheat straw is cooked using an organic acid solution of formic acid and acetic acid having a total acid concentration of 80% by weight, and the quality of acetic acid and formic acid in the organic acid solution of the present embodiment
  • the ratio is 1:12
  • 1 wt% of hydrogen peroxide (H 2 O 2 ) which is the raw material of the wheat straw, is added as a catalyst before the addition of the raw materials, and the reaction temperature is controlled at 120 ° C for 30 minutes, and the solid-liquid mass ratio is 1:10.
  • the obtained reaction liquid is subjected to a first solid-liquid separation; the solid obtained by the first solid-liquid separation is added to an organic acid solution having a total acid concentration of 75 wt% of formic acid and acetic acid for acid washing, wherein the total acid concentration is 75 wt. % of the organic acid solution was added with 8 wt% of hydrogen peroxide (H 2 O 2 ) as the catalyst, and the mass ratio of acetic acid to formic acid was 1:12, the control temperature was 90 ° C, and the washing time was 1 h.
  • H 2 O 2 hydrogen peroxide
  • the liquid mass ratio is 1:9, and the reaction liquid is subjected to a second solid-liquid separation; the liquid obtained by the first and second solid-liquid separation is collected, and subjected to high-temperature high-pressure evaporation at 120 ° C and 301 kPa until evaporation.
  • the obtained formic acid and acetic acid vapor are condensed and refluxed to the step (1).
  • the cooking kettle is used as a cooking liquid for cooking in the step (1); the solid obtained by the second solid-liquid separation is collected, and washed with water, the washing water temperature is controlled to 80 ° C, the water washing slurry is concentrated to 6 wt%, and the obtained water is washed.
  • the slurry is subjected to a third solid-liquid separation; the liquid obtained by the third solid-liquid separation is collected, and the water and acid distillation are carried out, and the obtained mixed acid liquid is used in the reaction vessel of the step (1) as a cooking liquid for the step ( 1) cooking, the obtained water is used for the step (5) to act as water washing water; the solid obtained by the third solid-liquid separation is collected and screened to obtain the desired fine pulp cellulose (this step can be borrowed from the publication number CN103898782A). Patent document).
  • the carbon nanostructure-containing composite prepared in Example 11 was subjected to Raman spectroscopy, and the results showed that the height ratio of the peak of the G peak and the peak of the peak of D was 3;
  • the first non-carbon non-oxygen content determination method was used to detect that the carbon-containing nanostructure-containing composite mainly contained P, Si, Ca, Al, Na, Fe, and Mg elements in an amount of 0.7 wt%.
  • step (2) is:
  • the cellulose and ferric chloride obtained in the step (1) of Example 11 were mixed at a mass ratio of 1:1, and subjected to catalytic treatment at 200 ° C for 8 hours, and dried to a moisture content of the precursor of 8 wt% to obtain a precursor; a protective atmosphere;
  • the precursor was heated to 350 ° C at a rate of 5 ° C / min, kept for 2 h, then programmed to 1050 ° C, and kept for 4 h to obtain a crude product; the temperature rising rate of the programmed temperature was 20 ° C / min; 55 ⁇ 65 ° C,
  • the crude product was pickled with hydrochloric acid having a concentration of 6 wt%, and washed with water to obtain a composite containing carbon nanostructures.
  • the carbon nanostructure-containing composite prepared in Example 12 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 4.8;
  • the first non-carbon non-oxygen content determination method was used to detect that the carbon-containing nanostructure-containing composite mainly contained P, Si, Ca, Al, Na, Fe, and Mg elements, and the content was 3.1 wt%.
  • the treated lignocellulosic biomass is subjected to acid hydrolysis using a concentration of 90% formic acid and a concentration of 5% acetic acid and 5% water of an organic acid solution.
  • the solid isolated is added to a concentration of 90% formic acid and a concentration of 5% acetic acid and 5% water of the organic acid solution.
  • the carbon nanostructure-containing composite prepared in Example 13 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 4.6;
  • the first non-carbon non-oxygen content determination method was used to detect that the carbon-containing nanostructure-containing composite mainly contained P, Si, Ca, Al, Na, Fe, Mg, Ni, and K elements, and the content was 3.6 wt%.
  • step (2) is:
  • the eucalyptus cellulose and nickel chloride obtained in the step (1) of Example 13 were mixed at a mass ratio of 1:0.5, and subjected to catalytic treatment at 170 ° C for 5 hours, and dried to a moisture content of the precursor of 6 wt% to obtain a precursor; a protective atmosphere;
  • the precursor was heated to 300 ° C at a rate of 4 ° C / min, kept for 3 h, then programmed to 1000 ° C, and kept for 4 h to obtain a crude product; the temperature rising rate of the programmed temperature was 17 ° C / min; at 60 ° C, the crude product After pickling with a concentration of 5 wt% hydrochloric acid, the mixture was washed with water to obtain a carbon nanostructure-containing composite.
  • the carbon nanostructure-containing composite prepared in Example 14 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 2.1;
  • the first non-carbon non-oxygen content determination method was used to detect that the carbon-containing nanostructure-containing composite mainly contained P, Si, Ca, Al, Na, Fe, Mg, Ni, and K elements, and the content was 1.6 wt%.
  • step (2) is:
  • the poplar cellulose and the ferrous chloride obtained in Preparation Example 3 were mixed at a mass ratio of 1:3, and subjected to catalytic treatment at 180 ° C for 5 hours, and dried to a moisture content of the precursor of 6 wt% to obtain a precursor; in a protective atmosphere, The precursor was heated to 300 ° C at a rate of 4 ° C / min, and kept for 3 h, then programmed to 1000 ° C, and kept for 4 h to obtain a crude product; the temperature rising rate was 17 ° C / min; at 60 ° C, the crude product was subjected to concentration After pickling with 5 wt% hydrochloric acid, it was washed with water to obtain a composite containing carbon nanostructures.
  • the carbon nanostructure-containing composite prepared in Example 15 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 2.1;
  • the first non-carbon non-oxygen content determination method was used to detect that the carbon-containing nanostructure-containing composite mainly contained P, Si, Ca, Al, Na, Fe, Mg, Ni, and K elements, and the content was 4.7 wt%.
  • Example 7 The graphene obtained in Example 7 disclosed in the "Method for Producing Porous Graphene" of CN104016341A was used as Comparative Example 1.
  • the graphene prepared in the comparative example was subjected to Raman spectroscopy, and the results showed that the height ratio of the G peak and the D peak was 13.
  • the liquid-solid ratio of hydrogen peroxide solution to graphite is 10mL:1g, stirred for 10min, and the mixture is pumped. Filtration, and then washing the solids with dilute hydrochloric acid and deionized water respectively.
  • the solid-liquid ratio of dilute hydrochloric acid, deionized water and graphite is 100 mL: 150 mL: 1 g, and washed a total of 3 times. Finally, the solid matter is in a vacuum oven at 60 ° C.
  • the graphite oxide was obtained by drying for 12 hours; the graphite oxide and the phosphorus pentoxide were uniformly mixed at a mass ratio of 1:2, and placed in an argon atmosphere at a flow rate of 300 ml/min, and the temperature was raised at a temperature rising rate of 15 ° C/min. To 900 ° C, keep 2h, then cooled to room temperature in an argon atmosphere at a flow rate of 300ml / min, to obtain phosphorus-doped graphene;
  • the nitrogen-doped graphene prepared in Comparative Example 2 was subjected to Raman spectroscopy, and the results showed that the height ratio of G peak and D peak was 5;
  • the first non-carbon non-oxygen element content determination method detects that the carbon-containing nanostructure-containing composite mainly contains P element.
  • an activated carbon containing graphene and an element containing P, Si, Ca, Fe, Mg, and Mn are prepared.
  • the activated carbon/graphene composite prepared in Comparative Example 3 was subjected to Raman spectroscopy, and the results showed that the height ratio of G peak and D peak was 0.5;
  • the first non-carbon non-oxygen non-hydrogen element content determination method was used to detect that the obtained activated carbon/graphene composite contained S, N, and Cl elements.
  • the functionalized regenerated cellulose fibers were prepared by using the carbon nanostructure-containing composites prepared in Examples 1-15 and Comparative Examples 1-3.
  • the viscose liquid used in the present invention is a viscose liquid well known in the prior art, and is prepared by using a pulp as a raw material for impregnation, pressing, pulverizing, aging, yellowing, and dissolving. , ripening, filtration, defoaming and other processes.
  • the pulp is impregnated with an aqueous solution of sodium hydroxide having a concentration of about 18% to convert the cellulose into alkali cellulose, the hemicellulose is eluted, and the degree of polymerization is partially lowered; and the excess alkali solution is removed by pressing.
  • the bulky alkali cellulose is pulverized on a pulverizer and becomes a loose floc, and the uniformity of chemical reaction is improved by the increase in surface area.
  • Alkali cellulose undergoes oxidative cleavage under the action of oxygen to lower the average degree of polymerization, a process called aging. After aging, the alkali cellulose is reacted with carbon disulfide to form a cellulose xanthate, which is yellowed, further weakening the hydrogen bond between the macromolecules, and the cellulose xanthate in the dilute alkali solution due to the hydrophilicity of the xanthate group The solubility performance is greatly improved.
  • the solid cellulose xanthate is dissolved in a dilute lye, which is a viscose.
  • the newly formed viscose is not easy to be formed due to its high viscosity and salt value. It must be placed at a certain temperature for a certain period of time, which is called ripening, so that the sodium cellulose sodium silicate in the viscose is gradually hydrolyzed and saponified, the degree of esterification is lowered, the viscosity and the The stability of the electrolyte action also changes. Defoaming and filtration should be carried out after ripening to remove bubbles and impurities. details as follows:
  • Viscose fiber filament process see Figure 1, Figure 1 is a filament process flow diagram of viscose fiber.
  • a graphene structure and a non-carbon non-oxygen element may be introduced in various steps of preparing the viscose solution described above, for example, before pulverization, or before aging, or before thawing, or before aging. Pass Often not introduced after the filtration or defoaming step.
  • the present invention is preferably introduced after the aging, before the filtration, and the inventors have found that the addition of the graphene structure and the substance containing the non-carbon non-oxygen element (for example, the composite containing carbon nanostructures) is more efficient and can be mixed. Time is reduced to more than half and can usually be reduced to one-third.
  • the present invention it is preferred to first form a graphene structure and a substance containing a non-carbon non-oxygen element into a dispersion system, and then uniformly mix the dispersion solution with the viscose liquid.
  • a preferred dispersion solvent is water.
  • the composite containing the graphene structure is made into a dispersion having a solid content of 0.1 to 10%.
  • the composite containing the graphene structure is first dispersed in a dilute alkali solution for dissolving the cellulose xanthate, and then the yellowed cellulose, that is, the cellulose xanthate, is added.
  • the advantage of this method is that it is not necessary to additionally introduce water due to the introduction of the graphene structure, and the cellulose is combined with the graphene structure after dissolution, and the mixing is more uniform.
  • the graphene structure when the graphene structure is dispersed in the dilute alkali solution and after the addition of the cellulose xanthate, it is not necessary to stir for a long time, and after stirring for a short time, the graphene structure can be greatly improved. Dispersion efficiency.
  • the corn cob is used as a raw material, and after alkalizing, pressing, pulverizing, aging, yellowing, dissolving, and aging, a viscose liquid having a solid content of 8% is obtained; and Examples 1-8 and Comparative Examples 1-3 are obtained.
  • the material containing the graphene structure is dispersed in 5 times by mass of water, and then the graphene structure dispersion is blended with the viscose liquid, and stirred in a high speed mixer for 1 hour to form a blend solution, and the amount of the graphene-containing composite is cellulose. 0.7%, 1.5%, 3%, 5% and 10% of the mass.
  • the composition of the coagulation bath sulfuric acid 105g / l, sodium sulfate 200g / l, zinc sulfate 12g / l.
  • the far-infrared and antibacterial properties of functional fibers are tested. The test criteria are as follows:
  • the infrared detection data is based on: the National Textile Products Quality Supervision and Inspection Center, in accordance with the FZ/T64010-2000 inspection method for inspection;
  • Antibacterial test data based on: National Textile Products Quality Supervision and Inspection Center, in accordance with GB/T20944.3-2008 test method.
  • the functional viscose fiber is prepared:
  • the functional viscose fiber is prepared:
  • the carbon-containing nanostructure composite When the carbon-containing nanostructure composite is added in an amount exceeding 5% by weight, especially more than 10% by weight, the agglomeration phenomenon is liable to occur, resulting in uneven dispersion of the carbon-containing nanostructure composite in the fiber, resulting in a decrease in far-infrared and antibacterial effects. . As long as the carbon-containing nanostructure composite has good dispersibility in the fiber, it can be continuously added.

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Abstract

L'invention concerne une fibre de cellulose régénérée fonctionnelle comportant une structure de graphène et des éléments sans oxygène non carbonés ; les éléments sans oxygène non carbonés comportant des éléments Fe, Si et Al ; et les éléments sans oxygène non carbonés représentent 0,03 % en poids à 1 % en poids de la fibre de cellulose régénérée. Au moyen de la fibre de cellulose régénérée fonctionnelle fournie par la présente invention, des substances contenant une structure de graphène et des éléments sans oxygène non carbonés sont amenées dans de la fibre de cellulose régénérée classique ; par la mise en correspondance et la combinaison de la structure de graphène et des éléments de Fe, Si, et Al, la fibre de cellulose régénérée fournie par la présente invention possède différentes propriétés telles que la propriété dans l'infrarouge lointain et la résistance et l'inhibition des bactéries ; et par le contrôle d'une proportion spécifique d'ajout, la fibre de cellulose régénérée peut avoir un meilleur effet dans l'infrarouge lointain et un meilleur effet d'inhibition des bactéries.
PCT/CN2016/105641 2015-11-20 2016-11-14 Fibre de cellulose régénérée fonctionnelle, procédé de préparation pour celle-ci, et application de celle-ci WO2017084542A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10494263B2 (en) 2015-03-04 2019-12-03 Heilongjiang University Method for preparing biomass graphene by using cellulose as raw material
CN114588317A (zh) * 2022-03-09 2022-06-07 诺一迈尔(苏州)生命科技有限公司 一种柔性无机纳米纤维复合支架及其制备方法
CN115627553A (zh) * 2022-07-22 2023-01-20 新乡化纤股份有限公司 一种生物质菌草再生纤维素纤维及其制备方法
CN116356441A (zh) * 2023-03-02 2023-06-30 东华大学 一种基于玉米芯的再生纤维素纤维制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112899814B (zh) * 2021-02-03 2022-12-06 广西大学 一种仿生纤维功能材料及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120063857A (ko) * 2010-12-08 2012-06-18 금오공과대학교 산학협력단 셀룰로스 유도체-그래핀 나노복합체 및 그 제조방법
KR20120082287A (ko) * 2011-01-13 2012-07-23 경북대학교 산학협력단 라이오셀/그래핀 나노복합체를 포함하는 전구체 섬유와 이를 이용한 탄소섬유 및 그 제조방법
CN103046151A (zh) * 2012-12-18 2013-04-17 青岛大学 一种石墨烯共混再生纤维素纤维及其制备方法
CN103508444A (zh) * 2012-06-21 2014-01-15 海洋王照明科技股份有限公司 一种磷掺杂石墨烯及其制备方法
CN104016341A (zh) * 2014-07-01 2014-09-03 济南圣泉集团股份有限公司 一种多孔石墨烯的制备方法
CN104328523A (zh) * 2014-11-20 2015-02-04 济南圣泉集团股份有限公司 包含石墨烯的粘胶纤维及其制备方法
CN104724699A (zh) * 2015-03-04 2015-06-24 黑龙江大学 纤维素为原料制备生物质石墨烯的方法
CN104831389A (zh) * 2015-05-22 2015-08-12 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

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4803374B2 (ja) 2006-07-28 2011-10-26 レンゴー株式会社 セルロース系繊維構造物の製造方法
JP5566368B2 (ja) 2009-02-18 2014-08-06 日本製紙株式会社 セルロースナノファイバーおよび金属ナノ粒子を含む複合体、ならびにその製造方法
EP2224045A1 (fr) * 2009-02-27 2010-09-01 Basf Se Procédé de production de nanofibres de carbone et/ou nanotubes de carbone
EP2408953A4 (fr) * 2009-03-16 2012-09-05 Ilhan A Aksay Fibres polymères et articles fabriques a partir de celles-ci
JP5528760B2 (ja) 2009-09-30 2014-06-25 日本製紙株式会社 セルロースナノファイバーを添加して抄紙した紙およびその製造方法
JP5544510B2 (ja) * 2010-03-30 2014-07-09 国立大学法人信州大学 コンポジット繊維およびコンポジット繊維の製造方法
FR2997097B1 (fr) * 2012-10-22 2015-04-10 Arkema France Procede de fabrication d'une fibre de carbone, materiau precurseur utilise par le procede et fibre de carbone obtenue.
CN103451757A (zh) * 2013-06-17 2013-12-18 江南大学 一种具有抗静电、耐酸碱、隔热阻燃特性的纤维
CN103603081B (zh) * 2013-09-24 2015-12-02 青岛大学 一种石墨烯增强聚合物多孔海绵纤维的制备方法
EP2889400A1 (fr) * 2013-12-24 2015-07-01 SAPPI Netherlands Services B.V. Fibres ou filaments cellulosiques renforcés par des particules inorganiques et leur procédé de production
KR101566959B1 (ko) 2014-08-13 2015-11-16 충남대학교산학협력단 내염화성 셀룰로오스계 탄소섬유 제조방법 및 이에 의해 제조된 셀룰로오스계 탄소섬유
CN104878465A (zh) * 2015-06-08 2015-09-02 苏州威尔德工贸有限公司 一种碳纳米管再生竹纤维及其生产方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120063857A (ko) * 2010-12-08 2012-06-18 금오공과대학교 산학협력단 셀룰로스 유도체-그래핀 나노복합체 및 그 제조방법
KR20120082287A (ko) * 2011-01-13 2012-07-23 경북대학교 산학협력단 라이오셀/그래핀 나노복합체를 포함하는 전구체 섬유와 이를 이용한 탄소섬유 및 그 제조방법
CN103508444A (zh) * 2012-06-21 2014-01-15 海洋王照明科技股份有限公司 一种磷掺杂石墨烯及其制备方法
CN103046151A (zh) * 2012-12-18 2013-04-17 青岛大学 一种石墨烯共混再生纤维素纤维及其制备方法
CN104016341A (zh) * 2014-07-01 2014-09-03 济南圣泉集团股份有限公司 一种多孔石墨烯的制备方法
CN104328523A (zh) * 2014-11-20 2015-02-04 济南圣泉集团股份有限公司 包含石墨烯的粘胶纤维及其制备方法
CN104724699A (zh) * 2015-03-04 2015-06-24 黑龙江大学 纤维素为原料制备生物质石墨烯的方法
CN104831389A (zh) * 2015-05-22 2015-08-12 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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10494263B2 (en) 2015-03-04 2019-12-03 Heilongjiang University Method for preparing biomass graphene by using cellulose as raw material
CN114588317A (zh) * 2022-03-09 2022-06-07 诺一迈尔(苏州)生命科技有限公司 一种柔性无机纳米纤维复合支架及其制备方法
CN115627553A (zh) * 2022-07-22 2023-01-20 新乡化纤股份有限公司 一种生物质菌草再生纤维素纤维及其制备方法
CN115627553B (zh) * 2022-07-22 2023-11-21 新乡化纤股份有限公司 一种生物质菌草再生纤维素纤维及其制备方法
CN116356441A (zh) * 2023-03-02 2023-06-30 东华大学 一种基于玉米芯的再生纤维素纤维制备方法

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