WO2017214480A1 - Fibres de cellulose régénérées fonctionnelles - Google Patents

Fibres de cellulose régénérées fonctionnelles Download PDF

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Publication number
WO2017214480A1
WO2017214480A1 PCT/US2017/036700 US2017036700W WO2017214480A1 WO 2017214480 A1 WO2017214480 A1 WO 2017214480A1 US 2017036700 W US2017036700 W US 2017036700W WO 2017214480 A1 WO2017214480 A1 WO 2017214480A1
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WIPO (PCT)
Prior art keywords
nanoparticle
fabric
alkyl
methyl
regenerated cellulose
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PCT/US2017/036700
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English (en)
Inventor
Jonathan Y. Chen
Liangfeng Sun
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Board Of Regents, The University Of Texas System
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Application filed by Board Of Regents, The University Of Texas System filed Critical Board Of Regents, The University Of Texas System
Priority to US16/307,303 priority Critical patent/US20190136415A1/en
Publication of WO2017214480A1 publication Critical patent/WO2017214480A1/fr
Priority to US17/854,626 priority patent/US20220364272A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B1/00—Shirts
    • A41B1/08—Details
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D1/00—Garments
    • A41D1/02—Jackets
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/0005—Materials specially adapted for outerwear made from a plurality of interconnected elements
    • 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
    • D01D5/04—Dry 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
    • D01D5/06—Wet spinning methods
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/22—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes specially adapted for knitting goods of particular configuration
    • D04B1/24—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes specially adapted for knitting goods of particular configuration wearing apparel
    • D04B1/246—Upper torso garments, e.g. sweaters, shirts, leotards
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/20—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes specially adapted for knitting articles of particular configuration
    • D04B21/207—Wearing apparel or garment blanks
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/02—Synthetic cellulose fibres
    • D21H13/08—Synthetic cellulose fibres from regenerated cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/13—Silicon-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B2500/00—Materials for shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass
    • A41B2500/10—Knitted
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2500/00—Materials for garments
    • A41D2500/10—Knitted
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments

Definitions

  • This disclosure relates generally to regenerated cellulose fibers, more particularly, to regenerated cellulose fibers comprising a functional material.
  • HVAC Building heating, ventilation, and air conditioning
  • LTMS Localized Thermal Management Systems
  • a raised question for apparel manufacturers is if they could bring a purely passive thermal solution for their suiting products (typically suit and shirt for men and blazer and blouse for women), that is, capability of preventing 18 W heat loss due to the 4°F setpoint decrease in winter, and of removing an extra heat of 23 W due to the 4°F setpoint increase in summer.
  • thermal regulating fibers have been made in synthetic fiber manufacture, by use of specific inorganic particles as functional fillers added into polymers during fiber spinning.
  • nylon 6 fibers comprising 2% of a-type AI2O3 (AKP-30, APS 400 nm) is reported to have a thermal conductivity of 0.024 W/mK (Unitika Ltd., 1995).
  • polyester fibers comprising 90% polyester, 6% a-type AI2O3, and 4% ZrC which is reported to have a thermal conductivity as high as 2900 W/mK (Unitika Ltd., 1996), compared to regular polyester fiber (0.14 W/mK).
  • Fabrics comprising regenerated cellulose fibers and a nanoparticle (e.g., a plurality of nanoparticles) dispersed throughout the fabric are disclosed herein.
  • the regenerated cellulose fibers can be derived from a biomass such as a fibrous cellulose, wood pulp, cotton, paper, bast fiber, bagasse, or a combination thereof.
  • the nanoparticle included in the fabric can be chosen to confer a desirable property to the fabric.
  • the nanoparticle can be selected from a thermally conductive or insulating material, an electrically conductive material, an electromagnetic wave absorption or shielding material, a hydrophobic material, a fire retardant or suppressant, a water repellent material, a water absorbent material, a soil repellent material, a reflective material, an antimicrobial agent, a sunblock agent, a dye, a pigment, a fragrance, an insect repellent, a fabric softener, a UV-protective material, an oxidation resistant material, or a combination thereof.
  • the nanoparticle can include a thermal insulating material.
  • thermal insulating nanoparticles include far infrared radiation ceramics.
  • the fabric can include a nanoparticle comprising aluminum, iron, silver, cerium, zinc, gold, copper, cobalt, nickel, platinum, manganese, rhodium, ruthenium, palladium, titanium, vanadium, chromium, molybdenum, cadmium, mercury, calcium, zirconium, iridium, silicon, an oxide thereof, zeolite, graphite, a carbon nanotube, or a combination thereof.
  • the nanoparticle can comprise alumina, silica, titanium oxide, tin oxide, iron oxide, cesium oxide, zinc oxide, graphite, a carbon nanotube, or a combination thereof.
  • the nanoparticle can be reactive or unreactive with the regenerated cellulose fibers.
  • the nanoparticle can include a silicon oxide nanoparticle, a silver nanoparticle, a cerium oxide nanoparticle, a zinc oxide nanoparticle, a poly(vinyl) alcohol nanoparticle, or a combination thereof.
  • the nanoparticle can be present in an amount of from 0.01% to 10% by weight, based on the total weight of the fabric.
  • the method can include (a) at least partially dissolving a cellulose substrate in a medium comprising one or more ionic liquids; and dissolving or suspending a nanoparticle in the medium.
  • the one or more ionic liquids can have a cation portion derived from an imidazole, a pyrazole, a thiazole, an isothiazole, an azathiozole, an oxothiazole, an oxazine, an oxazoline, an oxazaborole, a dithiozole, a triazole, a selenozole, an oxaphosphole, a pyrrole, a borole, a furan, a thiophen, a phosphole, a pentazole, an indole, an indoline, an oxazole, an isoxazole, an isoxazole, an isotriazole, a tetrazole, a benzofuran, a dibenzofuran, a benzothiophen, a dibenzothiophen, a thiadiazole, pyridine, a pyrimidine,
  • the one or more ionic liquids can have an anionic portion selected from a halogen, a pseudo-halogen, BX 4" wherein X is halogen, PF 6" , AsF 6" , SbF 6" , NO 2" , NO 3" , S0 4 2" , BR 4 " , phosphates, phosphites, polyoxometallates, carboxylates, substituted carboxylates, triflates, carboranes, substituted carboranes, metallocarboranes, and substituted metallocarboranes; wherein R is selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, hetero cycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino,
  • the one or more ionic liquids can be selected from 1-C 2 alkyl-3- methyl-imidazolium chloride, I-C3 alkyl-3 -methyl-imidazolium chloride, 1-C 4 alkyl-3 - methylimidazolium chloride, 1-C 6 alkyl-3-methyl-imidazolium chloride, l-Cs alkyl-3-methyl- imidazolium chloride, I-C2 alkyl-3 -methyl-imidazolium iodide, 1-C 4 alkyl-3 -methyl- imidazolium iodide, 1-C 4 alkyl-3-methyl-imidazolium hexafluorophosphate, I-C2 alkyl-3 -methyl- imidazolium hexafluorophosphate, I-C3 alkyl-3 -methyl-imidazolium hexafluorophosphate, 1-iso- C3 alkyl-3 -methyl-imidazolium chloride
  • the method of making the fabrics comprising the regenerated cellulose fibers and nanoparticle can include (b) recovering a solid nanoparticle-modified regenerated cellulose material comprising the cellulose substrate and the nanoparticle. Recovering the solid nanoparticle-modified regenerated cellulose material can include extruding, spinning, casting, coating, or a combination thereof. The method can also include (c) processing the solid nanoparticle-modified regenerated cellulose material to form the fabric.
  • FIG 1 is a schematic drawing of a bench-scale spinning line for producing regenerated cellulose fiber/film products.
  • This spinning line includes a cellulose solution preparation system, an extruder, a spin bath, a heater, and a fiber/film winder.
  • Figure 2 is a graph showing the degree of crystallinity in a regenerated bagasse fiber.
  • Figure 3 is a flow chart showing the steps for preparing thermally functioning fibers including ionic liquid (IL) solution preparation, fiber fabrication, fabric knitting, fabric thermal testing, and apparel thermal modeling.
  • IL ionic liquid
  • compositions, articles, and systems comprising regenerated cellulose fibers.
  • the compositions can further include nanoparticles. Methods of making and using the compositions are also described herein.
  • compositions and methods described herein can be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples included therein. However, before the present compositions and methods are described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.
  • fabric refers to a web having a structure of individual fibers or threads which are interlaid by weaving (woven), knitting, braiding, or in an irregular, non- repetitive manner (non-woven).
  • a nonwoven fabric or web can be formed from for example, melt-blowing processes, spun-bonding processes, and bonded carded web processes.
  • references in the specification and concluding claims to the molar ratio of a particular element or component in a composition denotes the molar relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed.
  • X and Y are present at a molar ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
  • a weight percent (wt%) of a component is based on the total weight of the formulation or composition in which the component is included.
  • the term "ion,” as used herein, refers to any molecule, portion of a molecule, cluster of molecules, molecular complex, moiety, or atom that contains a charge (positive, negative, or both at the same time within one molecule, cluster of molecules, molecular complex, or moiety (e.g., zwitterions)) or that can be made to contain a charge.
  • Methods for producing a charge in a molecule, portion of a molecule, cluster of molecules, molecular complex, moiety, or atom can be accomplished by methods known in the art, e.g., protonation, deprotonation, oxidation, reduction, alkylation acetylation, esterification, deesterification, hydrolysis, etc.
  • anion is a type of ion and is included within the meaning of the term “ion.”
  • An “anion” is any molecule, portion of a molecule (e.g., zwitterion), cluster of molecules, molecular complex, moiety, or atom that contains a net negative charge or that can be made to contain a net negative charge.
  • anion precursor is used herein to specifically refer to a molecule that can be converted to an anion via a chemical reaction (e.g., deprotonation).
  • cation is a type of ion and is included within the meaning of the term “ion.”
  • a “cation” is any molecule, portion of a molecule (e.g., zwitterion), cluster of molecules, molecular complex, moiety, or atom, that contains a net positive charge or that can be made to contain a net positive charge.
  • cation precursor is used herein to specifically refer to a molecule that can be converted to a cation via a chemical reaction (e.g., protonation or alkylation).
  • alkyl refers to a saturated straight, branched, primary, secondary or tertiary hydrocarbons, including those having 1 to 20 atoms.
  • alkyl groups will include C1-C12, C1-C10, Ci-C 8 , Ci-C 6 , C1-C5, C1-C4, C1-C3, or C1-C2 alkyl groups.
  • C1-C10 alkyl groups include, but are not limited to, methyl, ethyl, propyl, 1- methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2- methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2- dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1- dimethylbutyl, 1 ,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1 ,2,2-trimethylpropyl
  • Cl-C4-alkyl groups include, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, and 1,1-dimethylethyl groups.
  • Cyclic alkyl groups or "cycloalkyl” groups include cycloalkyl groups having from 3 to 10 carbon atoms. Cycloalkyl groups can include a single ring, or multiple condensed rings. In some examples, cycloalkyl groups include C3-C4, C4-C7, C5-C7, C4-C6, or C5-C6 cyclic alkyl groups.
  • Non-limiting examples of cycloalkyl groups include adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
  • Alkyl and cycloalkyl groups can be unsubstituted or substituted with one or more moieties chosen from alkyl, halo, haloalkyl, hydroxyl, carboxyl, acyl, acyloxy, amino, alkyl- or dialkylamino, amido, arylamino, alkoxy, aryloxy, nitro, cyano, azido, thiol, imino, sulfonic acid, sulfate, sulfonyl, sulfanyl, sulfinyl, sulfamonyl, ester, phosphonyl, phosphinyl, phosphoryl, phosphine, thioester, thioether, acid halide, anhydride, oxime, hydrazine, carbamate, phosphoric acid, phosphate, phosphonate, or any other viable functional group that does not inhibit the biological activity of the compounds of the invention, either un
  • alkyl such as “alkylamino” or “dialkylamino,” will be understood to comprise an alkyl group as defined above linked to another functional group, where the group is linked to the compound through the last group listed, as understood by those of skill in the art.
  • aryl refers to a monovalent aromatic carbocyclic group of from 6 to 14 carbon atoms.
  • Aryl groups can include a single ring or multiple condensed rings. In some examples, aryl groups include C 6 -Cio aryl groups.
  • Aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, tetrahydronaphtyl, phenylcyclopropyl and indanyl.
  • Aryl groups can be unsubstituted or substituted by one or more moieties chosen from halo, cyano, nitro, hydroxy, mercapto, amino, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, halocycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, haloalkenyloxy, haloalkynyloxy, cycloalkoxy, cycloalkenyloxy, halocycloalkoxy, halocycloalkenyloxy, alkylthio, haloalkylthio, cycloalkylthio, halocycloalkylthio, alkylsulfinyl, alkenylsulfinyl, alky
  • alkoxy refers to alkyl-O-, wherein alkyl refers to an alkyl group, as defined above.
  • alkenyloxy refers to the groups alkenyl-O-, alkynyl-O-, and cycloalkyl-O-, respectively, wherein alkenyl, alkynyl, and cycloalkyl are as defined above.
  • Cl-C6-alkoxy groups include, but are not limited to, methoxy, ethoxy, C2H5-CH2O-, (CH 3 )2CHO-, n-butoxy, C2H 5 -CH(CH 3 )0-, (CH3)2CH-CH20-, (CH3)3CO-, n-pentoxy, 1 methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2 dimethylpropoxy, 2,2-dimethyl-propoxy, 1-ethylpropoxy, n-hexoxy, 1 methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1 dimethylbutoxy, 1,2- dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3 dimethylbutoxy, 3,3- dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2 trimethylpropoxy, 1,2,2-trimethylpropoxy, 1 -ethoxy
  • heteroaryl refers to a monovalent aromatic group of from 1 to 15 carbon atoms (e.g., from 1 to 10 carbon atoms, from 2 to 8 carbon atoms, from 3 to 6 carbon atoms, or from 4 to 6 carbon atoms) having one or more heteroatoms within the ring.
  • the heteroaryl group can include from 1 to 4 heteroatoms, from 1 to 3 heteroatoms, or from 1 to 2 heteroatoms.
  • the heteroatom(s) incorporated into the ring are oxygen, nitrogen, sulfur, or combinations thereof. When present, the nitrogen and sulfur heteroatoms can optionally be oxidized.
  • Heteroaryl groups can have a single ring (e.g., pyridyl or furyl) or multiple condensed rings provided that the point of attachment is through a heteroaryl ring atom.
  • Preferred heteroaryls include pyridyl, piridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolyl, indolyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinnyl, furanyl, thiophenyl, furyl, pyrrolyl, imidazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrazolyl benzofuranyl, and
  • Heteroaryl rings can be unsubstituted or substituted by one or more moieties as described for aryl above.
  • Exemplary monocyclic heterocyclic groups include, but are not limited to, pyrrolidinyl, pyrrolyl, pyrazolyl, oxetanyl, pyrazolinyl, imidazolyl, imidazolinyl, imidazolidinyl, oxazolyl, oxazolidinyl, isoxazolinyl, isoxazolyl, thiazolyl, thiadiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, furyl, tetrahydrofuryl, thienyl, oxadiazolyl, piperidinyl, piperazinyl, 2- oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolodinyl, 2-oxoazepinyl, azepinyl, 4-piperidonyl, pyridinyl, pyrazinyl, pyrimi
  • halogen refers to the atoms fluorine, chlorine, bromine, and iodine.
  • halo- e.g., as illustrated by the term haloalkyl
  • haloalkyl refers to all degrees of halogen substitution, from a single substitution to a perhalo substitution (e.g., as illustrated with methyl as chloromethyl (-CH2CI), dichloromethyl (-CHCI2), trichloromethyl (- CCb)).
  • cyclic group or "ring” is used herein to refer to either aryl groups, non-aryl groups (i.e. , cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl groups), or both. Cyclic groups have one or more ring systems that can be substituted or unsubstituted. A cyclic group or ring can contain one or more aryl groups, one or more non-aryl groups, or one or more aryl groups and one or more non-aryl groups.
  • amine or “amino” as used herein are represented by the formula NR ⁇ R 3 , where R 1 , R 2 , and R 3 can be, independently, hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
  • Carboxylate as used herein is represented by the formula -C(0)0 .
  • the term "substituted" is contemplated to include all permissible substituents of organic compounds.
  • the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds.
  • Illustrative substituents include, for example, those described below.
  • the permissible substituents can be one or more and the same or different for appropriate organic compounds.
  • the heteroatoms, such as nitrogen can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms.
  • substitution or “substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc.
  • a group is identified as being "substituted” it is meant that the group is substituted with one or more alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfonyl, sulfone, sulfoxide, or thiol groups.
  • ionic liquid describes a salt with a melting point below 150°C, whose melt is composed of discrete ions.
  • the crystalline structure of the regenerated cellulose can be determined by deconvoluting the X-ray diffraction pattern of the regenerated cellulose ( Figure 2), such as determined in L. Sun et al., Carbohydrate Polymers, 2015, 118: 150-155.
  • Biomass refers to living or dead biological material that can be used in one or more of the disclosed processes.
  • Biomass can include any cellulosic or lignocellulosic material and includes materials comprising cellulose, and optionally further comprising hemicellulose, lignin, starch, oligosaccharides and/or monosaccharides, biopolymers, natural derivatives of biopolymers, their mixtures, and breakdown products (e.g., metabolites).
  • Biomass can also comprise additional components, such as protein and/or lipid.
  • Biomass can be derived from a single source, or biomass can comprise a mixture derived from more than one source.
  • biomass examples include trees (e.g., pine), branches, roots, leaves, wood chips, wood pulp, sawdust, bamboo, shrubs and bushes, vegetables, fruits, flowers, animal manure, multi-component feed, bioenergy crops, agricultural residues, municipal solid waste, industrial solid waste, sludge from paper manufacture, yard waste, wood and forestry waste, corn grain, corn cobs, crop residues such as corn husks, corn stover, grasses, wheat, wheat straw, hay, rice straw, switchgrass, waste paper, sugar cane bagasse, sorghum, soy, or components obtained from milling of grains.
  • the regenerated cellulose described herein can be derived from fibrous cellulose, paper, cotton (such as cotton balls or linters), wood pulp, bagasse, bast fiber, or a combination thereof.
  • the regenerated cellulose can be formed into compositions (e.g. fabrics) having various properties.
  • a nanoparticle can be incorporated into the regenerated cellulose fibers to confer certain desirable properties to the regenerated cellulose fibers.
  • the term "nanoparticle” as used herein, refers to any structure with one or more nanosized features.
  • a nanosized feature can be any feature with at least one dimension less than 1 ⁇ in size.
  • the nanoparticle can have any of a wide variety of shapes including for example, spheroidal and elongated nanostructures.
  • the term nanoparticle includes nanowires, nanotubes, spheroidal nanoparticles, and the like, or combinations thereof.
  • the nanoparticles used herein can have an average diameter of 900 nanometers (nm) or less.
  • the average diameter of the nanoparticle can be 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, 100 nm or less, or 50 nm or less.
  • the average diameter of the nanoparticle can be 5 nm or greater, 50 nm or greater, 100 nm or greater, 150 nm or greater, 200 nm or greater, 250 nm or greater, 300 nm or greater, 350 nm or greater, 400 nm or greater, 450 nm or greater, 500 nm or greater, 600 nm or greater, 700 nm or greater, 800 nm or greater, or 900 nm or greater.
  • the average diameter of the nanoparticle can range from any of the minimum values described above to any of the maximum values described above.
  • the average diameter of the nanoparticle can range from 5 nm to 700 nm, from 5 nm to 500 nm, from 50 nm to 500 nm, or from 50 nm to 250 nm.
  • the nanoparticles can be encapsulated within the regenerated cellulose fibers, dispersed throughout the regenerated cellulose material, or form a layer/coating on the regenerated cellulose fibers.
  • the nanoparticles can attach permanently or semi-permanently to the regenerated cellulose fibers.
  • the nanoparticles can adhere to the regenerated cellulose fibers covalently or non-covalently. In some cases, the nanoparticle is unreactive with the regenerated cellulose fibers.
  • the nanoparticles can confer certain desirable properties to the regenerated cellulose fibers.
  • the nanoparticle can be selected from a thermally conductive or thermally insulating material, an electrically conductive material, an electromagnetic wave absorption or shielding material, a hydrophobic material, a fire retardant or suppressant, a water repellent material, a water absorbent material, a soil repellent material, a reflective material (such as a metallic reflector), a magnetic material, a thermochromic material, a bioactive agent (such as an anti-microbial agent, anti-fungal agent, or an insect repellent), a sunblock agent, a dye, a pigment, a fragrance, an insect repellent, a fabric softener, a UV- protective material, an oxidation resistant material, or a combination thereof.
  • the nanoparticle included in the regenerated cellulose fibers is a thermally conductive or thermally insulating nanoparticle. In some examples, the nanoparticle included in the regenerated cellulose fibers is a thermally conductive or thermally insulating nanoparticle.
  • the thermal insulating material can include a far infrared radiation ceramic, a thermal conductive carbon material, or a combination thereof.
  • thermal insulating material can include aluminum, iron, silver, cerium, zinc, gold, copper, cobalt, nickel, platinum, manganese, rhodium, ruthenium, palladium, titanium, vanadium, chromium, molybdenum, cadmium, mercury, calcium, zirconium, iridium, silicon, an oxide thereof, zeolite, graphite, carbon nanotubes, or a combination thereof.
  • Specific examples of thermal insulating nanoparticle includes alumina, silica, titanium oxide, tin oxide, iron oxide, cesium oxide, zinc oxide, graphite, carbon nanotubes, or a combination thereof.
  • the regenerated cellulose can include a nanoparticle selected from silicon oxide nanoparticles, silver nanoparticles, cerium oxide nanoparticles, zinc oxide nanoparticles, polyvinyl alcohol nanoparticles, and combinations thereof.
  • compositions described herein can comprise 0.01% or greater by weight nanoparticle (i.e. based on the total weight of the regenerated cellulose and the nanoparticle).
  • the compositions can comprise 0.1% or greater, 0.2% or greater, 0.5% or greater, 1% or greater, 1.5% or greater, 2% or greater, 3% or greater, 4% or greater, 5% or greater, 6% or greater, 7% or greater, 8% or greater, 9% or greater, 10% or greater, 12% or greater, 15% or greater, 20% or greater, or 25% or greater by weight nanoparticle, based on the weight of the composition.
  • the compositions can comprise 25% or less, 20% or less, 15% or less, 12% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2.5% or less, 2% or less, 1.5% or less, 1% or less, 0.5% or less by weight nanoparticle, based on the weight of the composition.
  • the amount of nanoparticles in the composition can range from any of the minimum values described above to any of the maximum values described above.
  • the amount of nanoparticle in the composition can range from 0.01% to 25%, 0.01% to 20%, 0.01% to 15%, 0.01% to 10%, 0.01% to 5%, 0.5% to 10%, 0.5% to 5%, or 1% to 5% by weight, based on the weight of the composition.
  • the weight ratio of the nanoparticles to regenerated cellulose in the composition can be 1:4 or less.
  • the weight ratio of the nanoparticle to regenerated cellulose in the composition can be 1 :5 or less, 1 :7.5 or less, 1: 10 or less, 1 : 15 or less, 1:20 or less, 1 :25 or less, 1:50 or less, 1 :75 or less, or 1 : 100 or less.
  • the weight ratio of the nanoparticles to regenerated cellulose in the composition can be 1: 100 (e.g.
  • the weight ratio of nanoparticle to regenerated cellulose in the composition can range from any of the minimum values described above to any of the maximum values described above.
  • the weight ratio of nanoparticles to regenerated cellulose in the composition can range from 1 : 100 to 1:4 (e.g. , from 1: 100 to 1 :25, from 1: 100 to 1 :20, or from 1 :50 to 1:20).
  • the nanoparticle modified regenerated cellulose material can be a fabric.
  • the methods can include at least partially dissolving a cellulose substrate in a medium comprising one or more ionic liquids.
  • the cellulose substrate can be a biomass as described herein.
  • the medium can be heated or irradiated to aid in dissolution of the cellulose substrate.
  • ionic liquid has many definitions in the art, but is used herein to refer to salts (i.e., compositions comprising cations and anions) that are liquid at a temperature of at or below about 150°C, e.g., at or below about 120, 100, 80, 60, 40, or 25°C. That is, at one or more temperature ranges or points at or below about 150°C the disclosed ionic liquid compositions are liquid; although, it is understood that they can be solids at other temperature ranges or points.
  • liquid to describe the disclosed ionic liquid compositions is meant to describe a generally amorphous, non-crystalline, or semi-crystalline state.
  • the disclosed ionic liquid compositions have minor amounts of such ordered structures and are therefore not crystalline solids.
  • the compositions disclosed herein can be fluid and free-flowing liquids or amorphous solids such as glasses or waxes at a temperature at or below about 150°C.
  • the disclosed ionic liquid compositions are liquid at which the composition is applied (i.e. , ambient temperature).
  • the disclosed ionic liquid compositions are materials composed of one or more cations and one or more anions.
  • the mixture of cations and anions may be selected and optimized for the dissolution of a particular cellulose substrate material.
  • the cation portion of the ionic liquid can be derived from an imidazole, a pyrazole, a thiazole, an isothiazole, an azathiozole, an oxothiazole, an oxazine, an oxazoline, an oxazaborole, a dithiozole, a triazole, a selenozole, an oxaphosphole, a pyrrole, a borole, a furan, a thiophen, a phosphole, a pentazole, an indole, an indoline, an oxazole, an isoxazole, an isotriazole, a tetrazole, a benzofuran,
  • the one or more ionic liquids have an anionic portion which can be selected from a halogen, a pseudohalogen, BX 4 " wherein X is halogen, PF6 ⁇ , AsF6 ⁇ , SbF6 ⁇ , N0 2 ⁇ , NO3 " , S0 4 2 ⁇ , BR 4 " , phosphates, phosphites, polyoxometallates, carboxylates, substituted carboxylates, triflates, carboranes, substituted carboranes, metallocarboranes, and substituted metallocarboranes;
  • R is selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, hetero cycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, acyl, silyl, boryl, phosphino, amino, thio, seleno, or a combination thereof.
  • the one or more ionic liquids may be selected from I-C2 alkyl-3- methyl-imidazolium chloride, I-C3 alkyl-3 -methyl-imidazolium chloride, 1-C 4 alkyl-3 - methylimidazolium chloride, 1-C 6 alkyl-3-methyl-imidazolium chloride, l-Cs alkyl-3-methyl- imidazolium chloride, I-C2 alkyl-3 -methyl-imidazolium iodide, 1-C 4 alkyl-3 -methylimidazolium iodide, 1-C 4 alkyl-3-methyl-imidazolium iodide, 1-C 4 alkyl-3-methyl-imidazolium hexafluorophosphate, I-C2 alkyl-3 -methyl- imidazolium hexafluorophosphate, I-C3 alkyl-3 -methyl-imidazolium hexafluorophosphate,
  • the method of preparing the nanoparticle modified regenerated cellulose material can include dissolving and/or suspending one or more nanoparticle in the medium comprising the one or more ionic liquids.
  • the nanoparticle can be substantially uniformly distributed within the medium.
  • the amount of nanoparticle included in the medium can be 0.001% to 5% by weight, based on the total weight of the medium (i.e. including the one or more ionic liquid).
  • the nanoparticle can be added in an amount to the medium such that the spinnability of the medium is not significantly affect but would significantly increase thermal insulation or thermal conductivity of the regenerated cellulose fiber.
  • the method of preparing the nanoparticle modified regenerated cellulose material can include recovering a solid nanoparticle modified regenerated cellulose material comprising the cellulose substrate and the nanoparticle.
  • Recovering the solid nanoparticle-modified regenerated cellulose material can comprise spinning, extruding, casting, or a combination thereof.
  • the nanoparticle modified regenerated cellulose fibers can be recovered by a spinning process such as a gap/dry- wet spinning process or by a wet- wet spinning process.
  • recovering the nanoparticle modified regenerated cellulose fibers can include feeding the mixture comprising the cellulose substrate and nanoparticle into an extruder for fiber spinning with a dry-wet spinning method.
  • the regenerated cellulose-containing mixture can be extruded into a non-solvent such as water, an alcohol, or other hydric liquids.
  • a non-solvent such as water, an alcohol, or other hydric liquids.
  • nanoparticle modified regenerated cellulose fibers can be precipitated through solution quenching and anti-solvent (water) addition into the solution system.
  • the addition of the anti- solvent reduces the solubility of cellulose in the ionic liquid, resulting in a condition of supersaturation that is a driving force for cellulose nucleation and growth.
  • the regenerated nanoparticle modified cellulose fiber can then be drawn, dried (for example by passing through a heater), and then wound onto a spool using a winding device.
  • the fibers can be ran a second-time washing and drying under the same dry setting.
  • the nanoparticle modified cellulose mixture can be fed into a mixing extruder.
  • the method of dry-jet and wet-spinning can be carried out with an air gap of from 20-25 mm through an orifice with a 1-2 mm diameter.
  • the extruder rotating speed can be kept at from 170-220 rpm.
  • the extruding temperature can be from 25-50 ° C.
  • a water bath container can be used for nanoparticle modified cellulose fiber coagulation.
  • the water bath can be kept at room temperature (about 20 ° C).
  • the spun fibers can pass through a glass tube for drying with hot air flow (at least 60 ° C).
  • the dried fibers can be picked up by a take-up device that can determine the drawing speeds.
  • Table 1 lists some embodiments of control parameters for preparing regenerated nanoparticle modified cellulose fibers.
  • Table 1 Control parameters for preparing regenerated nanoparticle modified cellulose fibers.
  • the nanoparticle-modified regenerated cellulose fibers can be formed into a fabric.
  • the produced fibers can be converted into a fabric using a fiber analysis knitter sampler.
  • the fabric can exhibit thermal control at various basis weight, depending on the end use of the fabric (such as the type of apparel that will be produced).
  • the basis weight of the fabric can be 20 g/m 2 or greater.
  • the basis weight of the fabric can be 25 g/m 2 or greater, 30 g/m 2 or greater, 35 g/m 2 or greater, 40 g/m 2 or greater, 45 g/m 2 or greater, 50 g/m 2 or greater, 55 g/m 2 or greater, 60 g/m 2 or greater, 65 g/m 2 or greater, 70 g/m 2 or greater, 80 g/m 2 or greater, 90 g/m 2 or greater, 100 g/m 2 or greater, 110 g/m 2 or greater, 120 g/m 2 or greater, 130 g/m 2 or greater, 140 g/m 2 or greater, 150 g/m 2 or greater, 160 g/m 2 or greater, 170 g/m 2 or greater, 180 g/m 2 or greater, or 190 g/m 2 or greater.
  • the basis weight of the fabric can be 200 g/m 2 or less.
  • the basis weight of the fabric can be 190 g/m 2 or less, 180 g/m 2 or less, 170 g/m 2 or less, 160 g/m 2 or less, 150 g/m 2 or less, 140 g/m 2 or less, 130 g/m 2 or less, 120 g/m 2 or less, 110 g/m 2 or less, 100 g/m 2 or less, 90 g/m 2 or less, 80 g/m 2 or less, 70 g/m 2 or less, 65 g/m 2 or less, 60 g/m 2 or less, 55 g/m 2 or less, or 50 g/m 2 or less.
  • the basis weight of the fabric can range from any of the minimum values described above to any of the maximum values described above.
  • the basis weight of the fabric can range from 25 g/m 2 to 200 g/m 2 , from 50 g/m 2 to 200 g/m 2 , from 50 g/m 2 to 190 g/m 2 , or from 50 g/m 2 to 150 g/m 2 .
  • the fabrics described herein can range from heavy to light.
  • the fabrics can be made into textiles including jackets, coats, skirts, pants, suits, slacks, vests, gloves, and the like.
  • the fabrics can also be used in non-apparel applications such as furniture and carpets.
  • the nanoparticle incorporated into the regenerated cellulose fibers can provide various properties to the fabric, and ultimately to the apparel it is used to make.
  • the properties associated with the nanoparticles incorporated into the fabric include aesthetics (e.g., luminescence), shrink resistance, anti-microbial, stain resistance, electrical conductivity, thermal conductivity, thermal insulation, static protection, fire resistance, UV protection, fragrance release, water repellent (hydrophobic), high strength, wrinkle resistance, moisture management, and/or self-cleaning properties.
  • silver nanoparticles can inhibit bacterial metabolism, which causes infection and odor, causing the bacteria to die.
  • Rare earth metals can fluoresce to detect infrared in textile electroluminescent tagging systems.
  • the procedure to measure the fiber linear density complies with ASTM D 1577.
  • An Instron tensile tester can be used for measuring the fiber and film tensile strength and break elongation.
  • the test method for tensile strength (tenacity in g/denier) is in accordance with the standard method ASTM D 3822 for single textile fiber break strength.
  • the regenerated nanoparticle modified cellulose fibers or fabrics produced therefrom can exhibit improved thermal insulation.
  • the regenerated nanoparticle modified cellulose fibers can exhibit an increase in the total thermal resistance of up to 1.17 times that of current non-thermal regulating winter suits.
  • Exemplary non-thermal winter suits include suits made up of 100% wool fabric (or wool-rich fabric including 50% or greater wool such as 50/50 wool/polyester) as a surface and 100% rayon fabric as a lining.
  • the non- thermal winter suit (including top and pant) can have a weight of about 2 lbs.
  • the regenerated nanoparticle modified cellulose fibers can exhibit a reduction in the total thermal resistance to 0.78 times that of current non-thermal regulating summer suits.
  • the thermal properties of the nanoparticle modified cellulose fibers and films can be characterized. In particular, the thermal stability can be measured from 30 to 600°C at a heating rate of 5°C/min by a Shimadzu TGA-50 thermogravimetric analyzer.
  • Thermal conductivity is a measure of the ability of material to conduct heat (W/mK).
  • Thermal diffusivity measures the ability of a material to conduct thermal energy relative to its ability to store energy (mm2/s).
  • Thermal effusivity is defined as the square root of the product of thermal conductivity (k), density (p) and heat capacity (cp) of a material (Ws 1/2 /m 2 K).
  • the regenerated nanoparticle modified cellulose fibers or fabrics produced therefrom can exhibit improved thermal conductivity.
  • the regenerated nanoparticle modified cellulose fibers can exhibit an increase in the total thermal conductivity of up to two times or greater that of cellulose.
  • the regenerated nanoparticle modified cellulose fibers can exhibit a conductivity of greater than 0.04 W/mK (e.g., 0.05 W/mK or greater, 0.06 W/mK or greater, or 0.07 W/mK or greater, or from 0.05 to 0.1 W/mK, or from 0.05 to 0.08 W/mK).
  • the regenerated nanoparticle modified cellulose fibers or fabrics produced therefrom can exhibit improved effusivity.
  • the regenerated nanoparticle modified cellulose fibers can exhibit an increase in the effusivity of up to three times or greater than that of cellulose.
  • the regenerated nanoparticle modified cellulose fibers can exhibit an effusivity of greater than 100 W s 1 ⁇ 2 m ⁇ 2 K "1 (e.g., 120 W s 1 ⁇ 2 m ⁇ 2 K “1 or greater, 130 W s 1 ⁇ 2 m “2 K “1 or greater, 140 W s 1 ⁇ 2 m “2 K “1 or greater, 150 W s 1 ⁇ 2 m “2 K “1 or greater, 160 W s 1 ⁇ 2 m 2 K 1 or greater, 170 W s 1 ⁇ 2 m “2 K 1 or greater, from 130 to 200 W s 1 ⁇ 2 m “2 K 1 , or from 150 to lSO W s' ⁇ m ⁇ K 1 ).
  • W s 1 ⁇ 2 m ⁇ 2 K “1 e.g., 120 W s 1 ⁇ 2 m ⁇ 2 K "1 or greater, 130 W s 1 ⁇ 2 m “2 K “1 or greater, 140 W s 1 ⁇ 2 m “2 K “1 or greater,
  • the nanoparticle interface and dispersion in the cellulose matrix can be analyzed using a FEI Quanta FEG 650 environmental scanning electron microscope (SEM) equipped with an energy dispersive spectroscopy and a field emission SEM with a capacity of scanning- transmission electron microscopy (STEM) imaging.
  • SEM environmental scanning electron microscope
  • STEM field emission SEM with a capacity of scanning- transmission electron microscopy
  • the nanoparticle distribution and cluster size can be analyzed using an image analysis mode.
  • the morphological structure of the regenerated cellulose can be evaluated using an instrument of transmission electron microscopy, JEOL 201 OF HRTEM.
  • Rayon fiber is the first man-made fiber entering into textile and apparel uses over 120 years ago. However, it remains one of the favorite apparel fibers because of its silky luster, soft hand, elegant drapability, and excellent water absorbency.
  • Current world production capacity of the cellulosic manufactured fibers is about 6,600 million pounds (3.0 million metric tons) per annum, of which 97% is rayon fiber; 2% is acetate fiber; and 1% is lyocell (Tencel®) fiber. This production capacity accounts for approximately 5% of the world man-made fiber production. It shows that global rayon production and demand keeps growing at an increasing rate of 3.8% per year from 2009 to 2014 (Blagoev, Bizzari, & Inoguchi, 2011).
  • Lyocell fiber is a new generation of regenerated cellulose fiber produced from an environmentally- friendly cellulose process with no chemical reactions or effluents. Lyocell fiber is manufactured by directly dissolving cellulose into the solvent N-methylmorpholine-n-oxide ( ⁇ ) and extruding the cellulose solution into a water bath for fiber formation.
  • ⁇ N-methylmorpholine-n-oxide
  • current production capacity of Lyocell fiber is too limited to compete with the well-established manufacture of viscose rayon fiber, and consumers pay higher prices for Lyocell-related textile and apparel products.
  • Table 2 below lists three far infrared (FIR) ceramic nanoparticles (ZrC , Fe203, and AI2O3) and two carbon nanoparticles, carbon nanotube (CNT) and nanographite (C), that were selected for producing cellulose/nanoparticle composite solutions using [EMIMJAc purchased from Sigma- Aldrich Corp.
  • FIR far infrared
  • CNT carbon nanotube
  • C nanographite
  • nanoparticles were directly dispersed in a small amount of [EMIMJAc vibrated by an ultrasonic device (VWR Model 50T) for 1 h.
  • VWR Model 50T ultrasonic device
  • nanoparticles with low wettability they were added into a small amount of NN- dimethylformamide (DMF) for a homogeneous dispersion using an ultrasonic device.
  • DMF NN- dimethylformamide
  • the DMF suspension was added into [EMIM]Ac, mixed for 0.5 h to remove DMF under heating and vacuuming, before adding the cellulose powder.
  • the dispersed nanoparticle and ground cellulose power from wood pulp (provided by Rayonier Inc.) were added into [EMIMJAc in a planetary mixer to prepare cellulose solutions.
  • the cellulose dissolution was processed with controlled temperature, time, shear rate, and vacuum pressure as shown in Table 3 below.
  • the prepared pure cellulose and cellulose/nanoparticle solutions were fed into a lab-scale extruder (LE-075, CSI Inc.) respectively for fiber spinning with a dry- wet spinning method.
  • a lab-scale extruder LE-075, CSI Inc.
  • cellulose fiber was precipitated through solution quenching and anti-solvent (water) addition into the solution system.
  • the addition of the anti-solvent reduces the solubility of cellulose in
  • An Instron tensile tester can be used for measuring the fiber and film tensile strength and break elongation.
  • the test method for tensile strength (tenacity in g/denier) is in accordance with the standard method ASTM D 3822 for single textile fiber break strength.
  • Thermal properties of the nanoparticle/cellulose fibers and films can be characterized.
  • the thermal stability can be measured from 30 to 600°C at a heating rate of 5°C/min by a thermogravimetry analyzer Shimazu TGA-50.
  • a WAXD instrument Rigaku Model RAPID II can be used for measuring the cellulose crystalline structure.
  • a mathematical model can be used for curve fitting (Gallagher, 2002), in order to calculate the degree of crystallinity that is described by the crystallinity index (CI), a ratio between sum of area under each crystalline peak and area under total diffraction curve (Fink, Weigel, & Purz, 2001).
  • the cellulose crystallite orientation along fiber axis can be determined by Herman' s crystal orientation factor.
  • the crystallite size L can be calculated by the Scherrer equation (Guerin & Alvarez, 1995).
  • the produced thermal fibers were converted into test samples using a fiber analysis knitter sampler (LH-122, Lawson-Hemphill). For a need of comparison and thermal modeling, two control fabrics were also produced, one knitted with a pure wool yarn (60s) and the other knitted with a pure cotton yarn (60s). Information of the fabric test samples is listed in Table 4.
  • a commonly-used suiting garment system consists of a suit and shirt for men (or a blazer and blouse for women).
  • the suiting garment can be a 3 -layer apparel structure with Inner Layer (1) (shirting fabric), In-Between Layer (2) (suit lining fabric), and Outer Layer (3) (suiting fabric). While shirts are considered wearable all year round, suits are categorized as winter suits and summer suits mainly dependent on fabric thickness and weight.
  • LTMS typical suiting garment system
  • three models of suiting garment system are established. Each model addresses the need for both winter and summer thermal regulation.
  • evaluation of total thermal resistance of the suiting garment set is based on a dry heat transfer occurring in the suiting garment fabrics dominated by conduction and surface convection only.
  • thermal resistance R ⁇ / ⁇ , where x is fabric thickness (m).
  • a heat transfer coefficient (W/m 2 K) and ⁇ is temperature difference.
  • the heat transfer coefficient is related to air velocity v (m/s).
  • a 8.3v 0 ' 5 .
  • Table 5 Thermal properties of some experimental functional regenerated cellulose fiber.

Abstract

L'invention concerne des étoffes comprenant des fibres de cellulose régénérées et des nanoparticule dispersées à travers l'étoffe. Les fibres de cellulose régénérées peuvent être dérivées d'une biomasse telle qu'une cellulose fibreuse, de la pâte de bois, du coton, du papier, de la fibre libérienne, de la bagasse ou d'une combinaison de ceux-ci. Les nanoparticules comprises dans l'étoffe peuvent être choisies pour conférer à l'étoffe une propriété désirable, telle qu'une propriété d'isolation thermique. L'invention concerne également des procédés de fabrication des étoffes comprenant les fibres de cellulose régénérée et les nanoparticules. Le procédé peut comprendre (a) dissolution au moins partielle d'un substrat de cellulose dans un milieu comprenant un ou plusieurs liquides ioniques ; et dissolution ou suspension de nanoparticules dans le milieu ; (b) récupération d'un matériau cellulosique régénéré modifié par des nanoparticules solides comprenant le substrat de cellulose et les nanoparticules ; et (c) traitement du matériau cellulosique régénéré modifié par des nanoparticules solides afin de former l'étoffe.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107963996A (zh) * 2018-01-18 2018-04-27 江西师范大学 一锅法制备3-三氟甲基异噁唑化合物的方法
CN109440213A (zh) * 2018-07-24 2019-03-08 江南大学 一种氧化石墨烯改性阻燃纤维素纤维及其制备方法
CN110042491A (zh) * 2019-05-28 2019-07-23 冉国庆 一种碳纳米管（cnt）粘胶纤维的制造方法
CN112829395A (zh) * 2021-02-05 2021-05-25 义乌市皓祺服饰有限公司 一种防水透气冲锋衣面料的制备方法
CN113638069A (zh) * 2021-07-08 2021-11-12 山东银鹰化纤有限公司 一种面膜基布用备长炭复合改性纳米铂金竹浆纤维及其制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ2017817A3 (cs) * 2017-12-19 2018-11-21 Adam LuÄŤanĂ­k Protipožární vodní roucho
CN110512416B (zh) * 2019-07-30 2022-05-03 黄山永瑞生物科技有限公司 一种棉织物用含纳米银的抗菌整理剂
CN110735195B (zh) * 2019-09-03 2022-07-29 冯杰宝 一种含乳木果油的再生纤维素纤维及其制备方法
CN112853522A (zh) * 2021-01-07 2021-05-28 华中科技大学 一种湿法纺丝辐射制冷纤维、制备方法及其应用
WO2023034885A1 (fr) * 2021-08-31 2023-03-09 Apani Systems Inc. Recyclage des textiles
EP4187004A1 (fr) * 2021-11-25 2023-05-31 AGXX Intellectual Property Holding GmbH Matière fibreuse à effet antimicrobien et neutralisant les odeurs

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030013369A1 (en) * 1999-07-19 2003-01-16 Soane David S. Nanoparticle-based permanent treatments for textiles
US20070006774A1 (en) * 2005-06-29 2007-01-11 Rogers Robin D Ionic liquid reconstituted cellulose composites as solid support matrices
US20100178825A1 (en) * 2007-01-03 2010-07-15 Lockheed Martin Corporation Cnt-infused carbon fiber materials and process therefor
WO2014066297A1 (fr) * 2012-10-22 2014-05-01 North Carolina State University Matières fibreuses non tissées

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030013369A1 (en) * 1999-07-19 2003-01-16 Soane David S. Nanoparticle-based permanent treatments for textiles
US20070006774A1 (en) * 2005-06-29 2007-01-11 Rogers Robin D Ionic liquid reconstituted cellulose composites as solid support matrices
US20100178825A1 (en) * 2007-01-03 2010-07-15 Lockheed Martin Corporation Cnt-infused carbon fiber materials and process therefor
WO2014066297A1 (fr) * 2012-10-22 2014-05-01 North Carolina State University Matières fibreuses non tissées

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KHALIL: "Production and modification of nanofibrillated cellulose using various mechanical processes: A review", CARBOHYDRATE POLYMERS, vol. 99, 2 January 2014 (2014-01-02), pages 649 - 665 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107963996A (zh) * 2018-01-18 2018-04-27 江西师范大学 一锅法制备3-三氟甲基异噁唑化合物的方法
CN107963996B (zh) * 2018-01-18 2021-06-11 江西师范大学 一锅法制备3-三氟甲基异噁唑化合物的方法
CN109440213A (zh) * 2018-07-24 2019-03-08 江南大学 一种氧化石墨烯改性阻燃纤维素纤维及其制备方法
CN110042491A (zh) * 2019-05-28 2019-07-23 冉国庆 一种碳纳米管（cnt）粘胶纤维的制造方法
CN112829395A (zh) * 2021-02-05 2021-05-25 义乌市皓祺服饰有限公司 一种防水透气冲锋衣面料的制备方法
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CN113638069A (zh) * 2021-07-08 2021-11-12 山东银鹰化纤有限公司 一种面膜基布用备长炭复合改性纳米铂金竹浆纤维及其制备方法
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