CN112779626A - Preparation method of photocatalytic composite antibacterial spandex - Google Patents
Preparation method of photocatalytic composite antibacterial spandex Download PDFInfo
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- CN112779626A CN112779626A CN202011597649.8A CN202011597649A CN112779626A CN 112779626 A CN112779626 A CN 112779626A CN 202011597649 A CN202011597649 A CN 202011597649A CN 112779626 A CN112779626 A CN 112779626A
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- spandex
- tio
- antibacterial
- photocatalytic composite
- modified
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 91
- 229920002334 Spandex Polymers 0.000 title claims abstract description 81
- 239000004759 spandex Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 88
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 40
- 238000009987 spinning Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 20
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000011550 stock solution Substances 0.000 claims abstract description 12
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 8
- 238000000578 dry spinning Methods 0.000 claims abstract description 5
- 239000003242 anti bacterial agent Substances 0.000 claims description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 15
- 239000003093 cationic surfactant Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229920000289 Polyquaternium Polymers 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002250 absorbent Substances 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 239000004970 Chain extender Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000001580 bacterial effect Effects 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002715 modification method Methods 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims 1
- 239000003945 anionic surfactant Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 abstract description 20
- 239000010452 phosphate Substances 0.000 abstract description 17
- 239000004814 polyurethane Substances 0.000 abstract description 14
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- 239000004408 titanium dioxide Substances 0.000 abstract description 12
- 238000010790 dilution Methods 0.000 abstract description 11
- 239000012895 dilution Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- -1 phosphate radical modified titanium dioxide Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 45
- 239000007788 liquid Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000003287 bathing Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 241000222122 Candida albicans Species 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 5
- 241000191967 Staphylococcus aureus Species 0.000 description 5
- 229940095731 candida albicans Drugs 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000006916 nutrient agar Substances 0.000 description 5
- 239000008055 phosphate buffer solution Substances 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000004714 phosphonium salts Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a preparation method of photocatalytic composite antibacterial spandex, which comprises the steps of reacting polytetramethylene ether glycol with 4, 4-diphenylmethane diisocyanate to obtain a prepolymer, adding N, N-dimethylacetamide for dilution, adding an N, N-dimethylacetamide solution dissolved with 1, 2-propylene diamine, 1, 5-pentamethylene diamine and ethanolamine for chain extension reaction and termination reaction, adding a delustering agent and a phosphate radical modified titanium dioxide antioxidant P-TiO2And curing the antibacterial spandex spinning solution, and then performing dry spinning in a high-temperature channel to obtain the antibacterial spandex. The invention adds phosphate radical modified titanium dioxide antioxidant P-TiO into polyurethane stock solution2So that the density of hydroxyl groups on the surface of the titanium dioxide is increased, and further the method improvesHigh antibacterial property of spandex and high adsorption capacity of titanium dioxide in spandex.
Description
Technical Field
The invention relates to a preparation method of spandex, which mainly utilizes the antibacterial principle of the photocatalytic performance of titanium dioxide to realize the antibacterial effect on spandex, and in particular relates to a preparation method of photocatalytic composite antibacterial spandex.
Background
Spandex is an elastic fiber, has the longest extensibility in synthetic fibers, can obtain good comfort by adding a small amount of spandex in textile fabrics due to excellent elasticity and recovery rate, but can breed germs after being used in daily necessities, and particularly becomes a good environment for breeding various microorganisms in a high-temperature and humid environment, so that healthy life is influenced.
Currently, common spandex antibacterial agents include polyquaternium, polyquaternium phosphonium salt, alcohol, phenol, guanidine, pyridine, imidazole and the like, wherein the polyquaternium is most widely applied. The organic antibacterial agent has stronger initial bactericidal power and better bactericidal aging and universality, but has the problems of easy loss, poor thermal stability and poor chemical stability.
In order to improve the efficiency of spandex preparation, a method of dry spinning at a high temperature chimney is often adopted for spandex spinning preparation, so that the antibacterial agent in the spandex stock solution can be lost or structurally damaged due to the action of high temperature in the spinning process.
TiO2Has good thermal structural stability, although TiO has been used in the prior art2Is used for spandex antibiosis, however, because the preparation of spandex fiber utilizes high-temperature channel dry spinning, TiO2The adsorption at high temperature is greatly reduced, so that TiO2The antibacterial effect used in spandex is limited. At present, silane coupling agent is adopted to modify TiO in the prior art2Or modifying polyurethanes to increase TiO2Adsorption capacity on polyurethane, but modification of TiO by silane coupling agent2Also consumes TiO2The hydroxyl groups on the surface, and thus also cause a problem of deterioration in photocatalytic performance.
Therefore, there is a need to provide a new method for preparing photocatalytic composite antibacterial spandex.
Disclosure of Invention
The invention provides an antibacterial agent which utilizes phosphate radical modified titanium dioxide to increase the density of hydroxyl groups on the surface of the titanium dioxide, and a method for preparing photocatalytic composite antibacterial spandex by adding the phosphate radical modified titanium dioxide antibacterial agent into a polyurethane stock solution, which comprises the following specific steps:
step 1: mixing polytetramethylene ether glycol and 4, 4-diphenylmethane diisocyanate according to the mass ratio of 1: 1.6-1.9 for polymerization reaction to obtain-NCO-terminated prepolymer, adding N, N-dimethylacetamide solvent, and fully dissolving the prepolymer;
step 2: adding N, N-dimethylacetamide dissolved with a chain extender and a terminator into the prepolymer solution obtained in the step 1 to perform a chain extension reaction and a termination reaction;
and step 3: adding a composite modified antibacterial agent, an antioxidant, an ultraviolet absorbent and a cationic surfactant into the product obtained in the step 2 to obtain an antibacterial spandex spinning stock solution;
the addition amount of the composite modified antibacterial agent is 0.5-1.8% of the mass of the solute of the spandex spinning solution;
the compound modified antibacterial agent is P-TiO2(the mass ratio of P is 1-3%), P-TiO2The mass ratio of the cationic surfactant to the cationic surfactant is 2-3: 3-4.
And 4, step 4: curing the antibacterial spandex spinning solution obtained in the step 3, and then carrying out dry spinning in a high-temperature shaft to obtain the antibacterial spandex, wherein the temperature of the shaft can be set to be 180-270 ℃, and is preferably 240-250 ℃.
P-TiO of the invention2Is through PO4 3-The titanium dioxide is modified by salt, so that the surface hydroxyl groups of the titanium dioxide are enhanced, and the photocatalytic performance of the titanium dioxide is improved.
Phosphate radical and TiO2Bonding is carried out due to PO4 3-And [ TiO ]6]The octahedron generates polydentate chelation to cause TiO2The surface collects a large amount of negative charges to form surface negative electrostatic fields which can promote electrons and airSeparation of the cavities, suppression of charge and TiO2And (3) recombination of (1). In addition, phosphate ions can have strong interaction with water molecules through hydrogen bonds and can be used as a good anchoring group in a photocatalytic system to effectively complete TiO2And transfer of electrons between chromophores. These characteristics contribute to TiO2Electron transfer between oxygen vacancy on crystal face and water molecule, thereby increasing nano TiO2Surface hydroxyl group density. Thereby influencing the adsorption and catalysis characteristics of the nano TiO, and realizing the nano TiO through the phosphoric acid immersion process2Surface chemical modification of (1) to increase TiO2The surface hydroxyl groups of the titanium dioxide can improve the photocatalytic performance of the titanium dioxide.
Further, the polymerization reaction temperature in the step 1 is 65-73 ℃, and the reaction time is 60-90 min. The polymerization reaction is an exothermic reaction, and by controlling the reaction temperature appropriately, the reaction can be sufficiently performed, and the progress of the reaction can be controlled.
Further, the chain extender in the step 2 is 1, 2-propane diamine and 1, 5-pentane diamine, the terminator is ethanolamine, and the mass ratio of the 1, 2-propane diamine, the 1, 5-pentane diamine and the ethanolamine is 5: 3: 2.
further, the antioxidant in the step 3 is AT245, and the ultraviolet absorbent is UV-320.
Further, the P-TiO in the step 32Wherein the mass ratio of P is 1-3 percent, and P-TiO2Is PO4 3-A salt-modified titanium dioxide. In the present invention, titanium dioxide also functions as a matting agent.
PO4 3-Has higher negative charge and stronger attraction with Ti4+ ions, so that the phosphate radical is easier to combine with a titanium basic unit, and can be combined with TiO when the adding amount of the phosphate radical is more than 1.0 percent2On the surface, but as the amount of phosphate added increases, phosphate is deposited on TiO2Surface of TiO so that2The specific surface area is reduced, the particle size is increased, the surface energy is reduced, and the phosphate radical and TiO are enabled to react2The binding energy of (2) is reduced and excessive phosphate addition results in TiO2Agglomeration, therefore, 1% > E was chosen for the present invention3 percent of phosphate radical addition amount to obtain P-TiO2Wherein the mass ratio of P is 1-3%.
Further, the P-TiO2Is prepared by nano-dioxide and phosphoric acid solution through a hydrothermal synthesis method.
Realization of nano TiO by phosphoric acid immersion process2Surface chemical modification of (1) to increase TiO2The surface hydroxyl groups of the titanium dioxide can improve the photocatalytic performance of the titanium dioxide.
And 7, the P-TiO2 is a compound modified antibacterial agent modified by a silane coupling agent. The silane coupling agent is an amphoteric organic substance consisting of a hydrophilic polar group and an oleophilic nonpolar group. Hydrophilic group and nano TiO2the-OH reaction on the surface of the particle changes the hydrophilicity of the surface of the nanoparticle into lipophilicity, and improves the dispersibility of the nanoparticle in the polyurethane prepolymer and the binding capacity of the nanoparticle and the polyurethane prepolymer.
Further, the P-TiO2The modification method through silane coupling agent is to mix P-TiO2Mixing the nano particles and a silane coupling agent according to the mass ratio of 1: 0.01-0.02, then blending the mixture into 40-60% ethanol water solution, fully dispersing the mixture in an environment with the pH value of 4-5, and then washing, filtering and drying the mixture to obtain the nano particles.
Further, the silane coupling agent is one of N-octyl trimethoxy silane, gamma-glycidyl ether oxygen propyl trimethoxy silane and gamma-methyl acrylic oxygen propyl trimethoxy silane.
Further, the cationic surfactant in step 3 is one of polyquaternium and polyquaternium. The polyquaternium and the polyquaternium phosphate are cationic surfactants and are organic antibacterial agents, and the antibacterial performance of the polyurethane can be improved.
The invention has the beneficial effects that:
1. the invention adds TiO modified by phosphate radical2To obtain P-TiO2Increasing the TiO content2Surface hydroxyl radical, increasing TiO2The photocatalysis performance of the antibacterial spandex is improved.
2. The invention also relates to P-TiO2On the basis of the (A), utilizing a silane coupling agent to P-TiO2Further modified to improve P-TiO2The adsorption capacity and the dispersibility on polyurethane ensure that the obtained spandex has lasting antibacterial performance and overcomes the defects of common TiO2After the antibacterial agent passes through the high-temperature channel spinning of polyurethane raw liquid, a large amount of TiO2The falling off affects the antibacterial performance of the spandex. P-TiO prepared by simultaneous silane coupling agent pair2Modification by P-TiO2The hydroxyl group on the surface reacts with silane coupling agent to lead P-TiO to react2The surface has epoxy groups which can react with carbamate in polyurethane to strengthen P-TiO2The interaction between the P-TiO modified polyurethane and polyurethane can greatly improve the P-TiO2The compatibility in a polyurethane system can effectively improve P-TiO2Dispersibility in urethane systems.
3. The invention utilizes silane coupling agent to P-TiO2The modification is carried out, thereby overcoming the defect that the prior art adopts silane coupling agent to modify TiO2To produce TiO2The surface hydroxyl density is reduced by one step, and TiO is influenced2The invention adopts silane coupling agent to modify P-TiO2Albeit P-TiO2The hydroxyl group on the surface reacts with silane coupling agent to lead P-TiO to react2Having epoxy groups on the surface consumes a portion of the hydroxyl groups but due to the P-TiO2High density of surface hydroxyl groups to P-TiO2Has less influence on the photocatalytic performance.
4. The invention utilizes TiO modified by phosphate radical2As an antibacterial agent, TiO can be reinforced without adding a silane coupling agent2Binding ability to polyurethane due to phosphate modified TiO2Then, TiO22The surface is added with a large number of hydroxyl groups, and most of the hydroxyl groups exist in a protonated structure, so that the special hydroxyl groups can enable TiO to be coated2The material is combined with molecules in the polyurethane prepolymer, so that more hydroxyl groups and molecules in the polyurethane stock solution form hydrogen bonds, and TiO is improved2Binding ability in polyurethane stock solution.
Detailed Description
Example one
A preparation method of photocatalytic composite antibacterial spandex comprises the following specific steps:
step 1: 101.55kg of polytetramethylene ether glycol with the average molecular weight of 1800 and 30kg of 4, 4-diphenylmethane diisocyanate were mixed together to carry out a polymerization reaction in a reaction kettle at 73 ℃ for 1 hour to obtain a-NCO-terminated prepolymer, and 197.3kg of N, N-dimethylacetamide solvent was added to sufficiently dissolve the prepolymer;
step 2: dissolving 3.77kg of 1, 2-propanediamine, 3.12kg of 1, 5-pentanediamine and 1.24kg of ethanolamine in 30kg of N, N-dimethylacetamide solvent, and adding the mixture into the prepolymer solution obtained in the step (1) to carry out chain extension reaction and termination reaction;
and step 3: adding 0.27kg of AT245 antioxidant and 0.69kg of composite modified antibacterial agent P-TiO into the product obtained in the step 22(the mass ratio of P is 3%), 0.25kg of UV-320 ultraviolet absorbent and 1.05kg of polyquaternium cationic surfactant to obtain the antibacterial spandex spinning solution;
wherein P-TiO2The preparation method comprises the following steps: dissolving spherical nanometer dioxide in phosphoric acid solution, water-bathing at 40 deg.C for 2 hr, heating to 100 deg.C, water-bathing for 5 hr, drying, washing with distilled water, and drying to obtain P-TiO2。
And 4, step 4: curing the antibacterial spandex spinning stock solution obtained in the step (3), and then carrying out spinning in a shaft at the temperature of 240-250 ℃ by a dry method to obtain the antibacterial spandex.
Adding a certain amount of the prepared spandex into a triangular flask containing a test bacterium culture solution, sterilizing at high temperature and high pressure, cooling to room temperature, inoculating a test bacterium therein, ensuring that the bacterium solution is uniformly distributed on the spandex, plugging a plug to prevent volatilization, and measuring the bacterium concentration by a dilution plate method (at 37 ℃ for 24 hours). After the fiber and the test bacteria are contacted for a period of time, washing with phosphate buffer solution, after gradient dilution, taking a small amount of bacteria liquid, pouring the bacteria liquid on a nutrient agar plate, and measuring the concentration of the bacteria liquid of the residual viable bacteria in the triangular flask so as to test the antibacterial and bactericidal performance of the spandex. The antibacterial and bactericidal rate of staphylococcus aureus is 98.76%, the antibacterial and bactericidal rate of escherichia coli is 98.82%, and the antibacterial and bactericidal rate of candida albicans is 98.79%, which are shown in table 1.
Example two
A preparation method of photocatalytic composite antibacterial spandex comprises the following specific steps:
step 1: 101.55kg of polytetramethylene ether glycol having an average molecular weight of 1800 and 30kg of 4, 4-diphenylmethane diisocyanate were mixed together and subjected to a polymerization reaction at 65 ℃ for 1.5 hours in a reaction vessel to obtain an-NCO-terminated prepolymer, and 197.3kg of an N, N-dimethylacetamide solvent was added to sufficiently dissolve the prepolymer;
step 2: dissolving 3.77kg of 1, 2-propanediamine, 3.12kg of 1, 5-pentanediamine and 1.24kg of ethanolamine in 30kg of N, N-dimethylacetamide solvent, and adding the mixture into the prepolymer solution obtained in the step (1) to carry out chain extension reaction and termination reaction;
and step 3: 0.77kg of AT245 antioxidant and 2.51kg of composite modified antibacterial agent P-TiO modified by N-octyltrimethoxysilane are added into the product obtained in the step 22(the mass ratio of P is 2%), 0.63kg of UV-320 ultraviolet absorbent and 3.27kg of polyquaternary phosphonium salt cationic surfactant to obtain the antibacterial spandex spinning solution;
wherein N-octyl trimethoxy silane modified composite modified antibacterial agent P-TiO2The preparation method comprises the following steps:
preparing P-TiO2. Dissolving spherical nanometer dioxide in phosphoric acid solution, water-bathing at 40 deg.C for 2 hr, heating to 100 deg.C, water-bathing for 5 hr, drying, washing with distilled water, and drying to obtain P-TiO2。
② modifying P-TiO by N-octyltrimethoxysilane2. Taking 2.48kgP-TiO2Mixing nanoparticles and 0.025kg N-octyltrimethoxysilane in 20L deionized water, adding into 50L ethanol, adjusting pH to 4.5 with glacial acetic acid and 25% ammonia water, dispersing at 50 deg.C for 1 hr, washing, filtering, and dryingThen obtaining the N-octyl trimethoxy silane modified P-TiO2。
And 4, step 4: curing the antibacterial spandex spinning stock solution obtained in the step (3), and then carrying out spinning in a shaft at the temperature of 240-250 ℃ by a dry method to obtain the antibacterial spandex.
Adding a certain amount of the prepared spandex into a triangular flask containing a test bacterium culture solution, sterilizing at high temperature and high pressure, cooling to room temperature, inoculating a test bacterium therein, ensuring that the bacterium solution is uniformly distributed on the spandex, plugging a plug to prevent volatilization, and measuring the bacterium concentration by a dilution plate method (at 37 ℃ for 24 hours). After the fiber and the test bacteria are contacted for a period of time, washing with phosphate buffer solution, after gradient dilution, taking a small amount of bacteria liquid, pouring the bacteria liquid on a nutrient agar plate, and measuring the concentration of the bacteria liquid of the residual viable bacteria in the triangular flask so as to test the antibacterial and bactericidal performance of the spandex. The antibacterial rate of staphylococcus aureus is 98.28%, the antibacterial rate of escherichia coli is 98.24%, and the antibacterial rate of candida albicans is 98.29%, which are shown in table 1.
EXAMPLE III
A preparation method of photocatalytic composite antibacterial spandex comprises the following specific steps:
step 1: 101.55kg of polytetramethylene ether glycol having an average molecular weight of 1800 and 30kg of 4, 4-diphenylmethane diisocyanate were mixed together and subjected to a polymerization reaction at 70 ℃ for 1.2 hours in a reaction vessel to give a-NCO-terminated prepolymer, and 197.3kg of an N, N-dimethylacetamide solvent was added to sufficiently dissolve the prepolymer;
step 2: dissolving 3.77kg of 1, 2-propanediamine, 3.12kg of 1, 5-pentanediamine and 1.24kg of ethanolamine in 30kg of N, N-dimethylacetamide solvent, and adding the mixture into the prepolymer solution obtained in the step (1) to carry out chain extension reaction and termination reaction;
and step 3: adding 0.55kg of AT245 antioxidant and 1.82kg of composite modified antibacterial agent P-TiO modified by gamma-glycidoxypropyltrimethoxysilane into the product obtained in the step 22(the mass ratio of P is 1%), 0.42kg of UV-320 ultraviolet absorbent and 2.36kg of polyquaternium cationic surfactant to obtain the antibacterial spandex spinning solution;
wherein gamma-glycidoxypropyltrimethoxysilane is utilized for modifying the composite modified antibacterial agent P-TiO2The preparation method comprises the following steps:
preparing P-TiO2. Dissolving spherical nanometer dioxide in phosphoric acid solution, water-bathing at 40 deg.C for 2 hr, heating to 100 deg.C, water-bathing for 5 hr, drying, washing with distilled water, and drying to obtain P-TiO2。
② gamma-glycidol ether oxygen propyl trimethoxy silane is utilized to modify P-TiO2. 1.80kg of P-TiO was taken2Mixing the nano-particles and 0.018kg of gamma-glycidoxypropyltrimethoxysilane in 15L of deionized water, adding into 35L of ethanol, adjusting pH to 4.5 by using glacial acetic acid and 25% ammonia water, dispersing at 50 ℃ for 1 hour, washing, filtering and drying to obtain N-octyltrimethoxysilane modified P-TiO2。
And 4, step 4: curing the antibacterial spandex spinning stock solution obtained in the step (3), and then carrying out spinning in a shaft at the temperature of 240-250 ℃ by a dry method to obtain the antibacterial spandex.
Adding a certain amount of the prepared spandex into a triangular flask containing a test bacterium culture solution, sterilizing at high temperature and high pressure, cooling to room temperature, inoculating a test bacterium therein, ensuring that the bacterium solution is uniformly distributed on the spandex, plugging a plug to prevent volatilization, and measuring the bacterium concentration by a dilution plate method (at 37 ℃ for 24 hours). After the fiber and the test bacteria are contacted for a period of time, washing with phosphate buffer solution, after gradient dilution, taking a small amount of bacteria liquid, pouring the bacteria liquid on a nutrient agar plate, and measuring the concentration of the bacteria liquid of the residual viable bacteria in the triangular flask so as to test the antibacterial and bactericidal performance of the spandex. The antibacterial rate of the staphylococcus aureus is 99.29%, the antibacterial rate of the escherichia coli is 99.36%, and the antibacterial rate of the candida albicans is 99.32%, which are shown in table 1.
Comparative example 1
A preparation method of photocatalytic composite antibacterial spandex comprises the following specific steps:
step 1: 101.55kg of polytetramethylene ether glycol with the average molecular weight of 1800 and 30kg of 4, 4-diphenylmethane diisocyanate were mixed together to carry out a polymerization reaction in a reaction kettle at 73 ℃ for 1 hour to obtain a-NCO-terminated prepolymer, and 197.3kg of N, N-dimethylacetamide solvent was added to sufficiently dissolve the prepolymer;
step 2: dissolving 3.77kg of 1, 2-propanediamine, 3.12kg of 1, 5-pentanediamine and 1.24kg of ethanolamine in 30kg of N, N-dimethylacetamide solvent, and adding the mixture into the prepolymer solution obtained in the step (1) to carry out chain extension reaction and termination reaction;
and step 3: to the product obtained in step 2, 0.27kg of AT245 antioxidant and 0.69kg of TiO were added2Antibacterial agent, UV-320 ultraviolet absorbent of 0.25kg, polyquaternium cationic surfactant of 1.05kg to obtain antibacterial spandex spinning solution;
and 4, step 4: curing the antibacterial spandex spinning stock solution obtained in the step (3), and then carrying out spinning in a shaft at the temperature of 240-250 ℃ by a dry method to obtain the antibacterial spandex.
Adding a certain amount of the prepared spandex into a triangular flask containing a test bacterium culture solution, sterilizing at high temperature and high pressure, cooling to room temperature, inoculating a test bacterium therein, ensuring that the bacterium solution is uniformly distributed on the spandex, plugging a plug to prevent volatilization, and measuring the bacterium concentration by a dilution plate method (at 37 ℃ for 24 hours). After the fiber and the test bacteria are contacted for a period of time, washing with phosphate buffer solution, after gradient dilution, taking a small amount of bacteria liquid, pouring the bacteria liquid on a nutrient agar plate, and measuring the concentration of the bacteria liquid of the residual viable bacteria in the triangular flask so as to test the antibacterial and bactericidal performance of the spandex. The antibacterial rate of the staphylococcus aureus is 83.93 percent, the antibacterial rate of the escherichia coli is 83.26 percent, and the antibacterial rate of the candida albicans is 83.13 percent, which are detailed in table 1.
Comparative example No. two
A preparation method of photocatalytic composite antibacterial spandex comprises the following specific steps:
step 1: 101.55kg of polytetramethylene ether glycol having an average molecular weight of 1800 and 30kg of 4, 4-diphenylmethane diisocyanate were mixed together and subjected to a polymerization reaction at 65 ℃ for 1.5 hours in a reaction vessel to obtain an-NCO-terminated prepolymer, and 197.3kg of an N, N-dimethylacetamide solvent was added to sufficiently dissolve the prepolymer;
step 2: dissolving 3.77kg of 1, 2-propanediamine, 3.12kg of 1, 5-pentanediamine and 1.24kg of ethanolamine in 30kg of N, N-dimethylacetamide solvent, and adding the mixture into the prepolymer solution obtained in the step (1) to carry out chain extension reaction and termination reaction;
and step 3: to the product obtained in step 2, 0.77kg of AT245 antioxidant and 2.51kg of antibacterial agent TiO modified with N-octyltrimethoxysilane were added20.63kg of UV-320 ultraviolet absorbent and 3.27kg of polyquaternary phosphonium salt cationic surfactant to obtain antibacterial spandex spinning solution;
in which antibacterial agent TiO modified by N-octyl trimethoxy silane is used2The preparation method comprises the following steps:
2.48kg of TiO are taken2Mixing the nano-particles and 0.025kg of N-octyltrimethoxysilane in 20L of deionized water, then melting the mixture into 50L of ethanol, adjusting the pH to 4.5 by using glacial acetic acid and 25% ammonia water, dispersing the mixture at the temperature of 50 ℃ for 1 hour, and then washing, filtering and drying the dispersion to obtain the N-octyltrimethoxysilane modified TiO2。
And 4, step 4: curing the antibacterial spandex spinning stock solution obtained in the step (3), and then carrying out spinning in a shaft at the temperature of 240-250 ℃ by a dry method to obtain the antibacterial spandex.
Adding a certain amount of the prepared spandex into a triangular flask containing a test bacterium culture solution, sterilizing at high temperature and high pressure, cooling to room temperature, inoculating a test bacterium therein, ensuring that the bacterium solution is uniformly distributed on the spandex, plugging a plug to prevent volatilization, and measuring the bacterium concentration by a dilution plate method (at 37 ℃ for 24 hours). After the fiber and the test bacteria are contacted for a period of time, washing with phosphate buffer solution, after gradient dilution, taking a small amount of bacteria liquid, pouring the bacteria liquid on a nutrient agar plate, and measuring the concentration of the bacteria liquid of the residual viable bacteria in the triangular flask so as to test the antibacterial and bactericidal performance of the spandex. The antibacterial and bactericidal rate of staphylococcus aureus is 84.63%, the antibacterial and bactericidal rate of escherichia coli is 84.92%, and the antibacterial and bactericidal rate of candida albicans is 84.85%, which are shown in table 1.
TABLE 1 antibacterial and bactericidal ratio of Spandex of each example to different bacterial species
In comparative example 1, since there is no TiO, the material is not oxidized2Is modified, thus, TiO2The antibacterial property and the adsorption capacity of the composite material are weak, and after high-temperature channel spinning, TiO can be obtained2Falls off to affect antibacterial property, and is not modified into TiO2The hydroxyl group of (a) is less, and the antibacterial performance is also influenced.
Comparative example 2, TiO without phosphate2The modification is carried out, so that the density of hydroxyl groups on the surface of the TiO2 is smaller, and the silane coupling agent and the TiO are mixed2The hydroxyl on the surface reacts to consume partial hydroxyl groups and generate epoxy groups, so that TiO is formed2The surface hydroxyl is further reduced, the photocatalytic performance is reduced, and the antibacterial performance of the antibacterial spandex is reduced.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of photocatalytic composite antibacterial spandex is characterized by comprising the following specific steps:
step 1: mixing polytetramethylene ether glycol and 4, 4-diphenylmethane diisocyanate according to the mass ratio of 1: 1.6-1.9 for polymerization reaction to obtain-NCO-terminated prepolymer, adding N, N-dimethylacetamide solvent, and fully dissolving the prepolymer;
step 2: adding N, N-dimethylacetamide dissolved with a chain extender and a terminator into the prepolymer solution obtained in the step 1 to perform a chain extension reaction and a termination reaction;
and step 3: adding a composite modified antibacterial agent, an antioxidant, an ultraviolet absorbent and a cationic surfactant into the product obtained in the step 2 to obtain an antibacterial spandex spinning stock solution;
the addition amount of the composite modified antibacterial agent is 0.5-1.8% of the mass of the solute of the spandex spinning solution;
the compound modified antibacterial agent is P-TiO2(the mass ratio of P is 1-3%), P-TiO2The mass ratio of the cationic surfactant to the cationic surfactant is 2-3: 3-4;
and 4, step 4: and (4) curing the antibacterial spandex spinning solution obtained in the step (3), and then carrying out dry spinning in a high-temperature channel to obtain the antibacterial spandex.
2. The preparation method of the photocatalytic composite antibacterial spandex according to claim 1, wherein the polymerization reaction temperature in the step 1 is 65-73 ℃ and the reaction time is 60-90 min.
3. The method for preparing photocatalytic composite antibacterial spandex as claimed in claim 1, wherein the chain extender in step 2 is 1, 2-propanediamine or 1, 5-pentanediamine, the terminator is ethanolamine, and the mass ratio of the 1, 2-propanediamine to the 1, 5-pentanediamine to the ethanolamine is 5: 3: 2.
4. the method for preparing the photocatalytic composite antibacterial spandex as claimed in claim 1, wherein the antioxidant in step 3 is AT245, the ultraviolet absorber is UV-320, the addition amount of the antioxidant is 0.2-0.55% of the solute mass of the spandex spinning solution, and the addition amount of the ultraviolet absorber is 0.18-0.45% of the solute mass of the spandex spinning solution.
5. The method for preparing the photocatalytic composite antibacterial spandex of claim 1, wherein the P-TiO in the step 32Is PO4 3-A salt-modified titanium dioxide.
6. The photocatalytic composite antibody as set forth in claim 1 or 5The preparation method of the bacterial spandex is characterized in that the P-TiO2Is prepared by nano-dioxide and phosphoric acid solution through a hydrothermal synthesis method.
7. The method for preparing the photocatalytic composite antibacterial spandex of claim 6, wherein the P-TiO is2Is a compound modified antibacterial agent after being modified by a silane coupling agent.
8. The method for preparing the photocatalytic composite antibacterial spandex of claim 7, wherein the P-TiO is2The modification method through silane coupling agent is to mix P-TiO2Mixing the nano particles and a silane coupling agent according to a mass ratio of 1: 0.01-0.02, fully melting into ethanol, fully dispersing in an environment with pH of 4-5, washing, filtering and drying to obtain the nano-particles.
9. The method for preparing photocatalytic composite antibacterial spandex as claimed in claim 7 or 8, wherein the silane coupling agent is one of N-octyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-methacryloxypropyltrimethoxysilane.
10. The method for preparing photocatalytic composite antibacterial spandex according to claim 1, wherein the anionic surfactant in the step 3 is one of polyquaternium and polyquaternium.
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