WO2017063492A1 - 一种含碳纳米结构的复合物、使用其的高分子材料及制备方法 - Google Patents

一种含碳纳米结构的复合物、使用其的高分子材料及制备方法 Download PDF

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WO2017063492A1
WO2017063492A1 PCT/CN2016/099750 CN2016099750W WO2017063492A1 WO 2017063492 A1 WO2017063492 A1 WO 2017063492A1 CN 2016099750 W CN2016099750 W CN 2016099750W WO 2017063492 A1 WO2017063492 A1 WO 2017063492A1
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Prior art keywords
carbon
composite
graphene
combination
nanostructure
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PCT/CN2016/099750
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English (en)
French (fr)
Inventor
唐一林
张金柱
郑应福
刘晓敏
刘顶
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Jinan Shengquan Group Share Holding Co Ltd
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Jinan Shengquan Group Share Holding Co Ltd
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Priority claimed from CN201510672279.2A external-priority patent/CN105502330A/zh
Priority claimed from CN201510819312.XA external-priority patent/CN105504341B/zh
Priority to AU2016339389A priority Critical patent/AU2016339389B2/en
Priority to CA2975634A priority patent/CA2975634C/en
Priority to EP16854583.8A priority patent/EP3202711A4/en
Priority to KR1020177006293A priority patent/KR101935697B1/ko
Application filed by Jinan Shengquan Group Share Holding Co Ltd filed Critical Jinan Shengquan Group Share Holding Co Ltd
Priority to JP2017523533A priority patent/JP6432071B2/ja
Priority to US15/521,534 priority patent/US10836640B2/en
Priority to MX2017011043A priority patent/MX2017011043A/es
Priority to BR112017018488-5A priority patent/BR112017018488A2/zh
Priority to RU2017129230A priority patent/RU2703170C1/ru
Publication of WO2017063492A1 publication Critical patent/WO2017063492A1/zh
Anticipated expiration legal-status Critical
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B1/008—Nanostructures not provided for in groups B82B1/001 - B82B1/007
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0095—Manufacture or treatments or nanostructures not provided for in groups B82B3/0009 - B82B3/009
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01B32/194—After-treatment
    • 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
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • 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
    • C08K2003/0812—Aluminium
    • 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
    • C08K2003/0856—Iron

Definitions

  • the invention relates to the technical field of materials, in particular to a composite and a preparation method thereof, and a polymer material and a preparation method thereof.
  • a nanocarbon material refers to a carbon material having a dispersed phase dimension of at least one dimension of less than 100 nm.
  • the dispersed phase may be composed of carbon atoms or heterogeneous atoms (non-carbon atoms), and may even be nanopores.
  • Nano carbon materials mainly include carbon nanotubes, carbon nanofibers, nanocarbon spheres and graphene.
  • Graphene is a material of a single-layer sheet structure composed of carbon atoms. Graphene is almost completely transparent, absorbing only 2.3% of light; thermal conductivity is as high as 5300W/m ⁇ K, higher than that of carbon nanotubes and diamond; graphene has electron mobility at room temperature exceeding 15000cm2/V ⁇ s, exceeding nanocarbon Tube or silicon crystal; graphene has a resistivity of only 10-8 ⁇ m, which is lower than copper or silver, and is the material with the lowest resistivity in the world. Because graphene has the advantages of good transparency, low resistivity, and fast electron migration, it can be used to manufacture transparent touch screens, light panels, and solar cells.
  • the preparation methods of graphene mainly include mechanical stripping method, chemical vapor deposition method, pyrolysis epitaxial growth method, etc. Among them, the preparation of graphene by chemical vapor deposition method is simple and easy, and a large-area high-quality graphene can be obtained.
  • the graphene prepared by the prior art preparation method is used in the application, especially in the application of the polymer material, in order to make it and the polymer material better.
  • the technical problem to be solved by the present invention is to provide a composite and a preparation method thereof, and a polymer material and a preparation method thereof, and the prepared composite has excellent far-infrared effect and antibacterial and antibacterial effect.
  • One of the objects of the present invention is to provide a carbon nanostructure-containing composite comprising 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% by weight to 6% by weight of the composite.
  • 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 non-carbon non-oxygen element further includes any one or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S, and Co.
  • the composite has a ratio of carbon element G peak to peak D height in the Raman spectrum of 1 to 20, such as 2, 5, 7, 8, 10, 12, 13, 16, 18, and the like.
  • 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 provided by the present invention is a carbon-based composite containing an impurity element, wherein the carbon element is mainly present in the form of sp2 hybridization.
  • the composite has a ratio of carbon element G peak to peak D height in the Raman spectrum of from 2 to 20, preferably from 3 to 20, further preferably from 5 to 20, particularly preferably from 7 to 20, most preferably from 10 to 20.
  • the complex also has a 2D peak under Raman spectroscopy.
  • the 2D peak characterizes the thickness of the sheet structure, and the higher the 2D peak intensity, the thinner the layer.
  • the non-carbon non-oxygen element further comprises P, Ca, Na.
  • the non-carbon non-oxygen element further comprises any one of Ni, Mn, K, Mg, Cr, S, and Co, or a combination of at least two.
  • other elements contained may be a combination of P, Si, Ca, Al, Na, Fe, P, Si, Ca, Al, Na. , combination of Mn, combination of P, Si, Ca, Al, Na, Cr, combination of P, Si, Ca, Al, Na, Fe, Mn, K, P, Si, Ca, Al, Na, Fe, Ni
  • P, Si, Ca, Al, Na, Ni a combination of P, Si, Ca, Al, Na, Fe, K, a combination of P, Si, Ca, Al, Na, Mn, Cr, and the like.
  • the non-carbon non-oxygen element is present in the form of a simple substance and/or a compound.
  • the non-carbon non-oxygen element is adsorbed on the surface and/or inside of the carbon nanostructure in the form of any one or more of a simple substance, an oxide or a carbide, specifically the non-carbon non-oxygen element. It is a metal compound and/or a non-metal compound.
  • the carbon content in the composite is ⁇ 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 wt%. .
  • 80 wt% or more of the carbon element structure in the composite is a graphitized structure, and preferably 90 wt% or more is a graphitized structure; the degree of graphitization of the graphitized structure is different, and the degree of graphitization is different, that is, the crystallinity is different, but both are graphitized. .
  • the non-carbon non-oxygen element comprises from 1.5 wt% to 5 wt% of the composite, such as 2 wt%, 2.5 wt%, 2.8 wt%, 3.3 wt%, 3.6 wt%, 4.3 wt%, 4.8 wt%, and the like.
  • the graphene has a six-membered ring-shaped honeycomb sheet structure of carbon having a thickness of 100 nm or less, preferably a six-membered ring-shaped honeycomb sheet structure having carbon having a thickness of 20 nm or less, and more preferably has a number of layers of 1 to Any one or a combination of at least two of the 10-layer carbon six-membered ring-shaped honeycomb sheet structure is preferably a combination of any one of a single layer, a double layer, or a three to ten layer structure, or a combination of at least two.
  • the six-membered ring-shaped honeycomb sheet structure of carbon in the composite microscopically exhibits any one or a combination of at least two of a warped, curled or folded conformation.
  • non-carbon non-oxygen elements P, Si, Ca, Al, and Na are introduced through a carbon source;
  • the carbon source is preferably a biomass carbon source, and the biomass resource is selected from the group consisting of plants and / or a combination of any one or at least two of agricultural and forestry waste; preferably one or a combination of at least two of softwood, hardwood, forestwood or agricultural and forestry waste.
  • 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 stalk, husk and reed, or at least 2 species.
  • a combination of corn cobs is preferred.
  • Another object of the present invention is to provide a process for the preparation of a composite containing carbon nanostructures.
  • the specific steps include:
  • the heating rate in the steps (3) and (4) is from 14 ° C / min to 18 ° C / min.
  • 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 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 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 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 iron chloride, ferrous chloride, iron nitrate, ferrous nitrate, iron sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium ferric acid trihydrate, 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, and in some specific embodiments of the invention, 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;
  • 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 temperature of the washing 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 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 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 specific steps include:
  • the precursor is incubated at 280-350 ° C, for example 282 ° C, 288 ° C, 295 ° C, 300 ° C, 332 ° C, 340 ° C, etc., for 1.5 to 2.5 h, for example 1.6 h, 1.8 h, 2h, 2.2h, 2.4h, etc., then the temperature is programmed to 950 ⁇ 1050 ° C, such as 960 ° C, 970 ° C, 980 ° C, 990 ° C, 1010 ° C, 1020 ° C, 1030 ° C, 1040 ° C, etc., heat preservation 3 ⁇ 4h, for example 3.1h, 3.3h, 3.5h, 3.8h, 3.9h, etc., to obtain a crude product; the temperature rising rate of the programmed temperature is 15-20 ° C / min, such as 16 ° C / min, 18 ° C / min, 19 ° C / min, etc. ;
  • the invention selects a specific temperature programmed step temperature (15-20 ° C/min), and the programmed temperature (280-350 ° C) and holding time, and the holding temperature of the end point (950 ⁇ 1050 ° C) and holding time (3 ⁇ 4h),
  • the biomass carbon source and the catalyst have a mass ratio of 1:0.1 to 10, such as 1:0.5, 1:1, 1; 3, 1:5, 1:8, 1:9, etc., preferably 1:0.5 to 5, further preferably 1:1 to 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 iron chloride and/or iron bromide or the like.
  • 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 salt of a mineral acid containing a cobalt element.
  • the cobalt halogen compound may be cobalt chloride and/or cobalt bromide or the like.
  • 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 or the like.
  • 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, 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 stirring is subjected to the catalytic treatment is 150 to 200 ° C, for example, 160 ° C, 170 ° C, 180 ° C, 190 ° C, etc., and the time is ⁇ 4 h, for example, 4.2 h, 7 h, 9 h, 12 h, 16 h, 19 h, 23 h, etc., preferably 4 to 14h.
  • the moisture content in the precursor is 10 wt% or less, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 1 wt%, and the like.
  • the precursor is heated to a temperature of 280 to 350 ° C at a rate of 3 to 5 ° C / min, such as 3.5 ° C / min, 3.8 ° C / min, 4.2 ° C / min, 4.5 ° C / min, 4.8 ° C / min, etc. .
  • the protective atmosphere is any one or a combination of at least two of nitrogen, helium and argon, 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 Or distilled water;
  • the temperature of the washing 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 fiber Prime.
  • 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 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 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 preparation method of the composite of the invention 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 complex of the present invention can also be prepared by various methods as follows:
  • 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 non-carbon non-carbon is controlled by the later pickling, washing and the like.
  • the content of oxygen element is based on which graphene is introduced so that the non-carbon non-oxygen element accounts for 0.5% by weight to 6% by weight of the composite.
  • the lignin is commercially available, carbonized at a high temperature under an inert gas or subjected to incomplete graphitization reaction, and then graphene is added, and nano P, Si, Ca, Al, Na, Fe, Ni, Mn, K, Mg are introduced later.
  • the combination of any three or more of Cr, S or Co and the content thereof is controlled to be 0.5 wt% to 6 wt%.
  • organic wastes such as phenolic resin foam sheets
  • graphene is introduced, and later introduced into nano P, Si, Ca, Al, Na, Fe, Ni, Mn, K, Mg, Cr, S or Co.
  • the combination of any three or more elements is controlled to a content of 0.5% by weight to 6% by weight.
  • Activated carbon and graphene are added to the nano-graphite, and a combination of any three or more elements of nano P, Si, Ca, Al, Na, Fe, Ni, Mn, K, Mg, Cr, S or Co is introduced later. Its content is controlled to be from 0.5% by weight to 6% by weight.
  • the carbon nanostructure-containing composite to be protected by the present invention is not limited to the above-exemplified production methods.
  • the far-infrared and antibacterial properties of the product containing the carbon nanostructure composite to be protected by the above method are superior to those of the methods 3 to 6 by the methods 1 and 2, but they are not necessary for preparing the downstream product. After activation or modification, it can be dispersed evenly and has a certain effect.
  • a third object of the present invention is to provide a polymer material comprising the above composite or a composite prepared by the above production method.
  • the invention also provides a preparation method of a polymer material, comprising:
  • the composite prepared by the above composite or the above preparation method is directly compounded with the polymer raw material without activation or modification of the composite;
  • the polymer raw material is any one or more of rubber, plastic, fiber, paint, adhesive, and polymer matrix composite.
  • the invention also provides the application of the above polymer materials in the fields of knitting, bedding, household, automobile products, furniture, pipes, profiles and garments.
  • the present invention provides a carbon nanostructure-containing composite containing graphene, amorphous carbon and non-carbon non-oxygen elements; the non-carbon non-oxygen element accounts for 0.5 wt% of the composite ⁇ 6wt%.
  • the invention obtains an excellent far-infrared effect and an antibacterial and antibacterial effect by controlling the content of non-carbon non-oxygen elements in the composite, and the normal emissivity of the far-infrared performance reaches 0.85 or more, and the antibacterial rate reaches 95% or more.
  • the carbon nanostructure-containing composite disclosed by the invention is applied to a polymer material in a low amount of addition, and the polymer material is modified without prior modification and activation treatment.
  • the invention overcomes the technical prejudation that needs to be purified for graphene in the prior art, and the higher the purity, the better the effect; and overcomes the prior art, when graphene is introduced into the polymer material, the graphene must be pretreated.
  • Technical problems such as activation, modification, and the like.
  • Example 1 is a transmission electron micrograph of a carbon nanostructure-containing composite prepared in Example 1 of the present invention.
  • Example 2 is a transmission electron micrograph of a carbon nanostructure-containing composite prepared in Example 2 of the present invention.
  • Example 3 is a transmission electron micrograph of a carbon nanostructure-containing composite prepared in Example 3 of the present invention.
  • the present invention provides a carbon nanostructure-containing composite comprising 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% by weight to 6% by weight of the composite.
  • the invention obtains an excellent far-infrared effect and an antibacterial and antibacterial effect by controlling the content of non-carbon non-oxygen elements in the composite, and the normal emissivity of the far-infrared performance reaches 0.85 or more, and the antibacterial rate reaches 95% or more.
  • the carbon nanostructure-containing composite disclosed by the invention is applied to a polymer material in the case of a low amount of addition, and the polymer material is modified without prior modification and activation treatment. It can achieve significant far-infrared performance and antibacterial performance.
  • the invention overcomes the technical prejudation that needs to be purified for graphene in the prior art, and the higher the purity, the better the effect; and overcomes the prior art, when graphene is introduced into the polymer material, the graphene must be pretreated.
  • Technical problems such as activation, modification, and the like.
  • the present invention provides a carbon nanostructure-containing composite comprising graphene, amorphous carbon and non-carbon non-oxygen elements;
  • the non-carbon non-oxygen element accounts for 0.5% by weight to 6% by weight of the composite, preferably 1.5% by weight to 5% by weight, more preferably 2% by weight to 5% by weight, still more preferably 2.3% by weight to 4.5% by weight;
  • the non-carbon non-oxygen element is present in an amount of 0.7 wt%, 1.1 wt%, 1.3 wt%, 1.6 wt%, 2 wt%, 2.8 wt%, 3.5 wt%, 4.2 wt%. 5.3 wt% or 5.8 wt%.
  • the non-carbon non-oxygen element in the composite includes Fe, Si, and Al elements; preferably further includes any one or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S, or Co;
  • Non-carbon non-oxygen element It is present in the form of any one of a simple substance and a compound, or a combination of at least two.
  • the compounds typically, but not exclusively, include carbides, oxides, and the like.
  • other elements contained may be a combination of P, Si, Fe, Al, and Ca, and a combination of Si, Fe, Ca, and Al, P. , a combination of Si, Fe, Al, Ca, Na, Cr, a combination of Si, Ca, Al, Na, Fe, Mn, K, a combination of P, Si, Al, Na, Fe, Ni, Ca, Si, Fe A combination of Al, Na, and Ni, a combination of P, Si, Al, Na, Fe, and K, a combination of Si, Fe, Ca, Al, Mn, and Cr.
  • the carbon nanostructure-containing composite prepared by the invention contains a plurality of components, and the interaction between the components is closely linked to play a synergistic role, so that the non-carbon non-oxygen content can be used for the composite.
  • the role is very important.
  • the content of carbon elements in the composite is ⁇ 80 wt%, preferably 85 wt% to 97 wt%, further preferably 90 wt% to 95 wt%; in some specific embodiments of the invention, the carbon element content is 82 wt%, 86 wt% %, 89 wt%, 91 wt%, 94 wt%, 97 wt% or 99 wt%.
  • the content of the non-carbon non-oxygen element and carbon element can be determined by elemental analysis.
  • the far-infrared detection normal emissivity of the carbon nanostructure-containing composite is greater than 0.80, preferably greater than 0.85, more preferably greater than 0.88; in some embodiments of the invention, the far-infrared detection normal emissivity is 0.81. 0.83, 0.84, 0.86, 0.87, 0.88, 0.89, 0.91, 0.92, 0.93.
  • the composite has a ratio of carbon element G peak to peak D height in the Raman spectrum of greater than 1, preferably from 1 to 20, more preferably from 2 to 20, still more preferably from 3 to 20, still more preferably from 5 to 20, particularly preferably 7 -20, most preferably 10-20; in some embodiments of the invention, the ratio is 2, 5, 7, 8, 10, 12, 13, 16, 18.
  • 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 provided by the present invention is a carbon-based composite containing an impurity element, wherein the carbon element is mainly present in the form of sp2 hybridization.
  • the graphene content is 10% or more, preferably 10% to 80%, based on the total amount of carbon.
  • the graphene has a six-membered ring-shaped honeycomb sheet structure of carbon having a thickness of 100 nm or less, preferably a six-membered ring-shaped honeycomb sheet structure having carbon having a thickness of 20 nm or less, and more preferably having a number of layers of 1 to 10 layers of carbon. Any one or a combination of at least two of the six-membered ring-shaped honeycomb sheet structures is preferably one of a single layer, a double layer, or a three to ten layer structure, or a combination of at least two.
  • the six-membered ring-shaped honeycomb sheet structure of carbon in the graphene exhibits microscopically any one or a combination of at least two of warp, curl and folded conformations.
  • 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 six-membered ring-shaped honeycomb sheet structure is called a biomass graphene nanosheet layer; the six-membered loop honeycomb sheet layer structure with a layer number of 1 to 10 layers of carbon, called graphene, is prepared by using biomass as a carbon source.
  • the six-membered ring-shaped honeycomb sheet structure having a layer of 1 to 10 layers of carbon is called biomass graphene.
  • the carbonaceous material having the above structure is referred to as having a graphene structure. See Figures 1-3 provided by the present invention for details.
  • Single-layer graphene A single layer of carbon atoms formed by a carbon atom combined with three surrounding carbon atoms to form a honeycomb structure.
  • Layer Graphene A two-dimensional carbon material consisting of 3-10 layers of SP2 hybridized carbon monolayer.
  • Graphene nanosheet a two-dimensional carbon nanomaterial composed of a single layer or a small layer of graphene, having a layer number of less than 10 layers and a transverse dimension of the sheet greater than 100 nm.
  • Biomass Graphene A composite carbon material containing a single layer of graphene, a small layer of graphene, a graphene nanosheet structure, and a metal/nonmetal compound, prepared from biomass.
  • the non-carbon non-oxygen element is adsorbed on the surface or inside of the carbon nanostructure in any one of a simple substance, an oxide, or a carbide, or a combination of at least two.
  • a non-carbon non-oxygen element is introduced through a carbon source;
  • the carbon source is preferably a biomass carbon source, and the biomass carbon source is selected from any of plant and/or agricultural and forestry waste.
  • One type or a combination of at least two types preferably one of a combination of softwood, hardwood, woodwood, and agricultural and forestry waste, or a combination of at least two.
  • 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 stalk, husk and reed, or at least 2 species.
  • a combination of corn cobs is preferred.
  • the biomass carbon source is cellulose and/or lignin, preferably cellulose, further preferably porous cellulose.
  • the source of the porous cellulose of the present invention is not particularly limited and may be a porous cellulose well known in the art.
  • the porous cellulose is 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 at least two of plant and/or agricultural and forestry waste; preferably any one or a combination of at least two of agricultural and forestry waste.
  • 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.
  • Preferred jade Rice core 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.
  • the amorphous carbon is a two-dimensional graphite layer or a three-dimensional graphite crystallite, and a large number of irregular bonds exist on the edge of the crystallite.
  • 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 detection method can be as follows:
  • the method for determining the non-carbon non-oxygen element is not limited in the present invention, and any method known in the art or a new measurement 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 "one of the methods for determining the content of non-carbon non-oxygen elements" is measured, and in the examples of the present invention, "one of the non-carbon non-oxygen element content determination methods" is used for the measurement.
  • the infrared detection data of the composite is based on: GBT 7286.1-1987 "Test method for full normal emissivity of metal and non-metal materials";
  • the bacteriostatic test data of the complex is based on: according to the test method of GB/T20944.3-2008, taking Staphylococcus aureus as an example.
  • the sample was placed in a sample well of a powder resistivity meter, pressed into a sheet shape using a pressure of 180 kg, and then the height coefficient of the sample was set by a four-probe tester to calculate the conductivity of the sample.
  • the sample was attached to a SiO 2 /Si substrate, and the sample was subjected to Raman imaging using an excitation wavelength of 532 nm or 655 nm, and the D peak, the G peak, and the 2D peak of the graphene sample were detected.
  • the peak thickness of the graphene and the degree of SP2 hybridization can be determined by the peak shape.
  • the present invention also provides a polymer material comprising the above composite or the composite prepared by the above preparation method.
  • the polymer material further includes any one or more of rubber, plastic, fiber, paint, adhesive or polymer matrix composite.
  • the polymeric material is a polyester, polyurethane or viscose fiber.
  • the invention also provides a preparation method of the above polymer material, comprising:
  • the composite prepared by the above composite or the above preparation method is directly compounded with the polymer raw material without activation or modification of the composite;
  • the polymer raw material is any one or more of rubber, plastic, fiber, paint, adhesive, and polymer matrix composite.
  • the invention also provides the application of the above polymer materials in the fields of knitting, bedding, household, automobile products, furniture, pipes, profiles and garments.
  • the above polymer material is used to make a product, which includes fabric, film, pillow, mattress, cushion, cushion, sofa, waist protector, insole, bra, car seat, toilet seat cushion, hand warmer , pipes, furniture, profiles.
  • a product which includes fabric, film, pillow, mattress, cushion, cushion, sofa, waist protector, insole, bra, car seat, toilet seat cushion, hand warmer , pipes, furniture, profiles.
  • the above products can be prepared by prior art processes.
  • the carbon nanostructure-containing composite according to the present invention can be well compounded with a polymer material, and can be well dispersed in a polymer material without first modifying or activating it, and plays a proper role. Roles such as far infrared performance and antibacterial properties.
  • the preparation method of the porous cellulose can be specifically referred to the patent document disclosed as CN104016341A, specifically:
  • the obtained lignocellulose is immersed in acidic sulfite for 1 h at 70 ° C to obtain porous cellulose; wherein the acid is sulfuric acid, the sulfite is magnesium sulfite, and the quality of the sulfuric acid is the wood 4% of the cellulose mass, liquid to solid ratio of 2:1; ready for use after preparation.
  • the preparation method of the conventional cellulose can be specifically referred to the patent document disclosed as CN103898782A, specifically:
  • 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, and 1 wt% of hydrogen peroxide (H2O2), which is the raw material of wheat straw, is added as a catalyst before the feedstock is added.
  • the reaction temperature is controlled at 120 ° C, the reaction is carried out for 30 min, and the solid-liquid mass ratio is 1:10.
  • the reaction solution 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 of 75 wt% of the organic acid solution is added to the wheat straw.
  • step (3) collecting the liquid obtained by the first and second solid-liquid separation, performing high-temperature and high-pressure evaporation at 120 ° C, 301 kPa until evaporation to dryness, and condensing the obtained formic acid and acetic acid vapor back to the reaction kettle of the step (1). Used as a cooking liquor for the cooking of step (1);
  • step (5) collecting the liquid obtained by the third solid-liquid separation, performing water and acid distillation, and returning the obtained mixed acid solution to the reaction vessel of the step (1) for use as a cooking liquid for the cooking of the step (1).
  • Water is used in step (5) to act as water for washing;
  • 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. Controlling the reaction temperature at 165 ° C, reacting for 10 min, the liquid-solid mass ratio of the mixed acid solution of formic acid and acetic acid to the biomass raw material is 1:20, and the obtained reaction liquid is subjected to the first solid-liquid separation;
  • the solid separated in the step (1) is added to a concentration of 90% formic acid and a concentration of 5% acetic acid and 5% water of an organic acid solution for acid washing at a temperature of 60 to 80 ° C, a washing time of 0.5. ⁇ 1h, and the reaction liquid is subjected to a second solid-liquid separation, and the separated solid is washed with water to obtain a solution.
  • Required cellulose
  • the concentrate obtained in the step (3) is diluted with water, the mass ratio of the auxiliary agent to the concentrated liquid is 2:1, the temperature is controlled at 60-70 ° C for 0.5-1 h, and the third solid-liquid is performed. Separation, the obtained solid was added with water (mass ratio of water to the solid was 3:1), and stirred at 75-80 ° C for 2-3 h for washing with water to deesterify to obtain the desired lignin.
  • a composite of carbon nanostructures obtained by the following method:
  • the precursor is heated to 280 ° C at a rate of 3 ° C / min, and kept for 2 h, then the temperature is programmed to 950 ° C, and kept for 3 h to obtain a crude product; the temperature rising rate of the programmed temperature 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 peak of D was 1.1;
  • the carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, Fe, and Mg elements.
  • a composite of carbon nanostructures obtained by the following method:
  • the precursor is heated to 350 ° C at a rate of 5 ° C / min, kept for 2 h, then programmed to 1050 ° C, 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 20 ° C / min;
  • 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 carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, Fe, Mg, and S elements.
  • a composite of carbon nanostructures obtained by the following method:
  • the precursor is heated to 350 ° C at a rate of 5 ° C / min, kept for 2 h, then programmed to 1050 ° C, 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 20 ° C / min;
  • 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 carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, Fe, and Ni elements.
  • a composite of carbon nanostructures obtained by the following method:
  • the precursor is heated to 350 ° C at a rate of 5 ° C / min, kept for 2 h, then programmed to 1000 ° C, 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 20 ° C / min;
  • 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 6.8;
  • the carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, and K elements.
  • a composite of carbon nanostructures obtained by the following method:
  • the precursor is heated to 300 ° C at a rate of 4 ° C / min, kept for 3 h, then programmed to 1000 ° C, 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 17 ° C / min;
  • the carbon nanostructure-containing composite prepared in Example 5 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 2.1;
  • the carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, Fe, Mg, Ni, and K elements.
  • a composite of carbon nanostructures obtained by the following method:
  • the precursor is heated to 300 ° C at a rate of 4 ° C / min, kept for 3 h, then programmed to 1000 ° C, 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 17 ° C / min;
  • the carbon nanostructure-containing composite prepared in Example 6 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 13.2;
  • the carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, Fe, K, and Mg elements.
  • a composite of carbon nanostructures obtained by the following method:
  • the precursor is heated to 300 ° C at a rate of 4 ° C / min, kept for 3 h, then programmed to 1000 ° C, 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 17 ° C / min;
  • the carbon nanostructure-containing composite prepared in Example 7 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 15;
  • Carbon-containing nanostructured composites were detected using one of the "non-carbon non-oxygen element content determination methods" It mainly contains P, Si, Ca, Al, Na, Fe, Mg, Mn, and S elements.
  • Example 6 The difference from Example 6 is that lignin is used instead of poplar cellulose.
  • the carbon nanostructure-containing composite prepared in Example 8 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 10.8;
  • the carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, Fe, K, Mg, Co elements.
  • Example 7 The difference from Example 7 was that the washing was carried out for 4 h with a 10% strength NaOH solution prior to pickling.
  • 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 15;
  • the carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, and Cr elements.
  • Example 2 The difference from Example 1 is that the catalyst used is changed from 0.1% by weight to 8% by weight.
  • 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 16.2;
  • the carbon-containing nanostructure-containing composite contains P, Si, Ca, Al, Na, Fe, and Mg elements.
  • Example 1 The difference from Example 1 is that the catalyst used is changed from 0.1% by weight to 10% by weight.
  • the carbon nanostructure-containing composite prepared in Example 11 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 18;
  • the carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, Fe, Mg, and K elements.
  • Example 2 The difference from Example 1 was that the catalyst used was changed from 0.1% by weight to 13% by weight.
  • 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 20;
  • the carbon-containing nanostructure-containing composite mainly contains P, Si, Ca, Al, Na, Fe, and Mg elements.
  • 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 by the comparative example was subjected to Raman spectroscopy, and the results showed that the height ratio of G peak and D peak was 13;
  • porous graphene mainly contained P, Si, Ca, Al, Na, Fe, Mg, and K elements.
  • 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. Drying for 12 hours to obtain graphite oxide;
  • 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 obtained phosphorus-doped graphene mainly contained P, Si, Ca, Fe, Mn, Mg, and S elements.
  • the graphene prepared in Comparative Example 3 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 18.
  • the precursor is heated to 400 ° C at a rate of 8 ° C / min, kept for 2 h, then programmed to 800 ° C, 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 25 ° C / min;
  • the composite prepared in Comparative Example 4 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 0.3.
  • the first non-carbon non-oxygen element content determination method is used to detect that the composite mainly contains P, Si, Ca, Al, Na, Fe, and Mg elements.
  • a composite containing carbon nanostructures is obtained by the following method:
  • 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 13 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 composite containing carbon nanostructures mainly contains P, Si, Ca, Al, Fe, and Mg elements, and the specific content is shown in Table 2, Table 2 is the same.
  • Table 2 is the same. The performance test results of the examples and comparative examples were applied.
  • Fig. 1 is a transmission electron micrograph of the carbon nanostructure-containing composite prepared in Example 13 of the present invention.
  • a composite containing carbon nanostructures is obtained by the following method:
  • the carbon nanostructure-containing composite prepared in Example 14 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 the D peak was 3.5;
  • the composite containing carbon nanostructures mainly contains P, Si, Ca, Al, Fe, and Mg elements, and the specific content is shown in Table 2, Table 2 is the same.
  • Table 2 is the same. The performance test results of the examples and comparative examples were applied.
  • a composite containing carbon nanostructures is obtained by the following method:
  • the carbon nanostructure-containing composite prepared in Example 15 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 4.5;
  • the first non-carbon non-oxygen element content determination method is used to detect that the carbon nanostructure-containing composite mainly contains P, Si, Ca, Al, Fe, and Mg elements, and the specific content thereof is shown in Table 2.
  • Table 2 is the present application. Performance test results of the examples and comparative examples.
  • Example 13 The corncob cellulose of Example 13 was replaced with reed cellulose.
  • the carbon nanostructure-containing composite prepared in Example 16 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 4.8;
  • the composite containing carbon nanostructures mainly contains Si, Ca, Al, Fe, Mg, and S elements, and the specific content thereof is shown in Table 2, Table 2 is the use of "non-carbon non-oxygen element content determination method". The performance test results of the examples and comparative examples were applied.
  • Fig. 2 is a transmission electron micrograph of the carbon nanostructure-containing composite prepared in Example 16 of the present invention.
  • Example 13 The corncob cellulose of Example 13 was replaced with poplar cellulose.
  • the carbon nanostructure-containing composite prepared in Example 17 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 4.6;
  • the composite containing carbon nanostructures mainly contains P, Si, Al, Na, Fe, and Ni elements, and the specific content thereof is shown in Table 2, Table 2 is the use of "non-carbon non-oxygen element content determination method". The performance test results of the examples and comparative examples were applied.
  • Fig. 3 is a transmission electron micrograph of the carbon nanostructure-containing composite prepared in Example 17 of the present invention.
  • Example 13 The corncob cellulose of Example 13 was replaced with corncob lignin.
  • the carbon nanostructure-containing composite prepared in Example 18 was subjected to Raman spectroscopy, and the results showed that the G peak and the D peak height ratio were 2.8;
  • the composite containing carbon nanostructures mainly contains P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, and K elements, and the specific content thereof is determined by "one of the non-carbon non-oxygen element content determination methods". See Table 2, Table 2 for performance test results of the examples and comparative examples of the present application.
  • the composite containing carbon nanostructures mainly contains P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, and K elements, and the specific content thereof is determined by "one of the non-carbon non-oxygen element content determination methods". See Table 2, Table 2 for performance test results of the examples and comparative examples of the present application.
  • 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.
  • the composite containing carbon nanostructures mainly contains P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, and K elements, and the specific content thereof is determined by "one of the non-carbon non-oxygen element content determination methods". See Table 2, Table 2 for performance test results of the examples and comparative examples of the present application.
  • a nano-material containing carbon nanostructures is obtained by using nanometer materials such as nanometer phosphorus pentoxide, nano silicon, nano calcium carbonate, nano aluminum oxide, nano iron, and nano magnesium.
  • the composite containing carbon nanostructures mainly contains P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, and K elements, and the specific content thereof is determined by "one of the non-carbon non-oxygen element content determination methods". See Table 2, Table 2 for performance test results of the examples and comparative examples of the present application.
  • Adding activated carbon and graphene to nano-graphite, introducing graphene on the basis of this, and introducing P, Si, Ca, Al, Fe, Mg elements, specifically nano phosphorus pentoxide, nano silicon powder, nano calcium carbonate, nano A nanomaterial of aluminum oxide, nano iron, and nano magnesium provides a composite containing carbon nanostructures.
  • the composite containing carbon nanostructures mainly contains P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, and K elements, and the specific content thereof is determined by "one of the non-carbon non-oxygen element content determination methods". See Table 2, Table 2 for performance test results of the examples and comparative examples of the present application.
  • the corn cob is hydrolyzed in nitric acid for 10 h at 180 ° C to obtain lignocellulose, the mass of the nitric acid being 20% of the mass of the corn cob;
  • the lignocellulose was subjected to an acidic sulfite treatment at 180 ° C for 6 hours to obtain a porous cellulose.
  • the pH of the acidic sulfite treatment was 7, the acid was sulfuric acid, and the sulfite was sulfite. Is sodium sulfite, the mass of the sulfuric acid is 30% of the mass of the lignocellulose, the liquid to solid ratio is 20:10;
  • the porous cellulosic channel was bleached with hydrogen peroxide having a mass of 5% by mass of the porous cellulosic, a bleaching temperature of 100 ° C for the hydrogen peroxide bleaching, and a bleaching time of 5 h.
  • the prepared porous cellulose and ferric nitrate were subjected to catalytic treatment at 180 ° C for 10 hours, and the mass ratio of the ferric nitrate to the porous cellulose was 2:1; and the obtained catalytically treated product was at 120 ° C. Drying down gives a first intermediate having a water content of less than 5% by weight.
  • the first intermediate product was placed in a carbonization furnace, and oxygen gas was introduced into the carbonization furnace as a shielding gas at a gas permeation amount of 800 mL/min, and the first intermediate product was taken at a rate of 20 ° C/min.
  • the cooled fourth intermediate product was washed in an aqueous solution of 55% by mass of sodium hydroxide at 120 ° C for 24 hours to obtain a first washed product; at 150 ° C, the first washed product was in quality.
  • the second washing product was obtained by washing in a 10% aqueous hydrochloric acid solution for 24 hours to obtain a second washing product; the second washing product was washed with steamed water to neutrality and then dried to obtain graphene.
  • the graphene prepared by 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 heated at a temperature increase rate of 15 ° C/min. To 900 ° C, keep After 2 h, it was then cooled to room temperature in an argon atmosphere at a flow rate of 300 mL/min to prepare a phosphorus-doped graphene.
  • the nitrogen-doped graphene prepared in Comparative Example 2 was subjected to Raman spectroscopy, and the results showed G peak and D peak.
  • the height ratio is 5;
  • the activated carbon/graphene composite was prepared from organic biomass and prepared by the following steps:
  • the activated carbon/graphene composites mainly contain P, Si, Ca, Fe, Mg, and Mn elements, and the specific contents thereof are shown in Table 1, Table 1 by using "one of the non-carbon non-oxygen element content determination methods". It is the performance test result of the examples and comparative examples of the present application.
  • Examples 1-12 and Comparative Examples 1-4 are shown in Table 1, and Examples 13-22 and Comparative Examples 5-7 are shown in Table 2.
  • the far-infrared and antibacterial effects are not very good; although the phosphorus element exceeds 0.5 wt% in Comparative Example 2, it is deliberately introduced during the preparation process, and the far-infrared and antibacterial properties are not ideal; the first in Comparative Example 3 The content of non-carbon non-oxygen elements is almost zero, the far-infrared effect is very poor, and the antibacterial effect is ok.
  • Example The sum of non-carbon non-oxygen content, wt% Far infrared (normal emissivity) Antibacterial rate% Example 13 4.5 0.92 95
  • Example 15 4.6 0.92 98
  • Example 16 1.3 0.86
  • Example 17 3.96 0.88
  • Example 18 5.24 0.89
  • Example 19 1.6 0.81 85
  • Example 20 2.3 0.82
  • Example 21 2.8 0.82 89
  • Example 22 4.6 0.84 92 Comparative example 5 0.3 0.77 66
  • the present invention obtains an excellent far-infrared effect and an antibacterial bacteriostatic effect by controlling the content of non-carbon non-oxygen elements in the composite.
  • the corn core is used as a raw material, and after being alkalized, pressed, pulverized, aged, yellowed, dissolved, and matured, a viscose liquid having a solid content of 8% is prepared; and the carbon nanostructure-containing composite prepared in Example 1 is prepared.
  • the graphene structure dispersion liquid is dispersed by 5 times mass of water, and then the graphene structure dispersion liquid is blended with the viscose liquid, and stirred by a high speed mixer for 1 hour to form a blend solution, and the amount of the carbon nanostructure-containing composite is cellulose. 3% of the mass. Filtration, defoaming, and then spinning, desulfurization, water washing, and drying to obtain functional viscose fibers.
  • 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 the functional fibers were tested as follows: the far-infrared normal emissivity of the viscose fiber was 0.92, and the antibacterial property was 95%.
  • the added carbon nanostructure-containing composite can achieve good results without being activated or modified in advance and directly utilized.
  • the infrared detection data is based on: According to the National Textile Products Quality Supervision and Inspection Center, 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 method includes the following steps:
  • step (3) The mixture of the step (2) is poured into a mold to be foamed and solidified to obtain a functional polyurethane foam.
  • the far-infrared and antibacterial properties of the functional polyurethane foam were tested. As a result, the far-infrared normal emissivity of the polyurethane foam was 0.88, and the antibacterial property was 90%.
  • the added carbon nanostructure-containing composite can achieve good results without being activated or modified in advance and directly utilized.
  • Antibacterial test data according to: GB/T 31402-2015 "plastic and plastic surface antibacterial performance test method", taking Staphylococcus aureus as an example.
  • Example 1 100 g of the carbon nanostructure-containing composite prepared in Example 1 was mixed with 8.52 kg of PTA and 3.5 L of ethylene glycol, and ball-milled for 20 min, directly introduced into a beating kettle for 30 min, and polymerized by using three-pot PET. The process proceeds, the polymerization is carried out, and the polymerization is completed to obtain a melt;
  • the melt is discharged at 40 ° C cooling water at a draw speed of 0.5 m/s, and directly granulated to obtain a functional PET material.
  • the far-infrared and antibacterial properties of the functional polyester materials were tested. The results showed that the far-infrared normal emissivity of the PET material was 0.89 and the antibacterial property was 91%.
  • the added carbon nanostructure-containing composite can achieve good results without being activated or modified in advance and directly utilized.
  • the infrared detection data is based on: GBT 7286.1-1987 "Test method for full normal emissivity of metal and non-metal materials";
  • Antibacterial test data according to: GB/T 31402-2015 "plastic and plastic surface antibacterial performance test method", taking Staphylococcus aureus as an example.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

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Abstract

提供一种含碳纳米结构的复合物及其制备方法、以及含有该复合物的高分子材料及其制备方法和应用。该复合物含有石墨烯、无定形碳和非碳非氧元素；非碳非氧元素占复合物的0.5wt％～6wt％。通过控制复合物中非碳非氧元素含量，其远红外性能的法向发射率达到0.85以上，抑菌率达到95％以上。同时，将该复合物以较低的加入量应用于高分子材料中，不需对其进行前期改性和活化处理，就可以带来显著的远红外性能和抗菌杀菌性能。

Description

一种含碳纳米结构的复合物、使用其的高分子材料及制备方法 技术领域
本发明涉及材料技术领域，尤其涉及一种复合物及其制备方法以及一种高分子材料及其制备方法。
背景技术
纳米碳材料是指分散相尺度至少有一维小于100nm的碳材料。分散相既可以由碳原子组成，也可以由异种原子(非碳原子)组成，甚至可以是纳米孔。纳米碳材料主要包括碳纳米管，碳纳米纤维，纳米碳球及石墨烯。
石墨烯是一种由碳原子构成的单层片状结构的材料。石墨烯几乎是完全透明的，只吸收2.3％的光；导热系数高达5300W/m·K，高于碳纳米管和金刚石；石墨烯常温下的电子迁移率超过15000cm2/V·s，超过纳米碳管或硅晶体；石墨烯的电阻率只有10-8Ω·m，比铜或银更低，为世上电阻率最小的材料。由于石墨烯具有透明性好，电阻率小，电子迁移速度快等优点，可用来制造透明触控屏幕、光板、以及太阳能电池。
目前，石墨烯的制备方法主要有机械剥离法、化学气相沉积法、热解外延生长法等，其中，化学气相沉积法制备石墨烯简单易行，可以得到大面积高质量的石墨烯。
现有技术虽然有用生物质原料制备石墨烯的记载，但是都偏重于得到纯度较高的石墨烯，并且偏向于石墨烯的sp2杂化程度比较高、片层薄、导电率高的特点，并且现有技术中，对于石墨烯的技术认知为石墨烯纯度越高越好。
另一方面，利用现有技术的制备方法制备得到的石墨烯，在应用中，尤其是将其引入高分子材料，对高分子材料进行改性的应用中，为了使其和高分子材料更好地结合，一般需要对石墨烯进行前期改性或活化等处理，使石墨烯表面具有足够的活性官能团或者能够使石墨烯更好地与高分子材料进行复合，以实现石墨烯能够带来的特点。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种复合物及其制备方法以及一种高分子材料及其制备方法，制备的复合物具有优异的远红外效果和抗菌抑菌效果。
本发明的目的之一是提供一种含碳纳米结构的复合物，含有石墨烯、无定形碳和非碳非氧元素；
所述非碳非氧元素包括Fe、Si和Al元素；
所述非碳非氧元素含量为复合物的0.5wt％～6wt％。
对于所述含碳纳米结构的复合物，典型但非限制性的可以是具有表a所述的性能的物质①、物质②、物质③或物质④中的任意1种或至少2种的组合：
表a
Figure PCTCN2016099750-appb-000001
表a中，IG/ID为拉曼光谱中G峰和D峰的峰高比值。
本领域技术人员应该明了，对于表a所列举的含碳纳米结构的复合物的性能指标，均指含碳纳米结构的复合物的粉体的指标，若所述含碳纳米结构的复合物为浆料，则上述指标为制备浆料前粉体的指标。
当所述含碳纳米结构的复合物为粉体时，除可以具有表a所述的性能指标以外，所述含碳纳米结构的复合物粉体还具有如下性能：
黑色粉末，细度均匀，无明显大颗粒，含水量≤3.0％，粒度D90≤10.0μm，pH为5.0～8.0，表观密度0.2～0.4g/cm3。
当所述含碳纳米结构的复合物为浆料时，其为将含碳纳米结构的复合物分散在溶剂中的产品，除可以具有表a所述的性能指标以外，所述含碳纳米结构的复合物浆料还具有如下性能：
固含量1.0～10.0％，粒度D50≤0.7um，pH为8.0～10.0，Zeta电位≤-10mV，粘度为5.0～8.0mpa·s。
优选地，所述非碳非氧元素还包括P、Ca、Na、Ni、Mn、K、Mg、Cr、S和Co中的任意一种或多种。
优选地，所述复合物在拉曼光谱下碳元素G峰与D峰峰高比值为1～20，例如2、5、7、8、10、12、13、16、18等。
拉曼光谱下碳元素G峰体现了sp2杂化程度；D峰体现了晶格缺陷，例如sp3的碳结构。
本发明提供的含碳纳米结构的复合物是一种以碳元素为主的含有杂质元素的复合物，其中碳元素主要以sp2杂化的形式存在。
优选地，所述复合物在拉曼光谱下碳元素G峰与D峰峰高比值为2～20，优选3～20，进一步优选5～20，特别优选7～20，最优选10～20。
所述复合物在拉曼光谱下还存在2D峰。
2D峰表征了片层结构的厚薄，2D峰强度越高，代表其片层越薄。
优选地，所述非碳非氧元素还包括P、Ca、Na。
优选地，所述非碳非氧元素还包括Ni、Mn、K、Mg、Cr、S和Co中的任意一种或至少两种的组合。
本发明提供的含碳纳米结构的复合物中，除了碳元素和氧元素，所含有的其他元素可以是P、Si、Ca、Al、Na、Fe的组合，P、Si、Ca、Al、Na、Mn的组合，P、Si、Ca、Al、Na、Cr的组合，P、Si、Ca、Al、Na、Fe、Mn、K的组合，P、Si、Ca、Al、Na、Fe、Ni的组合，P、Si、Ca、Al、Na、Ni的组合，P、Si、Ca、Al、Na、Fe、K的组合，P、Si、Ca、Al、Na、Mn、Cr的组合等。
优选地，所述非碳非氧元素以单质和/或化合物的形式存在。
优选地，所述非碳非氧元素以单质、氧化物或碳化物中的任意1种或几种的形式吸附在碳纳米结构的表面和/或内部，具体来说所述非碳非氧元素为金属化合物和/或非金属化合物。
优选地，所述复合物中碳元素含量≥80wt％，例如82wt％、86wt％、89wt％、91wt％、94wt％、97wt％、99wt％等，优选85～97wt％，进一步优选90～95wt％。
复合物中碳元素结构80wt％以上为石墨化结构，优选的90wt％以上为石墨化结构；所述石墨化结构的石墨化度不同，所谓石墨化程度不同即结晶度不同，但都已石墨化。
优选地，所述非碳非氧元素占复合物的1.5wt％～5wt％，例如2wt％、2.5wt％、2.8wt％、3.3wt％、3.6wt％、4.3wt％、4.8wt％等。
优选地，所述石墨烯具有厚度在100nm以下的碳的六元环蜂窝状片层结构，优选具有厚度在20nm以下的碳的六元环蜂窝状片层结构，进一步优选具有层数为1～10层碳的六元环蜂窝状片层结构中的任意1种或至少2种的组合，优选单层、双层或3～10层结构中的任意1种或至少2种的组合。
优选地，所述复合物中碳的六元环蜂窝状片层结构微观上呈现翘曲、卷曲或折叠构象中的任意1种或至少2种的组合。
优选地，所述含碳纳米结构的复合物中，非碳非氧元素P、Si、Ca、Al和Na通过碳源引入；所述碳源优选生物质碳源，生物质资源选自植物和/或农林废弃物中的任意1种或至少2种的组合；优选针叶木、阔叶木、林叶木或农林废弃物中的任意1种或至少2种的组合。
优选地，所述农林废弃物选自玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆、果壳和芦苇中的任意1种或至少2种的组合，优选玉米芯。
本发明的目的之二是提供含碳纳米结构的复合物的制备方法。
作为本发明所述含碳纳米结构的复合物的制备方法的方法1，具体步骤包括：
(1)在催化剂的作用下，将生物质碳源进行催化处理，得到前驱体；
(2)在保护性气体的条件下，将所述前驱体在140℃～180℃保温1.5h～2.5h，得到第一中间体；
(3)在保护性气体的条件下，将所述第一中间体升温至350℃～450℃保温3h～4h，得到第二中间体；
(4)在保护性气体的条件下，将所述第二中间体升温至1100℃～1300℃保温2h～4h，得到第三中间体；
(5)将所述第三中间体依次碱洗、酸洗、水洗，得到复合物；
所述步骤(3)、(4)中的升温速率为14℃/min～18℃/min。
在所述方法1中，具体地：
首先混合生物质碳源和催化剂，搅拌进行催化处理后，干燥得到前驱体；
然后在保护性气氛中，将前驱体在140～180℃，保温1.5～2.5h，得到第一中间体；在本发明的某些具体实施例中，所述温度为142℃、148℃、155℃、1600℃、172℃或178℃；所述保温时间为1.6h、1.8h、2h、2.2h或2.4h。
之后程序升温至350～450℃，保温3～4h，得到第二中间体；在本发明的某些具体实施例中，所述温度为360℃、370℃、380℃、390℃、410℃、420℃、430℃或440℃；所述保温时间为3.1h、3.3h、3.5h、3.8h或3.9h。
然后再升温至1100～1300℃，保温2～4h，得到第三中间体，即产物粗品；在本发明的某些具体实施例中，所述温度为1130℃、1170℃、1210℃或1280℃；所述时间为2.2h、2.4h、2.6h、2.8h、3.0h、3.2h、3.4h、3.6h或3.8h。
所述程序升温的升温速率为14℃/min～18℃/min，在本发明的某些具体实施例中，所述升温速率为15℃/min、16℃/min或17℃/min。
最后将第三中间体(即产物粗品)碱洗、酸洗、水洗后，得到复合物。
本发明中，所述生物质碳源和催化剂的质量比为1∶(0.5～5)，优选1∶(1～3)；在本发明的某些具体实施例中，所述比例为1∶0.5、1∶1或1∶3。
本发明中，所述催化剂选自锰的卤素化合物、含铁化合物、含钴化合物和含镍化合物中的任意1种或至少2种的组合。
优选地，所述含铁化合物选自铁的卤素化合物、铁的氰化物和含铁酸盐中的任意1种或至少2种的组合。所述含铁酸盐为含有铁元素的有机酸的盐或含有铁元素的无机酸的盐。所述铁的卤素化合物可以是氯化铁和/或溴化铁。
优选地，所述含钴化合物选自钴的卤素化合物和含钴酸盐中的任意1种或至少2种的组合。所述含钴酸盐为含有钴元素的有机酸的盐或含有钴元素的无机酸的盐。所述钴的卤素化合物可以是氯化钴和/或溴化钴。
优选地，所述含镍化合物选自镍的氯化盐和含镍酸盐中的任意1种或至少2种的组合。所述含镍酸盐为含有镍元素的有机酸的盐或含有镍元素的无机酸的盐。所述镍的卤素化合物可以是氯化镍和/或溴化镍。
优选地，所述催化剂选自氯化铁、氯化亚铁、硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、铁氰化钾、亚铁氰化钾、三草酸合铁酸钾、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍和乙酸镍中的任意1种或至少2种的组合。
本发明所述催化剂的组合典型但非限制性的实例有氯化亚铁和硫酸铁的组合，铁氰化钾和三草酸合铁酸钾的组合，氯化钴、硝酸钴和氯化铁的组合，硫酸钴、乙酸钴和硝酸镍的组合，氯化铁、氯化钴和乙酸镍的组合。
所述搅拌进行催化处理的温度为150℃～200℃，例如160℃、170℃、180℃190℃等，时间≥4h，优选4h～14h，在本发明的某些具体实施例中，所述时间为4.2h、7h、9h、12h、16h、19h、23h。
优选地，所述前驱体中的水分含量为10wt％以下，在本发明的某些具体实施例中，所述水分含量为1wt％、2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、10wt％等。
优选地，所述保护性气氛为氮气、氦气、氩气中的任意1种或至少2种的组合，优选氮气。
优选地，所述酸洗使用浓度为3wt％～6wt％的盐酸水溶液，进一步优选浓度为5wt％的盐酸水溶液；所述水洗优选使用去离子水和/或蒸馏水；所述碱洗使用浓度为5wt％～15wt％的氢氧化钠水溶液，进一步优选浓度为10wt％的氢氧化钠水溶液。
优选地，所述洗涤的温度为55～65℃，例如56℃、57℃、58℃、60℃、63℃等，优选60℃。
所述生物质碳源为纤维素和/或木质素，优选纤维素，进一步优选多孔纤维素。
本发明所述多孔纤维素可以通过现有技术获得，典型但非限制性的获得多孔纤维素的现有技术有：例如专利公开号CN104016341A公开的方法制备多孔纤维素，采用CN103898782A公开的方法制备纤维素。
优选地，所述多孔纤维素通过如下方法获得：
将生物质资源进行酸水解得到木质纤维素，之后经过多孔化后处理得到多孔纤维素；可选地，多孔纤维素经漂白后使用。
所述生物质资源选自植物和/或农林废弃物中的任意1种或至少2种的组合；优选农林废弃物中的任意1种或至少2种的组合。
优选地，所述农林废弃物选自玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆和芦苇中的任意1种或至少2种的组合，优选玉米芯。
本发明所述生物质资源典型但非限制性的组合实例包括玉米杆和玉米芯的组合，甘蔗渣、高粱杆和木屑的组合，甜菜渣、甘蔗渣和玉米芯的组合、高粱杆、甜菜渣和木糖渣的组合等。
作为本发明所述含碳纳米结构的复合物的制备方法的方法2，具体步骤包括：
(1)混合生物质碳源和催化剂，搅拌进行催化处理后，干燥得到前驱体；
(2)保护性气氛中，将前驱体在280～350℃，例如282℃、288℃、295℃、300℃、332℃、340℃等，保温1.5～2.5h，例如1.6h、1.8h、2h、2.2h、2.4h等，之后程序升温至950～1050℃，例如960℃、970℃、980℃、990℃、1010℃、1020℃、1030℃、1040℃等，保温3～4h，例如3.1h、3.3h、3.5h、3.8h、3.9h等，得到粗品；所述程序升温的升温速率为15～20℃/min，例如16℃/min、18℃/min、19℃/min等；
(3)将粗品洗涤后，得到复合物。
本发明选择特定的程序升温步进温度(15～20℃/min)，和程序升温的起始温度(280～350℃)和保温时间，以及终点的保温温度(950～1050℃)和保温时间(3～4h)，
所述生物质碳源和催化剂的质量比为1∶0.1～10，例如1∶0.5、1∶1、1；3、1∶5、 1∶8、1∶9等，优选1∶0.5～5，进一步优选1∶1～3。
优选地，所述催化剂选自锰的卤素化合物、含铁化合物、含钴化合物和含镍化合物中的任意1种或至少2种的组合。
优选地，所述含铁化合物选自铁的卤素化合物、铁的氰化物和含铁酸盐中的任意1种或至少2种的组合。所述含铁酸盐为含有铁元素的有机酸的盐或含有铁元素的无机酸的盐。所述铁的卤素化合物可以是氯化铁和/或溴化铁等。
优选地，所述含钴化合物选自钴的卤素化合物和含钴酸盐中的任意1种或至少2种的组合。所述含钴酸盐为含有钴元素的有机酸的盐或含有钴元素的无机酸的盐。所述钴的卤素化合物可以是氯化钴和/或溴化钴等。
优选地，所述含镍化合物选自镍的氯化盐和含镍酸盐中的任意1种或至少2种的组合。所述含镍酸盐为含有镍元素的有机酸的盐或含有镍元素的无机酸的盐。所述镍的卤素化合物可以是氯化镍和/或溴化镍等。
优选地，所述催化剂选自氯化铁、氯化亚铁、硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、铁氰化钾、亚铁氰化钾、三草酸合铁酸钾、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍和乙酸镍中的任意1种或至少2种的组合。
本发明所述催化剂的组合典型但非限制性的实例有氯化亚铁和硫酸铁的组合，铁氰化钾和三草酸合铁酸钾的组合，氯化钴、硝酸钴和氯化铁的组合，硫酸钴、乙酸钴和硝酸镍的组合，氯化铁、氯化钴和乙酸镍的组合等。
所述搅拌进行催化处理的温度为150～200℃，例如160℃、170℃、180℃、190℃等，时间≥4h，例如4.2h、7h、9h、12h、16h、19h、23h等，优选4～14h。
优选地，所述前驱体中的水分含量为10wt％以下，例如1wt％、2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、1wt％等。
优选地，所述前驱体升温至280～350℃的升温速率为3～5℃/min，例如3.5℃/min、3.8℃/min、4.2℃/min、4.5℃/min、4.8℃/min等。
优选地，所述保护性气氛为氮气、氦气、氩气中的任意1种或至少2种的组合，优选氮气。
优选地，所述粗品洗涤为依次进行的酸洗和水洗；所述酸洗优选使用浓度为3～6wt％的盐酸，进一步优选浓度为5wt％的盐酸；所述水洗优选使用去离子水和/或蒸馏水；
优选地，所述洗涤的温度为55～65℃，例如56℃、57℃、58℃、60℃、63℃等，优选60℃。
所述生物质碳源为纤维素和/或木质素，优选纤维素，进一步优选多孔纤维 素。
本发明所述多孔纤维素可以通过现有技术获得，典型但非限制性的获得多孔纤维素的现有技术有：例如专利公开号CN104016341A公开的方法制备多孔纤维素，采用CN103898782A公开的方法制备纤维素。
优选地，所述多孔纤维素通过如下方法获得：
将生物质资源进行酸水解得到木质纤维素，之后经过多孔化后处理得到多孔纤维素；可选地，多孔纤维素经漂白后使用。
所述生物质资源选自植物和/或农林废弃物中的任意1种或至少2种的组合；优选农林废弃物中的任意1种或至少2种的组合。
优选地，所述农林废弃物选自玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆和芦苇中的任意1种或至少2种的组合，优选玉米芯。
本发明所述生物质资源典型但非限制性的组合实例包括玉米杆和玉米芯的组合，甘蔗渣、高粱杆和木屑的组合，甜菜渣、甘蔗渣和玉米芯的组合、高粱杆、甜菜渣和木糖渣的组合等。
本发明所述复合物的制备方法包括如下步骤：
(1’)将玉米芯进行酸水解得到木质纤维素，之后经过多孔化后处理得到多孔纤维素，将多孔纤维素漂白后备用；
(1)按质量比1∶0.5～1.5混合步骤(1’)多孔纤维素和催化剂，在150～200℃下搅拌进行催化处理4h以上后，干燥至前驱体水分含量低于10wt％，得到前驱体；
(2)保护性气氛中，以3～5℃/min速率将前驱体升温至280～350℃，保温2h，之后程序升温至950～1050℃，保温3～4h得到粗品；所述程序升温的升温速率为15～20℃/min；
(3)55～65℃下，将粗品经过浓度为5wt％的盐酸酸洗后，水洗得到复合物。本发明所述复合物还可以通过以下多种方法制备：
作为本发明所述含碳纳米结构的复合物的制备方法，还可以示例性的列举出如下的方法：
方式3：
利用生物质资源通过现有工艺制备得到活性炭，因为不同植物体内微量元素种类和含量是有很大区别的，所以通过后期的酸洗、水洗等步骤控制非碳非 氧元素的含量，在此基础上引入石墨烯，使非碳非氧元素占复合物的0.5wt％～6wt％。
方式4：
市场购得木质素，在惰性气体下高温炭化或者对其进行不彻底的石墨化反应，再加入石墨烯，后期引入纳米P、Si、Ca、Al、Na、Fe、Ni、Mn、K、Mg、Cr、S或Co中的任意3种及以上元素的组合并使其含量控制在0.5wt％～6wt％。
方式5：
对一些有机废料，例如酚醛树脂泡沫板，对其炭化后，引入石墨烯，后期引入纳米P、Si、Ca、Al、Na、Fe、Ni、Mn、K、Mg、Cr、S或Co中的任意3种及以上元素的组合并使其含量控制在0.5wt％～6wt％。
方式6：
向纳米石墨中加入活性炭和石墨烯，后期引入纳米P、Si、Ca、Al、Na、Fe、Ni、Mn、K、Mg、Cr、S或Co中的任意3种及以上元素的组合并使其含量控制在0.5wt％～6wt％。
本发明所要保护的含有碳纳米结构复合物不限于以上所列举的制备方法。
通过以上方法制备得到的本发明所要保护的含有碳纳米结构复合物的产品，远红外性能及抗菌性能以方法1和方法2得到的优于方法3～6，但是都可以在制备下游产品时不必经过活化或改性处理即可分散均匀，起到一定的效果。
本发明的目的之三是提供一种高分子材料，包括上述复合物，或上述制备方法制备得到的复合物。
本发明还提供了一种高分子材料的制备方法，包括：
将上述复合物，或上述制备方法制备得到的复合物直接与高分子原材料进行复合，无需对所述复合物进行活化或改性；
所述高分子原材料为橡胶、塑料、纤维、涂料、胶粘剂和高分子基复合材料中的任意一种或多种。
本发明还提供了上述高分子材料在针织、床上用品、家居、汽车制品、家具、管材、型材、服装领域的应用。
与现有技术相比，本发明提供了一种含碳纳米结构的复合物，含有石墨烯、无定形碳和非碳非氧元素；所述非碳非氧元素占复合物的0.5wt％～6wt％。本发明通过控制复合物中非碳非氧元素含量，获得了优异的远红外效果和抗菌抑菌效果，其远红外性能的法向发射率达到0.85以上，抑菌率达到95％以上。同时， 本发明公开的含有碳纳米结构的复合物，在加入量较低的情况下，应用于高分子材料中，对高分子材料进行改性，不需对其进行前期改性和活化处理，就可以实现带来显著的远红外性能和抗菌杀菌性能。既克服了现有技术中需要对石墨烯进行纯化，并且纯度越高效果越好的技术偏见；又克服了现有技术中，将石墨烯引入高分子材料中时，必须将石墨烯进行前处理，例如活化、改性等等的技术难题。
附图说明
图1是本发明实施例1制备的含有碳纳米结构的复合物的透射电镜图；
图2是本发明实施例2制备的含有碳纳米结构的复合物的透射电镜图；
图3是本发明实施例3制备的含有碳纳米结构的复合物的透射电镜图。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
本发明提供了一种含碳纳米结构的复合物，所述复合物含有石墨烯、无定形碳和非碳非氧元素；
所述非碳非氧元素包括Fe、Si和Al元素；
所述非碳非氧元素含量为复合物的0.5wt％～6wt％。
本发明通过控制复合物中非碳非氧元素含量，获得了优异的远红外效果和抗菌抑菌效果，其远红外性能的法向发射率达到0.85以上，抑菌率达到95％以上。同时，本发明公开的含有碳纳米结构的复合物，在加入量较低的情况下，应用于高分子材料中，对高分子材料进行改性，不需对其进行前期改性和活化处理，就可以实现带来显著的远红外性能和抗菌杀菌性能。既克服了现有技术中需要对石墨烯进行纯化，并且纯度越高效果越好的技术偏见；又克服了现有技术中，将石墨烯引入高分子材料中时，必须将石墨烯进行前处理，例如活化、改性等等的技术难题。
本发明提供了一种含碳纳米结构的复合物，所述复合物含有石墨烯、无定形碳和非碳非氧元素；
其中，所述非碳非氧元素占复合物的0.5wt％～6wt％，优选占1.5wt％～5wt％，更优选为2wt％～5wt％，进一步优选为2.3wt％～4.5wt％；在本发明的某些具体实施例中，所述非碳非氧元素的含量为0.7wt％、1.1wt％、1.3wt％、1.6wt％、2wt％、2.8wt％、3.5wt％、4.2wt％、5.3wt％或5.8wt％。
所述复合物中的非碳非氧元素包括Fe、Si和Al元素；优选还包括P、Ca、Na、Ni、Mn、K、Mg、Cr、S或Co中的任意一种或多种；所述非碳非氧元素 以单质、化合物中的任意1种或至少2种的组合的形式存在。所述化合物典型但非限制性的包括碳化物、氧化物等。
本发明提供的含碳纳米结构的复合物中，除了碳元素和氧元素，所含有的其他元素可以是P、Si、Fe、Al、Ca的组合，Si、Fe、Ca、Al的组合，P、Si、Fe、Al、Ca、Na、Cr的组合，Si、Ca、Al、Na、Fe、Mn、K的组合，P、Si、Al、Na、Fe、Ni的组合，Ca、Si、Fe、Al、Na、Ni的组合，P、Si、Al、Na、Fe、K的组合，Si、Fe、Ca、Al、Mn、Cr的组合等。
本发明制备得到的含碳纳米结构的复合物中含有多种成分，各成分之间的作用紧密相连，起到相互协同辅助的作用，因此非碳非氧元素含量对于复合物所能起到的作用是很重要的。
所述复合物中碳元素的含量≥80wt％，优选85wt％～97wt％，进一步优选90wt％～95wt％；在本发明的某些具体实施例中，所述碳元素的含量为82wt％、86wt％、89wt％、91wt％、94wt％、97wt％或99wt％。
本发明中，所述非碳非氧元素、碳元素的含量可以通过元素分析测定。
所述含有碳纳米结构的复合物远红外检测法向发射率大于0.80，优选大于0.85，更优选大于0.88；在本发明的某些具体实施例中，其远红外检测法向发射率为0.81、0.83、0.84、0.86、0.87、0.88、0.89、0.91、0.92、0.93。
所述复合物在拉曼光谱下碳元素G峰与D峰峰高比值大于1，优选为1～20，更优选为2～20，更优选3～20，进一步优选5～20，特别优选7～20，最优选10～20；在本发明的某些具体实施例中，所述比值为2、5、7、8、10、12、13、16、18。
拉曼光谱下碳元素G峰体现了sp2杂化程度；D峰体现了晶格缺陷，例如sp3的碳结构。
本发明提供的含碳纳米结构的复合物是一种以碳元素为主的含有杂质元素的复合物，其中碳元素主要以sp2杂化的形式存在。
本发明中，所述石墨烯含量为含碳总量的10％以上，优选10％～80％。
所述石墨烯具有厚度在100nm以下的碳的六元环蜂窝状片层结构，优选具有厚度在20nm以下的碳的六元环蜂窝状片层结构，进一步优选具有层数为1～10层碳的六元环蜂窝状片层结构中的任意1种或至少2种的组合，优选单层、双层或3～10层结构的中的任意1种或至少2种的组合。
优选地，所述石墨烯中碳的六元环蜂窝状片层结构微观上呈现翘曲、卷曲和折叠构象中的任意1种或至少2种的组合。
关于复合物中的片层结构的微观形貌典型的可以通过电子显微镜观察获得，可以是透射电镜或扫描电镜。
层数多于10层，厚度在100nm以内碳的六元环蜂窝状片层结构，称为石墨烯纳米片层，以生物质为碳源制备的层数多于10层，厚度在100nm以内碳的六元环蜂窝状片层结构，称为生物质石墨烯纳米片层；层数为1～10层碳的六元环蜂窝状片层结构，称为石墨烯，以生物质为碳源制备的层数为1～10层碳的六元环蜂窝状片层结构，称为生物质石墨烯。具有以上结构的含碳物质称之为具有石墨烯结构。详见本发明提供的附图1～3。
或者说：
单层石墨烯：由一个碳原子与周围三个近邻碳原子结合形成蜂窝状结构的碳原子单层。
少层石墨烯：由3-10层以SP2杂化的炭单层堆垛而成的二维炭材料。
石墨烯纳米片：由单层或少层石墨烯组成的，层数小于10层，片层横向尺寸大于100纳米的二维碳纳米材料。
生物质石墨烯：以生物质为原料制备的含有单层石墨烯、少层石墨烯、石墨烯纳米片层结构，并负载金属/非金属化合物的复合炭材料。
所述含碳纳米结构的复合物中，非碳非氧元素以单质、氧化物或碳化物中的任意1种或至少2种的组合的形式吸附在碳纳米结构的表面或内部。
优选地，所述含碳纳米结构的复合物中，非碳非氧元素通过碳源引入；所述碳源优选生物质碳源，生物质碳源选自植物和/或农林废弃物中的任意1种或至少2种的组合；优选针叶木、阔叶木、林叶木、农林废弃物中的任意1种或至少2种的组合。
优选地，所述农林废弃物选自玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆、果壳和芦苇中的任意1种或至少2种的组合，优选玉米芯。
所述生物质碳源为纤维素和/或木质素，优选纤维素，进一步优选多孔纤维素。
本发明对所述多孔纤维素的来源并无特殊限定，可以为本领域熟知的多孔纤维素，优选地，所述多孔纤维素通过如下方法获得：
将生物质资源进行酸水解得到木质纤维素，之后经过多孔化后处理得到多孔纤维素；可选地，多孔纤维素经漂白后使用。
优选地，所述生物质资源选自植物和/或农林废弃物中的任意1种或至少2种的组合；优选农林废弃物中的任意1种或至少2种的组合。
优选地，所述农林废弃物选自玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆和芦苇中的任意1种或至少2种的组合。优选玉 米芯。
本发明中，所述无定形碳为二维石墨层面或三维石墨微晶，在微晶边缘上存在大量不规则的键，除含有大量的sp2碳外，还含有不少的sp3碳。实际上它们的内部结构并不是真正的无定形体，而是具有和石墨一样结构的晶体，只是由碳原子六角形环状平面形成的层状结构零乱且不规则，晶体形成有缺陷，大部分无定形碳是石墨层型结构的分子碎片大致相互平行地，无规则地堆积在一起，可简称为乱层结构。层间或碎片之间用金刚石结构的四面体成键方式的碳原子键连起来。
本发明制备得到上述复合物后，检测方法可以如下：
1、对其非碳非氧元素含量进行测试：
非碳非氧元素含量测定方法之一：
将含碳纳米结构的复合物经硝酸(ρ＝1.42g/mL)、高氯酸(ρ＝1.67g/mL)、氢氟酸(ρ＝1.16g/mL)分解，在硝酸介质中保温，定容后，用电感耦合等离子体原子发射光谱仪，采用标准曲线法定量分析含碳纳米结构的复合物中P、Si、Ca、Al、Na等元素含量。
非碳非氧元素含量测定方法之二：
采用国标GB/T17359-1998，电子探针和扫描电镜X射线能谱定量分析通则；
本发明对所述非碳非氧元素的测定方法没有限定，任何本领域已知的或者新的测定方法均可用于本发明；本发明提供了两种非碳非氧元素含量的测定方法，优选“非碳非氧元素含量测定方法之一”进行测定，本发明实施例中选用“非碳非氧元素含量测定方法之一”进行测定。
对所述复合物的红外检测数据依据：GBT 7286.1-1987《金属与非金属材料全法向发射率试验方法》；
对所述复合物的抑菌检测数据依据：按照GB/T20944.3-2008检验方法，以金黄色葡萄球菌为例。
2、电导率的测定
将样品置于粉末电阻率仪的样品孔中，采用180kg的压力将其压制成片状，然后通过四探针测试仪设定样品的高度系数，进而计算出样品的电导率。
3、比表面积的测定
按照GB/T 7702.20的规定进行。
4、拉曼光谱的测定
将样品附着在SiO2/Si衬底上，采用532nm或655nm激发波长，对样品进行拉曼成像，可以检测到石墨烯样品的D峰、G峰以及2D峰。通过峰形可以鉴 定石墨烯的片层厚度以及SP2杂化程度。
5、C/O的测定
取0.1g粉状样品，将样品置于载玻片上，将其进行XPS分析，测定C/O。
本发明还提供了一种高分子材料，包括上述复合物，或上述制备方法制备得到的复合物。
所述高分子材料还包括橡胶、塑料、纤维、涂料、胶粘剂或高分子基复合材料中的任意一种或多种。
在本发明的某些具体实施例中，所述高分子材料为聚酯、聚氨酯或粘胶纤维。
本发明还提供了上述高分子材料的制备方法，包括：
将上述复合物，或上述制备方法制备得到的复合物直接与高分子原材料进行复合，无需对所述复合物进行活化或改性；
所述高分子原材料为橡胶、塑料、纤维、涂料、胶粘剂和高分子基复合材料中的任意一种或多种。
本发明还提供了上述高分子材料在针织、床上用品、家居、汽车制品、家具、管材、型材、服装领域的应用。
具体的，利用以上高分子材料做成一种制品，所述制品包括织物、膜、枕头、床垫、坐垫、靠垫、沙发、护腰、鞋垫、乳罩、汽车座椅、马桶坐垫、暖手宝、管材、家具、型材。以上所述制品都是通过现有技术工艺即可制备完成。
本发明所述的含有碳纳米结构的复合物能够很好的与高分子材料进行复合，无需先对其改性或活化，就能很好的在高分子材料中分散，并且起到应有的作用，例如远红外性能和抗菌性能。
为了进一步说明本发明，下面结合实施例对本发明提供的复合物及其制备方法以及一种高分子材料及其制备方法进行详细描述。
制备例1
多孔纤维素的制备方法，具体可以借鉴公开号为CN104016341A的专利文件，具体为：
在90℃下，用硫酸调节玉米芯水溶液至pH＝3，浸泡10min进行水解，得到木质纤维素，所述硫酸的质量为所述玉米芯质量的3％；
然后，在70℃下，将得到的木质纤维素浸泡在酸性亚硫酸盐中1h，得到多孔纤维素；其中，酸为硫酸，亚硫酸盐为亚硫酸镁，所述硫酸的质量为所述木质纤维素质量的4％，液固比为2∶1；制成后备用。
制备例2
常规纤维素的制备方法，具体可以借鉴公开号为CN103898782A的专利文件，具体为：
(1)将小麦秸杆粉碎预处理后，使用总酸浓为80wt％的甲酸和乙酸的有机酸液对处理后的小麦秸杆进行蒸煮，本实施例的有机酸液中乙酸与甲酸的质量比为1∶12，并在加入原料前加入占小麦秸杆原料1wt％的过氧化氢(H2O2)作为催化剂，控制反应温度120℃，反应30min，固液质量比为1∶10，并将得到的反应液进行第一次固液分离；
(2)将第一次固液分离得到的固体加入总酸浓为75wt％的甲酸和乙酸的有机酸液进行酸洗涤，其中上述总酸浓为75wt％的有机酸液中加入了占小麦秸杆原料8wt％的过氧化氢(H2O2)作为催化剂且乙酸与甲酸的质量比为1∶12，控制温度为90℃，洗涤时间1h，固液质量比为1∶9，并将反应液进行第二次固液分离；
(3)收集第一次和第二次固液分离得到的液体，于120℃，301kPa下进行高温高压蒸发，直至蒸干，将得到的甲酸和乙酸蒸气冷凝回流至步骤(1)的反应釜中作为蒸煮液，用于步骤(1)的蒸煮；
(4)收集第二次固液分离得到的固体，并进行水洗，控制水洗温度为80℃，水洗浆浓为6wt％，并将得到的水洗浆进行第三次固液分离；
(5)收集第三次固液分离得到的液体，进行水、酸精馏，得到的混合酸液回用于步骤(1)的反应釜中作为蒸煮液用于步骤(1)的蒸煮，得到的水回用于步骤(5)作用水洗用水；
(6)收集第三次固液分离得到的固体并进行筛选得到所需的细浆纤维素。
制备例3
制备杨树的木质素和纤维素、桉树的木质素和纤维素，可以借鉴公开号为CN103131018A的“一种木质纤维素生物质的综合利用工艺”，具体为：
(1)将杨树或桉树枝叶粉碎预处理后，使用浓度为90％的甲酸和浓度为5％的乙酸以及5％的水的有机酸液对处理后的木质纤维素生物质进行酸水解，控制反应温度165℃，反应10min，所述甲酸和乙酸的混合酸液与生物质原料的液固质量比为1∶20，并将得到的反应液进行第一次固液分离；
(2)将步骤(1)中分离得到的固体加入浓度为90％的甲酸和浓度为5％的乙酸以及5％的水的有机酸液进行酸洗涤，温度为60～80℃，洗涤时间0.5～1h，并将反应液进行第二次固液分离，将分离得到的固体经水洗处理后得到所 需的纤维素；
(3)收集步骤(1)和步骤(2)中固液分离得到的液体，进行减压蒸馏浓缩，得到甲酸和乙酸蒸气，以及浓度为原来液体浓度4-5倍的浓缩液；
(4)将步骤(3)中蒸馏出的甲酸和乙酸蒸气冷凝回流至步骤(1)的反应釜中，用于步骤(1)的酸解；
(5)将步骤(3)中所得的浓缩液加水稀释，所述助剂与所述浓缩液的质量比为2∶1，控制60-70℃搅拌0.5-1h，并进行第三次固液分离，所得到的固体加水(水与所述固体的质量比为3∶1)，并于75-80℃搅拌2-3h进行水洗去酯化后，得到所需的木质素。
实施例1
一种含碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶0.1混合制备例2得到的纤维素和氯化亚铁，在150℃下搅拌进行催化处理4h，干燥至前驱体水分含量10wt％，得到前驱体；
(2)保护性气氛中，以3℃/min速率将前驱体升温至280℃，保温2h，之后程序升温至950℃，保温3h得到粗品；所述程序升温的升温速率为15℃/min；
(3)55～65℃下，将粗品经过浓度为4wt％的盐酸酸洗后，水洗得到含碳纳米结构的复合物。
将实施例1制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰峰高比值高度比为1.1；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg元素。
实施例2
一种含碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶1混合制备例2得到的纤维素和氯化铁，在200℃下搅拌进行催化处理8h，干燥至前驱体水分含量8wt％，得到前驱体；
(2)保护性气氛中，以5℃/min速率将前驱体升温至350℃，保温2h，之后程序升温至1050℃，保温4h得到粗品；所述程序升温的升温速率为20℃/min；
(3)55～65℃下，将粗品经过浓度为6wt％的盐酸酸洗后，水洗得到含碳纳米结构的复合物。
将实施例2制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高比值为4.8；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg、S元素。
实施例3
一种含碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶1混合制备例3得到的杨树纤维素和氯化铁，在200℃下搅拌进行催化处理8h，干燥至前驱体水分含量8wt％，得到前驱体；
(2)保护性气氛中，以5℃/min速率将前驱体升温至350℃，保温2h，之后程序升温至1050℃，保温4h得到粗品；所述程序升温的升温速率为20℃/min；
(3)55～65℃下，将粗品经过浓度为6wt％的盐酸酸洗后，水洗得到含碳纳米结构的复合物。
将实施例3制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为4.6；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Ni元素。
实施例4
一种含碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶1混合制备例1得到的多孔纤维素和氯化铁，在200℃下搅拌进行催化处理8h，干燥至前驱体水分含量4wt％，得到前驱体；
(2)保护性气氛中，以5℃/min速率将前驱体升温至350℃，保温2h，之后程序升温至1000℃，保温4h得到粗品；所述程序升温的升温速率为20℃/min；
(3)55～65℃下，将粗品经过浓度为4wt％的盐酸酸洗后，水洗得到含碳纳米结构的复合物。
将实施例4制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为6.8；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg、Fe、Mg、K元素。
实施例5
一种含碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶0.5混合制备例3得到的桉树纤维素和氯化镍，在170℃下搅拌进行催化处理5h，干燥至前驱体水分含量6wt％，得到前驱体；
(2)保护性气氛中，以4℃/min速率将前驱体升温至300℃，保温3h，之后程序升温至1000℃，保温4h得到粗品；所述程序升温的升温速率为17℃/min；
(3)60℃下，将粗品经过浓度为5wt％的盐酸酸洗后，水洗得到含碳纳米结构的复合物。
将实施例5制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为2.1；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg、Ni、K元素。
实施例6
一种含碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶3混合制备例3得到的杨树纤维素和氯化亚铁，在180℃下搅拌进行催化处理5h，干燥至前驱体水分含量6wt％，得到前驱体；
(2)保护性气氛中，以4℃/min速率将前驱体升温至300℃，保温3h，之后程序升温至1000℃，保温4h得到粗品；所述程序升温的升温速率为17℃/min；
(3)60℃下，将粗品经过浓度为5wt％的盐酸酸洗后，水洗得到含碳纳米结构的复合物。
将实施例6制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为13.2；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、K、Mg元素。
实施例7
一种含碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶5混合制备例1得到的多孔纤维素和氯化猛，在180℃下搅拌进行催化处理5h，干燥至前驱体水分含量6wt％，得到前驱体；
(2)保护性气氛中，以4℃/min速率将前驱体升温至300℃，保温3h，之后程序升温至1000℃，保温4h得到粗品；所述程序升温的升温速率为17℃/min；
(3)60℃下，将粗品经过浓度为5wt％的盐酸酸洗后，水洗得到含碳纳米结构的复合物。
将实施例7制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为15；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物 中主要含有P、Si、Ca、Al、Na、Fe、Mg、Mn、S元素。
实施例8
与实施例6的区别在于，选用木质素替代杨树纤维素。将实施例8制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为10.8；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、K、Mg、Co元素。
实施例9
与实施例7的区别在于，在用酸洗之前先用浓度为10％的NaOH溶液进行洗涤4h。将实施例9制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为15；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Cr元素。
实施例10
与实施例1的区别在于，在所用催化剂由0.1wt％变为8wt％。将实施例10制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为16.2；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中含有P、Si、Ca、Al、Na、Fe、Mg元素。
实施例11
与实施例1的区别在于，在所用催化剂由0.1wt％变为10wt％。将实施例11制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为18；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg、K元素。
实施例12
与实施例1的区别在于，在所用催化剂由0.1wt％变为13wt％。将实施例12制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为20；
采用“非碳非氧元素含量测定方法之一”检测到，含碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg元素。
对比例中以纳米材料之一的石墨烯为对比物进行论述，但是不限于其他的纳米材料：
对比例1
以CN104016341A名称为“一种多孔石墨烯的制备方法”公开的实施例7得到的石墨烯作为对比例1。将对比例制备的石墨烯进行拉曼光谱检测，结果显示G峰、D峰高度比为13；
采用“非碳非氧元素含量测定方法之一”检测到，得到的多孔石墨烯中主要含有P、Si、Ca、Al、Na、Fe、Mg、K元素。
对比例2
采用CN103508444A公开的方法制备一种磷掺杂石墨烯及其制备方法，具体为：
将1g纯度为95％的石墨加入24mL质量分数为65％的浓硝酸与90mL质量分数为98％的浓硫酸中混合，将混合物置于冰水混合浴环境下进行搅拌20分钟，再慢慢地往混合物中加入高锰酸钾，高锰酸钾与石墨的质量比为5∶1，搅拌1小时，接着将混合物加热至85℃下保持30min，之后加入去离子水继续在85℃下保持30min，去离子水与石墨的液固比为90mL∶1g，最后加入质量分数为30％的过氧化氢溶液，过氧化氢溶液与石墨的液固比为10mL∶1g，搅拌10min，对混合物进行抽滤，再依次分别用稀盐酸和去离子水对固体物进行洗涤，稀盐酸、去离子水与石墨的固液比为100mL∶150mL∶1g，共洗涤3次，最后固体物质在60℃真空烘箱中干燥12小时得到氧化石墨；
按质量比取5份氧化石墨和0.3份五氧化二磷、0.3份二氧化硅粉末、0.2份氯化钙、0.1份氯化镁和0.1份氯化亚铁混合均匀，置于流速为300mL/min的氩气氛围中，以15℃/min的升温速度升温至900℃，保持2h，随后在流速为300mL/min的氩气氛围中降至室温，制得磷掺杂石墨烯；
将对比例2制备的氮掺杂石墨烯进行拉曼光谱检测，结果显示G峰、D峰高度比为5；
采用“非碳非氧元素含量测定方法之一”检测到，得到的磷掺杂石墨烯中主要含有P、Si、Ca、Fe、Mn、Mg、S元素。
对比例3
以石墨为原料制备石墨烯的方法：
(1)向5g鳞片石墨和150mL浓硫酸的混合溶液中加入50mL的浓硝酸，常温下搅拌24h，用去离子水清洗3次，60℃中烘干，得到石墨层间化合物；
(2)将上述得到的石墨层间化合物在1050℃中迅速膨胀30s，得到膨胀石墨；
(3)将3g高锰酸钾缓慢加入0.3g上述所得的膨胀石墨和60mL浓硫酸的混合物中，在60℃的条件下搅拌24h，在冰浴条件下加入60mL去离子水和15mL过氧化氢，将混合物水洗至中性，获得氧化石墨烯；
(4)将上述所得的氧化石墨烯在水中分散，用离心法将氧化石墨烯分离；用转速、时间分别为8000rmp和40min进行离心，得到上层清液1和沉淀物1，所得的上层清液1即为小尺寸氧化石墨烯；将上层清液1分散，用转移印花法将氧化石墨烯转移到聚对苯二甲酸塑料(PET)基体上，用HI酸在50℃下还原60min，即得到石墨烯。
将对比例3制备的石墨烯进行拉曼光谱检测，结果显示G峰、D峰高度比为18。
采用“非碳非氧元素含量测定方法之一”检测到，得到的石墨烯中主要含有Mn、S元素。
对比例4
一种复合物，通过如下方法获得：
(1)按质量比1∶1混合制备例2得到的纤维素和氯化铁，在100℃下搅拌进行催化处理4h，干燥至前驱体水分含量8wt％，得到前驱体；
(2)保护性气氛中，以8℃/min速率将前驱体升温至400℃，保温2h，之后程序升温至800℃，保温4h得到粗品；所述程序升温的升温速率为25℃/min；
(3)55～65℃下，将粗品经过浓度为6wt％的盐酸酸洗后，水洗得到该复合物。
将对比例4制备的复合物进行拉曼光谱检测，结果显示G峰、D峰高比值为0.3。
采用第一种非碳非氧元素含量测定方法检测到，该复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg元素。
实施例13
一种含有碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶1混合玉米芯纤维素和氯化亚铁，在150℃下搅拌进行催化处理4h，干燥至前驱体水分含量10wt％，得到前驱体；
(2)N2气氛中，以3℃/min速率将前驱体升温至170℃，保温2h，之后程序升温至400℃，保温3h，之后升温至1200℃，保温3h后得到粗品；所述程序升温的升温速率为15℃/min；
(3)55～65℃下，将粗品经过浓度为10％的氢氧化钠溶液、4wt％的盐酸酸洗后，水洗得到含有碳纳米结构的复合物。
将实施例13制备的含有碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰峰高比值高度比为3；
采用“非碳非氧元素含量测定方法之一”检测到，含有碳纳米结构的复合物中主要含有P、Si、Ca、Al、Fe、Mg元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
对制备的复合物进行检测，结果见图1，图1是本发明实施例13制备的含有碳纳米结构的复合物的透射电镜图。
实施例14
一种含有碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶0.5混合玉米芯纤维素和氯化铁，在180℃下搅拌进行催化处理8h，干燥至前驱体水分含量5wt％，得到前驱体；
(2)N2气氛中，180℃继续保温2.5h，之后以14℃/min速度将温度升至450℃，保温4h，之后以18℃/min速度将温度升至1300℃，保温2h后得到粗品；
(3)55～65℃下，将粗品经过浓度为15％的氢氧化钠溶液、6wt％的盐酸酸洗后，水洗得到含有碳纳米结构的复合物。
将实施例14制备的含有碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰峰高比值高度比为3.5；
采用“非碳非氧元素含量测定方法之一”检测到，含有碳纳米结构的复合物中主要含有P、Si、Ca、Al、Fe、Mg元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
实施例15
一种含有碳纳米结构的复合物，通过如下方法获得：
(1)按质量比1∶5混合玉米芯纤维素和氯化铁与氯化钴的混合物(氯化铁 与氯化钴的质量比为20∶1)，在200℃下搅拌进行催化处理14h，干燥至前驱体水分含量1wt％，得到前驱体；
(2)氩气气氛中，降温至140℃继续保温1.5h，之后以16℃/min速度将温度升至350℃，保温4h，之后以17℃/min速度将温度升至1100℃，保温4h后得到粗品；
(3)55～65℃下，将粗品经过浓度为5％的氢氧化钠溶液、3wt％的盐酸酸洗后，水洗得到含有碳纳米结构的复合物。
将实施例15制备的含有碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰峰高比值高度比为4.5；
采用第一种非碳非氧元素含量测定方法检测到，含有碳纳米结构的复合物中主要含有P、Si、Ca、Al、Fe、Mg元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
实施例16
将实施例13中玉米芯纤维素替换为芦苇纤维素。
将实施例16制备的含碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高比值为4.8；
采用“非碳非氧元素含量测定方法之一”检测到，含有碳纳米结构的复合物中主要含有Si、Ca、Al、Fe、Mg、S元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
对制备的复合物进行检测，结果见图2，图2是本发明实施例16制备的含有碳纳米结构的复合物的透射电镜图。
实施例17
将实施例13中玉米芯纤维素替换为杨树纤维素。
将实施例17制备的含有碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为4.6；
采用“非碳非氧元素含量测定方法之一”检测到，含有碳纳米结构的复合物中主要含有P、Si、Al、Na、Fe、Ni元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
对制备的复合物进行检测，结果见图3，图3是本发明实施例17制备的含有碳纳米结构的复合物的透射电镜图。
实施例18
将实施例13中玉米芯纤维素替换为玉米芯木质素。
将实施例18制备的含有碳纳米结构的复合物进行拉曼光谱检测，结果显示G峰、D峰高度比为2.8；
采用“非碳非氧元素含量测定方法之一”检测到，含有碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg、Fe、Mg、K元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
实施例19
将玉米芯备用料加入3倍量的44％氯化锌液(用盐酸调pH＝1)，充分搅拌浸渍，静置吸收5小时，再充分搅拌复静置吸收5小时，至氯化锌液全被吸收干，移入敞口平底炭化炉中密闭炭化，于400℃炭化3小时，隔30分钟左右彻底搅拌一次，搅拌前将炉温降至100℃以下，搅拌后再升温密闭炭化，直至变成黑焦，出料冷却，用2倍量的44％氯化锌液(pH＝1)浸渍，充分搅拌，使氯化锌液全部被吸收，移入活化炉中，于650℃活化70分钟，出料冷却，移入木桶内，加入等量的40％氯化铵液，充分搅拌洗涤，静置澄清，虹吸出清液，依次用30％、12％和3％的氯化铵液搅拌洗涤，再用等量的30％盐酸搅拌洗涤，滤取炭粒，入锅，加入等体积的清水，煮沸洗涤至洗涤无氯化铵为止，加热蒸发，搅拌翻炒，弃掉水分，烘干、粉碎，过120目筛，得活性炭。在此基础上引入石墨烯，并引入P、Si、Ca、Al、Fe、Mg元素，具体为纳米五氧化二磷、纳米硅粉、纳米碳酸钙、纳米铝粉、纳米铁、纳米镁粉的纳米材料，得到含有碳纳米结构的复合物。
采用“非碳非氧元素含量测定方法之一”检测到，含有碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg、Fe、Mg、K元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
实施例20
将木质素在炭化炉中密闭炭化，于400℃炭化3小时，隔30分钟左右彻底搅拌一次，搅拌前将炉温降至100℃以下，搅拌后再在氩气条件下升温至2200℃密闭进行石墨化2h，出料冷却，依次用30％、12％和3％的氯化铵液搅拌洗涤，再用等量的30％盐酸搅拌洗涤，烘干、粉碎，过120目筛，得石墨与活性炭混合碳材料。在此基础上引入石墨烯，并引入P、Si、Ca、Al、Fe、Mg元素，具体为纳米五氧化二磷、纳米硅粉、纳米碳酸钙、纳米三氧化二铝、纳米铁、纳 米镁粉的纳米材料，得到含有碳纳米结构的复合物。
采用“非碳非氧元素含量测定方法之一”检测到，含有碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg、Fe、Mg、K元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
实施例21
利用酚醛树脂泡沫板，在330℃进行一次炭化，去除氢氧元素，然后在700℃进行高温炭化，在此基础上引入石墨烯，并引入P、Si、Ca、Al、Fe、Mg元素，具体为纳米五氧化二磷、纳米硅、纳米碳酸钙、纳米三氧化二铝、纳米铁、纳米镁的纳米材料，得到含有碳纳米结构的复合物。
采用“非碳非氧元素含量测定方法之一”检测到，含有碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg、Fe、Mg、K元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
实施例22
向纳米石墨中加入活性炭和石墨烯，在此基础上引入石墨烯，并引入P、Si、Ca、Al、Fe、Mg元素，具体为纳米五氧化二磷、纳米硅粉、纳米碳酸钙、纳米三氧化二铝、纳米铁、纳米镁的纳米材料，得到含有碳纳米结构的复合物。
采用“非碳非氧元素含量测定方法之一”检测到，含有碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg、Fe、Mg、K元素，其具体含量见表2，表2是本申请实施例和对比例的性能测试结果。
对比例5
按照现有技术制备石墨烯，具体的：
在180℃下，将玉米芯在硝酸中进行10h的水解，得到木质纤维素，所述硝酸的质量为所述玉米芯质量的20％；
在180℃下，对所述木质纤维素进行6小时的酸性亚硫酸盐法处理，得到多孔纤维素，所述酸性亚硫酸盐法处理过程中的pH值为7，酸为硫酸，亚硫酸盐为亚硫酸纳，所述硫酸的质量为所述木质纤维素质量的30％，液固比为20∶10；
将所述多孔纤维素道行双氧水漂白，所述双氧水的质量为所述多孔纤维素质量的5％，所述双氧水漂白的漂白温度为100℃，漂白时间为5h。
将制备得到的多孔纤维素和硝酸铁，在180℃下搅拌10小时进行催化处理，所述硝酸铁和多孔纤维素的质量比为2：1；将得到的催化处理后的产物在120℃ 下干燥，得到含水量低于5wt％的第一中间产物。
将所述第一中间产物置于炭化炉中，以800mL/min的气体通入量向所述碳化炉中通入氧气作为保护气，将所述第一中间产物以20℃/min的速率从20℃升温至400℃，保温8小时，得到第二中间产物；将所述第二中间产物以50℃/min的速率从400℃升温至900℃，保温7小时，得到第三中间产物；将所述第三中间产物以60℃/min的速率从900℃升温至1300℃，保温8小时，得到第四中间产物；将所述第四中间产物以50℃/min的速率从1300℃降温至1000℃，保温4小时；将所述降温后的第四中间产物冷却至20℃。
在120℃下，将上述冷却后的第四中间产物在质量浓度为55％的氢氧化纳水溶液中洗涤24小时，得到第一洗涤产物；在150℃下，将所述第一洗涤产物在质量浓度为10％的盐酸水溶液中洗涤24小时，得到第二洗涤产物；将所述第二洗涤产物用蒸馆水洗涤至中性后干燥，得到石墨烯。
将对比例制备的石墨烯进行拉曼光谱检测，结果显示G峰、D峰高度比为13：
采用“非碳非氧元素含量测定方法之一”检测到，得到的石墨烯中主要含有P、Si、Ca、Al、Na、Fe、Mg、K元素，其具体含量见表1，表1是本申请实施例和对比例的性能测试结果。
对比例6
按照现有技术制备石墨烯，具体的：
将1g纯度为95％的石墨加入24mL质量分数为65％的浓硝酸与90mL质量分数为98％的浓硫酸中混合，将混合物置于冰水混合浴环境下进行搅拌20分钟，再慢慢地往混合物中加入高锰酸钾，高锰酸钾与石墨的质量比为5∶1，搅拌1小时，接着将混合物加热至85℃下保持30min，之后加入去离子水继续在85℃下保持30min，去离子水与石墨的液固比为90mL∶1g，最后加入质量分数为30％的过氧化氢溶液，过氧化氢溶液与石墨的液固比为10mL∶1g，搅拌10min，对混合物进行抽滤，再依次分别用稀盐酸和去离子水对固体物进行洗涤，稀盐酸、去离子水与石墨的固液比为100mL∶150mL∶1g，共洗涤3次，最后固体物质在60℃真空烘箱中干燥12小时得到氧化石墨；按质量比为1∶2的比例取氧化石墨和五氧化二磷混合均匀，置于流速为300mL/min的氩气氛围中，以15℃/min的升温速度升温至900℃，保持2h，随后在流速为300mL/min的氩气氛围中降至室温，制得磷掺杂石墨烯。
将对比例2制备的氮掺杂石墨烯进行拉曼光谱检测，结果显示G峰、D峰 高度比为5；
采用“非碳非氧元素含量测定方法之一”检测到，得到的磷掺杂石墨烯中主要含有P元素，其含量为2wt％。
对比例7
用有机生物质制备活性炭/石墨烯复合物，通过如下步骤制备得到∶
(1)按如下质量分数称取各组分原料：秸轩碎粒45％、三聚氰胺50％，硝酸铁5％；
(2)将上述各组分混合均匀后，放入温度为300℃的炉中加热3h，得到灰色、结构蓬松的块状材料；
(3)将上述得到的块状材料放入温度为600℃通有氮气的炉中加热10min，得到活性炭/石墨烯复合物。
采用“非碳非氧元素含量测定方法之一”检测到，得到的活性炭/石墨烯复合物中主要含有P、Si、Ca、Fe、Mg、Mn的元素，其具体含量见表1，表1是本申请实施例和对比例的性能测试结果。
实施例1-12及对比例1-4数据见表1，实施例13-22及对比例5-7见表2。
表1
Figure PCTCN2016099750-appb-000002
Figure PCTCN2016099750-appb-000003
从表1可以看出，采用实施例4制备的多孔纤维素去制备得到的碳纳米复合物的远红外和抗菌性能优于实施例2和3采用普通纤维素制备的碳纳米复合物；实施例12看出，第一非碳非氧元素含量高于4wt％后，远红外和抗菌性能的下降明显；对比例1可以看出，生物质为原料制备的第一非碳非氧元素低于0.5wt％时，远红外和抗菌效果不是很好；对比例2中虽然磷元素超过0.5wt％，但是在制备过程中刻意引入，结果远红外和抗菌性能也不是很理想；对比例3中第一非碳非氧元素含量几乎为0，远红外效果很差，抑菌效果还可以。
表2
实施例 非碳非氧元素含量之和，wt％ 远红外(法向发射率) 抗菌率％
实施例13 4.5 0.92 95
实施例14 4.3 0.91 97
实施例15 4.6 0.92 98
实施例16 1.3 0.86 96
实施例17 3.96 0.88 96
实施例18 5.24 0.89 97
实施例19 1.6 0.81 85
实施例20 2.3 0.82 88
实施例21 2.8 0.82 89
实施例22 4.6 0.84 92
对比例5 0.3 0.77 66
对比例6 2 0.75 65
对比例7 7 0.70 75
从表2可以看出，对比例5中，非碳非氧元素低于0.Swt％时，远红外和抗菌效果不是很好；对比例6中虽然磷元素超过0.Swt％，但是由于元素单一，结果远红外和抗菌性能也不是很理想；对比例7中，非碳非氧元素含量高于6wt％后，远红外和抗菌性能的下降明显。
由上述实施例及比较例可知，本发明通过控制复合物中非碳非氧元素含量，获得了优异的远红外效果和抗菌抑菌效果。
对实施例7-9、13-15制备得到的复合物进行性能检测，测试pH值、电导率、比表面积、片径和C/O比，测试结果见表3。
表3
实施例 电导率S/m 比表面积m2/g C/O比
实施例7 6000 280 46
实施例8 6500 250 47
实施例9 6300 260 47
实施例13 5500 200 46
实施例14 5700 220 47
实施例15 2800 210 46
实施例23
一种利用实施例1制备得到的含碳纳米结构的复合物制备粘胶纤维：
具体以玉米芯为原料，经浸渍碱化、压榨、粉碎、老化、黄化、溶解、熟成后制得固含为8％的粘胶液；将实施例1制备的含碳纳米结构的复合物以5倍质量的水分散得到石墨烯结构分散液，然后石墨烯结构分散液与粘胶液共混，以高速搅拌机搅拌1小时，形成共混溶液，含碳纳米结构的复合物用量是纤维素质量的3％。过滤、脱泡，然后经过纺丝、脱硫、水洗、干燥，制得功能性粘胶纤维。其中，凝固浴的组成：硫酸105g/L，硫酸钠200g/L，硫酸锌12g/L。
对功能性纤维的远红外性能和抗菌性能进行检测，检测标准如下：粘胶纤维的远红外法向发射率0.92，抗菌性能95％。
加入的含碳纳米结构的复合物无需提前活化或者改性，直接利用，就能达到很好的效果。
其中，红外检测数据依据：经国家纺织制品质量监督检验中心，按照 FZ/T64010-2000检验方法进行检验；
抑菌检测数据依据：经国家纺织制品质量监督检验中心，按照GB/T20944.3-2008检验方法。
实施例24
一种利用实施例1制备得到的含碳纳米结构的复合物制备聚氨酯泡沫体：
所述方法包括如下步骤：
(1)向100份(以下都为重量份)聚醚多元醇中加入5份实施例1制备得到的含碳纳米结构的复合物，再加入3份甲基苯基硅油、2份二甲基乙醇胺、6份水，搅拌混合均匀，得到聚醚多元醇单体组合物；
(2)向步骤(1)的聚醚多元醇单体组合物中加入50份多异氰酸酯，混合均匀；
(3)将步骤(2)的混合物倒入模具进行发泡、固化，得到功能性聚氨酯泡沫。
对功能性聚氨酯泡沫体的远红外性能和抗菌性能进行检测，结果为：聚氨酯泡沫体的远红外法向发射率0.88，抗菌性能90％。
加入的含碳纳米结构的复合物无需提前活化或者改性，直接利用，就能达到很好的效果。
性能测试：
红外检测数据依据：GBT 7286.1-1987《金属与非金属材料全法向发射率试验方法》；
抑菌检测数据依据：GB/T 31402-2015《塑料、塑料表面抗菌性能试验方法》中，以金黄色葡萄球菌为例。
实施例25
一种复合聚酯材料，通过如下方法制备得到：
(1)将100g实施例1制备得到的含碳纳米结构的复合物与8.52kg PTA、3.5L乙二醇投料混匀，球磨处理20min后直接引入到打浆釜打浆30min，按照利用三釜PET聚合工艺进行反应，进行聚合反应，聚合反应完毕得到熔体；
(2)熔体在40℃冷却水，0.5m/s牵伸速度条件下出料，直接造粒得到功能性PET材料。
对功能性聚酯材料的远红外性能和抗菌性能进行检测，结果为：PET材料的远红外法向发射率0.89，抗菌性能91％。
加入的含碳纳米结构的复合物无需提前活化或者改性，直接利用，就能达到很好的效果。
其中，红外检测数据依据：GBT 7286.1-1987《金属与非金属材料全法向发射率试验方法》；
抑菌检测数据依据：GB/T 31402-2015《塑料、塑料表面抗菌性能试验方法》，以金黄色葡萄球菌为例。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (11)

  1. 一种含碳纳米结构的复合物，其特征在于，所述复合物含有石墨烯、无定形碳和非碳非氧元素；
    所述非碳非氧元素包括Fe、Si和Al元素；
    所述非碳非氧元素含量为复合物的0.5wt％～6wt％。
  2. 根据权利要求1所述的复合物，其特征在于，所述复合物在拉曼光谱下碳元素G峰与D峰峰高比值为1～20。
  3. 根据权利要求1所述的复合物，其特征在于，所述复合物在拉曼光谱下还存在2D峰。
  4. 根据权利要求1～3之一所述的复合物，其特征在于，所述非碳非氧元素还包括P、Ca、Na；
    优选地，所述非碳非氧元素还包括Ni、Mn、K、Mg、Cr、S和Co中的任意一种或至少两种的组合；
    优选地，所述非碳非氧元素以单质和/或化合物的形式存在；
    优选地，所述非碳非氧元素以单质、氧化物或碳化物中的任意1种或几种的形式吸附在碳纳米结构的表面或内部。
  5. 根据权利要求1～3之一所述的复合物，其特征在于，所述复合物中碳元素含量≥80wt％；
    优选地，所述非碳非氧元素占复合物的1.5wt％～5wt％；
    优选地，所述含碳纳米结构的复合物中，P、Si、Ca、Al和Na的质量百分比为0.5～4wt％。
  6. 根据权利要求1～3之一所述的复合物，其特征在于，所述含碳纳米结构的复合物远红外检测法向发射率大于0.88；
    优选地，所述石墨烯具有厚度在100nm以下的碳的六元环蜂窝状片层结构，优选具有厚度在20nm以下的碳的六元环蜂窝状片层结构，进一步优选具有层数为1～10层碳的六元环蜂窝状片层结构中的任意1种或至少2种的组合，优选单层、双层或3～10层结构中的任意1种或至少2种的组合；
    优选地，所述复合物中碳的六元环蜂窝状片层结构微观上呈现翘曲、卷曲或折叠构象中的任意1种或至少2种的组合；
    优选地，所述含碳纳米结构的复合物中，非碳非氧元素P、Si、Ca、Al和Na通过碳源引入；所述碳源优选生物质碳源，生物质资源选自植物和/或农林废弃物中的任意1种或至少2种的组合；优选针叶木、阔叶木、林叶木或农林废弃物中的任意1种或至少2种的组合；
    优选地，所述农林废弃物选自玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、 糠醛渣、木糖渣、木屑、棉秆、果壳和芦苇中的任意1种或至少2种的组合，优选玉米芯。
  7. 一种含碳纳米结构的复合物的制备方法，其特征在于，所述制备方法包括：
    (1)在催化剂的作用下，将生物质碳源进行催化处理，得到前驱体；
    (2)在保护性气体的条件下，将所述前驱体在140℃～180℃保温1.5h～2.5h，得到第一中间体；
    (3)在保护性气体的条件下，将所述第一中间体升温至350℃～450℃保温3h～4h，得到第二中间体；
    (4)在保护性气体的条件下，将所述第二中间体升温至1100℃～1300℃保温2h～4h，得到第三中间体；
    (5)将所述第三中间体依次碱洗、酸洗、水洗，得到复合物；
    所述步骤(3)、(4)中的升温速率为14℃/min～18℃/min；
    优选地，所述含碳纳米结构的复合物包括权利要求1～6之一所述的含碳纳米结构的复合物。
  8. 一种含碳纳米结构的复合物的制备方法，其特征在于，所述制备方法包括如下步骤：
    (1)混合生物质碳源和催化剂，搅拌进行催化处理后，干燥得到前驱体；
    (2)保护性气氛中，将前驱体在280～350℃保温1.5～2.5h，之后程序升温至950～1200℃，保温3～4h得到粗品；所述程序升温的升温速率为15～20℃/min；
    (3)将粗品洗涤后，得到含碳纳米结构的复合物；
    优选地，所述含碳纳米结构的复合物包括权利要求1～6之一所述的含碳纳米结构的复合物。
  9. 一种高分子材料，包括权利要求1～6任一项所述的复合物，或权利要求8所述的制备方法制备得到的复合物。
  10. 一种高分子材料的制备方法，包括：
    将权利要求1～6任一项所述的复合物，或权利要求8所述的制备方法制备得到的复合物直接与高分子原材料进行复合，无需对所述复合物进行活化或改性；
    所述高分子原材料为橡胶、塑料、纤维、涂料、胶粘剂和高分子基复合材料中的任意一种或多种。
  11. 权利要求9所述的高分子材料在针织、床上用品、家居、汽车制品、家具、管材、型材、服装领域的应用。
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