WO2017071360A1 - 一种复合聚酯材料、复合聚酯纤维、其制备方法和用途 - Google Patents

一种复合聚酯材料、复合聚酯纤维、其制备方法和用途 Download PDF

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Publication number
WO2017071360A1
WO2017071360A1 PCT/CN2016/093116 CN2016093116W WO2017071360A1 WO 2017071360 A1 WO2017071360 A1 WO 2017071360A1 CN 2016093116 W CN2016093116 W CN 2016093116W WO 2017071360 A1 WO2017071360 A1 WO 2017071360A1
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Prior art keywords
composite
carbon
combination
carbon nanostructure
polyester material
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PCT/CN2016/093116
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English (en)
French (fr)
Inventor
唐一林
张金柱
张安
栾峰
刘顶
Original Assignee
济南圣泉集团股份有限公司
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Publication date
Priority claimed from CN201510707240.XA external-priority patent/CN105525381B/zh
Priority claimed from CN201510706656.XA external-priority patent/CN105504700B/zh
Priority claimed from CN201510705758.XA external-priority patent/CN105504696B/zh
Priority claimed from CN201510707397.2A external-priority patent/CN105506771B/zh
Application filed by 济南圣泉集团股份有限公司 filed Critical 济南圣泉集团股份有限公司
Priority to US15/522,476 priority Critical patent/US10689501B2/en
Priority to KR1020177010374A priority patent/KR101965990B1/ko
Priority to EP16854582.0A priority patent/EP3202848B1/en
Priority to CA3002276A priority patent/CA3002276C/en
Priority to JP2017523541A priority patent/JP6487551B2/ja
Priority to AU2016345040A priority patent/AU2016345040B2/en
Publication of WO2017071360A1 publication Critical patent/WO2017071360A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D01D5/0885—Cooling filaments, threads or the like, leaving the spinnerettes by means of a liquid
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2507/00—Use of elements other than metals as filler
    • B29K2507/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention belongs to the field of polymer materials, and particularly relates to a composite polyester material, a composite polyester fiber, a preparation method and a use thereof, in particular to a carbon nanostructure composite composite polyester material, composite polyester fiber, and preparation method thereof And use.
  • Polyester a general term for polymers obtained by polycondensation of polyols and polybasic acids. It mainly refers to polyethylene terephthalate (PET), and it is customary to include linear thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylate. It is a kind of engineering plastic with excellent performance and wide application. It can also be made into polyester fiber and polyester film. Polyesters include polyester resins and polyester elastomers. The polyester resin further includes polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate (PAR), and the like.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PAR polyarylate
  • the polyester elastomer is generally polymerized from dimethyl terephthalate, 1,4-butanediol, and polybutanol, and the segment includes a hard segment portion and a soft segment portion, and is a thermoplastic elastomer.
  • the carbon nanomaterial refers to a carbon material having a dispersed phase size of at least one dimension of less than 100 nm, such as carbon nanotubes, graphene, and the like.
  • Graphene is a two-dimensional material of a honeycomb structure composed of a single layer of sp2 hybridized carbon atoms, and has many excellent properties. Since its discovery in 2004, graphene has become a research hotspot in the scientific community. While studying the physical and chemical properties of graphene, graphene-related composite materials are emerging one after another. In the direction of nanoscience, graphene is also used to prepare related nanocomposites, especially graphene/metal or graphene/metal oxide nanocomposites. Due to the excellent properties of graphene, these nanocomposites have broad research prospects in new energy, biosensing, catalysis, optical materials and other fields.
  • Polyester fibre refers to a variety of diols and aromatic dicarboxylic acids or their esters.
  • the polyester produced by the polycondensation is a general term for the fibers produced by the raw materials.
  • Common polyester fibers generally include polyethylene terephthalate fibers, polybutylene terephthalate fibers, polytrimethylene terephthalate fibers, and polytetramethylene terephthalate-1,4-cyclohexane Methyl ester fiber, poly-2,6-naphthalenedicarboxylate fiber, and various modified polyethylene terephthalate fibers (eg, CDP, ECDP, EDDP).
  • polyester fiber made of polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the Chinese name is polyester. It is the largest variety of chemical fiber products, accounting for nearly 80% of the market for chemical fiber products. Share; fiber-grade polyester chips are direct raw materials for the processing of polyester fiber fibers for the production of polyester staple fibers and polyester filaments.
  • the chemical structure is:
  • the PET melt is produced by esterification and polycondensation of terephthalic acid (PTA) and ethylene glycol (EG), which is then pelletized by underwater to form a PET masterbatch, which is then spun.
  • PTA terephthalic acid
  • EG ethylene glycol
  • the industrial synthesis process of polyester generally includes the following three main sections:
  • Raw material mixing and mixing section mainly complete raw materials, including PTA (terephthalic acid), EG (ethylene glycol), catalyst, other additives;
  • Prepolymerization section of polyester complete prepolymerization of the reactants and form a small molecule polymer. This section is often split into two esterification and diesterification reaction stages in the specific production to complete the reaction by-products such as water. Removal and introduction of functional fillers;
  • Polycondensation section mainly to realize the mutual polymerization of small molecular polymers, the process of chain extension and thickening. In actual production, the section is often divided into two stages: precondensation (low vacuum polymerization) and final polycondensation (high vacuum polymerization). .
  • polyester fiber products but poor hygroscopicity, it is easy to accumulate electrostatic charges formed in a dry climate, and the use of static electricity during wearing, and it is difficult comfort comparable to natural cotton fibers (synthetic fibers generally in a volume resistivity 10 15 ⁇ ⁇ Above cm, and to make the human body feel comfortable, no discharge phenomenon, the volume resistivity of the fiber should be below 10 10 ⁇ cm).
  • improving the antibacterial properties of polyester fibers, flame retardant, anti-melting, and anti-UV are also important directions for improving the application value of polyester fibers.
  • the carbon nanomaterial refers to a carbon material having a dispersed phase size of at least one dimension of less than 100 nm, such as carbon nanotubes, graphene, and the like.
  • Graphene is a two-dimensional material of a honeycomb structure composed of a single layer of sp2 hybridized carbon atoms, and has many excellent properties. Since its discovery in 2004, graphene has become a research hotspot in the scientific community. While studying the physical and chemical properties of graphene, graphene-related composite materials are emerging one after another. In the direction of nanoscience, graphene is also used to prepare related nanocomposites, especially graphene/metal or graphene/metal oxide nanocomposites. Due to the excellent properties of graphene, these nanocomposites have broad research prospects in new energy, biosensing, catalysis, optical materials and other fields.
  • CN103938293A discloses a far-infrared polyester fiber and a preparation method thereof, and the raw material of the far-infrared polyester fiber is arranged in parts by weight, comprising: 65-85 parts of polyester chips and 15-35 parts of far-infrared masterbatch, the far The raw materials of the infrared masterbatch are arranged in parts by weight, including: 75-90 parts of polyester chips, 10-20 parts of nano far-infrared powder, 0.5-5 parts of silane coupling agent, 0.5-5 parts of polyethylene wax, three [2.4] 0.05 to 1 part of di-tert-butylphenyl]phosphite and 0.05 to 1 part of tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester.
  • CN1308148A discloses a far-infrared radiation hollow three-dimensional crimped polyester fiber and a preparation method thereof, and a composite inorganic far-infrared ultrafine material of 0.3-0.5 ⁇ m, a titanate coupling agent and a surfactant The mixture is added to a high-speed mixer for dry surface treatment, and the surface-treated ultrafine material powder is mixed with the polyester carrier in a high-speed mixer, and the obtained mixed powder is sent to a twin-screw extruder for blending and extruding.
  • the working temperature is 10-30 ° C lower than the temperature of the conventional masterbatch, and the far-infrared masterbatch and the polyester chip obtained above are fed to the mixer through the metering feeder, and then sent to the screw spinning for making the hollow three-dimensional crimped fiber.
  • the machine is spun, and the final product obtained is the far-infrared radiation hollow three-dimensional crimped polyester fiber of the invention.
  • the plurality of far-infrared inorganic materials the basic component of which is a mixture of silica, alumina, titania and zirconia, is pulverized by an ultrafine jet mill, and pulverized to a particle diameter of 0.3-0.5 ⁇ m.
  • the pulverized far-infrared inorganic material powder is sintered in a high-temperature furnace at a sintering temperature of 800-1100 ° C, and then pulverized after sintering to make the particle size still controlled at 0.3-0.5 ⁇ m, thereby obtaining a composite inorganic of 0.3-0.5 ⁇ m.
  • Far infrared superfine material is
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a composite polyester material containing a carbon nanostructure composite;
  • the carbon nanostructure composite contains carbon element, 0.5 to 4 wt% of a first non-carbon non-oxygen element and 0 to 4 wt% of a second non-carbon non-oxygen element, and the first non-carbon non-oxygen element is a combination of any one or at least two of the first non-carbon non-oxygen element; the first non-carbon non-oxygen element being P, Si, Ca, Al, and Na; and the second non-carbon non- The oxygen element is present in the form of a simple substance, any one of the compounds, or a combination of at least two; the second non-carbon non-oxygen element is selected from any of Fe, Ni, Mn, K, Mg, Cr, S or Co. 1 or a combination of at least 2;
  • the carbon nanostructure 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, etc.;
  • the carbon nanostructured composite also has a 2D peak under the Raman spectrum.
  • the invention selects a specific carbon nanostructure composite as a composite raw material, and is compounded with a polyester material.
  • An exemplary composite mode may employ any one of in-situ polymerization, melt mixing, or solution mixing.
  • it is not necessary to modify the carbon nanostructure composite, and it is only necessary to simply mix the polymerizable monomer and carbon of the polyester material.
  • a second object of the present invention is to provide a composite polyester fiber containing a carbon nanostructured composite
  • the carbon nanostructure composite contains carbon element, 0.5 to 4 wt% of a first non-carbon non-oxygen element and 0 to 4 wt% of a second non-carbon non-oxygen element, and the first non-carbon non-oxygen element is a combination of any one or at least two of the first non-carbon non-oxygen element; the first non-carbon non-oxygen element being P, Si, Ca, Al, and Na; and the second non-carbon non- The oxygen element is present in the form of a simple substance, any one of the compounds, or a combination of at least two; the second non-carbon non-oxygen element is selected from any of Fe, Ni, Mn, K, Mg, Cr, S or Co. 1 or a combination of at least 2;
  • the carbon nanostructure composite has a ratio of carbon element G peak to peak D height in the Raman spectrum of 1 to 20; alternatively, the carbon nanostructure composite has a 2D peak in the Raman spectrum.
  • the Ra element spectrum of the carbon element G shows the degree of sp2 hybridization; the D peak reflects the lattice defect, such as the carbon structure of sp3; the 2D peak reflects the thickness of the graphene sheet.
  • the carbon nanostructure composite of 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 invention selects a specific carbon nanostructure composite as a composite raw material, and combines the polyester material without modifying the carbon nanostructure composite in advance, and only needs to simply add the carbon nanostructure composite to the existing one. Polyester fiber can be used in the polymerization process.
  • the polyester material of the present invention contains graphene
  • the graphene is introduced in the form of a carbon nanostructure composite; the carbon nanostructure composite It includes graphene and carbon of the SP3 hybrid structure.
  • the polyester fiber of the present invention contains graphene
  • the graphene is introduced in the form of a carbon nanostructure composite; the carbon nanostructure composite includes graphene, and carbon of the SP3 hybrid structure.
  • the far-infrared detection normal emissivity of the carbon nanostructure composite is greater than 0.85, such as 0.87, 0.89, 0.91, 0.92, 0.93, etc.; preferably, the far-infrared detection normal emissivity of the carbon nanostructure composite is greater than 0.88.
  • the content of the carbon element is ⁇ 80 wt%, for example, 82 wt%, 86 wt%, 89 wt%, 91 wt%, 94 wt%, 97 wt%, 99 wt%, etc., preferably 85 to 97 wt%, further It is preferably 90 to 95% by weight.
  • the carbon nanostructure composite has a ratio of carbon element G peak to peak D height in the Raman spectrum of 2 to 20, preferably 3 to 20.
  • the carbon nanostructure composite 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 further preferably has a number of layers Any one or a combination of at least two of the six-membered ring-shaped honeycomb sheet structures of 1 to 10 layers of carbon 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 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 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 warp, curl, and folded conformation.
  • 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 first non-carbon non-oxygen element is adsorbed on the surface or inside of the carbon nanostructure in the form of any one or a combination of at least two of a simple substance, an oxide or a carbide. .
  • the first non-carbon non-oxygen element is introduced by a carbon source;
  • the carbon source is preferably a biomass carbon source, and the biomass resource is selected from any of plant and/or agricultural and forestry waste. 1 or a combination of at least 2; preferably any one or a combination of at least 2 of softwood, hardwood, forestwood, and agricultural and forestry waste;
  • the agricultural and forestry waste is preferably selected from cornstalks, corn cobs, high masts,
  • a corn cob is preferred from any one or a combination of at least two of beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalks, husks, and reeds.
  • the content of the carbon nanostructure composite is 0.1 to 10 wt%, for example, 0.2 wt%, 1 wt%, 3 wt%, 4 wt%, 6 wt%, 8 wt%, 9 wt%, etc., preferably 0.5 to 7 wt%, further preferably 1 to 5 wt%, particularly preferably 2 to 4 wt%.
  • the far-infrared detection normal emissivity of the carbon nanostructure composite is greater than 0.88.
  • polyester is not specifically limited in the present invention, and typical but non-limiting polyesters include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and poly Terephthalic acid-1,4-cyclohexanedimethyl ester, poly-2,6-naphthalenedicarboxylate, and various modified polyethylene terephthalates (eg CDP, ECDP, EDDP) Any polyester which can be known to those skilled in the art can be used in the present invention; the present invention preferably industrializes mass production of PET polyester.
  • typical but non-limiting polyesters include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and poly Terephthalic acid-1,4-cyclohexanedimethyl ester, poly-2,6-naphthalenedicarboxylate, and various modified polyethylene terephthalates (eg CDP, ECDP, EDDP) Any polyester which can be known to those skilled in the
  • a third object of the present invention is to provide a method for preparing a composite polyester material according to one of the objects, which comprises: melting a polyester material, and then adding a carbon nanostructure composite thereto, and cooling to obtain a purpose.
  • One of the composite polyester materials; preferably, the carbon nanostructure composite does not need to be modified.
  • the carbon nanostructure composite is added in an amount of 0.1 to 10% by weight of the polyester material, for example, 0.2% by weight, 1% by weight, 3% by weight, 4% by weight, 6% by weight, 8% by weight, 9% by weight, etc., preferably 0.5. ⁇ 7% by weight, further preferably 1 to 5% by weight, particularly preferably 2 to 4% by weight.
  • a fourth object of the present invention is to provide a second method for preparing a composite polyester material according to one of the objects, which comprises dissolving a polyester material in a solvent, and then adding a carbon nanostructure composite thereto to remove The solvent is followed by a composite polyester material as described in one of the objects; preferably, the carbon nanostructured composite does not need to be modified.
  • the carbon nanostructure composite is added in an amount of 0.1 to 10% by weight of the polyester material, for example, 0.2% by weight, 1% by weight, 3% by weight, 4% by weight, 6% by weight, 8% by weight, 9% by weight, etc., preferably 0.5. ⁇ 7% by weight, further preferably 1 to 5% by weight, particularly preferably 2 to 4% by weight.
  • the solvent is a combination of fluoroacetic acid, a mixed solution of phenol and tetrachloroethane, or any one or at least two of tetrahydrofuran; the combination typically but not limited includes a combination of fluoroacetic acid and phenol, A combination of a mixed solution of phenol and tetrachloroethane and tetrahydrofuran, a combination of fluoroacetic acid and tetrahydrofuran, and the like.
  • the means for removing the solvent is distillation.
  • a fifth object of the present invention is to provide a third method for preparing a composite polyester material according to one of the objects, the method comprising the steps of:
  • the carbon nanostructure composite is added in an amount of 0.1 to 10% by weight of the polyester material, for example, 0.2% by weight, 1% by weight, 3% by weight, 4% by weight, 6% by weight, 8% by weight, 9% by weight, and the like.
  • the carbon nanostructure composite is added in the form of a carbon nanostructured composite dry powder, Alternatively, it is added in the form of a carbon nanostructured composite dispersion.
  • the dispersing agent of the carbon nanostructure composite dispersion is selected from the group consisting of deionized water, distilled water, ethanol, ethylene glycol, terephthalic acid, sodium acetate solution, dodecylbenzenesulfonic acid, and castor oil. Any one or a combination of at least two of oxyethylene ethers.
  • the timing of introducing the carbon nanostructure composite is selected from any one or a combination of at least two of a raw material beating stage, an esterification prepolymerization stage, a precondensation stage, and a final polycondensation stage, preferably a raw material beating stage.
  • the melt discharge is carried out under the conditions of cooling water at 20 to 75 ° C and a drafting speed of 0.01 to 1 m/s.
  • the preparation method of the composite polyester material of the present invention comprises the following steps:
  • the melt is discharged at a cooling water of 20 to 75 ° C at a drafting speed of 0.01 to 1 m/s, and directly granulated to obtain the composite polyester material of one of the objectives.
  • the carbon nanostructure composite is obtained by the following method:
  • the precursor incubated at 280-350 ° C, such as 282 ° C, 288 ° C, 295 ° C, 300 ° C, 332 ° C, 340 ° C, etc., for 1.5 ⁇ 2.5h, such as 1.6h, 1.8h, 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 biomass carbon source and the catalyst have a mass ratio of 1:0.1 to 10, such as 1:2, 1:4, 1:6, 1:8, etc., preferably 1:0.5 to 5, further preferably 1: 1 to 3.
  • the catalyst is selected from the group consisting of a manganese compound, an iron-containing compound, a cobalt-containing compound, and a nickel-containing compound, or a combination of at least two;
  • the iron-containing compound is selected from the group consisting of iron halogen compounds, iron cyanide a combination of any one or at least two of a compound and a ferrite;
  • the cobalt-containing compound is selected from any one or a combination of at least two of a cobalt compound and a cobalt salt;
  • the compound is selected from any one or a combination of at least two of a nickel chloride salt and a nickel acid salt.
  • 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, Any one or a combination of at least two of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, and nickel acetate.
  • Typical, but non-limiting examples of combinations of catalysts according to the invention are combinations of ferrous chloride and ferric sulfate, combinations of potassium ferricyanide and potassium trioxalate, cobalt chloride, cobalt nitrate and ferric chloride.
  • the temperature at which the stirring is carried out in the step (i) 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, 19h, 23h, etc., preferably 4 to 14 h;
  • the moisture content in the precursor is preferably 10 wt% or less, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 1 wt.
  • the temperature rising rate of the precursor in step (ii) to 280-350 ° C is preferably 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 of nitrogen, helium, argon or a combination of at least two, preferably nitrogen;
  • the crude washing of step (iii) is carried out in sequence Pickling and water washing;
  • the pickling preferably uses hydrochloric acid at a concentration of 3 to 6 wt%, further preferably hydrochloric acid at a concentration of 5 wt%;
  • the water washing preferably uses deionized water and/or distilled water;
  • the washing temperature is 55 ⁇ 65 ° C, for example, 56 ° C, 57 ° C, 58 ° C, 60 ° C, 63 ° C, etc., preferably 60
  • the biomass carbon source is cellulose and/or lignin, preferably cellulose, further preferably porous cellulose.
  • porous cellulose of the present invention can be obtained by the prior art.
  • Typical, but non-limiting, prior art methods for obtaining porous cellulose include, for example, the preparation of porous cellulose by the method disclosed in Patent Publication No. CN104016341A, and the preparation of fibers by the method disclosed in CN103898782A. Prime.
  • the porous cellulose is obtained by the following method:
  • the biomass resource is subjected to acid hydrolysis to obtain lignocellulose, which is then subjected to porous treatment to obtain porous cellulose; optionally, the porous cellulose is used after bleaching; the biomass resource is preferably selected from plants and/or agricultural and forestry waste. Any one or a combination of at least two; preferably any one or a combination of at least two of agricultural and forestry waste; the agricultural and forestry waste is preferably selected from corn stalks, corn cobs, sorghum, beet pulp, bagasse, furfural A combination of any one or at least two of slag, xylose, wood chips, cotton stalks and reeds is preferably a corn cob.
  • 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.
  • a sixth object of the present invention is to provide a preparation method of the composite polyester fiber according to the second object:
  • the composite polyester material obtained in the fifth objective is pelletized to obtain a composite polyester masterbatch, and the composite polyester masterbatch is melt-spun to obtain a carbon nanostructured composite composite polyester fiber.
  • the melt spinning process is a pre-oriented silk process
  • the pre-oriented filament has a filament discharge temperature of 30 to 70 ° C, a filament moisture of 10 to 90%; a preferred filament temperature of 55 to 65 ° C, and a filament humidity of 40 to 50%; further preferably a silk is produced.
  • the temperature is 62 ° C, and the filament moisture is 42%;
  • the wire is air-cooled or water-cooled
  • the temperature of the cooling water when the melt is discharged is 20 to 75 ° C, preferably 40 ° C;
  • the melt discharge has a draw speed of from 0.01 to 1 m/s.
  • the method for preparing the composite polyester fiber comprises the following steps:
  • the masterbatch is subjected to air-cooling or water-cooling at a spinning temperature of 30 to 70 ° C and a temperature of 10 to 90%, and melt-spinning to obtain a carbon nanostructure composite composite polyester fiber.
  • a seventh object of the present invention is to provide a use of a composite polyester material according to one of the objects, which comprises preparing a polyester fiber by melt spinning, the composite polyester material being prepared by a cast coating method a polyester film for use in the preparation of pipes, furniture, profiles, including but not limited to the further use of the above composite polyester materials, as long as the composite polyester material prepared by the present invention and its masterbatch are passed.
  • the polyester product further prepared by the reprocessing method belongs to the protection scope of the present invention.
  • An eighth object of the present invention is to provide a use of the composite polyester fiber according to the second object, wherein the composite polyester fiber is used for preparing a civilian garment, a home textile, an ultraviolet protective fabric, an industrial special protective garment, etc., including However, it is not limited to the above products, as long as it is a composite polyester fiber prepared by the principle of the present invention. Any form of textile, fabric or other form of product obtained by reprocessing means is within the scope of the present invention.
  • the present invention has the following beneficial effects:
  • the present invention obtains a superior bacteriostasis and low-temperature far-infrared performance by selecting a specific carbon nanostructure composite, and the far-infrared normal emissivity is greater than 0.85;
  • the carbon nanostructure composite composite polyester material provided by the invention has a simple preparation method, and the carbon nanostructure composite does not need to be modified, and the melt of the composite polyester material obtained after the polymerization can be directly discharged. No post-processing is required and the process is simple.
  • the method for preparing a carbon nanostructure composite composite polyester fiber provided by the present invention does not require modification of a carbon nanostructure composite, and retains inherent properties of the carbon nanostructure composite, which reduces cost and simplifies
  • the process flow can be directly prepared by using the existing polyester synthesis and spinning equipment, and the seamless combination of the carbon nanostructure composite composite polyester composite process and the conventional polyester masterbatch preparation and spinning process is realized. Easy to industrialize;
  • the carbon nanostructure composite composite polyester fiber prepared by the invention can obtain the expected multiple excellent performance without post-treatment, for example, the far-infrared normal emissivity can reach 0.85 or more, and has good suppression. Bacterial effect.
  • Reference CN104016341A index porous cellulose is specifically:
  • the porous cellulose and the catalyst are mixed at a mass ratio of 1:0.1 to 10, stirred at 150 to 200 ° C for catalytic treatment for 4 hours or more, and dried to a moisture content of the precursor of 10 wt% or less to obtain a precursor; and then, in a protective atmosphere,
  • the precursor is heated to 280-350 ° C at a rate of 3 ⁇ 5 ° C / min, and the temperature is maintained for 1.5 ⁇ 2.5 h, then the temperature is programmed to 950 ⁇ 1200 ° C, and the heat is maintained for 3 ⁇ 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 15 ⁇ 20 ° C / min; at 55 ⁇ 65 ° C, the crude product was acidified by hydrochloric acid at a concentration of 3 to 6 wt%, and then washed with water to obtain a carbon nanostructured composite.
  • the preparation conditions of the 1# carbon nanostructure composite are:
  • the catalyst is ferrous chloride; the mixed mass ratio of the porous cellulose to the catalyst is 1:0.1; the catalytic treatment temperature is 150 ° C, the time is 4 h; the moisture content in the precursor is 10 wt%;
  • the process of obtaining the crude product is: heating to 280 ° C at a rate of 3 ° C / min, holding for 2 h, then raising the temperature to 950 ° C at a rate of 15 ° C / min, holding for 3 h;
  • the pickling temperature is 55 ° C, the hydrochloric acid used in pickling is 4 wt%;
  • the composite of 1# carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg elements; and the Raman spectrum shows that the height ratio of G peak and D peak to height ratio is 7; there is 2D peak;
  • the preparation process of the 2# carbon nanostructure composite is different from the preparation process of the 1# carbon nanostructure composite only in that the ratio of the porous cellulose to the ferrous chloride in the step (2) becomes 1:10;
  • the composite of 2# carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg elements; and the Raman spectrum shows that the height ratio of G peak and D peak to height ratio is 20.
  • the preparation process of the 3# carbon nanostructure composite is different from the preparation process of the 1# carbon nanostructure composite only in that the ratio of the porous cellulose to the ferrous chloride in the step (2) becomes 1:0.5;
  • the 2# carbon nanostructured composite mainly contains P, Si, Ca, Al, Na, Fe, and Mg elements; and the Raman spectrum shows that the height ratio of the G peak and the D peak to the peak height ratio is 1.5.
  • the wire is cooled by water mist, the cooling temperature is 40 ° C, the drying temperature is 35 ° C, and the composite polyester fiber is obtained by melt spinning.
  • polyester material and the polyester fiber were prepared by the composite of 1# carbon nanostructure, the composite of 2# carbon nanostructure and the composite of 3# carbon nanostructure, respectively, and the polyester materials were respectively recorded as product 1a (1# carbon nanometer).
  • Structure composite composite PET material product 1b (1# carbon nanostructure composite composite PET material
  • Product 1c PET material composited with 3# carbon nanostructure composite
  • polyester fiber is recorded as product 1a' (1# carbon nanostructure composite composite polyester fiber
  • product 1b' (1# carbon Nanostructured composite composite polyester fiber and product 1c' (3# carbon nanostructure composite composite polyester fiber);
  • the far-infrared normal emissivity of products 1a and 1a' can reach 0.87; the antibacterial inhibition rate of Staphylococcus aureus is 70%; the far-infrared normal emissivity of products 1b and 1b' can reach 0.89; antibacterial inhibition against Staphylococcus aureus The bacterial rate is 82%; the far-infrared normal emissivity of products 1c and 1c' can reach 0.85; the antibacterial inhibition rate against Staphylococcus aureus is 60%;
  • 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 wire is cooled by water mist, the cooling temperature is 40 ° C, the drying temperature is 35 ° C, and the carbon nanostructured composite polyester fiber is obtained by melt spinning.
  • polyester material and the polyester fiber were prepared by the composite of 1# carbon nanostructure, the composite of 2# carbon nanostructure and the composite of 3# carbon nanostructure, respectively, and the polyester materials were respectively recorded as product 2a (1# carbon nanometer).
  • Structural composite composite PET material product 2b (1# carbon nanostructure composite composite PET material) and product 2c (3# carbon nanostructure composite composite PET material);
  • polyester fiber is recorded as Product 2a' (1# carbon nanostructure composite composite polyester fiber), product 2b' (1# carbon nanostructure composite composite polyester fiber) and product 2c' (3# carbon nanostructure composite) Composite polyester fiber);
  • Product 2a and product 2a' far-infrared normal emissivity can reach 0.90; antibacterial inhibition rate against Staphylococcus aureus is 95%; product 2b and product 2b' far-infrared normal emissivity can reach 0.92; against Staphylococcus aureus The antibacterial inhibition rate is 97%; the far-infrared normal emissivity of product 2c and product 2c' can reach 0.88; the antibacterial inhibition rate against Staphylococcus aureus is 90%;
  • test method is the same as in the first embodiment.
  • the wire is cooled by water mist, the cooling temperature is 40 ° C, the drying temperature is 35 ° C, and the melt spinning is performed to obtain carbon nanostructures.
  • polyester material and the polyester fiber were prepared by the composite of 1# carbon nanostructure, the composite of 2# carbon nanostructure and the composite of 3# carbon nanostructure, respectively, and the polyester materials were respectively recorded as product 3a (1# carbon nanometer).
  • Structural composite composite PET material product 3b (1# carbon nanostructure composite composite PET material) and product 3c (3# carbon nanostructure composite composite PET material);
  • polyester fiber is recorded as Product 3a' (1# carbon nanostructure composite composite polyester fiber), product 3b' (1# carbon nanostructure composite composite polyester fiber) and product 3c' (3# carbon nanostructure composite) Composite polyester fiber);
  • Products 3a and 3a' have a far-infrared normal emissivity of 0.89; antibacterial inhibition against Staphylococcus aureus is 90%; products 3b and 3b' have a far-infrared normal emissivity of 0.90; against Staphylococcus aureus
  • the antibacterial inhibition rate is 95%; the products of 3c and 3c' have a far-infrared normal emissivity of 0.87; the antibacterial inhibition rate to Staphylococcus aureus is 88%;
  • test method is the same as in the first embodiment.
  • the melt is discharged at 40 ° C cooling water at a draw speed of 0.5 m / s, and directly granulated to obtain a carbon nanostructure composite composite PET material (PET masterbatch);
  • a composite polyester fiber which is subjected to step (3) after step (2) to complex the carbon nanostructure
  • the composite PET masterbatch is directly used for melt spinning after drum drying at 110 ° C for 24 hours.
  • the spinning filament is cooled by water mist, the cooling temperature is 40 ° C, the drying temperature is 35 ° C, and the carbon nanometer is melt-spun.
  • Composite composite composite polyester fiber
  • polyester material and the polyester fiber were prepared by the composite of 1# carbon nanostructure, the composite of 2# carbon nanostructure and the composite of 3# carbon nanostructure, respectively, and the polyester materials were respectively recorded as product 4a (1# carbon nanometer).
  • Structural composite composite PET material product 4b (1# carbon nanostructure composite composite PET material) and product 4c (3# carbon nanostructure composite PET material);
  • polyester fiber is recorded as Product 4a' (1# carbon nanostructure composite composite polyester fiber), product 4b' (1# carbon nanostructure composite composite polyester fiber) and product 4c' (3# carbon nanostructure composite) Composite polyester fiber);
  • Products 4a and 4a' have a far-infrared normal emissivity of 0.91; antibacterial inhibition against Staphylococcus aureus is 99%; products 4b and 4b' have a far-infrared normal emissivity of 0.93; against Staphylococcus aureus The antibacterial and antibacterial rate is 99%; the far-infrared normal emissivity of products 4c and 4c' can reach 0.89; the antibacterial inhibition rate against Staphylococcus aureus is 93%;
  • test method is the same as in the first embodiment.
  • polyester material and the polyester fiber were prepared by the composite of 1# carbon nanostructure, the composite of 2# carbon nanostructure and the composite of 3# carbon nanostructure, respectively, and the polyester materials were respectively recorded as product 5a (1# carbon nanometer).
  • Structural composite composite PET material product 5b (1# carbon nanostructure composite composite PET material) and product 5c (3# carbon nanostructure composite composite PET material);
  • polyester fiber is recorded as Product 5a' (1# carbon nanostructure composite composite polyester fiber), product 5b' (1# carbon nanostructure composite composite polyester fiber) and product 5c' (3# carbon nanostructure composite) Composite polyester fiber);
  • the far-infrared normal emissivity of products 5a and 5a' can reach 0.87; the antibacterial inhibition rate to Staphylococcus aureus is 68%; the far-infrared normal emissivity of products 5b and 5b' can reach 0.88; antibacterial inhibition against Staphylococcus aureus
  • the bacterial rate is 75%; the far-infrared normal emissivity of products 5c and 5c' can reach 0.85; the antibacterial inhibition rate against Staphylococcus aureus is 60%;
  • test method is the same as in the first embodiment.
  • Example 2 The difference from Example 1 was that the carbon nanostructure composite was added in an amount of 500 g.
  • polyester material was prepared by the composite of 1# carbon nanostructure, which was recorded as product 6a (1# carbon nanostructure composite composite PET material); polyester fiber prepared by 1# carbon nanostructure composite was recorded as product 6a' (1# carbon nanostructure composite composite polyester fiber);
  • test method is the same as in the first embodiment.
  • Example 2 The difference from Example 1 is that the carbon nanostructure composite is added in an amount of 1000 g.
  • polyester material was prepared by the composite of 1# carbon nanostructure, and recorded as product 7a (1# carbon nanostructure composite composite PET material); polyester fiber prepared by 1# carbon nanostructure composite was recorded as product 7a' (1# carbon nanostructure composite composite polyester fiber);
  • Product 7a far infrared normal emissivity can reach 0.93; antibacterial inhibition rate for Staphylococcus aureus is 99%; product 7a' far infrared normal emissivity can reach 0.93; antibacterial inhibition rate for Staphylococcus aureus is 99% ;
  • test method is the same as in the first embodiment.
  • Example 2 The difference from Example 1 was that the carbon nanostructure composite was added to 1200 g.
  • polyester material was prepared by the composite of 1# carbon nanostructure, and it was recorded as product 8a (1# carbon nanostructure composite composite PET material); polyester fiber was prepared by 1# carbon nanostructure composite, which was recorded as product 8a' (1# carbon nanostructure composite composite polyester fiber);
  • Product 8a far infrared normal emissivity can reach 0.93; antibacterial inhibition rate for Staphylococcus aureus is 99%; product 8a' far infrared normal emissivity can reach 0.93; antibacterial inhibition rate for Staphylococcus aureus is 99% ;
  • test method is the same as in the first embodiment.
  • Example 1 The only difference from Example 1 is that no composite of carbon nanostructures is added during the polymerization of the polyester.
  • the polyester material prepared in Comparative Example 1 has a far-infrared normal emissivity of 0.76; the antibacterial inhibition rate against Staphylococcus aureus is 0%;
  • the polyester fiber prepared in Comparative Example 1 has a far-infrared normal emissivity of 0.76; the antibacterial inhibition rate against Staphylococcus aureus is 0%;
  • test method is the same as in the first embodiment.
  • Example 2 The difference from Example 1 was that the carbon nanostructure composite was added to 1400 g.
  • Comparative Example 2 The far-infrared normal emissivity of the polyester material prepared by the composite of 1# carbon nanostructure can reach 0.83; the antibacterial inhibition rate to Staphylococcus aureus is 80%;
  • Comparative Example 2 The far-infrared normal emissivity of the polyester fiber prepared by the composite of 1# carbon nanostructure can reach 0.83; the antibacterial inhibition rate to Staphylococcus aureus is 80%;
  • test method is the same as in the first embodiment.
  • a method for preparing a composite polyurethane foam the specific conditions are different from that of the first embodiment, except that the carbon nanostructure composite prepared in the embodiment is not used, but the commercially available graphene is used instead of the carbon nanometer prepared in the embodiment.
  • the structural composite is added to the polyether polyol after mixing with 1 g of phosphorus pentoxide, 1 g of silica powder, 1 g of calcium chloride, 1 g of alumina, 1 g of sodium carbonate, 1 g of magnesium chloride and 1 g of ferrous chloride.
  • the P, Si, Ca, Al, Na, Fe, and Mg elements were introduced, and the Raman spectrum showed a height ratio of the peak of the G peak and the peak of the D peak to 6.8.
  • the polyester material prepared in Comparative Example 3 had a far-infrared normal emissivity of 0.87 and an antibacterial inhibition rate of 88% against Staphylococcus aureus.
  • the polyester fiber prepared in Comparative Example 3 had a far-infrared normal emissivity of 0.87 and an antibacterial inhibition rate of 88% against Staphylococcus aureus.
  • test method is the same as in the first embodiment.
  • the present invention illustrates the process of the present invention by the above-described embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the materials selected for the present invention, and the addition of the auxiliary ingredients, the selection of the specific means, etc., are all within the scope of the present invention.

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Abstract

一种复合聚酯材料、聚酯纤维、制备方法和用途，所述聚酯材料和聚酯纤维中均含有碳纳米结构的复合物；所述碳纳米结构的复合物含有碳元素、0.5~4wt%的第一非碳非氧元素物质和0~4wt%的第二非碳非氧元素，所述第一非碳非氧元素为P、Si、Ca、Al和Na；所述第二非碳非氧元素选自Fe、Ni、Mn、K、Mg、Cr、S或Co中的任意1种或至少2种的组合；所述碳纳米结构的复合物在拉曼光谱下碳元素G峰与D峰峰高比值为1~20。通过选用特定碳纳米结构的复合物来复合聚酯材料和聚酯纤维，获得了具有更加优良的抗菌和低温远红外的性能，且提供的碳纳米结构的复合物复合的聚酯材料制备方法简单。

Description

一种复合聚酯材料、复合聚酯纤维、其制备方法和用途 技术领域
本发明属于高分子材料领域，具体涉及一种复合聚酯材料、复合聚酯纤维、制备方法和用途，特别涉及一种碳纳米结构的复合物复合的聚酯材料、复合聚酯纤维、制备方法和用途。
背景技术
聚酯，由多元醇和多元酸缩聚而得的聚合物总称。主要指聚对苯二甲酸乙二酯(PET)，习惯上也包括聚对苯二甲酸丁二酯(PBT)和聚芳酯等线型热塑性树脂。是一类性能优异、用途广泛的工程塑料。也可制成聚酯纤维和聚酯薄膜。聚酯包括聚酯树脂和聚酯弹性体。聚酯树脂又包括聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸丁二酯(PBT)和聚芳酯(PAR)等。聚酯弹性体(TPEE)一般由对苯二甲酸二甲酯、1，4-丁二醇和聚丁醇聚合而成，链段包括硬段部分和软段部分，为热塑性弹性体。
碳纳米材料是指分散相尺度至少有一维小于100nm的碳材料，例如碳纳米管、石墨烯等。石墨烯是一种由单层sp2杂化碳原子组成的蜂窝状结构的二维材料，具有许多优异的性能。自从2004年被发现起，石墨烯就成为了科学界的一大研究热点，在对石墨烯的物理化学性质进行研究的同时，与石墨烯相关的复合材料层出不穷。在纳米科学方向上，石墨烯也被用来制备相关的纳米复合材料，尤其是石墨烯/金属或石墨烯/金属氧化物的纳米复合材料。由于石墨烯的优异性能，这些纳米复合材料在新型能源、生物传感、催化、光学材料等领域有着广阔的研究前景。
聚酯纤维(polyester fibre)是指由多种二元醇和芳香族二元羧酸或其酯经 缩聚生成的聚酯为原料所制得纤维的统称。常见的聚酯纤维一般包括聚对苯二甲酸乙二酯纤维，聚对苯二甲酸丁二酯纤维，聚对苯二甲酸丙二酯纤维，聚对苯二甲酸-1，4-环己二甲酯纤维，聚-2，6-萘二酸乙二酯纤维，以及多种改性的聚对苯二甲酸乙二酯纤维(如：CDP，ECDP，EDDP)等。
工业化大量生产的聚酯纤维是用聚对苯二甲酸乙二醇酯(PET)制成的，中国的商品名为涤纶，是化纤制品中产量最大的品种，占据着化纤产品近80％的市场份额；纤维级聚酯切片是供给涤纶纤维企业加工纤维用于制造涤纶短纤和涤纶长丝的直接原材料，其化学结构式为：
Figure PCTCN2016093116-appb-000001
由对苯二甲酸(PTA)和乙二醇(EG)经过酯化和缩聚产生PET熔体，PET熔体再通过水下切粒而生成PET母粒，然后进行纺丝。
以PET为例，聚酯的工业化合成工艺一般包括如下三个主要工段：
①原料打浆混合工段：主要完成原料，包括PTA(对苯二甲酸)、EG(乙二醇)、催化剂、其他助剂)的均匀混合；
②聚酯的预聚合工段：完成反应物的预聚合并形成了小分子聚合物，这一工段在具体生产中常分拆为一酯化、和二酯化两个反应段来完成反应副产物如水的脱除和功能性填料的引入；
③缩聚工段：主要是实现小分子聚合物的相互聚合，扩链增粘的过程，实际生产中该工段常拆分为预缩聚(低真空聚合)和终缩聚(高真空聚合)两个反应段。
④纺丝工段。
但纯聚酯纤维产品吸湿性能较差，在干燥气候下容易积聚电荷形成静电，穿着和使用时产生静电，舒适感难于与天然棉纤维相媲美(一般合成纤维的体积电阻率在1015Ω·cm以上，而要使人体感觉舒适，不产生放电现象，纤维的体积电阻率应在1010Ω·cm以下)。此外，改善聚酯纤维的抗菌性、阻燃抗熔滴、抗紫外也是提高聚酯纤维应用价值的重要方向。
碳纳米材料是指分散相尺度至少有一维小于100nm的碳材料，例如碳纳米管、石墨烯等。石墨烯是一种由单层sp2杂化碳原子组成的蜂窝状结构的二维材料，具有许多优异的性能。自从2004年被发现起，石墨烯就成为了科学界的一大研究热点，在对石墨烯的物理化学性质进行研究的同时，与石墨烯相关的复合材料层出不穷。在纳米科学方向上，石墨烯也被用来制备相关的纳米复合材料，尤其是石墨烯/金属或石墨烯/金属氧化物的纳米复合材料。由于石墨烯的优异性能，这些纳米复合材料在新型能源、生物传感、催化、光学材料等领域有着广阔的研究前景。
普通碳纳米材料由于其表面无官能团，很难与PET进行复合，从而阻碍改性PET制备高性能材料的发展。
CN103938293A公开了一种远红外聚酯纤维及其制备方法，该远红外聚酯纤维的原料按照重量份数配置包括：聚酯切片65～85份和远红外母粒15～35份，所述远红外母粒的原料按照重量份数配置包括：聚酯切片75～90份，纳米远红外粉体10～20份，硅烷偶联剂0.5～5份，聚乙烯蜡0.5～5份，三[2.4-二叔丁基苯基]亚磷酸酯0.05～1份和四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯0.05～1份。
CN1308148A公开了一种远红外辐射中空三维卷曲聚酯纤维及其制作方法，将0.3～0.5μm的复合无机远红外超细材料，与钛酸酯类偶联剂和表面活性剂 一同加入到高速搅拌机中进行干法表面处理，表面处理后的超细材料粉体与聚酯载体在高速混合机中混合，得到的混合粉料送到双螺杆挤出机中共混挤出，其工作温度较常规制作色母粒温度低10～30℃，将上述得到的远红外母粒和聚酯切片经计量加料器加料送至混合器混合，然后送至制作中空三维卷曲纤维的螺杆纺丝机进行纺丝，最后得到的成品即为本发明远红外辐射中空三维卷曲聚酯纤维。所述多种远红外无机材料，其基本成份为二氧化硅、三氧化二铝、二氧化钛、二氧化锆的混合体，用超细气流粉碎机粉碎，粉碎至其粒径在0.3-0.5μm，将粉碎后的远红外无机材料粉体置于高温炉中烧结，烧结温度为800-1100℃，烧结冷却后再粉碎，使粒径仍控制在0.3-0.5μm，得到0.3-0.5μm的复合无机远红外超细材料。
发明内容
本发明为解决以上问题，本发明目的之一在于提供一种复合聚酯材料，所述聚酯材料中含有碳纳米结构的复合物；
所述碳纳米结构的复合物含有碳元素、0.5～4wt％的第一非碳非氧元素物质和0～4wt％的第二非碳非氧元素，所述第一非碳非氧元素物质为第一非碳非氧元素的单质、化合物中的任意1种或至少2种的组合；所述第一非碳非氧元素为P、Si、Ca、Al和Na；所述第二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；所述第二非碳非氧元素选自Fe、Ni、Mn、K、Mg、Cr、S或Co中的任意1种或至少2种的组合；
所述碳纳米结构的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；可选地，所述碳纳米结构的复合物在拉曼光谱下还存在2D峰。
本发明选用特定的碳纳米结构的复合物作为复合原料，与聚酯材料复合， 示例性的复合方式可以采用原位聚合、熔融混合或溶液混合中的任意1种，优选地，无需对碳纳米结构的复合物进行改性，只需要简单混合聚酯材料的聚合单体和碳纳米结构的复合物，或者简单混合聚酯材料和碳纳米结构的复合物即可。
本发明的目的之二是提供一种复合聚酯纤维，所述聚酯纤维中含有碳纳米结构的复合物；
所述碳纳米结构的复合物含有碳元素、0.5～4wt％的第一非碳非氧元素物质和0～4wt％的第二非碳非氧元素，所述第一非碳非氧元素物质为第一非碳非氧元素的单质、化合物中的任意1种或至少2种的组合；所述第一非碳非氧元素为P、Si、Ca、Al和Na；所述第二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；所述第二非碳非氧元素选自Fe、Ni、Mn、K、Mg、Cr、S或Co中的任意1种或至少2种的组合；
所述碳纳米结构的复合物在拉曼光谱下碳元素G峰与D峰峰高比值为1～20；可选地，所述碳纳米结构的复合物在拉曼光谱下还存在2D峰。
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；2D峰体现了石墨烯片层厚薄程度。
本发明所述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。
本发明选用特定的碳纳米结构的复合物作为复合原料，与对聚酯材料进行复合，无需提前对碳纳米结构的复合物进行改性，只需要简单将碳纳米结构的复合物加入现有的聚酯纤维的聚合工艺中即可。
本发明所述聚酯材料中含有石墨烯；
所述石墨烯是通过碳纳米结构复合物的形式引入；所述碳纳米结构复合物 中包括石墨烯，以及SP3杂化结构的碳。
本发明所述聚酯纤维中含有石墨烯；
所述石墨烯是通过碳纳米结构复合物的形式引入；所述碳纳米结构复合物中包括石墨烯，以及SP3杂化结构的碳。
所述碳纳米结构复合物的远红外检测法向发射率大于0.85，例如0.87、0.89、0.91、0.92、0.93等；优选地，碳纳米结构复合物的远红外检测法向发射率大于0.88。
所述碳纳米结构的复合物中，所述碳元素的含量≥80wt％，例如82wt％、86wt％、89wt％、91wt％、94wt％、97wt％、99wt％等，优选85～97wt％，进一步优选90～95wt％。
优选地，所述碳纳米结构的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。
优选地，碳纳米结构的复合物具有厚度在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。
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。
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、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。
优选地，所述碳纳米结构的复合物中，第一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，所述碳纳米结构的复合物中，第一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、农林废弃物中的任意1种或至少2种的组合；所述农林废弃物优选自玉米杆、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。
优选地，所述复合聚酯材料中，碳纳米结构的复合物的含量为0.1～10wt％，例如0.2wt％、1wt％、3wt％、4wt％、6wt％、8wt％、9wt％等，优选0.5～7wt％，进一步优选1～5wt％，特别优选2～4wt％。
优选地，所述碳纳米结构复合物的远红外检测法向发射率大于0.88。
本发明对聚酯的种类不做具体限定，典型但非限制性的聚酯包括聚对苯二甲酸乙二酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二酯、聚对苯二甲酸-1，4-环己二甲酯、聚-2，6-萘二酸乙二酯、以及多种改性的聚对苯二甲酸乙二酯(如：CDP，ECDP，EDDP)等，任何一种本领域技术人员能够获知的聚酯均可用于本发明；本发明优选工业化大量生产PET聚酯。
本发明目的之三是提供一种如目的之一所述复合聚酯材料的制备方法，所述方法为：将聚酯材料熔融，然后向其中加入碳纳米结构的复合物，冷却后得到如目的之一所述复合聚酯材料；优选地，碳纳米结构的复合物无需进行改性。
优选地，所述碳纳米结构的复合物的添加量为聚酯材料的0.1～10wt％，例如0.2wt％、1wt％、3wt％、4wt％、6wt％、8wt％、9wt％等，优选0.5～7wt％，进一步优选1～5wt％，特别优选2～4wt％。
本发明目的之四是提供第二种如目的之一所述复合聚酯材料的制备方法，所述方法为：将聚酯材料溶解于溶剂中，然后向其中加入碳纳米结构的复合物，除去溶剂后得到如目的之一所述复合聚酯材料；优选地，碳纳米结构的复合物无需进行改性。
优选地，所述碳纳米结构的复合物的添加量为聚酯材料的0.1～10wt％，例如0.2wt％、1wt％、3wt％、4wt％、6wt％、8wt％、9wt％等，优选0.5～7wt％，进一步优选1～5wt％，特别优选2～4wt％。
优选地，所述溶剂为氟乙酸、苯酚与四氯乙烷的混合溶液、四氢呋喃中的任意1种或至少2种的组合；所述组合典型但非限制性的包括氟乙酸和苯酚的组合，苯酚与四氯乙烷的混合溶液和四氢呋喃的组合，氟乙酸和四氢呋喃的组合等。
优选地，所述除去溶剂的方式为蒸馏。
本发明目的之五是提供第三种如目的之一所述复合聚酯材料的制备方法，所述方法包括如下步骤：
在聚酯材料聚合过程中引入碳纳米结构的复合物进行原位复合，反应完毕得到熔体，熔体出料得到如目的之一所述复合聚酯材料；优选地，碳纳米结构的复合物无需进行改性。
优选地，所述碳纳米结构的复合物的添加量为聚酯材料的0.1～10wt％，例如0.2wt％、1wt％、3wt％、4wt％、6wt％、8wt％、9wt％等。
优选地，所述碳纳米结构的复合物以碳纳米结构的复合物干粉的形式加入， 或者以碳纳米结构的复合物分散液的形式加入。
优选地，所述碳纳米结构的复合物分散液的分散剂选自去离子水、蒸馏水、乙醇、乙二醇、对苯二甲酸、醋酸钠溶液、十二烷基苯磺酸、蓖麻油聚氧乙烯醚中的任意1种或至少2种的组合。
优选地，引入碳纳米结构的复合物的时机选自原料打浆阶段、酯化预聚合阶段、预缩聚阶段、终缩聚阶段中的任意1种或至少2种的组合，优选为原料打浆阶段。
优选地，所述熔体出料的条件为：在20～75℃冷却水，0.01～1m/s牵伸速度的条件下出料。
作为目的之五的优选技术方案，本发明所述复合聚酯材料的制备方法包括如下步骤：
(1)将多元酸、多元醇和碳纳米结构的复合物打浆混匀后投入反应釜，之后经过酯化预聚合阶段、预缩聚阶段、终缩聚阶段完成聚合反应，得到熔体；
(2)熔体在20～75℃冷却水，0.01～1m/s牵伸速度的条件下出料，直接造粒得到目的之一所述复合聚酯材料。
在本发明目的之三、目的之四和目的之五提供的复合聚酯材料的制备方法中，所述碳纳米结构的复合物通过如下方法获得：
(i)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；
(ii)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；
(iii)将粗品洗涤后，得到碳纳米结构的复合物。
优选地，所述生物质碳源和催化剂的质量比为1∶0.1～10，例如1∶2、1∶4、1∶6、1∶8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；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。
进一步优选地，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。
优选地，步骤(i)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；所述前驱体中的水分含量优选为10wt％以下，例如1wt％、2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、1wt％等；步骤(ii)所述前驱体升温至280～350℃的升温速率优选为3～5℃/min，例如3.5℃/min、3.8℃/min、4.2℃/min、4.5℃/min、4.8℃/min等；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；步骤(iii)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；所述洗涤的温度为55～65℃，例如56℃、57℃、58℃、60℃、63℃等，优选60℃。
优选地，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；所述生物质资源优选自植物和/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；所述农林废弃物优选自玉米杆、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。
本发明的目的之六是提供一种如目的之二所述复合聚酯纤维的制备方法为：
将目的之五得到的复合聚酯材料切粒得到复合聚酯母粒，复合聚酯母粒熔融纺丝，得到碳纳米结构的复合物复合的聚酯纤维。
所述熔融纺丝工艺为预取向丝工艺；
优选地，所述预取向丝的出丝温度为30～70℃，出丝湿度为10～90％；优选出丝温度为55～65℃，出丝湿度为40～50％；进一步优选出丝温度为62℃，出丝湿度为42％；
优选地，所述出丝采用风冷或水冷；
优选地，所述熔体出料时冷却水的温度为20～75℃，优选40℃；
优选地，所述熔体出料的牵伸速度为0.01～1m/s。
作为目的之六的优选技术方案，所述复合聚酯纤维的制备方法包括如下步骤：
(1)将多元酸、多元醇和碳纳米结构的复合物打浆混匀后投入反应釜，在催化剂作用下，酯化和缩聚完成聚合反应，得到熔体；
(2)熔体在20～75℃冷却水，0.01～1m/s牵伸速度的条件下出料，直接造粒得到母粒；
(3)将母粒在30～70℃出丝温度，10～90％出丝湿度条件下，采用风冷或水冷，熔融纺丝，得到碳纳米结构的复合物复合聚酯纤维。
本发明目的之七是提供一种目的之一所述的复合聚酯材料的用途，所述复合聚酯材料通过熔融纺丝制备聚酯纤维，所述复合聚酯材料通过流延刮涂法制备聚酯薄膜，所述复合聚酯材料用于制备管材、家具、型材，包括但不限于上述复合聚酯材料的进一步用途，只要是利用本发明制备得到的复合聚酯材料及其母料，通过再加工的方法进一步制备得到的聚酯产品都属于本发明的保护范围。
本发明目的之八是提供一种如目的之二所述复合聚酯纤维的用途，所述复合聚酯纤维用于制备民用服装、家纺织物、紫外防护织物、工业用特种防护服等，包括但不限于上述产品，只要是利用本发明原理制备得到的复合聚酯纤维 通过再加工手段得到任何形式的纺织品、织物或其他形式的产品都属于本发明保护的范畴。
与现有技术相比，本发明具有以下有益效果：
(1)本发明通过选用特定碳纳米结构的复合物，来复合聚酯材料，获得了具有更加优良的抑菌和低温远红外的性能，远红外法向发射率大于0.85；
(2)本发明提供的碳纳米结构复合物复合的聚酯材料制备方法简单，碳纳米结构的复合物无需进行改性处理，聚合后得到的复合聚酯材料的熔体直接出料即可，无需进行后处理，工艺简单。
(3)本发明提供的碳纳米结构的复合物复合的聚酯纤维的制备方法无需对碳纳米结构的复合物进行改性，保留碳纳米结构的复合物固有优良属性，降低了成本，简化了工艺流程；并且能够直接采用现有的聚酯合成和纺丝设备进行制备，实现了碳纳米结构的复合物复合的聚酯复合工艺与常规聚酯母粒制备和纺丝工艺的无缝对接，易于工业化推广；
(4)本发明制备得到的碳纳米结构的复合物复合的聚酯纤维无需进行后处理即可得到预期的多重优异性能，例如远红外法向发射率能达到0.85以上，并且具有很好的抑菌效果。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
碳纳米结构的复合物的制备
(1)参考CN104016341A指标多孔纤维素具体为：
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；
(2)制备碳纳米结构复合物，具体为：
按质量比1∶0.1～10混合多孔纤维素和催化剂，在150～200℃下搅拌进行催化处理4h以上，干燥至前驱体水分含量10wt％以下，得到前驱体；然后，在保护性气氛中，以3～5℃/min速率将前驱体升温至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；在55～65℃下，将粗品经过浓度为3～6wt％的盐酸酸洗后，水洗得到碳纳米结构的复合物。
1#碳纳米结构的复合物的制备条件为：
步骤(2)中，催化剂为氯化亚铁；多孔纤维素和催化剂的混合质量比为1∶0.1；催化处理温度为150℃，时间为4h；前驱体中的水分含量为10wt％；
得到粗品的过程为：以3℃/min的速率升温至280℃，保温2h，之后以15℃/min的速率升温至950℃，保温3h；
酸洗温度为55℃，酸洗使用的盐酸浓度为4wt％；
1#碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg元素；且拉曼光谱显示G峰、D峰峰高比值高度比为7；存在2D峰；
2#碳纳米结构的复合物的制备过程与1#碳纳米结构的复合物的制备过程的区别仅在于：步骤(2)中多孔纤维素与氯化亚铁的比值变为1∶10；得到的2#碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg元素；且拉曼光谱显示G峰、D峰峰高比值高度比为20。
3#碳纳米结构的复合物的制备过程与1#碳纳米结构的复合物的制备过程的区别仅在于：步骤(2)中多孔纤维素与氯化亚铁的比值变为1∶0.5；得到的2#碳纳米结构的复合物中主要含有P、Si、Ca、Al、Na、Fe、Mg元素；且拉曼光谱显示G峰、D峰峰高比值高度比为1.5。
实施例1
一种复合聚酯材料，通过如下方法制备得到：
(1)将100g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，直接造粒得到碳纳米结构复合物复合PET材料(PET母粒)；
一种复合聚酯纤维，是在步骤(2)之后进行步骤(3)将碳纳米结构的复合物复合PET母粒在110℃下，转鼓干燥24h后，直接用于熔融纺丝，纺丝出丝采用水雾冷却，冷却温度40℃，烘干温度35℃，熔融纺丝得到复合聚酯纤维。
分别以1#碳纳米结构的复合物、2#碳纳米结构的复合物、3#碳纳米结构的复合物制备聚酯材料和聚酯纤维，聚酯材料分别记为产品1a(1#碳纳米结构的复合物复合的PET材料)、产品1b(1#碳纳米结构的复合物复合的PET材料) 和产品1c(3#碳纳米结构的复合物复合的PET材料)；聚酯纤维分别记为产品1a’(1#碳纳米结构的复合物复合的聚酯纤维)、产品1b’(1#碳纳米结构的复合物复合的聚酯纤维)和产品1c’(3#碳纳米结构的复合物复合的聚酯纤维)；
产品1a和1a’远红外法向发射率能达到0.87；对金黄色葡萄球菌抗菌抑菌率为70％；产品1b和1b’远红外法向发射率能达到0.89；对金黄色葡萄球菌抗菌抑菌率为82％；产品1c和1c’远红外法向发射率能达到0.85；对金黄色葡萄球菌抗菌抑菌率为60％；
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。
实施例2
一种复合聚酯材料，通过如下方法制备得到：
(1)将200g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，直接造粒得到碳纳米结构复合物复合PET材料(PET母粒)；
一种复合聚酯纤维，是在步骤(2)之后进行步骤(3)将碳纳米结构的复合物复合PET母粒在110℃下，转鼓干燥24h后，直接用于熔融纺丝，纺丝出丝采用水雾冷却，冷却温度40℃，烘干温度35℃，熔融纺丝得到碳纳米结构的复合物复合聚酯纤维。
分别以1#碳纳米结构的复合物、2#碳纳米结构的复合物、3#碳纳米结构的复合物制备聚酯材料和聚酯纤维，聚酯材料分别记为产品2a(1#碳纳米结构的复合物复合的PET材料)、产品2b(1#碳纳米结构的复合物复合的PET材料)和产品2c(3#碳纳米结构的复合物复合的PET材料)；聚酯纤维分别记为产品2a’(1#碳纳米结构的复合物复合的聚酯纤维)、产品2b’(1#碳纳米结构的复合物复合的聚酯纤维)和产品2c’(3#碳纳米结构的复合物复合的聚酯纤维)；
产品2a和产品2a’远红外法向发射率能达到0.90；对金黄色葡萄球菌抗菌抑菌率为95％；产品2b和产品2b’远红外法向发射率能达到0.92；对金黄色葡萄球菌抗菌抑菌率为97％；产品2c和产品2c’远红外法向发射率能达到0.88；对金黄色葡萄球菌抗菌抑菌率为90％；
测试方法与实施例1相同。
实施例3：
一种复合聚酯材料，通过如下方法制备得到：
(1)PTA 8.52kg、EG 3.5L和催化剂乙二醇锑3.8g，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)将熔体溶解于三氟乙酸中，加入200g碳纳米结构的复合物研磨10min，分散均匀；
在40℃冷却水，0.5m/s牵伸速度条件下出料，直接造粒得到碳纳米结构的复合物复合PET材料(PET母粒)；
一种复合聚酯纤维，是在步骤(2)之后进行步骤(3)将碳纳米结构的复合物复合PET母粒在110℃下，转鼓干燥24h后，直接用于熔融纺丝，纺丝出丝采用水雾冷却，冷却温度40℃，烘干温度35℃，熔融纺丝得到碳纳米结构的 复合物复合聚酯纤维。
分别以1#碳纳米结构的复合物、2#碳纳米结构的复合物、3#碳纳米结构的复合物制备聚酯材料和聚酯纤维，聚酯材料分别记为产品3a(1#碳纳米结构的复合物复合的PET材料)、产品3b(1#碳纳米结构的复合物复合的PET材料)和产品3c(3#碳纳米结构的复合物复合的PET材料)；聚酯纤维分别记为产品3a’(1#碳纳米结构的复合物复合的聚酯纤维)、产品3b’(1#碳纳米结构的复合物复合的聚酯纤维)和产品3c’(3#碳纳米结构的复合物复合的聚酯纤维)；
产品3a和3a’其远红外法向发射率能达到0.89；对金黄色葡萄球菌抗菌抑菌率为90％；产品3b和3b’其远红外法向发射率能达到0.90；对金黄色葡萄球菌抗菌抑菌率为95％；产品3c和3c’其远红外法向发射率能达到0.87；对金黄色葡萄球菌抗菌抑菌率为88％；
测试方法与实施例1相同。
实施例4：
一种复合聚酯材料，通过如下方法制备得到：
(1)600mL乙二醇引入到含有8.52kg PTA和3L乙二醇的打浆釜中，加乙二醇锑3.8g继续打浆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；在聚合反应的二酯化和缩聚中应排除过量的EG；
(2)将熔体加热熔融后，加入300g碳纳米结构的复合物研磨10min；
熔体在40℃冷却水，0.5m/s牵伸速度条件下出料，直接造粒得到碳纳米结构的复合物复合的PET材料(PET母粒)；
一种复合聚酯纤维，是在步骤(2)之后进行步骤(3)将碳纳米结构的复 合物复合PET母粒在110℃下，转鼓干燥24h后，直接用于熔融纺丝，纺丝出丝采用水雾冷却，冷却温度40℃，烘干温度35℃，熔融纺丝得到碳纳米结构的复合物复合聚酯纤维。
分别以1#碳纳米结构的复合物、2#碳纳米结构的复合物、3#碳纳米结构的复合物制备聚酯材料和聚酯纤维，聚酯材料分别记为产品4a(1#碳纳米结构的复合物复合的PET材料)、产品4b(1#碳纳米结构的复合物复合的PET材料)和产品4c(3#碳纳米结构的复合物复合的PET材料)；聚酯纤维分别记为产品4a’(1#碳纳米结构的复合物复合的聚酯纤维)、产品4b’(1#碳纳米结构的复合物复合的聚酯纤维)和产品4c’(3#碳纳米结构的复合物复合的聚酯纤维)；
产品4a和4a’其远红外法向发射率能达到0.91；对金黄色葡萄球菌抗菌抑菌率为99％；产品4b和4b’其远红外法向发射率能达到0.93；对金黄色葡萄球菌抗菌抑菌率为99％；产品4c和4c’其远红外法向发射率能达到0.89；对金黄色葡萄球菌抗菌抑菌率为93％；
测试方法与实施例1相同。
实施例5：
一种复合聚酯材料，通过如下方法制备得到：
(1)称取8.52kg PTA和3.5L乙二醇的打浆釜中，加乙二醇锑3.8g打浆30min，按照利用三釜PET聚合工艺条件进行一酯化反应，一酯化40min后，倒料至二酯化釜，将球磨20min的碳纳米结构的复合物/乙二醇浆料(100g碳纳米结构的复合物/200mL乙二醇)引入到二酯化釜，完成后续聚合反应得到熔体；在聚合反应的二酯化和缩聚中应排除过量的EG；
(2)熔体在40℃冷却水，0.5m/s牵伸速度条件下出料，直接造粒得到碳纳 米结构的复合物复合PET材料(PET母粒)。
分别以1#碳纳米结构的复合物、2#碳纳米结构的复合物、3#碳纳米结构的复合物制备聚酯材料和聚酯纤维，聚酯材料分别记为产品5a(1#碳纳米结构的复合物复合的PET材料)、产品5b(1#碳纳米结构的复合物复合的PET材料)和产品5c(3#碳纳米结构的复合物复合的PET材料)；聚酯纤维分别记为产品5a’(1#碳纳米结构的复合物复合的聚酯纤维)、产品5b’(1#碳纳米结构的复合物复合的聚酯纤维)和产品5c’(3#碳纳米结构的复合物复合的聚酯纤维)；
产品5a和5a’远红外法向发射率能达到0.87；对金黄色葡萄球菌抗菌抑菌率为68％；产品5b和5b’远红外法向发射率能达到0.88；对金黄色葡萄球菌抗菌抑菌率为75％；产品5c和5c’远红外法向发射率能达到0.85；对金黄色葡萄球菌抗菌抑菌率为60％；
测试方法与实施例1相同。
实施例6
与实施例1的区别点在于加入碳纳米结构复合物为500g。
以1#碳纳米结构的复合物制备聚酯材料，记为产品6a(1#碳纳米结构的复合物复合的PET材料)；以1#碳纳米结构的复合物制备聚酯纤维，记为产品6a’(1#碳纳米结构的复合物复合的聚酯纤维)；
产品6a远红外法向发射率能达到0.92；对金黄色葡萄球菌抗菌抑菌率为99％；
产品6a远红外法向发射率能达到0.92；对金黄色葡萄球菌抗菌抑菌率为99％；
测试方法与实施例1相同。
实施例7
与实施例1的区别点在于加入碳纳米结构复合物为1000g。
以1#碳纳米结构的复合物制备聚酯材料，记为产品7a(1#碳纳米结构的复合物复合的PET材料)；以1#碳纳米结构的复合物制备聚酯纤维，记为产品7a’(1#碳纳米结构的复合物复合的聚酯纤维)；
产品7a远红外法向发射率能达到0.93；对金黄色葡萄球菌抗菌抑菌率为99％；产品7a’远红外法向发射率能达到0.93；对金黄色葡萄球菌抗菌抑菌率为99％；
测试方法与实施例1相同。
实施例8
与实施例1的区别点在于加入碳纳米结构复合物为1200g。
以1#碳纳米结构的复合物制备聚酯材料，记为产品8a(1#碳纳米结构的复合物复合的PET材料)；以1#碳纳米结构的复合物制备聚酯纤维，记为产品8a’(1#碳纳米结构的复合物复合的聚酯纤维)；
产品8a远红外法向发射率能达到0.93；对金黄色葡萄球菌抗菌抑菌率为99％；产品8a’远红外法向发射率能达到0.93；对金黄色葡萄球菌抗菌抑菌率为99％；
测试方法与实施例1相同。
对比例1
与实施例1的区别仅在于在聚酯聚合过程中不加入碳纳米结构的复合物。
对比例1制备的聚酯材料，远红外法向发射率能达到0.76；对金黄色葡萄球菌抗菌抑菌率为0％；
对比例1制备的聚酯纤维，远红外法向发射率能达到0.76；对金黄色葡萄球菌抗菌抑菌率为0％；
测试方法与实施例1相同。
对比例2
与实施例1的区别点在于加入碳纳米结构复合物为1400g。
对比例2以1#碳纳米结构的复合物制备聚酯材料的远红外法向发射率能达到0.83；对金黄色葡萄球菌抗菌抑菌率为80％；
对比例2以1#碳纳米结构的复合物制备聚酯纤维的远红外法向发射率能达到0.83；对金黄色葡萄球菌抗菌抑菌率为80％；
测试方法与实施例1相同。
对比例3
一种复合聚氨酯泡沫的制备方法，具体条件与实施例1相比，区别仅在于不使用实施例中制备的碳纳米结构复合物，而是采用商购的石墨烯替代实施例中制备的碳纳米结构复合物，并与1g五氧化二磷、1g二氧化硅粉末、1g份氯化钙、1g三氧化二铝、1g碳酸钠、1g氯化镁和1g氯化亚铁混合后加入聚醚多元醇中，引入P、Si、Ca、Al、Na、Fe、Mg元素，拉曼光谱显示G峰、D峰峰高比值高度比为6.8。
对比例3制备的聚酯材料，远红外法向发射率能达到0.87；对金黄色葡萄球菌抗菌抑菌率为88％。
对比例3制备的聚酯纤维，远红外法向发射率能达到0.87；对金黄色葡萄球菌抗菌抑菌率为88％。
测试方法与实施例1相同。
申请人声明，本发明通过上述实施例来说明本发明的工艺方法，但本发明并不局限于上述工艺步骤，即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (19)

  1. 一种复合聚酯材料，其特征在于，所述聚酯材料中含有碳纳米结构的复合物；
    所述碳纳米结构的复合物含有碳元素、0.5～4wt％的第一非碳非氧元素物质和0～4wt％的第二非碳非氧元素，所述第一非碳非氧元素物质为第一非碳非氧元素的单质、化合物中的任意1种或至少2种的组合；所述第一非碳非氧元素为P、Si、Ca、Al和Na；所述第二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；所述第二非碳非氧元素选自Fe、Ni、Mn、K、Mg、Cr、S或Co中的任意1种或至少2种的组合；
    所述碳纳米结构的复合物在拉曼光谱下碳元素G峰与D峰峰高比值为1～20；可选地，所述碳纳米结构的复合物在拉曼光谱下还存在2D峰。
  2. 如权利要求1所述的复合聚酯材料，其特征在于，所述碳纳米结构复合物的远红外检测法向发射率大于0.85。
  3. 如权利要求1或2所述的复合聚酯材料，其特征在于，所述复合聚酯材料中，碳纳米结构的复合物的含量为0.1～10wt％。
  4. 如权利要求1～3之一所述的复合聚酯材料，其特征在于，所述碳纳米结构的复合物中，所述碳元素的含量≥80wt％；
    优选地，碳纳米结构的复合物具有厚度在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、折叠构象中的任意1种或至少2种的组合；
    优选地，所述碳纳米结构的复合物中，第一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，所述碳纳米结构的复合物中，第一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、农林废弃物中的任意1种或至少2种的组合；所述农林废弃物优选自玉米杆、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。
  5. 一种如权利要求1～4之一所述复合聚酯材料的制备方法，其特征在于，所述方法为：将聚酯材料熔融，然后向其中加入碳纳米结构的复合物，冷却后得到复合聚酯材料；
    优选地，碳纳米结构的复合物无需进行改性；
    优选地，所述碳纳米结构的复合物的添加量为聚酯材料的0.1～10wt％，优选0.5～7wt％，进一步优选1～5wt％，特别优选2～4wt％。
  6. 一种如权利要求1～4之一所述复合聚酯材料的制备方法，其特征在于，所述方法为：将聚酯材料溶解于溶剂中，然后向其中加入碳纳米结构的复合物，除去溶剂后得到复合聚酯材料；
    优选地，所述碳纳米结构的复合物无需进行改性；
    优选地，所述生物质石墨烯的添加量为聚酯材料的0.1～10wt％；
    优选地，所述溶剂为氟乙酸、苯酚与四氯乙烷的混合溶液、四氢呋喃中的任意1种或至少2种的组合；
    优选地，所述除去溶剂的方式为蒸馏。
  7. 一种如权利要求1～4之一所述复合聚酯材料的制备方法，其特征在于， 所述方法包括如下步骤：
    在聚酯材料聚合过程中引入碳纳米结构的复合物进行原位复合，反应完毕得到熔体，熔体出料得到复合聚酯材料；
    优选地，碳纳米结构的复合物无需进行改性；
    优选地，所述碳纳米结构的复合物的添加量为聚酯材料的0.1～10wt％；
    优选地，所述碳纳米结构的复合物以碳纳米结构的复合物干粉的形式加入，或者以碳纳米结构的复合物分散液的形式加入；
    优选地，所述碳纳米结构的复合物分散液的分散剂选自去离子水、蒸馏水、乙醇、乙二醇、对苯二甲酸、醋酸钠溶液、十二烷基苯磺酸、蓖麻油聚氧乙烯醚中的任意1种或至少2种的组合。
  8. 如权利要求7所述的方法，其特征在于，引入碳纳米结构的复合物的时机选自原料打浆阶段、酯化预聚合阶段、预缩聚阶段、终缩聚阶段中的任意1种或至少2种的组合，优选为原料打浆阶段；
    优选地，所述熔体出料的条件为：在20～75℃冷却水，0.01～1m/s牵伸速度的条件下出料。
  9. 如权利要求7或8所述的方法，其特征在于，所述方法包括如下步骤：
    (1)将多元酸、多元醇和碳纳米结构的复合物经过打浆混匀后投入反应釜，之后经过酯化预聚合阶段、预缩聚阶段、终缩聚阶段完成聚合反应，得到熔体；
    (2)熔体在20～75℃冷却水，0.01～1m/s牵伸速度的条件下出料，直接造粒得到权利要求1所述复合聚酯材料。
  10. 如权利要求7～9之一所述的方法，其特征在于，所述碳纳米结构的复合物通过如下方法获得：
    (i)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；
    (ii)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；
    (iii)将粗品洗涤后，得到碳纳米结构的复合物；
    优选地，所述生物质碳源和催化剂的质量比为1∶0.1～10，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；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；
    进一步优选地，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；
    优选地，步骤(i)所述搅拌进行催化处理的温度为150～200℃，时间≥4h，优选4～14h；所述前驱体中的水分含量优选为10wt％以下；步骤(ii)所述前驱体升温至280～350℃的升温速率优选为3～5℃/min；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；步骤(iii)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；所述洗涤的温度为55～65℃，优选60℃。
    优选地，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；
    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；所述生物质资源优选自植物和/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；所述农林废弃物优选自玉米杆、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。
  11. 一种如权利要求1～4之一所述的复合聚酯材料的用途，其特征在于，所述复合聚酯材料通过熔融纺丝制备聚酯纤维；
    优选地，所述复合聚酯材料通过流延刮涂法制备聚酯薄膜；
    优选地，所述复合聚酯材料用于制备管材、家具、型材。
  12. 一种复合聚酯纤维，其特征在于，所述聚酯纤维中含有碳纳米结构的复合物；
    所述碳纳米结构的复合物含有碳元素、0.5～4wt％的第一非碳非氧元素物质和0～4wt％的第二非碳非氧元素，所述第一非碳非氧元素物质为第一非碳非氧元素的单质、化合物中的任意1种或至少2种的组合；所述第一非碳非氧元素为P、Si、Ca、Al和Na；所述第二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；所述第二非碳非氧元素选自Fe、Ni、Mn、K、Mg、Cr、S或Co中的任意1种或至少2种的组合；
    所述碳纳米结构的复合物在拉曼光谱下碳元素G峰与D峰峰高比值为1～20；可选地，所述碳纳米结构的复合物在拉曼光谱下还存在2D峰。
  13. 如权利要求12所述的复合聚酯纤维，其特征在于，所述碳纳米结构复合物的远红外检测法向发射率大于0.85。
  14. 如权利要求12或13所述的复合聚酯纤维，其特征在于，所述复合聚酯材料中，碳纳米结构的复合物的含量为0.1～10wt％。
  15. 如权利要求12～14之一所述的复合聚酯纤维，其特征在于，所述碳纳米结构的复合物中，所述碳元素的含量≥80wt％；
    优选地，碳纳米结构的复合物具有厚度在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、折叠构象中的任意1种或至少2种的组合；
    优选地，所述碳纳米结构的复合物中，第一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，所述碳纳米结构的复合物中，第一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、农林废弃物中的任意1种或至少2种的组合；所述农林废弃物优选自玉米杆、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。
  16. 一种如权利要求12～15之一所述复合聚酯纤维的制备方法，其特征在于，所述方法为：
    将权利要求7～10之一得到的复合聚酯材料切粒得到复合聚酯母粒，复合聚酯母粒熔融纺丝，得到碳纳米结构的复合物复合的聚酯纤维。
  17. 如权利要求16所述的方法，其特征在于，所述熔融纺丝工艺为预取向丝工艺；
    优选地，所述预取向丝的出丝温度为30～70℃，出丝湿度为10～90％；优选出丝温度为55～65℃，出丝湿度为40～50％；进一步优选出丝温度为62℃，出丝湿度为42％；
    优选地，所述出丝采用风冷或水冷；
    优选地，所述熔体出料时冷却水的温度为20～75℃，优选40℃；
    优选地，所述熔体出料的牵伸速度为0.01～1m/s。
  18. 如权利要求16或17所述的方法，其特征在于，所述方法包括如下步骤：
    在权利要求10的步骤(2)之后进行步骤(3)
    (3)将母粒在30～70℃出丝温度，10～90％出丝湿度条件下，采用风冷或水冷，熔融纺丝，得到碳纳米结构的复合物复合聚酯纤维。
  19. 一种如权利要求12所述的复合聚酯纤维的用途，其特征在于，所述复合聚酯纤维用于制备民用服装、家纺织物、紫外防护织物、工业用特种防护服。
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