CN111691004A - Multifunctional heat-preservation antibacterial elastic yarn and silk stockings - Google Patents
Multifunctional heat-preservation antibacterial elastic yarn and silk stockings Download PDFInfo
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- CN111691004A CN111691004A CN202010496427.0A CN202010496427A CN111691004A CN 111691004 A CN111691004 A CN 111691004A CN 202010496427 A CN202010496427 A CN 202010496427A CN 111691004 A CN111691004 A CN 111691004A
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- silver
- composite powder
- elastic yarn
- preservation
- aerogel composite
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 53
- 238000004321 preservation Methods 0.000 title claims abstract description 47
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000002042 Silver nanowire Substances 0.000 claims abstract description 88
- 239000004964 aerogel Substances 0.000 claims abstract description 71
- 239000002131 composite material Substances 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 47
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 34
- 238000009987 spinning Methods 0.000 claims abstract description 34
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 34
- 229920002635 polyurethane Polymers 0.000 claims abstract description 28
- 239000004814 polyurethane Substances 0.000 claims abstract description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000011240 wet gel Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 15
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 15
- 239000013638 trimer Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000000352 supercritical drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000499 gel Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009940 knitting Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000009965 tatting Methods 0.000 claims description 2
- 238000009941 weaving Methods 0.000 claims description 2
- 230000006870 function Effects 0.000 abstract description 21
- 239000000126 substance Substances 0.000 abstract description 19
- 230000008859 change Effects 0.000 abstract description 2
- 239000007822 coupling agent Substances 0.000 abstract description 2
- 150000004756 silanes Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 229920006306 polyurethane fiber Polymers 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011990 functional testing Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
- 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
- D01F6/94—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 other polycondensation products
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
- A41B11/00—Hosiery; Panti-hose
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
- A41B17/00—Selection of special materials for underwear
-
- 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
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof 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
- D01F1/09—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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
- A41B2400/00—Functions or special features of shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass
- A41B2400/34—Functions or special features of shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass antimicrobial or antibacterial
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a multifunctional heat-preservation antibacterial elastic yarn and silk stockings, wherein the elastic yarn is prepared by the following steps: preparing silver nanowires by adopting a solvothermal method; preparation of SiO2Adding silver nanowires in the process of preparing the silver nanowire aerogel composite powder; adding the silver nanowire aerogel composite powder, the silane coupling agent and the micromolecule polyisocyanate prepolymer into the molten thermoplastic polyurethane as additives, and spinning to obtain the multifunctional heat-preservation antibacterial elastic yarn. Silanes of the inventionThe coupling agent can further firmly combine the composite powder and the polyurethane, so that the heat preservation and antibacterial functions can be kept for a long time; the small molecular polyisocyanate prepolymer is added in the spinning process of the thermoplastic polyurethane, and reacts with a broken substance to change the polyurethane with a linear structure into a three-dimensional structure, so that the elasticity is improved.
Description
Technical Field
The invention relates to a multifunctional heat-preservation antibacterial elastic wire and silk stockings, in particular to an elastic wire and silk stockings which are improved in heat preservation, antibacterial property and elasticity by adopting aerogel, silver nanowires and micromolecule polyisocyanate prepolymers.
Background
The silk stockings are generally nylon stockings, and have a function of decorating feet and legs, so that the beauty is improved, and the silk stockings are favored by consumers. With the increasing market demand year by year, silk stockings having various functions are beginning to appear in the market, and have functions of heat preservation, antibiosis, deodorization, high elasticity and the like according to different occasions, different objects and different environments besides the original decoration function.
Chinese patent CN103704890A discloses a sock with heat preservation function, which uses aerogel layer with heat preservation function to realize the heat preservation function of the sock. Chinese patents CN101161136A, CN102178354, CN106473240A disclose that nano silver particles or nano silver wires are directly adopted to load on the sock fiber by impregnation method so that the sock fiber has antibacterial function. Chinese patents CN102383230A, CN106267581A disclose the use of nano silver fibers for textile to form antibacterial socks. Chinese patent CN107136575A discloses winding nano silver wire on the silk thread constituting the sock for antibiosis. Chinese patent CN107019248A discloses that nano silver is loaded on diatomite and blended into fiber yarn to make socks have deodorizing and sterilizing functions. Chinese patent CN205682452 discloses that longer-acting bactericidal effect can be obtained by loading nano silver in oxide and then loading the nano silver in fiber. Chinese patents CN107780011A, CN104532430A, CN108968169A disclose elastic yarn woven silk stockings mainly composed of polyurethane components, which make the silk stockings have high elasticity. Chinese patent CN104088050A discloses bacteriostatic stretch yarn comprising polyurethane and nano silver for realizing high elasticity and antibacterial property of silk stockings. Chinese patent CN105297450A discloses that treating silk stockings with a finishing agent containing nano silver and polyurethane makes the silk stockings softer and has a bactericidal effect. Chinese patent CN209546954U discloses that copper particle doped aerogel mats achieve good water retention and bactericidal properties. As is apparent from the above-mentioned functional silk stocking products, the incorporation of a substance having such a property into silk stockings for realizing the relevant property is generally carried out by loading the functional substance on the surface of the silk stockings by means of dipping or the like, or the incorporation of the functional substance during spinning is carried out by embedding the functional substance in fibers. However, the functional material loaded on the surface of the silk stocking fiber has a weak binding force with the silk stocking fiber, and loses the relevant function along with the falling off of the functional material after several times of washing. If the functional substance is embedded in the fiber, the action of the binding force between the functional substance and the fiber of the silk stocking can be overcome, but most of the functional substances can play relevant roles on the surface of the fiber of the silk stocking, for example, silver nanoparticles must be contacted with bacteria on the surface of the fiber to realize antibiosis, and the functional substance embedded on the surface is relatively weak in binding force relative to the functional substance embedded inside due to the fact that a part of the functional substance is exposed outside the fiber, and the functional substance still has the risk of falling off during washing. Therefore, further research is needed to further improve the functional substance binding to the silk stocking fiber to exert the function for a long period of time.
Disclosure of Invention
According to the invention, the silver nanowire aerogel composite powder is used as a functional reagent, the silane coupling agent is used as a cross-linking agent, and the thermoplastic polyurethane is added in the spinning process to prepare the elastic yarn with the heat preservation and antibacterial functions, wherein the silane coupling agent can enable the composite powder and the polyurethane to be further firmly combined, so that the heat preservation and antibacterial functions can be kept for a long time, and the silk stockings have high elasticity. Meanwhile, the invention discovers that the elasticity is reduced because the macromolecule cracks in the high-temperature melting process of the thermoplastic polyurethane and the elasticity is reduced, so that the micromolecule polyisocyanate prepolymer is added in the spinning process of the thermoplastic polyurethane and reacts with the cracked substance, the network structure of the polyurethane is more complex, and the elasticity is improved. Specifically, the technical scheme of the invention is as follows:
the multifunctional heat-preservation antibacterial elastic yarn is prepared by the following preparation steps:
1) preparing silver nanowires by adopting a solvothermal method;
2) preparation of SiO2Adding the silver nanowires prepared in the step 1) into the aerogel process to prepare silver nanowire aerogel composite powder;
3) adding the silver nanowire aerogel composite powder prepared in the step 2), a silane coupling agent and a micromolecular polyisocyanate prepolymer as additives into the process of preparing the molten thermoplastic polyurethane, and spinning to obtain the multifunctional heat-preservation antibacterial elastic yarn.
Preferably, in step 1), the alcoholic thermal method is adopted to prepare AgNO3Ethylene glycol as solvent, FeCl as silver source3And as an auxiliary agent, polyvinylpyrrolidone is used as a surfactant, a guiding agent and a reducing agent to synthesize and prepare the silver nanowire.
Preferably, in the step 1), uniformly dispersing polyvinylpyrrolidone into ethylene glycol by magnetic stirring to form a solution with the mass fraction of 0.2-20%, then respectively dispersing ferric chloride and silver nitrate into ethylene glycol to form a solution with the mass fraction of 0.5-1.0%, and sequentially and rapidly adding the solutions of 1-20mL of ferric chloride and silver nitrate into 200mL of 100-200mL of polyvinylpyrrolidone solution to be uniformly stirred to form a dispersion solution, wherein the interval time is not more than 1 minute; and transferring the dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out heat preservation reaction for 1-12h at the temperature of 80-150 ℃, carrying out centrifugal separation treatment after cooling at room temperature, discarding supernatant liquid, and washing with deionized water and ethanol for three times respectively to obtain the silver nanowires.
The growth mechanism of the silver nanowires is as follows: AgNO as silver source at the beginning of the reaction3Provided Ag+And FeCl3Provided Cl-Will react rapidly to generate AgCl deposition; the AgCl then slowly electrolyzes the lower concentration of Ag +, the rate of dissociation and Ag through a reversible reaction+The concentration is positively correlated with temperature. PVP as a weak reducing agent can reduce Ag+Reduced to elemental Ag and due to thisThe oxidation process is very slow, so that the oxygen in the atmosphere can etch the simple substance Ag in time to form single crystal Ag; at the same time, PVP is taken as a surfactant, and crystal face (111) is the most stable face through strong adsorption of amide groups of PVP, so that Ag is caused+And the silver nano-wire is aggregated with a newly grown silver core and grows according to a (111) plane, and finally, the nano silver continuously grows to form a silver nano-wire with a high length-diameter ratio. The diameter of the silver nanowire prepared by the method is 30-300 nanometers, and the length of the silver nanowire is 0.5-10 micrometers.
Preferably, in the step 2), the silver nanowires prepared in the step 1) are added into an ethyl orthosilicate solution, the mixture is uniformly dispersed, ammonia water is added to generate gel, hydrophobic modification is performed after solvent replacement, and then supercritical drying is performed to obtain the silver nanowire aerogel composite powder.
Preferably, in the step 2), ethyl orthosilicate, ethylene glycol, deionized water and hydrochloric acid are mixed and stirred by magnetic force until the mixture is clarified to obtain a clarified liquid, wherein the mass ratio of the ethyl orthosilicate to the ethylene glycol to the deionized water to the hydrochloric acid is 0.1-0.3:1:0.01-0.1: 0.01-0.05; adding the silver nanowires prepared in the step 1) into the clarified liquid, performing magnetic stirring and ultrasonic treatment to obtain uniformly dispersed dispersion liquid, slowly dropwise adding ammonia water to adjust the pH value to 5-8, and standing for 1-12h to obtain wet gel, wherein the mass ratio of the ethyl orthosilicate to the silver nanowires is 1: 0.05-0.2; adding absolute ethyl alcohol into the wet gel, displacing the solvent in the wet gel, performing multiple times of ethanol displacement, and adding hexamethyldisilazane to perform hydrophobic modification treatment on the alcohol gel, wherein the mass ratio of the wet gel after solvent displacement to the hydrophobic modifier is 1: 0.01-0.1; by CO2Drying by a supercritical drying process to obtain silver nanowire aerogel composite powder, wherein the supercritical state conditions are as follows: the temperature is 60-80 ℃, the pressure is 10-20MPa, and the heat preservation time is 1-10 h.
SiO2The growth mechanism of the aerogel is as follows: by controlling the hydrolysis process of the ethyl orthosilicate, a three-dimensional porous-O-Si-bond crosslinked wet gel is formed, then a solvent with a low boiling point is used for replacing a solvent with a high boiling point, and the aerogel with extremely high porosity is obtained under the supercritical drying condition. The porous material has high porosity, so that the porous material has high heat insulation performance. The invention takes silver nano-wire as raw material to be added into the mixtureTo SiO2The process of aerogel to obtain SiO2The aerogel wraps the silver nanowire composite powder. The particle size of the silver nanowire aerogel composite powder prepared by the method is 1-20 microns.
Preferably, in the step 3), the mass ratio of the thermoplastic polyurethane to the silver nanowire aerogel composite powder to the silane coupling agent to the micromolecular polyisocyanate prepolymer is 100:0.1-1:0.5-5:0.5-10, wherein the silane coupling agent is KH 550; the small-molecule polyisocyanate prepolymer is one or more of toluene diisocyanate trimer, hexamethylene diisocyanate trimer and diphenylmethane diisocyanate trimer.
Preferably, in the step 3), the thermoplastic polyurethane is dried and then sliced, and then the thermoplastic polyurethane, the silver nanowire aerogel composite powder and the silane coupling agent are sent into a screw extruder to form a polyurethane melt at the temperature of 200-250 ℃, and then the micromolecular polyisocyanate prepolymer is added to obtain a mixed melt; extruding the mixed melt by a screw extruder and conveying the mixed melt to a spinning part of a spinning box; quantitatively and uniformly pressing the mixed melt to a spinneret plate by using a spinning pump, extruding the mixed melt trickle from small holes of the spinneret plate, and cooling in a channel to obtain the multifunctional heat-preservation antibacterial elastic yarn.
Preferably, in the step 3), the additive further comprises a plasticizer, and the mass ratio of the plasticizer to the thermoplastic polyurethane is 100: 0.5-5.
The spinning mechanism is as follows: heating thermoplastic polyurethane to a temperature higher than the melting point to realize high-temperature melting, uniformly mixing the thermoplastic polyurethane with other additives, spraying the mixture through a spinneret orifice, and cooling and fixing the molten liquid into filaments under the cooling condition. The diameter of the elastic wire prepared by the invention can be 30-300 microns, and the length can be adjusted according to actual conditions.
A multifunctional elastic silk stocking is formed by spinning the multifunctional heat-preservation antibacterial elastic silk.
Preferably, the polyester low-stretch yarns and/or the polypropylene low-stretch yarns are used as traction yarns to form twisted tows with the multifunctional heat-preservation antibacterial elastic yarns, wherein a plurality of multifunctional heat-preservation antibacterial elastic yarns and a plurality of traction yarns are arranged according to a number ratio of 2:2-3, and then the multi-functional heat-preservation antibacterial elastic yarns and the traction yarns are spun into silk stockings; wherein the weaving mode comprises knitting and tatting; optionally, PTT shape memory filaments are added in the twisted filament bundle, so that the ratio of the traction filaments to the shape memory filaments to the composite fiber filaments is 2:2-3: 1.
The beneficial effect of this application:
(1) the applicant finds through market research and literature inquiry that the multifunctional performance of the silk stockings is generally realized by combining the functional agent with the silk stocking fibers, so that the firmness of the combination of the functional agent and the silk stocking fibers determines the long-lasting performance of the silk stocking functions. Taking an antibacterial agent as an example, nano silver is a widely used broad-spectrum antibacterial agent, and when the nano silver is loaded on the surface of the fiber of the silk stockings, the nano silver is usually bound with the fiber of the silk stockings through van der waals force or coordination with functional groups on the surface of the fiber of the silk stockings, the binding force is relatively weak, and compared with the way of loading the nano silver on the surface of the fiber of the silk stockings, the nano metal particles embedded in the fiber of the silk stockings not only have larger contact area with the fiber of the silk stockings so as to have higher van der waals force and coordination binding force, but also can be better bound with the fiber of the silk stockings due to steric hindrance. But the main binding force is still mainly physical binding force, and the functional reagent can be separated due to strong physical shock when the silk stockings are washed. In the prior art, the nano silver particles are loaded on other carriers and then are combined with the silk stocking fibers, but the nano silver particles still have the problem of the combination force with the carriers, and the combination force between the carriers and the silk stocking fibers also has a problem. The prior art also improves the hydrophilicity of the silk stocking fibers to enable the silk stocking fibers to be more compact to prevent the nano silver particles from falling off, but the bonding effect between the nano silver particles and the silk stocking fibers is not substantially improved. If the bonding force with the nano silver is enhanced by grafting the surface of the fiber of the silk stocking, the bonding force cannot be improved because the functional group is difficult to be bonded with the metal more firmly. The silk stocking fiber is connected with the aerogel through a chemical bond, and the aerogel wraps the silver nanowires, so that the two functional reagents are organically combined, and the connecting force between the silk stocking fiber and the aerogel is improved while the heat preservation and antibacterial effects are exerted. The invention adopts SiO2The aerogel is chemically connected with polyurethane fiber through a silane coupling agent KH550, and silane is usedSi-OC on coupling agent KH5502H5The bond is hydrolyzed to form Si-OH bond with SiO2The Si-OH on the aerogel undergoes hydrolytic condensation reaction, and simultaneously the C-NH on the KH5502The bond and the functional group on the surface of the polyurethane are subjected to bonding reaction under the heating condition, so that the KH550 anchors the silver nanowire aerogel composite powder on the polyurethane fiber, the interface bonding strength of the silver nanowire aerogel composite powder and the polyurethane fiber is improved, and the dispersibility of the composite powder in the polyurethane is improved. The present application uses silver nanowires as antimicrobial agents because their shape relative to nanospheres can be compatible with SiO2The aerogel has larger area contact, not only improves Van der Waals force and coordination binding force, but also greatly improves steric hindrance, one section of the silver nanowire is exposed out of the aerogel and plays an antibacterial role with the surface of the fiber, and the other end of the silver nanowire is deeply inserted into the aerogel and the interior of the fiber to play a rooting role, so that the silver nanowire is more difficult to be rooted from SiO2The aerogel and the polyurethane fiber are detached, whereby the heat-insulating and antibacterial effects can be maintained for a long period of time. The invention uses SiO2The aerogel is subjected to hydrophobic modification, so that the silver nanowire aerogel composite powder can be more uniformly dispersed in the polyurethane fiber. Although the prior art has the composite of aerogel and silver nanowires, the prior art does not provide the application in silk stockings and spinning processes, and does not consider the problem of combination of functional agents and silk stocking fibers. The invention utilizes the shape and SiO of the silver nanowire2The chemical crosslinking performance of the aerogel integrates two functions, skillfully solves the problem of combination of a functional reagent and silk stocking fibers, and realizes long-term retention of the functions.
(2) The invention discovers that macromolecule cracks can be broken in the high-temperature melting process of the thermoplastic polyurethane to cause elasticity reduction, so that micromolecule polyisocyanate prepolymer is added in the spinning process of the thermoplastic polyurethane, and the micromolecule polyisocyanate prepolymer reacts with broken substances to enable linear polyurethane to be changed into three-dimensional network polyurethane or enable the network structure of the broken three-dimensional network polyurethane to be reconnected. The prepolymer of the small molecular compound contains isocyanate functional groups, can react with isocyanate formed by breaking a macromolecular chain of polyurethane under the thermodynamic action, and can form a hydrogen bond association action with a carbamate group in the polyurethane, so that the three-dimensional network structure of the polyurethane is more complex, the tensile strength of the polyurethane is obviously improved, and the macro expression is that the elasticity is improved. After the reaction, the small molecular compound prepolymer can be regarded as a hard chain segment in a molecular chain, the polyurethane chain with high elasticity can be regarded as a soft chain segment in the molecular chain, and the hard chain segments in the molecular chain are mutually and regularly arranged to form a crystal region; the part of the molecular chain of the soft segment, which is not acted by external force, is in a relaxed state, and the molecular chain segment of the soft segment is stretched after the part is acted by the external force; when the external force is removed, the stretched molecular chain can freely slide and retract to a stress minimum state due to weak acting force between molecular chains, and therefore, the high-elasticity characteristic is shown.
(3) The silver nanowire aerogel composite powder has porosity and metal conductivity, and not only plays roles of heat preservation and antibiosis, but also can realize multiple functions of flame retardance, sweat absorption, odor removal, static resistance and the like.
(4) The invention can also add plasticizer to improve spinnability and crystallinity of polyurethane, and improve physical and mechanical properties and thermal stability of composite fiber.
(5) When the silk stockings are woven, the traction silk, the shape memory filament and the composite fiber filament can be compounded, and the elasticity of the silk stockings is further improved due to the synergistic effect.
(6) The silk stockings have the characteristics of high elasticity, comfort, heat insulation, flame retardance, sterilization, sweat absorption, odor removal, static resistance and the like, and the preparation process is similar to the existing polyurethane melt spinning process and is suitable for industrial production.
Detailed Description
The present invention is further described with reference to specific examples to enable those skilled in the art to better understand the present invention and to practice the same, but the examples are not intended to limit the present invention.
Example 1
1) Preparing silver nanowires by adopting a solvothermal method:
in the step 1), uniformly dispersing polyvinylpyrrolidone into ethylene glycol by magnetic stirring to form a solution with the mass fraction of 4%, then respectively dispersing ferric chloride and silver nitrate into the ethylene glycol to form a solution with the mass fraction of 0.8%, and sequentially and rapidly adding 10mL of ferric chloride and silver nitrate solutions into 150mL of polyvinylpyrrolidone solution to be uniformly stirred to form a dispersion liquid, wherein the interval time is not more than 1 minute; and transferring the dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out heat preservation reaction for 8 hours at the temperature of 100 ℃, carrying out centrifugal separation treatment after cooling at room temperature, removing supernatant liquid, and washing with deionized water and ethanol for three times respectively to obtain the silver nanowires. The silver nanowires had an average diameter of 112 nm and an average length of 1.2 μm.
2) Preparing silver nanowire aerogel composite powder:
in the step 2), mixing tetraethoxysilane, glycol, deionized water and hydrochloric acid, and stirring by magnetic force until the mixture is clarified to obtain a clarified liquid, wherein the mass ratio of tetraethoxysilane, glycol, deionized water and hydrochloric acid is 0.2:1:0.05: 0.02; adding the silver nanowires prepared in the step 1) into a clarified liquid, performing magnetic stirring and ultrasonic treatment to obtain a uniformly dispersed dispersion liquid, slowly dropwise adding ammonia water to adjust the pH value to 6.5, and standing for 6 hours to obtain wet gel, wherein the mass ratio of the ethyl orthosilicate to the silver nanowires is 1: 0.1; adding absolute ethyl alcohol into the wet gel, displacing the solvent in the wet gel, performing multiple times of ethanol displacement, and adding hexamethyldisilazane to perform hydrophobic modification treatment on the alcohol gel, wherein the mass ratio of the wet gel after solvent displacement to the hydrophobic modifier is 1: 0.05; by CO2Drying by a supercritical drying process to obtain silver nanowire aerogel composite powder, wherein the supercritical state conditions are as follows: the temperature is 65 ℃, the pressure is 15MPa, and the heat preservation time is 3 h. The average grain diameter of the silver nanowire aerogel composite powder is 12 microns.
3) Preparing the multifunctional heat-preservation antibacterial elastic yarn:
drying thermoplastic polyurethane, slicing, feeding the thermoplastic polyurethane, silver nanowire aerogel composite powder, a silane coupling agent KH550 and a commercially available plasticizer di (2-ethylhexyl) phthalate (DEHP) into a screw extruder, forming a polyurethane melt at 220 ℃, and adding a toluene diisocyanate trimer to obtain a mixed melt; wherein the mass ratio of the thermoplastic polyurethane to the silver nanowire aerogel composite powder to the KH550 to the toluene diisocyanate trimer to the plasticizer is 100:0.5:1:5: 1; extruding the mixed melt by a screw extruder and conveying the mixed melt to a spinning part of a spinning box; quantitatively and uniformly pressing the mixed melt to a spinneret plate with the aperture of 100 microns by using a spinning pump, extruding the mixed melt trickle from the small hole of the spinneret plate, and cooling at room temperature in a channel to obtain the multifunctional heat-preservation antibacterial elastic yarn.
Example 2
The silver nanowire aerogel composite powder prepared in example 1 was used for spinning:
drying and slicing thermoplastic polyurethane, then sending the thermoplastic polyurethane, silver nanowire aerogel composite powder and a silane coupling agent KH550 into a screw extruder, forming a polyurethane melt at 220 ℃, and then adding a toluene diisocyanate trimer to obtain a mixed melt; wherein the mass ratio of the thermoplastic polyurethane to the silver nanowire aerogel composite powder to the KH550 to the toluene diisocyanate trimer is 100:0.5:1: 5; extruding the mixed melt by a screw extruder and conveying the mixed melt to a spinning part of a spinning box; quantitatively and uniformly pressing the mixed melt to a spinneret plate with the aperture of 100 microns by using a spinning pump, extruding the mixed melt trickle from the small hole of the spinneret plate, and cooling at room temperature in a channel to obtain the multifunctional heat-preservation antibacterial elastic yarn.
Example 3
The silver nanowire aerogel composite powder prepared in example 1 was used for spinning:
drying thermoplastic polyurethane, slicing, feeding the thermoplastic polyurethane, silver nanowire aerogel composite powder, a silane coupling agent KH550 and a commercially available plasticizer di (2-ethylhexyl) phthalate (DEHP) into a screw extruder, forming a polyurethane melt at 220 ℃, and adding a toluene diisocyanate trimer to obtain a mixed melt; wherein the mass ratio of the thermoplastic polyurethane to the silver nanowire aerogel composite powder to the KH550 to the toluene diisocyanate trimer to the plasticizer is 100:0.1:5:10: 0.5; extruding the mixed melt by a screw extruder and conveying the mixed melt to a spinning part of a spinning box; quantitatively and uniformly pressing the mixed melt to a spinneret plate with the aperture of 100 microns by using a spinning pump, extruding the mixed melt trickle from the small hole of the spinneret plate, and cooling at room temperature in a channel to obtain the multifunctional heat-preservation antibacterial elastic yarn.
Comparative example 1
The same preparation steps as example 1, but the silver nanowires prepared in step 1) are used for preparing the silver nanowire aerogel composite powder in the melt spinning mode instead of the silver nanowire aerogel composite powder prepared in step 2).
Comparative example 2
The same procedure as in example 1 was followed, except that the silver nanowire was replaced with a self-made spherical silver nanoparticle having an average particle size of 80 nm to prepare a silver nanoparticle aerogel composite powder.
Comparative example 3
The same procedure as in example 1 was followed, except that no silane coupling agent KH550 was added in step 3.
Comparative example 4
The same procedure as in example 1 was followed, except that toluene diisocyanate trimer was not added in step 3.
Specific properties of the multifunctional heat-insulating antibacterial elastic yarn prepared in examples 1 to 3 are shown in table 1, and the elastic property, the heat-insulating property and the antibacterial property of the sample are respectively expressed by the elastic recovery rate, the thermal conductivity and the antibacterial rate.
TABLE 1
| Sample (I) | Elastic recovery rate% | Thermal conductivity, W/m.K | Antibacterial rate,% of |
| Example 1 | 96.5 | 0.035 | 99.9 |
| Example 2 | 94.1 | 0.034 | 99.9 |
| Example 3 | 97.6 | 0.038 | 99.9 |
From the experimental results shown in table 1, it can be seen that the multifunctional heat-preserving antibacterial elastic yarn of the present application has good heat-preserving property, antibacterial property and high elasticity, and the silk stockings made of the multifunctional heat-preserving antibacterial elastic yarn can also have the above functions. The comparison of examples 1 and 2 shows that the addition of the plasticizer can improve the elastic property of the product without obviously influencing the heat preservation property and the antibacterial property.
In order to detect the binding force of the functional reagent and the silk stocking fibers, the functional test is firstly carried out on the silk stocking fibers which are just prepared, then the sample is placed in tap water for stirring and ultrasonic treatment for 0.5h, the sample is subjected to the functional test again after separation, washing and drying, and the binding force of the functional reagent and the silk stocking fibers is reflected by observing the function reduction condition. The results of the tests relating example 1 to comparative examples 1 to 3 are shown in table 2.
TABLE 2
Example 1, comparative examples 1 to 3 can reflect the binding force of the functional agent to the silk stocking fiber by changing the experimental conditions under the same conditions. It was found that good sterilization rates were obtained due to the presence of silver nanoparticles in the fibers before treatment, while the comparative example 1, which did not employ the addition of aerogel, had a higher thermal conductivity. After treatment, due to stirring and ultrasonic action, part of the functional agent is separated from the fiber through vibration action, so that the related function is reduced. It can be seen from the comparison of example 1 and comparative example 1 that the nano silver wires and the fibers have relatively weak direct action if the aerogel is not used, so that the nano silver wires can be easily separated under the action of vibration. It can be seen from the comparison between example 1 and comparative example 2 that the shape of the nano silver wire is easier to be rooted in the aerogel than the shape of the nanosphere, and the spherical nano silver spheres distributed on the surface of the aerogel may be detached due to the vibration. It can be seen from the comparison of example 1 with comparative example 3 that the silane coupling agent KH550 can anchor the aerogel through chemical bonding, so that the aerogel can be relatively less affected after being subjected to vibration, and can be well retained in the fiber due to the rooting effect of the silver nanowires. The experiments show that the use of aerogel and silane coupling agent, the shape of silver nanowires and the composition of the silver nanowires and the aerogel are key technologies for improving the binding force of the functional reagent and the silk stocking fibers.
The present invention examines the effect of small molecule polyisocyanate prepolymers by way of example 1 and comparative example 4, and the results are shown in Table 3.
TABLE 3
| Sample (I) | Elastic recovery rate% |
| Example 1 | 96.5 |
| Comparative example 4 | 86.4 |
From the results of example 1 and comparative example 4, it can be seen that the addition of toluene diisocyanate trimer can improve the elasticity of the fiber. The method is mainly characterized in that molecular chain breakage can occur in the high-temperature melting process of part of polyurethane macromolecules, and the molecular chains can be reconnected by adding the toluene diisocyanate tripolymer capable of being crosslinked, so that the linear molecular chains are broken and then connected to form a three-dimensional net, or the broken three-dimensional net is reconnected to form a more complex three-dimensional net, and the elasticity of the fiber is improved.
According to the invention, the silver nanowire aerogel composite powder is embedded into the silk stocking fibers, the silane coupling agent is adopted to realize chemical bonding of the composite powder and the silk stocking fibers, the bonding force of a functional reagent and the silk stocking fibers is improved, meanwhile, the elasticity of polyurethane is further improved by adding the micromolecule polyisocyanate prepolymer, and the functional heat-preservation antibacterial elastic silk and the silk stockings are successfully prepared.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The multifunctional heat-preservation antibacterial elastic yarn is characterized by being prepared by the following steps:
1) preparing silver nanowires by a solvothermal method, wherein the diameter of each silver nanowire is 30-300 nanometers, and the length of each silver nanowire is 0.5-10 micrometers;
2) preparation of SiO2Adding the silver nanowires prepared in the step 1) into the aerogel process to prepare silver nanowire aerogel composite powder, wherein the particle size of the silver nanowire aerogel composite powder is 1-20 microns;
3) adding the silver nanowire aerogel composite powder prepared in the step 2), a silane coupling agent and a micromolecular polyisocyanate prepolymer as additives into the process of preparing the molten thermoplastic polyurethane, and spinning to obtain the multifunctional heat-preservation antibacterial elastic yarn, wherein the diameter of the elastic yarn is 30-300 microns;
wherein, in the step 3), the additive also comprises a plasticizer.
2. Root of herbaceous plantThe multifunctional heat-insulating antibacterial elastic yarn as claimed in claim 1, wherein in step 1), the alcohol heating method is adopted to prepare AgNO3Ethylene glycol as solvent, FeCl as silver source3As an auxiliary agent, polyvinylpyrrolidone is used as a surfactant, a guiding agent and a reducing agent to synthesize and prepare the silver nanowires; in the step 1), uniformly dispersing polyvinylpyrrolidone into ethylene glycol by magnetic stirring to form a solution with the mass fraction of 0.2-20%, then respectively dispersing ferric chloride and silver nitrate into the ethylene glycol to form a solution with the mass fraction of 0.5-1.0%, and sequentially and rapidly adding the solutions of 1-20mL of ferric chloride and silver nitrate into 200mL of 100-one polyvinylpyrrolidone solution to be uniformly stirred to form a dispersion liquid, wherein the interval time is not more than 1 minute; and transferring the dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out heat preservation reaction for 1-12h at the temperature of 80-150 ℃, carrying out centrifugal separation treatment after cooling at room temperature, discarding supernatant liquid, and washing with deionized water and ethanol for three times respectively to obtain the silver nanowires.
3. The multifunctional heat-preservation antibacterial elastic yarn as claimed in claim 2, wherein in the step 1), polyvinylpyrrolidone is uniformly dispersed in ethylene glycol by magnetic stirring to form a solution with a mass fraction of 4%, then ferric chloride and silver nitrate are respectively dispersed in ethylene glycol to form a solution with a mass fraction of 0.8%, 10mL of each solution of ferric chloride and silver nitrate is added into 150mL of polyvinylpyrrolidone solution in sequence and stirred uniformly to form a dispersion solution, and the interval time is not more than 1 minute; transferring the dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out heat preservation reaction for 8 hours at the temperature of 100 ℃, carrying out centrifugal separation treatment after cooling at room temperature, removing supernatant liquid, and washing with deionized water and ethanol for three times respectively to obtain silver nanowires; the silver nanowires had an average diameter of 112 nanometers and an average length of 1.2 micrometers.
4. The multifunctional heat-preservation antibacterial elastic yarn as claimed in claim 1, wherein in the step 2), the silver nanowires prepared in the step 1) are added into an ethyl orthosilicate solution, the silver nanowires are uniformly dispersed, ammonia water is added to the solution to form gel, and a solvent is added to the gelAfter replacement, carrying out hydrophobic modification, and then carrying out supercritical drying to obtain silver nanowire aerogel composite powder; in the step 2), mixing tetraethoxysilane, glycol, deionized water and hydrochloric acid, and stirring by magnetic force until the mixture is clarified to obtain a clarified liquid, wherein the mass ratio of tetraethoxysilane, glycol, deionized water and hydrochloric acid is 0.1-0.3:1:0.01-0.1: 0.01-0.05; adding the silver nanowires prepared in the step 1) into the clarified liquid, performing magnetic stirring and ultrasonic treatment to obtain uniformly dispersed dispersion liquid, slowly dropwise adding ammonia water to adjust the pH value to 5-8, and standing for 1-12h to obtain wet gel, wherein the mass ratio of the ethyl orthosilicate to the silver nanowires is 1: 0.05-0.2; adding absolute ethyl alcohol into the wet gel, displacing the solvent in the wet gel, performing multiple times of ethanol displacement, and adding hexamethyldisilazane to perform hydrophobic modification treatment on the alcohol gel, wherein the mass ratio of the wet gel after solvent displacement to the hydrophobic modifier is 1: 0.01-0.1; by CO2Drying by a supercritical drying process to obtain silver nanowire aerogel composite powder, wherein the supercritical state conditions are as follows: the temperature is 60-80 ℃, the pressure is 10-20MPa, and the heat preservation time is 1-10 h.
5. The multifunctional heat-preservation antibacterial elastic yarn as claimed in claim 4, wherein in the step 2), tetraethoxysilane, glycol, deionized water and hydrochloric acid are mixed and are stirred by magnetic force until the mixture is clarified to obtain a clarified liquid, wherein the mass ratio of tetraethoxysilane, glycol, deionized water and hydrochloric acid is 0.2:1:0.05: 0.02; adding the silver nanowires prepared in the step 1) into a clarified liquid, performing magnetic stirring and ultrasonic treatment to obtain a uniformly dispersed dispersion liquid, slowly dropwise adding ammonia water to adjust the pH value to 6.5, and standing for 6 hours to obtain wet gel, wherein the mass ratio of the ethyl orthosilicate to the silver nanowires is 1: 0.1; adding absolute ethyl alcohol into the wet gel, displacing the solvent in the wet gel, performing multiple times of ethanol displacement, and adding hexamethyldisilazane to perform hydrophobic modification treatment on the alcohol gel, wherein the mass ratio of the wet gel after solvent displacement to the hydrophobic modifier is 1: 0.05; by CO2Drying by a supercritical drying process to obtain silver nanowire aerogel composite powder, wherein the supercritical state conditions are as follows: the temperature is 65 ℃, the pressure is 15MPa, and the heat preservation time is 3 h; the silver isThe average grain diameter of the rice-flour aerogel composite powder is 12 microns.
6. The multifunctional heat-preservation antibacterial elastic yarn as claimed in claim 1, wherein in the step 3), the mass ratio of the thermoplastic polyurethane to the silver nanowire aerogel composite powder to the silane coupling agent to the micromolecular polyisocyanate prepolymer is 100:0.1-1:0.5-5:0.5-10, wherein the silane coupling agent is KH 550; the micromolecular polyisocyanate prepolymer is one or more of toluene diisocyanate tripolymer, hexamethylene diisocyanate tripolymer and diphenylmethane diisocyanate tripolymer; in the step 3), the thermoplastic polyurethane is dried and sliced, and then the thermoplastic polyurethane, the silver nanowire aerogel composite powder and the silane coupling agent are sent into a screw extruder to form a polyurethane melt at the temperature of 200-250 ℃, and then a small molecular polyisocyanate prepolymer is added to obtain a mixed melt; extruding the mixed melt by a screw extruder and conveying the mixed melt to a spinning part of a spinning box; quantitatively and uniformly pressing the mixed melt to a spinneret plate by using a spinning pump, extruding the mixed melt trickle from small holes of the spinneret plate, and cooling in a channel to obtain the multifunctional heat-preservation antibacterial elastic yarn; wherein the mass ratio of the plasticizer to the thermoplastic polyurethane is 100:0.5-5, and the plasticizer is di (2-ethylhexyl) phthalate.
7. The multifunctional heat-preservation antibacterial elastic yarn as claimed in claim 6, wherein the thermoplastic polyurethane is dried and sliced, and then the sliced thermoplastic polyurethane, the silver nanowire aerogel composite powder, the silane coupling agent KH550 and the commercially available plasticizer di (2-ethylhexyl) phthalate are fed into a screw extruder to form a polyurethane melt at 220 ℃, and then a toluene diisocyanate trimer is added to obtain a mixed melt; wherein the mass ratio of the thermoplastic polyurethane to the silver nanowire aerogel composite powder to the KH550 to the toluene diisocyanate trimer to the plasticizer is 100:0.5:1:5: 1; extruding the mixed melt by a screw extruder and conveying the mixed melt to a spinning part of a spinning box; quantitatively and uniformly pressing the mixed melt to a spinneret plate with the aperture of 100 microns by using a spinning pump, extruding the mixed melt trickle from the small hole of the spinneret plate, and cooling at room temperature in a channel to obtain the multifunctional heat-preservation antibacterial elastic yarn.
8. The multifunctional heat-preservation antibacterial elastic yarn as claimed in claim 6, wherein the thermoplastic polyurethane is dried and sliced, and then the sliced thermoplastic polyurethane, the silver nanowire aerogel composite powder, the silane coupling agent KH550 and the commercially available plasticizer di (2-ethylhexyl) phthalate are fed into a screw extruder to form a polyurethane melt at 220 ℃, and then a toluene diisocyanate trimer is added to obtain a mixed melt; wherein the mass ratio of the thermoplastic polyurethane to the silver nanowire aerogel composite powder to the KH550 to the toluene diisocyanate trimer to the plasticizer is 100:0.1:5:10: 0.5; extruding the mixed melt by a screw extruder and conveying the mixed melt to a spinning part of a spinning box; quantitatively and uniformly pressing the mixed melt to a spinneret plate with the aperture of 100 microns by using a spinning pump, extruding the mixed melt trickle from the small hole of the spinneret plate, and cooling at room temperature in a channel to obtain the multifunctional heat-preservation antibacterial elastic yarn.
9. A multifunctional elastic silk stocking which is woven from the multifunctional heat-insulating antibacterial elastic silk according to any one of claims 1 to 8.
10. The multifunctional elastic silk stockings of claim 9, wherein the multifunctional heat-preserving antibacterial elastic yarn is formed by twisting a plurality of multifunctional heat-preserving antibacterial elastic yarns and a plurality of traction yarns, which are arranged in a number ratio of 2:2-3, with a polyester low-stretch yarn and/or a polypropylene low-stretch yarn as the traction yarns, and further spun into the silk stockings; wherein the weaving mode comprises knitting and tatting; optionally, PTT shape memory filaments are added in the twisted filament bundle, so that the ratio of the traction filaments to the shape memory filaments to the composite fiber filaments is 2:2-3: 1.
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| CN115490898A (en) * | 2022-10-28 | 2022-12-20 | 江苏湘园化工有限公司 | Preparation method of high-strength transparent conductive silver nanowire-polyurethane composite film |
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| CN111534877B (en) * | 2020-06-04 | 2021-01-15 | 广州市中诚新型材料科技有限公司 | Compound Chinese medicinal multifunctional antibacterial fiber for resisting coronavirus and influenza virus |
| CN113964450A (en) * | 2020-07-17 | 2022-01-21 | 深圳市星源材质科技股份有限公司 | Battery diaphragm coating liquid and preparation method thereof, battery diaphragm and battery |
| CN113897786A (en) * | 2020-10-09 | 2022-01-07 | 单中妹 | Anti-static wear-resistant non-woven fabric |
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