WO2017084621A1 - Matériau synthétique fonctionnel et son procédé de préparation et article associé - Google Patents

Matériau synthétique fonctionnel et son procédé de préparation et article associé Download PDF

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WO2017084621A1
WO2017084621A1 PCT/CN2016/106434 CN2016106434W WO2017084621A1 WO 2017084621 A1 WO2017084621 A1 WO 2017084621A1 CN 2016106434 W CN2016106434 W CN 2016106434W WO 2017084621 A1 WO2017084621 A1 WO 2017084621A1
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synthetic material
functional
composite
carbon
graphene
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PCT/CN2016/106434
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English (en)
Chinese (zh)
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张金柱
刘顶
王双成
张小鸽
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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 CN201610125751.5A external-priority patent/CN106245140B/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
Publication of WO2017084621A1 publication Critical patent/WO2017084621A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to the field of synthetic material processing, in particular to a functional synthetic material, a preparation method thereof and an article.
  • the traditional synthetic fiber fabrics only have some common properties of the fiber materials themselves, but other properties such as environmental protection, moisture absorption, antibacterial, anti-ultraviolet, anti-radiation, etc. are very lacking, and the conventional film only has the ordinary film itself. It has common performance, but lacks performance such as antibacterial, environmental protection, anti-UV, and far infrared.
  • the carbon nanomaterial refers to a carbon material having a dispersed phase size of at least one dimension of less than 100 nm, such as carbon nanotubes, graphene, and the like.
  • Graphene is a two-dimensional material of a honeycomb structure composed of a single layer of sp2 hybridized carbon atoms, and has many excellent properties. Since its discovery in 2004, graphene has become a research hotspot in the scientific community. While studying the physical and chemical properties of graphene, graphene-related composite materials are emerging one after another. In the direction of nanoscience, graphene is also used to prepare related nanocomposites, especially graphene/metal or graphene/metal oxide nanocomposites. Due to the excellent properties of graphene, these nanocomposites have broad research prospects in new energy, biosensing, catalysis, optical materials and other fields.
  • the Chinese patent "CN201410830753” discloses an antistatic spandex fiber by adding a modified titanium dioxide antistatic agent to a polyurethane polymer solution. However, the spandex fibers prepared in this patent have only antistatic properties.
  • the Chinese patent “CN104278354 A” discloses a flesh-colored spandex fiber. The patent firstly adds three kinds of nano-pigments of white, red and yellow to DMAC, and then disperse and obtain a flesh pigment solution under high temperature ultrasonic conditions, and then After the prepolymerization is completed, the flesh pigment is added to the prepolymer, and then the flesh-colored spandex filament is obtained by aging and spinning.
  • the spandex fiber prepared in this patent only changes the color of the fiber, making the white spandex fiber into a flesh-colored spandex fiber.
  • the Chinese patent "CN201410611814” discloses a preparation method of chitosan modified spandex filament, and the spandex fiber prepared by the patent has improved toughness, antibacterial property, and the like compared with the traditional filament or natural fiber spun core-spun yarn. Odor, can also achieve waterproof, transparent A functional fabric that combines wet and antibacterial three-in-one. However, the far-infrared function of the spandex filament prepared by this patent is not outstanding.
  • the Chinese patent "CN201510117354" provides an antibacterial spandex fiber and a preparation method thereof.
  • the antibacterial spandex fiber prepared by the invention patent has stable and uniform properties, but has only antibacterial properties and has no special properties.
  • the Chinese patent "CN105295118A” provides an active packaging film for food, which is a sodium lactate-loaded montmorillonite modified chitosan/polyvinyl alcohol composite antibacterial barrier film, which introduces a montmorillonite modified shell into polyvinyl alcohol.
  • the polysaccharide has a good bacteriostatic effect.
  • a first object of the present invention is to provide a functional synthetic material which is obtained by incorporating a graphene-containing structure and a mineral element in a synthetic material preparation process, and the obtained composite material is excellent as a product.
  • the far-infrared, anti-ultraviolet, anti-radiation, anti-static, anti-bacterial and antibacterial properties can meet the needs of different groups of people, suitable for marketization, and also increase the added value of functional synthetic materials themselves.
  • a second object of the present invention is to provide a method for preparing a functional synthetic material, which has simple steps and convenient operation, and various aspects of the functional synthetic material prepared by the preparation method have excellent performance.
  • a third object of the present invention is to provide an article made of the above-mentioned functional synthetic material, which is widely used and favored by consumers, and has an added value of the synthetic material itself.
  • the present invention provides a functional synthetic material comprising a graphene structure and a mineral element in a synthetic material, the mineral element comprising Fe, Si and Al elements;
  • the content of the mineral element accounts for 0.0005-0.8 wt% of the functional synthetic material
  • the synthetic material comprises any one or a combination of at least two of a polypropylene synthetic material, a polyacrylonitrile synthetic material, a polyvinyl formal composite material, a polyamide synthetic material, and a polyurethane synthetic material.
  • the mineral element of the present invention is understood to be an element other than carbon, hydrogen or oxygen, and preferably includes elements other than carbon, hydrogen and oxygen which are mainly absorbed from the soil by the root system. Mineral elements are essential for plant growth, and plants that lack such elements will not grow healthily.
  • the present invention fully utilizes the characteristics of graphene and synthetic materials, and introduces the graphene structure into the synthetic material to make conductive, bacteriostatic, and far-reaching. Infrared warmth of graphene composite composite material, replacing traditional materials. Applying the functional synthetic material of the present invention to an article based on the conductivity, bacteriostasis, and far infrared thermal insulation properties of the material And can effectively improve its effect.
  • the graphene composite material is gray-black. If the synthetic material is black, it is not necessary to be dyed, which is more convenient to use and reduces the operation process. (In the prior art, when a synthetic material is required, a dye is added, so that Do environmental pollution seriously, or directly add carbon black in the preparation of synthetic materials, so that it becomes black).
  • the graphene structure and mineral elements of the present invention are introduced in the form of a composite containing carbon nanostructures.
  • the carbon nanostructure-containing composite of the present invention does not require modification.
  • the carbon nanostructure-containing composite is added in the form of a dry powder of a composite containing carbon nanostructures or in the form of a composite dispersion containing carbon nanostructures;
  • the dispersing agent of the carbon nanostructure-containing composite dispersion is selected from the group consisting of deionized water, distilled water, ethanol, ethylene glycol, terephthalic acid, sodium acetate solution, dodecylbenzenesulfonic acid, castor oil Any one or a combination of at least two of polyoxyethylene ethers.
  • the dispersing agent of the carbon nanostructure-containing composite dispersion of the present invention may be selected from the group consisting of a combination of deionized water and ethanol, a combination of ethylene glycol and ethanol, terephthalic acid and dodecylbenzenesulfonic acid.
  • the content of mineral elements accounts for 0.5-6 wt%, such as 0.6 wt%, 0.8 wt%, 0.9 wt%, 1.3 wt% of the carbon nanostructure-containing composite.
  • the mineral element further includes any one or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S, and Co elements.
  • the mineral 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, P, Ca, Na, Ni, Mn, K and Cr A combination of P, Ca, Na, Ni, Mn, K, Mg, Cr, S, and Co.
  • the carbon nanostructure-containing composite has a carbon content of 80% by weight or more, such as 82% by weight, 86% by weight, 89% by weight, 91% by weight, 94% by weight, and 97% by weight of the carbon nanostructure-containing composite. %, 99% by weight, etc., preferably 85 to 97% by weight, further preferably 90 to 95% by weight.
  • 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 ⁇ 10.0um, 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 functional synthetic material of the present invention contains a graphene structure, and the graphene structure of the present invention is not particularly limited, and may be defined by a person skilled in the art.
  • the graphene structure refers to a monolayer graphene structure. Or a multilayer graphene structure, more preferably a combination of the two, the graphene structure of the present invention is preferably a six-membered ring-shaped honeycomb sheet structure of 1-10 layers of carbon, and may also be a single layer, a double layer or a 3-10 layer.
  • a six-membered ring-shaped honeycomb sheet structure having a number of layers of more than 10 layers and a thickness of 100 nm or less is called a graphene nanosheet layer; a six-membered loop honeycomb sheet layer having a layer number of 1-10 layers of carbon , called graphene; six-membered ring honeycomb with more than 10 layers made of biomass as carbon source and carbon of 100 nm or less
  • the lamellar structure is called a biomass graphene nanosheet layer; the six-membered ring-shaped honeycomb sheet structure with a layer of 1-10 layers of carbon prepared by using biomass as a carbon source is called biomass graphene.
  • the six-membered ring-shaped honeycomb sheet structure of the graphene structure of the present invention which is preferably carbon on the microscopic appearance, exhibits a microscopic combination of any one or more of warp, curl, and folded conformation, with respect to the sheet layer in the composite.
  • the microstructure of the structure can typically be obtained by electron microscopy, which can 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, most preferably 20 nm or less, and may also be 10 nm, 11 nm, and 12 nm, etc., such as the number of layers, thickness, and the like of the graphene structure of the present invention. The restrictions are obtained by the inventors through a lot of practice, not by simple choice.
  • the functional synthetic material is tested to contain mineral elements including Fe, Si and Al elements, preferably including P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co.
  • One or more of the mineral elements are present in an amount of from 0.0005 to 0.8% by weight of the functional synthetic material, preferably from 0.005 to 0.6% by weight, more preferably from 0.02 to 0.3% by weight, most preferably from 0.03 to 0.2% by weight, It may also be from 0.05 wt% to 0.15 wt%, for example, also 0.05 wt%, 0.1 wt%, 0.12 wt%, 0.3 wt%, 0.45 wt%, 0.7 wt%, 0.72 wt%, 0.78 wt%, and the like.
  • the mineral element of the present invention accounts for the mass fraction of the functional synthetic material, and refers to the content of the mineral element in the functional synthetic material product.
  • the mineral element is adsorbed on the surface or inside of the graphene structure in the form of one or a combination of a simple substance, an oxide and a carbide in the material.
  • the carbon nanostructure-containing composite of the present invention is preferably a nanoscale material containing various mineral elements, and more preferably any one or more of a nanoscale elemental substance, a nanoscale oxide, and a nanoscale inorganic compound.
  • the graphene structure introduced by the present invention with a composite containing carbon nanostructures preferably has a six-membered ring-shaped honeycomb sheet structure having carbon having a thickness of 100 nm or less, and more preferably a six-membered ring-shaped honeycomb sheet layer having carbon having a thickness of 20 nm or less.
  • the structure is particularly preferably any one or a combination of six-membered ring-shaped honeycomb sheet structures having a layer number of 1-10 layers of carbon, most preferably any of a single layer, a double layer or a 3-10 layer structure. One or a combination of several.
  • the six-membered ring-shaped honeycomb sheet structure of carbon in the carbon nanostructure-containing composite microscopically exhibits any one or a combination of warping, curling, and folding conformation.
  • the carbon nanostructure composite has a peak height ratio of the carbon element G peak to the D peak in the Raman spectrum, and is preferably from 1 to 20, more preferably from 3 to 20.
  • the Ra element spectrum of the carbon element G shows the degree of sp2 hybridization; the D peak reflects the lattice defects, such as the carbon structure of sp3.
  • the carbon nanostructure-containing composite further contains carbon element, and the carbon element content is more than 80% by weight of the carbon nanostructure-containing composite; graphene and amorphous carbon are present in the carbon nanostructure-containing composite.
  • amorphous carbon also contains two-dimensional graphite layer or three-dimensional graphite crystallites, there are a large number of irregular bonds on the edge of the crystallites, in addition to a large amount of sp2 carbon, 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 content of the mineral element is from 0.5 to 8% by weight, preferably from 0.5 to 6% by weight, further preferably from 1 to 5% by weight, further preferably from 2 to 4% by weight, based on the carbon nanostructure composite.
  • the mineral elements are generally adsorbed on the surface or inside of the graphene structure in the form of one or a combination of a simple substance, an oxide, and a carbide.
  • the preparation method of the carbon nanostructure-containing composite of the present invention comprises the following steps (referred to as method 1):
  • the temperature of the catalytic treatment is controlled at 150-200 ° C, time ⁇ 4 h, preferably 4-14 h; the moisture content in the precursor is preferably 10 wt% or less; and the temperature rise rate of the precursor is raised to 140-180 ° C Preferably, it is 3-5 ° C / min; the protective atmosphere is any one or a combination of nitrogen, helium, argon, preferably nitrogen; the crude washing is followed by pickling and water washing; pickling is preferably used
  • the concentration is 3 to 6 wt% of hydrochloric acid, further preferably 5 wt% of hydrochloric acid, and the water washing is preferably carried out using deionized water and/or distilled water, and the washing temperature is controlled between 55 and 65 ° C, preferably 60 ° C.
  • the temperature is 142 ° C, 148 ° C, 155 ° C, 160 ° C, 172 ° C or 178 ° C
  • the holding time is 1.6 h, 1.8 h, 2 h, 2.2 h or 2.4. h.
  • the temperature is 360 ° C, 370 ° C, 380 ° C, 390 ° C, 410 ° C, 420 ° C, 430 ° C or 440 ° C; the holding time is 3.1 h, 3.3 h, 3.5h, 3.8h or 3.9h.
  • 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 heating rate in the steps (3) and (4) is from 14 ° C / min to 18 ° C / min, in some embodiments of the invention, the heating rate is 15 ° C / min, 16 °C/min or 17 °C/min.
  • the third intermediate (crude product) is sequentially subjected to alkali washing, pickling, and water washing to obtain a composite containing carbon nanostructures; that is, the above-described biomass graphene (composite containing carbon nanostructures) One).
  • the biomass carbon source in the above step is selected from any one or a combination of plants and/or agricultural and forestry wastes, preferably any one or several of softwood, hardwood, forestwood, and agricultural and forestry waste.
  • 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 stalk, husk, and reed. Combination, preferably corn cob.
  • the biomass carbon source is selected from a combination of one or more of lignocellulose, cellulose, lignin, more preferably cellulose and/or lignin, and may also be cellulose, further preferably porous cellulose.
  • the biomass graphene prepared above does not need to be activated or modified.
  • the biomass carbon source is preferably one or more of lignocellulose, cellulose and lignin, more preferably lignocellulose, cellulose or lignin.
  • the cellulose is a porous cellulose obtained by the following method:
  • the biomass resources are subjected to acid hydrolysis to obtain lignocellulose, which is then subjected to porous treatment to obtain porous cellulose; alternatively, the porous cellulose is used after being bleached.
  • the biomass resource is selected from any one or a combination of plants and/or agricultural and forestry waste; preferably any one or combination 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, preferably Corn cob.
  • the biomass carbon source of the present invention comprises a combination of corn cob and corn cob, a combination of bagasse, high mast and wood chips, a combination of beet pulp, bagasse and corn cob, a combination of high mast, beet pulp and xylose residue, etc. .
  • the mass ratio of the biomass carbon source to the catalyst used in the catalytic treatment is preferably 1: (0.5-5), preferably 1: (1-3); in some embodiments of the invention, the ratio is 1:0.5 , 1:1 or 1:3.
  • the catalyst is selected from the group consisting 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 the group consisting of a halogen compound of iron, a cyanide of iron, and a ferrite containing one or a combination of several.
  • 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 the group consisting of cobalt A combination of any one or more of a halogen compound and a cobalt-containing acid salt.
  • the cobalt-containing acid salt is a salt of an organic acid containing a cobalt element or a salt of a mineral acid containing a cobalt element.
  • 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 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 iron chloride, ferrous chloride, iron nitrate, ferrous nitrate, iron sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium ferric acid trihydrate, A combination of any one or more of cobalt chloride, 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 catalytic treatment is carried out is from 150 ° C to 200 ° C, such as 160 ° C, 170 ° C, 180 ° C 190 ° C, etc., time ⁇ 4 h, preferably 4 h - 14 h, in some embodiments of the invention, the time may It is 4.2h, 7h, 9h, 12h, 16h, 19h, 23h.
  • the moisture content in the precursor is controlled to be 10 wt% or less.
  • the moisture content may also be 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 nitrogen, helium and argon, preferably nitrogen.
  • the pickling uses a hydrochloric acid aqueous solution having a concentration of 3-6 wt%, further preferably a 5 wt% aqueous hydrochloric acid solution;
  • the water washing preferably uses deionized water and/or distilled water;
  • the alkali washing uses a concentration of 5-
  • a 15 wt% aqueous sodium hydroxide solution is further preferably an aqueous sodium hydroxide solution having a concentration of 10% by weight.
  • the temperature of the final washing is preferably controlled between 55 and 65 ° C, for example, 56 ° C, 57 ° C, 58 ° C, 60 ° C, 63 ° C, etc., preferably 60 ° C.
  • method 2 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 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 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 of the present invention comprises the following steps (referred to as method 3):
  • the corn cob is subjected to acid hydrolysis to obtain lignocellulose, which is then subjected to porous treatment.
  • 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 comprises biomass graphene nanosheets, preferably including biomass graphene.
  • the biomass graphene nanosheet or biomass graphene is prepared by using biomass as a raw material.
  • the mineral element is at least Fe, Si, Al, and may also contain any one or more of K, Na, Ca, Mg, P, Mn and Co.
  • the preparation method of the biomass graphene nanosheet and the biomass graphene is not particularly limited, and a method of preparing a similar composite well known to those skilled in the art may be used.
  • the present invention is preferably a preparation of biomass graphene, and a method of preparing biomass graphene well known to those skilled in the art can be selected.
  • Existing methods for preparing biomass graphene include, for example, the method disclosed in CN104118873A; the method disclosed in CN104016341A; the method disclosed in CN104724696A; the method disclosed in CN104724699A; and the method disclosed in CN105060289A.
  • the carbon nanostructure-containing composite of the present invention can also be prepared by various methods as follows:
  • Method 4 The activated carbon is prepared by the existing process using biomass resources. Because the types and contents of trace elements in different plants are very different, the mineral elements (including Fe and Si at least) are controlled by later pickling, washing and the like. And Al may further contain a content of any one of P, Ca, Na, Ni, Mn, K, Mg, Cr, S or Co and a combination of the above elements, and based on this, graphene is introduced to make mineral elements Accounting for 0.5-6 wt% of the composite;
  • Method 5 Commercially available lignin, carbonized at a high temperature under an inert gas, and then added graphene, and later introduced nano-mineral elements (containing at least Fe, Si, Al, and may also contain P, Ca, Na, Ni, Mn, a combination of any one of K, Mg, Cr, S or Co and the above elements), and the content thereof is controlled to be 0.5 to 6 wt%;
  • nano-mineral elements containing at least Fe, Si, Al, and may also contain P, Ca, Na, Ni, Mn, a combination of any one of K, Mg, Cr, S or Co and the above elements
  • Method 6 For some organic wastes, such as phenolic resin foam sheets, after carbonization, graphene is introduced, and nano-mineral elements (containing at least Fe, Si, Al, and possibly P, Ca, Na, Ni, Mn, etc.) are introduced later. a combination of any one of K, Mg, Cr, S or Co and the above elements), and the content thereof is controlled to be 0.5 to 6 wt%;
  • Method 7 Adding activated carbon and graphene to nano-graphite, and introducing mineral elements (containing at least Fe, Si, Al, and possibly P, Ca, Na, Ni, Mn, K, Mg, Cr, S or Co) a combination of any one or more of the elements), and its content is controlled at 0.5-6 wt%;
  • mineral elements containing at least Fe, Si, Al, and possibly P, Ca, Na, Ni, Mn, K, Mg, Cr, S or Co
  • the carbon nanostructure-containing composite to be protected by the present invention is not limited to the above production method.
  • the far-infrared property and the antibacterial property of the product containing the carbon nanostructure composite to be protected by the above method are superior to the methods 4 to 7 in the methods 1 to 3, but all of them can be used in the preparation of the downstream product.
  • the carbon nanostructure-containing composite can be dispersed uniformly in the functional synthetic material by activation or modification treatment, and has certain effects, especially methods 1 to 3.
  • the invention introduces a graphene structure and a mineral substance by means of a carbon nanostructure composite, and after the introduction, the preparation of the functional synthetic material does not require pretreatment of the introduced substance, such as activation, modification, etc., and can be synthesized.
  • the effective combination of the material polymers results in an additional enhanced far-infrared effect and bacteriostatic effect.
  • the present invention tests the content of mineral elements in a composite material or a carbon nanostructure composite by the following method:
  • the second method for determination of mineral elements using the national standard GB/T17359-1998, electron probe and scanning electron microscopy X-ray energy spectrum quantitative analysis.
  • the method for determining the mineral element in the present invention is not limited, and any method known in the art or new can be used in the present invention; the present invention provides a method for determining the content of mineral elements, preferably "the first type of mineral element determination" The method is carried out for measurement, and the "first method for determining the content of mineral elements" is selected in the examples of the present invention.
  • the antibacterial detection data of the carbon nanostructure composite is based on: according to the test method of GB/T20944.3-2008, taking Staphylococcus aureus as an example.
  • the preparation method of the functional synthetic material of the invention is improved by the existing preparation method, and the specific steps are as follows:
  • One of the methods is: melting the synthetic material, and then introducing a graphene structure and a mineral element thereto, and cooling to obtain a functional synthetic material.
  • the second method is: dissolving the synthetic material in a solvent, then introducing a graphene structure and a mineral element thereto, and removing the solvent to obtain a functional synthetic material;
  • the solvent is a combination of fluoroacetic acid, a mixed solution of phenol and tetrachloroethane, and any one or at least two of tetrahydrofuran;
  • the means for removing the solvent is distillation.
  • the third method is: introducing a graphene structure and a mineral element in the polymerization process of the synthetic material, performing in-situ polymerization, obtaining a melt after the reaction, and discharging the melt to obtain a functional synthetic material.
  • the present invention also provides a functional material article prepared from the functional synthetic material described above.
  • the functional material article comprises a functional synthetic fiber prepared by spinning using the functional synthetic material; preferably, the functional material article further comprises a textile made using the functional synthetic fiber,
  • the textiles include civilian garments, home textiles, ultraviolet protective fabrics, and industrial special protective garments, including towels, bath towels, bed sheets, and quilts;
  • the functional material article comprises a film prepared by a cast coating method using the functional synthetic material
  • the functional material article further comprises tubing, furniture, profiles prepared using the functional synthetic material.
  • the carrier containing the graphene structure and the mineral element is dissolved and dispersed by a solvent to prepare a mixed solution, and then introduced;
  • the functional synthetic fiber is prepared by one of a dry spinning method, a wet spinning method, a dry-wet spinning method, a reactive spinning method, and a melting method;
  • the solvent is an aqueous solvent, preferably water.
  • the following four preparation methods are common methods for preparing the above-mentioned functional synthetic fibers, wherein in the dry spinning method, the wet spinning method, and the melt spinning step, the polymerization and spinning steps are sequential, and not simultaneously performed. Two steps. In the reaction spinning method, the polymerization and spinning steps are carried out simultaneously, and the specific operation steps of the four preparation methods are as follows, taking spandex as an example:
  • the polyether reacts with diisocyanate to form a prepolymer. After the prepolymer is dissolved in a solvent, a diamine is added to carry out a chain extension reaction to form a block copolymer solution, which is then mixed, filtered, defoamed, etc. A spinning dope with uniform properties.
  • Spinning Spinning the original hydraulic pressure into the spinning head. Under the action of pressure, the spinning solution is extruded from the capillary hole of the spinneret to form a fine flow of the filament and enters the tunnel.
  • the tunnel is filled with hot air, so that the solvent in the fine stream of the filament is quickly volatilized and taken away by the air.
  • the concentration of the strand is continuously increased until solidification, while the filament flow is stretched and thinned, and finally wound into A certain package.
  • the polyether reacts with diisocyanate to form a prepolymer. After the prepolymer is dissolved in a solvent, a diamine is added to carry out a chain extension reaction to form a block copolymer solution, which is then mixed, filtered, defoamed, etc. A spinning dope with uniform properties.
  • the spinning is hydraulically injected into the spinning head. Under the action of pressure, the spinning solution is extruded from the capillary pores of the spinneret to form a fine stream of filaments and enters the coagulation bath.
  • the coagulation bath uses warm water (below 90 ° C) as a coagulation medium, and the solvent in the fine liquid stream diffuses into the coagulation bath, and the concentration of the polymer in the fine liquid stream is continuously increased, so that the polymer precipitates in the coagulation bath to form fibers, and then is washed. Winding is carried out after drying.
  • the reaction spinning method is also called chemical spinning.
  • the process in which the reaction spinning process forms a high polymer from a monomer or a prepolymer is carried out simultaneously with the fiber forming process.
  • spandex is a solution of a polyether or polyester prepolymer containing diisocyanate at both ends, which is extruded through a spinneret into a coagulation bath and reacted with a chain extender in the coagulation bath to form nascent fibers.
  • melt spinning can only be applied to polyurethane block copolymers with good thermal stability, such as polyurethane obtained by polycondensation of 4,4'-methylene diphenyl diisocyanate and 1,4-butanediol. Block copolymers and the like. Melt spinning of spandex is mainly done in 6 steps:
  • the polyether reacts with diisocyanate to form a prepolymer. After the prepolymer is dissolved in a solvent, a diamine is added to carry out a chain extension reaction to form a block copolymer solution, which is then mixed, filtered, defoamed, etc. A spinning dope with uniform properties.
  • Spinning Spinning the original hydraulic pressure into the spinning head. Under the action of pressure, the spinning solution is extruded from the capillary hole of the spinneret to form a fine flow of the filament, passing through the air layer, and then entering the coagulation bath.
  • the coagulation bath uses warm water (below 90 ° C) as a coagulation medium, and the solvent in the fine liquid stream diffuses into the coagulation bath, and the concentration of the polymer in the fine liquid stream is continuously increased, so that the polymer precipitates in the coagulation bath to form fibers, and then is washed. Winding is carried out after drying.
  • the invention detects the far infrared performance and the antibacterial performance of the functional synthetic 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.
  • Embodiments of the present invention provide a functional synthetic material, which introduces a graphene structure and a mineral element on the basis of a conventional synthetic material, and the present invention provides a combination of a graphene structure, Fe, Si, and Al elements.
  • the functional synthetic material has far-infrared performance and antibacterial and antibacterial properties, and can control the specific proportion of addition, can have high far-infrared effect and antibacterial effect, can meet the needs of different groups of people, and is suitable for marketization. , also increases the added value of the material itself;
  • the preparation method of the functional synthetic material of the invention has the advantages of simple steps, convenient operation, close connection between the front and the back steps, and mild operating conditions.
  • the preparation method is only a superior process route, and the preparation method is in the prior art.
  • Other preparation methods for synthetic materials are also applicable, and the operation is flexible, as long as the polymer is compounded with the composite containing carbon nanostructures, and no pretreatment of the substance, such as activation or modification, is required during the introduction process.
  • Sex, etc. the prepared functional synthetic materials have excellent performance in all aspects, and have a good far-infrared effect and bacteriostatic effect;
  • the far-infrared performance of the functional synthetic material of the present invention can reach up to 0.93, and the bacteriostatic performance can reach more than 99%, which shows that the practical application effect is very remarkable.
  • the precursor was 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 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 mineral element content determination method was used to detect that the carbon-containing nanostructured composite mainly contained P, Si, Ca, Al, Fe, and Mg elements, and the content was 3.2 wt%.
  • the mass ratio of corn cob cellulose and ferrous chloride of Preparation Example 1 for example, it may be 1:0.1, 1:0.5, 1:0.7, 1:0.9, 1:1.2, 1:1.4, 1:1.5, etc. It is possible to prepare biomass graphene having a mineral element content in the range of 0.5 to 6 wt%.
  • Examples 1-11 are the introduction of biomass graphene during the preparation of functional polyamide fibers, in particular during the preparation of the masterbatch.
  • the preparation of the masterbatch includes the following steps:
  • the biomass graphene obtained in Preparation Example 1 was mixed with the polyamide chips and stirred for 3-5 min, dried, and subjected to twin-screw extrusion, and the extrusion temperature was 250-275 ° C, the degree of vacuum was 0.05-0.08 MPa, and the water was cold-cut. That is, a functional synthetic material (polyamide masterbatch).
  • the preparation of the polyamide fiber comprises the following steps:
  • the polyamide masterbatch described above was mixed with a polyamide chip and stirred for 1-2 min, and then uniformly melt-spun to obtain a functional synthetic fiber (functional polyamide fiber).
  • Biomass graphene was introduced during the spinning process, and the quality of the biomass graphene was the same as in Example 3, and the amount added was also 2.2 wt%. After testing, the content of mineral elements in the fiber was 0.015 wt%, the far-infrared normal emissivity was 0.87, and the antibacterial rate was 90%.
  • the functional synthetic fibers of the embodiments 1-12 of the present invention can be used for making fibrous products such as civilian garments, home textile fabrics, ultraviolet protective fabrics, and industrial special protective garments.
  • the biomass graphene in Example 3 was replaced with pure graphene, and other conditions were unchanged.
  • the biomass graphene in Example 3 was replaced with bamboo charcoal, and other conditions were unchanged.
  • the biomass graphene in Example 3 was replaced with graphite, and other conditions were unchanged.
  • the functional synthetic fibers of the embodiments 13-17 of the present invention can be used for making fibrous products such as civilian garments, home textiles, ultraviolet protective fabrics, and industrial special protective garments.
  • Composites containing carbon nanostructures can also be obtained by several methods:
  • the carbon nanostructure-containing composite prepared in Preparation 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 mineral element content determination method was used to detect that the carbon-containing nanostructured composite mainly contained Si, Ca, Al, Fe, Mg, and S elements in an amount of 2.5 wt%.
  • the carbon nanostructure-containing composite prepared in Preparation Example 3 was subjected to Raman spectroscopy, and the result showed G
  • the peak to D peak height ratio is 4.6;
  • the first mineral element content determination method was used to detect that the carbon-containing nanostructured composite mainly contained P, Si, Al, Na, Fe, and Ni elements, and the content was 3.5 wt%.
  • the carbon nanostructure-containing composite prepared in Preparation Example 4 was subjected to Raman spectroscopy, and the results showed that the height ratio of G peak and D peak was 2.8;
  • the first mineral element 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 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).
  • step (2) mixing the porous cellulose and ferric chloride obtained in the step (1) at a mass ratio of 1:1, stirring at 200 ° C for catalytic treatment for 8 hours, drying to a moisture content of the precursor of 4 wt%, to obtain a precursor; protective atmosphere
  • the precursor was heated to 350 ° C at a rate of 5 ° C / min, kept for 2 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 20 ° C / min; 55 ⁇ 65 ° C,
  • the crude product was pickled by hydrochloric acid at a concentration of 4% by weight, and washed with water to obtain a composite containing carbon nanostructures.
  • the carbon nanostructure-containing composite prepared in Preparation Example 9 was subjected to Raman spectroscopy, and the results showed that the height ratio of G peak and D peak was 6.8;
  • the first mineral element 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 Preparation Example 10 was subjected to Raman spectroscopy, and the result showed G
  • the peak to D peak height ratio is 15;
  • the first mineral element content determination method was used to detect that the carbon-containing nanostructured 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 Preparation 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 D peak was 3;
  • the first mineral element content determination method was used to detect that the carbon-containing nanostructured 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 Preparation 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 mineral element content determination method was used to detect that the carbon-containing nanostructured 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 carbon nanostructure-containing composite prepared in Preparation Example 13 was subjected to Raman spectroscopy, and the results showed that the height ratio of G peak and D peak was 4.6;
  • the first mineral element content determination method detected that the carbon-containing nanostructured composite mainly contained P, Si, Ca, Al, Na, Fe, Mg, Ni, 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 Preparation 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 mineral element content determination method was used to detect that the carbon-containing nanostructured 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 Preparation 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 mineral element content determination method was used to detect that the carbon-containing nanostructured composite mainly contained P, Si, Ca, Al, Na, Fe, Mg, Ni, and K elements, and the content was 4.7 wt%.
  • Examples 18-21 are respectively a carbon nanostructure-containing composite prepared by preparing Preparation Example 2 - Preparation Example 5 during the preparation of the polyamide fiber, specifically: a synthetic monomer of the polyamide and a composite containing carbon nanostructures. After mixing, the polymerization reaction was carried out in accordance with the synthesis conditions of the polyamide to obtain a modified polyamide material, which was spun to obtain a polyamide fiber.
  • Examples 22-26 are respectively introduced into the carbon nanostructure-containing composite prepared in Preparation Examples 6-10 during the preparation of the polyacrylonitrile synthetic material, specifically: the composite monomer of polyacrylonitrile and the composite containing carbon nanostructures The mixture is mixed, and then polymerization is carried out according to the synthesis conditions of polyacrylonitrile to obtain modified polypropylene.
  • An acrylonitrile synthetic material is respectively introduced into the carbon nanostructure-containing composite prepared in Preparation Examples 6-10 during the preparation of the polyacrylonitrile synthetic material, specifically: the composite monomer of polyacrylonitrile and the composite containing carbon nanostructures The mixture is mixed, and then polymerization is carried out according to the synthesis conditions of polyacrylonitrile to obtain modified polypropylene.
  • An acrylonitrile synthetic material is respectively introduced into the carbon nanostructure-containing composite prepared in Preparation Examples 6-10 during the preparation of the polyacrylonitrile synthetic material, specifically: the composite monomer of polyacrylonitrile and the composite containing carbon nanostructures The mixture is mixed,
  • Examples 27-29 are the carbon nanostructure-containing composites prepared in Preparations 11-13, respectively, during the preparation of the polypropylene synthetic material, specifically: mixing the synthetic monomers of the polypropylene with the composite containing the carbon nanostructures. Then, polymerization was carried out in accordance with the synthesis conditions of polypropylene to obtain a modified polypropylene synthetic material.
  • Examples 30-31 are respectively a carbon nanostructure-containing composite prepared by preparing Preparation Examples 14-15 during the preparation of the polyurethane composite material, specifically: mixing the synthetic monomer of the polyurethane with the composite containing the carbon nanostructure, and then The polymerization reaction was carried out in accordance with the synthesis conditions of the polyurethane to obtain a modified polyurethane synthetic material.

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Abstract

La présente invention concerne un matériau synthétique fonctionnel ayant une structure de graphène et des éléments minéraux, les éléments minéraux comprenant le Fe, le Si et l'Al Le matériau synthétique fonctionnel de l'invention présente un large éventail d'applications, et l'article fibreux fabriqué à partir de ce dernier peut être utilisé pour fabriquer des vêtements civils, un tissu textile de maison, un tissu de protection contre les ultraviolets, des vêtements spéciaux industriels de protection et similaires, présentant une résistance au rayonnement infrarouge, des propriétés antistatiques, antibactériennes et bactériostatiques.
PCT/CN2016/106434 2015-11-20 2016-11-18 Matériau synthétique fonctionnel et son procédé de préparation et article associé WO2017084621A1 (fr)

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CN201610125751.5 2016-03-04
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