CN115852674A - Fiber product for realizing photo-thermal rapid sterilization based on in-situ deposited nanoparticles and finishing method thereof - Google Patents
Fiber product for realizing photo-thermal rapid sterilization based on in-situ deposited nanoparticles and finishing method thereof Download PDFInfo
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- CN115852674A CN115852674A CN202211389081.XA CN202211389081A CN115852674A CN 115852674 A CN115852674 A CN 115852674A CN 202211389081 A CN202211389081 A CN 202211389081A CN 115852674 A CN115852674 A CN 115852674A
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- 239000000835 fiber Substances 0.000 title claims abstract description 136
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 37
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229960002663 thioctic acid Drugs 0.000 claims abstract description 41
- 235000019136 lipoic acid Nutrition 0.000 claims abstract description 39
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002791 soaking Methods 0.000 claims abstract description 17
- -1 dimethyl siloxane Chemical class 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 14
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 239000004744 fabric Substances 0.000 claims description 51
- AGBQKNBQESQNJD-UHFFFAOYSA-N lipoic acid Chemical compound OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 claims description 34
- OOTFVKOQINZBBF-UHFFFAOYSA-N cystamine Chemical compound CCSSCCN OOTFVKOQINZBBF-UHFFFAOYSA-N 0.000 claims description 28
- 229940099500 cystamine Drugs 0.000 claims description 28
- 210000002268 wool Anatomy 0.000 claims description 23
- 229920001661 Chitosan Polymers 0.000 claims description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 17
- 239000004753 textile Substances 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 108010029541 Laccase Proteins 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 10
- AGBQKNBQESQNJD-SSDOTTSWSA-N (R)-lipoic acid Chemical compound OC(=O)CCCC[C@@H]1CCSS1 AGBQKNBQESQNJD-SSDOTTSWSA-N 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000002255 enzymatic effect Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 4
- 210000000085 cashmere Anatomy 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 230000002070 germicidal effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 24
- 230000035699 permeability Effects 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 230000002045 lasting effect Effects 0.000 abstract description 7
- 230000003373 anti-fouling effect Effects 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 23
- 238000003860 storage Methods 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
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- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DZGWFCGJZKJUFP-UHFFFAOYSA-N Tyramine Natural products NCCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 235000005607 chanvre indien Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000007730 finishing process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229960003732 tyramine Drugs 0.000 description 1
- DZGWFCGJZKJUFP-UHFFFAOYSA-O tyraminium Chemical compound [NH3+]CCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-O 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a fiber product for realizing photo-thermal rapid sterilization based on in-situ deposited nanoparticles and a finishing method thereof, belonging to the technical field of functional material processing. The finishing method of the fiber product for realizing photo-thermal rapid sterilization based on the in-situ deposited nanoparticles comprises the steps of introducing sulfydryl on natural fibers, then soaking the fiber product in a lipoic acid solution, and forming sulfur free radicals through ring opening of disulfide bonds in lipoic acid to realize graft polymerization of lipoic acid molecules and fibers; then adding a solution of template-loaded thiourea, and depositing nano copper sulfide particles on the surface of the fiber in situ through the interaction of copper ions and the template-loaded thiourea; finally, packaging the nano copper sulfide particles on the surface of the fiber by virtue of dimethyl siloxane to obtain the fiber product with the rapid sterilization function. The fiber product has the advantages of obvious photo-thermal sterilization effect, lasting photo-thermal sterilization effect and good air permeability and antifouling property.
Description
Technical Field
The invention relates to a fiber product for realizing photo-thermal rapid sterilization based on in-situ deposited nanoparticles and a finishing method thereof, belonging to the technical field of functional material processing.
Background
The natural fiber products comprise different textiles which take cotton, hemp, silk and wool as raw materials. Such natural fiber products have good hygroscopicity, but are also prone to be locations where microorganisms such as bacteria and mold grow under appropriate temperature and humidity conditions, so that the fiber products are mildewed and the wearability of the fiber products is reduced. Therefore, the natural fiber products are required to be finished for the purpose of improving antibacterial performance.
The antibacterial finishing agent applied to natural fiber products comprises silver ions, nano silver, quaternary ammonium salt, halamine compound and the like, and the finishing agent can provide antibacterial effect to the fiber products, and meanwhile, the problems of poor bonding fastness with fibers, insufficient antibacterial washfastness and the like exist partially, and the defects that the fiber strength is easily damaged in the finishing process of partial textiles are also caused. Moreover, although the traditional antibacterial fiber product has the bacteriostatic effect, the bacterial colony which is retained on the surface of the traditional antibacterial fiber product is difficult to realize high-efficiency and quick killing in a short time. Therefore, the preparation of the textile with the efficient and rapid sterilization function has positive significance.
Researches show that the photo-thermal nano particles deposited on the surface of the fiber can quickly kill bacterial colonies on the surface of a fiber product under the illumination condition, and the photo-thermal nano particles become an effective way for developing antibacterial textiles. The nano copper sulfide particles have good optical properties, have strong absorption capacity on near infrared light, and can rapidly raise the surface temperature of a substrate by triggering d-d energy band transition of copper ions, so that a rapid sterilization effect is realized, and the nano copper sulfide particles have application prospects in rapid sterilization, finishing and processing of fiber products. At present, although there are many reports of rapid sterilization textile preparation by in-situ deposition of nano copper sulfide particles on the fiber surface, there are three general problems to be solved: (1) the nano particles are less in deposition amount and poor in photo-thermal effect; (2) The nano-particle has low binding fastness, and the photo-thermal sterilization effect is reduced after washing; (3) The nano particles are easy to oxidize, and the photo-thermal effect attenuation in storage is obvious. Therefore, aiming at the defects of the photo-thermal sterilization textile prepared by the deposition of nano copper sulfide particles, a textile preparation method with efficient, lasting and rapid sterilization functions is urgently needed to be established.
Disclosure of Invention
[ problem ] to
The nanometer copper sulfide particles deposited by the conventional method have the problems of weak combination with fibers, poor photo-thermal sterilization effect of prepared textiles, non-lasting finishing effect and the like.
[ solution ]
Aiming at the problems, firstly, the natural fiber grafted cystamine is catalyzed and oxidized by laccase, and then, the disulfide bond is reduced, and the sulfydryl is introduced into a fiber product; then, soaking the fiber product containing the sulfydryl in a lipoic acid solution, and realizing the graft polymerization of the lipoic acid on the surface of the fiber by forming sulfur free radicals through ring opening of disulfide bonds in the lipoic acid at high temperature; in the process, on one hand, sulfur free radicals react with sulfydryl on the surface of the fiber to realize the grafting of lipoic acid and the fiber, on the other hand, the sulfur free radicals can be mutually combined to form a carboxyl-containing polythiooctanoic acid molecule by polymerization on the surface of the fiber; thirdly, capturing copper ammonia ions by virtue of carboxyl on the polythiooctanoic acid on the surface of the fiber, increasing the binding capacity of copper source ions on the surface of the fiber, adding thiourea solution taking quaternary ammonium chitosan as a template, and forming nano copper sulfide particles by in-situ deposition on the surface of the fiber through the interaction of the copper source ions and thiourea; and finally, soaking the fabric in a polydimethylsiloxane solution to realize the packaging and embedding of the nano copper sulfide particles on the surface of the fiber, and improving the bonding fastness and surface oxidation resistance of the nano copper sulfide particles to prepare the textile with the rapid and lasting sterilization function.
The invention provides a fiber product finishing method for realizing photo-thermal rapid sterilization based on in-situ deposited nanoparticles, which comprises the following steps:
(1) Introducing sulfydryl on the fiber: immersing the natural fiber product in a cystamine aqueous solution; adding laccase to enable the laccase to catalyze and oxidize phenolic hydroxyl of tyrosine in natural fibers to react with terminal amino in cystamine, and grafting cystamine with an enzymatic fiber product; then taking out the fiber product, soaking the fiber product in sodium bisulfite solution, and reducing the cystamine grafted on the fiber to obtain a fiber product containing sulfydryl;
(2) Lipoic acid graft polymerization: dipping the fiber product containing the sulfydryl obtained in the step (1) in a lipoic acid solution, and performing graft polymerization on the surface of the fiber to form poly lipoic acid through the reaction of the sulfydryl on the fiber and a lipoic acid free radical and the mutual reaction of lipoic acid free radicals;
(3) Deposition of nano copper sulfide particles: soaking the fiber product treated in the step (2) in a copper ammonia solution after being washed, treating the fiber product at 30-40 ℃ for 15-30 min, dropwise adding a solution of quaternary ammonium salt chitosan template loaded thiourea, continuing to react for 15-30 min after dropwise adding is finished, and depositing in situ on the surface of the fiber to obtain nano copper sulfide particles;
(4) And (3) antioxidant packaging of the nano particles: and (4) soaking the fiber product treated in the step (3) in an ethanol solution of polydimethylsilane, drying at room temperature, and baking to obtain the fiber product.
In one embodiment, the natural fiber product in step (1) is a composite fiber, yarn or fabric containing silk, pressed silk, wool and cashmere.
In one embodiment, the fiber product of step (1) is grafted with cystamine under the following treatment conditions: laccase is 2-5U/mL, cystamine is 5-10 g/L, the bath ratio is 1.
In one embodiment, the treatment conditions for the cystamine reduction are: sodium bisulfite 10-20 g/L, bath ratio 1.
In one embodiment, the processing conditions of the lipoic acid graft polymerization of step (2): the thioctic acid solution is prepared by 20-30% ethanol solution, the mass concentration of the thioctic acid is 5-10 g/L, the bath ratio is 1.
In one embodiment, the copper ammonia solution in step (3) is a copper ammonia solution of copper tetraammine complex ions, and the concentration of the copper ammonia solution is 0.1-0.2 mol/L.
In one embodiment, the mass concentration of the quaternary ammonium salt chitosan in the solution of the quaternary ammonium salt chitosan template loaded with thiourea in the step (3) is 20-25 g/L, and the mass concentration of the thiourea is 40-50 g/L.
In one embodiment, the molar ratio of thiourea to the copper ammonia solution is 1 to 2:1.
in one embodiment, the mass concentration of the ethanol solution of the polydimethylsilane in the step (4) is 5 to 10g/L.
In one embodiment, the baking temperature in the step (4) is 100-105 ℃ and the baking time is 10-20 min.
The second purpose of the invention is to obtain the photo-thermal fast-sterilization fiber product prepared by the method.
The third purpose of the invention is the application of the photo-thermal rapid sterilization fiber product in the preparation of functional textiles.
In one embodiment of the invention, the functional textile comprises clothing fabric, home textile products and medical and health products.
[ advantageous effects ]
According to the invention, sulfydryl is introduced to natural fibers, then the fiber product is immersed in a lipoic acid solution, and sulfur free radicals are formed through opening of disulfide bonds in lipoic acid to realize graft polymerization of lipoic acid molecules and the fibers; capturing copper ammonia ions by virtue of carboxyl on the polythiooctanoic acid on the surface of the fiber, and depositing nano copper sulfide particles in situ on the surface of the fiber through the interaction of the copper ions and thiourea loaded on a quaternary ammonium salt chitosan template; finally, the nano copper sulfide particles on the surface of the fiber are packaged by virtue of dimethyl siloxane, the bonding fastness and the oxidation resistance of the nano copper sulfide are improved, and the fiber product with the rapid sterilization function is obtained. Compared with the reported fiber product in-situ deposited by nano copper sulfide particles, the invention has the following advantages:
(1) The photo-thermal sterilization effect is obvious: on one hand, the pendant group of the polythiooctanoic acid molecule grafted on the surface of the fiber is negatively charged, so that the copper ammonia ions can be promoted to be combined with the fiber; on the other hand, thiourea can be efficiently combined with a quaternary ammonium salt chitosan template and transferred to the surface of the fiber through electrostatic attraction between quaternary ammonium salt chitosan and fiber macromolecules, so that the total number of sulfur source ions on the surface of the fiber is increased, the interaction between copper source ions and sulfur ions on the surface of the fiber is promoted, and then more nano copper sulfide particles are deposited on the surface of the fiber to endow the fiber product with efficient and rapid sterilization effect;
(2) The photo-thermal sterilization effect is lasting: after the nano copper sulfide particles on the surface of the fiber product are treated by the polydimethylsiloxane, a protective film on the surface of the nano particles is formed, so that the bonding fastness of the nano particles and a fiber substrate is improved, and the protective layer is formed on the surface of the nano copper sulfide particles, so that the oxidation of the nano copper sulfide particles under the temperature and humidity condition is prevented, and the fiber product has a durable and stable photo-thermal sterilization effect.
(3) Good air permeability and antifouling property: the hydrophilicity of the polythiooctanoic acid molecules grafted on the surface of the fiber is lower than that of polyacrylic acid, so that the defects that the fiber grafted polyacrylic acid molecules are easy to absorb moisture and swell when being adsorbed by copper ammonia ions, and the air permeability of a fiber product is obviously reduced are avoided; moreover, the polydimethylsiloxane formed on the fiber surface and the nano particles endows the fabric with water repellency and antifouling effect.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
In examples 1-2 and comparative examples 1-10, laccase was purchased from Sigma.
Example 1
A fiber product finishing method for realizing rapid photo-thermal sterilization based on in-situ deposited nanoparticles comprises the following steps:
(1) Introducing sulfydryl on the fiber: soaking 5g of real silk fabric in cystamine aqueous solution; adding laccase to catalyze and oxidize phenolic hydroxyl on tyrosine in real silk to react with terminal amino in cystamine; enzymatic real silk fabric grafting cystamine is realized; then taking the real silk fabric out, soaking the real silk fabric in sodium bisulfite solution, and reducing cystamine grafted on the fiber to obtain a real silk fabric containing sulfydryl;
the real silk fabric grafting cystamine treatment process formula and conditions are as follows: laccase is 2U/mL, cystamine is 5g/L, the bath ratio is 1; the cystamine reduction treatment process formula and conditions are as follows: sodium bisulfite 10g/L, bath ratio 1;
(2) Lipoic acid graft polymerization: dipping the real silk fabric treated in the step (1) in a lipoic acid solution, and performing graft polymerization on the surface of the real silk fabric to form poly-lipoic acid through the reaction of sulfydryl on the fiber and a lipoic acid free radical and the mutual reaction of lipoic acid free radicals; wherein the thioctic acid solution is prepared from 20% ethanol solution, the thioctic acid concentration is 5g/L, the bath ratio is 1:10, treating for 1 hour at the temperature of 60 ℃ and under the condition of pH 8;
(3) Deposition of nano copper sulfide particles: washing the real silk fabric treated in the step (2), soaking the real silk fabric in a copper ammonia solution of copper tetraammine complex ions, treating the real silk fabric at the temperature of 30 ℃ for 15min by using a bath ratio of 1;
wherein, the copper ammonia solution is 0.1mol/L; the concentration of the quaternary ammonium salt chitosan in the solution taking the quaternary ammonium salt chitosan as a template to load thiourea is 20g/L, and the concentration of the thiourea is 40g/L;
(4) And (3) antioxidant packaging of the nano particles: and (4) taking out the real silk fabric treated in the step (3), then soaking the real silk fabric in 5g/L of polydimethylsilane ethanol solution, drying at room temperature, and baking at 100 ℃ for 10min to realize surface packaging of the nano copper sulfide particles.
Example 2
A fiber product finishing method for realizing rapid sterilization based on in-situ deposited nanoparticles comprises the following steps:
(1) Introduction of sulfydryl on the fiber: immersing 5g of wool fabric in an aqueous solution of tyramine; adding laccase to catalyze and oxidize phenolic hydroxyl of tyrosine in wool to react with terminal amino in cystamine, and realizing enzymatic wool fabric grafting of cystamine; then taking out the wool fabric, soaking the wool fabric in sodium bisulfite solution, and reducing the cystamine grafted on the fiber to obtain the wool fabric containing sulfydryl;
the wool fabric grafting cystamine treatment process formula and conditions are as follows: 5U/mL of laccase, 10g/L of cystamine and 1 bath ratio, and treating for 6 hours at 50 ℃ and pH 6; the cystamine reduction treatment process formula and conditions are as follows: sodium bisulfite of 20g/L is reduced and treated for 4 hours at 40 ℃;
(2) Lipoic acid graft polymerization: dipping the wool fabric treated in the step (1) in a thioctic acid solution, and performing graft polymerization on the surface of wool to form poly-thioctic acid through the reaction of sulfydryl on the fiber and a thioctic acid free radical and the mutual reaction of thioctic acid free radicals; wherein, the lipoic acid solution is prepared by 30 percent ethanol solution, the lipoic acid concentration is 10g/L, the bath ratio is 1;
(3) Deposition of nano copper sulfide particles: washing the wool fabric treated in the step (2), soaking the wool fabric in a copper ammonia solution of copper tetraammine complex ions, treating the wool fabric at 40 ℃ for 30min by using a bath ratio of 1; wherein the concentration of the quaternary ammonium salt chitosan in the copper ammonia solution is 0.2mol/L, and the concentration of the quaternary ammonium salt chitosan in the solution taking the quaternary ammonium salt chitosan as a template to load thiourea is 25g/L, and the concentration of the thiourea is 50g/L;
(4) And (3) antioxidant packaging of the nano particles: and (4) taking out the wool fabric treated in the step (3), then soaking the wool fabric in 10g/L ethanol solution of polydimethylsilane, drying at room temperature, and baking at 105 ℃ for 20min to realize packaging of the nano copper sulfide particles on the surface of the fiber.
Comparative example 1
The real silk fabric of example 1 was not subjected to any treatment.
Comparative example 2
The real silk fabric in the example 1 is only treated in the step (3) and is not treated in the steps (1), (2) and (4).
Comparative example 3
The real silk fabric in the example 1 is only treated in the steps (2) and (3) and is not treated in the steps (1) and (4).
Comparative example 4
The real silk fabric in example 1 was treated in steps (1), (2), and (3) without being treated in step (4).
Comparative example 5
The real silk fabric in the example 1 is treated by the steps (1), (2), (3) and (4), but the thiourea solution added in the step (3) does not contain the quaternary ammonium salt chitosan template.
Comparative example 6
The wool fabric of example 2 was not subjected to any treatment.
Comparative example 7
The wool silk fabric in the example 2 is only treated by the step (3) and is not treated by the steps (1), (2) and (4).
Comparative example 8
The wool fabric in example 2 is treated only by the steps (2) and (3) and is not treated by the steps (1) and (4).
Comparative example 9
The wool fabric in example 2 was subjected to the steps (1), (2) and (3) without being subjected to the step (4).
Comparative example 10
The wool fabric of example 2 was treated by steps (1), (2), (3) and (4) except that the thiourea solution added in step (3) did not contain the quaternary ammonium salt chitosan template.
The fabrics obtained in examples 1 to 2 and comparative examples 1 to 10 were washed with water at 60 ℃ for 45min and then dried at room temperature, and the following tests were performed, respectively: (1) Simulating sunlight by using a xenon lamp to irradiate the fiber product for 10min, and detecting the surface temperature T of the sample at the position vertical to 30cm by using an infrared temperature measuring gun 1 ℃；
(2) Inoculating escherichia coli on the surface of the sample, irradiating for 10min by simulated sunlight, washing by using a buffer solution, collecting bacterial colonies on the surface of the sample, performing bacterial colony culture by using a sample which is not irradiated by the simulated sunlight as a reference and adopting GB/T20944.3-2008, and calculating the sterilization rate (%) of the fabric after irradiation;
(3) Measuring the air permeability of the fabric according to GB/T5453-1997, and measuring the contact angle of a water drop staying on the surface of the fabric for 10 seconds;
(4) Storing the fabric sample for 6 months at room temperature, irradiating the fiber product for 10min by using simulated sunlight of a xenon lamp, and detecting the surface temperature T of the sample at the position vertical to 30cm by means of an infrared temperature measuring gun 2 Measuring the lasting stability of the photo-thermal effect of the nanoparticles in the fiber product, and evaluating the antioxidant effect of the nanoparticles; the results of the above tests are shown in Table 1.
TABLE 1
As can be seen from Table 1:
a. after the fiber products (examples 1 and 2) prepared by the method of the invention are irradiated for 10min, the surface temperature T is 1 The sterilization rate reaches 95 and 102 ℃, and the sterilization rate is more than 99 percent, which shows that the fiber product has good rapid photo-thermal sterilization effect; compared with the untreated original fiber product, the fiber product has less air permeability reduction and better air permeability; water contact angle of fibre product surface>110 degrees, the sample has certain water repellency and antifouling effect; in addition, the surface temperature T of the textile product measured again after half a year of storage 2 From an initial temperature value T 1 And the approach shows that the sample has better storage photo-thermal effect stability, and the antioxidant effect of the polydimethylsilane on the nano particles is verified.
b. After the samples without any treatment (comparative examples 1 and 6) were irradiated for 10min, the surface temperature T of the samples was measured 1 The sterilization rate is less than 70%, which shows that the fiber product has no photothermal sterilization effect; the air permeability of the fiber product is good; the surface wettability of real silk fabrics is good, and the wettability of wool fabrics is slightly poor (the contact angle is larger than that of real silk) due to the lipoid structure of the fiber scale layer; the fabric measured again after half a year of storage also had no photothermal effect.
c. Only go through step (3)) The samples (comparative examples 2 and 7) which were treated without the treatment of the steps (1), (2) and (4) were irradiated for 10min, and then the surface temperature T was measured 1 The sterilizing rate is far lower than that of the examples 1 and 2 and is lower than 80 percent, which indicates that the rapid sterilizing capability of the fiber product is not ideal; compared with the untreated fiber product, the fiber product has no obvious difference in air permeability, and the fabric surface has similar hydrophilicity; in addition, the surface temperature T of the textile product measured again after half a year of storage 2 Lower than the initial temperature T 1 The obvious reduction shows that the photo-thermal effect stability of the sample is poor, and nano copper sulfide particles are oxidized in long-term storage.
d. Samples treated only in steps (2) and (3) and not treated in steps (1) and (4) (comparative example 3 and comparative example 8) were irradiated for 10min, and then the surface temperature T was measured 1 Higher than comparative example 2 and comparative example 7, in which lipoic acid was not used, but significantly lower than examples 1 and 2, the bactericidal rate was also between the two; furthermore, the hydrophilicity of the sample is slightly reduced due to the deposition of the polythiooctanoic acid on the fibrous article; in addition, the surface temperature T of the textile product measured again after half a year of storage 2 Lower than the initial temperature T 1 The significant decrease indicates that the stability of the photo-thermal effect of the sample under the storage condition is poor.
e. The samples (comparative examples 4 and 9) treated in the steps (1), (2) and (3) and not treated in the step (4) were irradiated for 10min, and then the surface temperature T was measured 1 And the sterilization rate values are respectively close to those of the embodiment 1 and the embodiment 2, which shows that the fiber grafting sulfydryl is beneficial to graft polymerization to form more polythiooctanoic acid, so that the deposition effect of the nano copper sulfide particles on the surface of the fiber is increased and is respectively superior to that of the comparative example 3 and the comparative example 8; in addition, the hydrophilicity of the fabric is slightly reduced after more polythiooctanoic acid is deposited on the fibers; measured again after half a year of storage 2 Lower than the initial temperature T 1 The obvious reduction shows that the sample which is not subjected to the encapsulation treatment has poor stability of the photo-thermal effect in storage and is easy to generate the oxidation of nano particles.
f. After the samples (comparative example 5 and comparative example 10) treated in the steps (1), (2), (3) and (4) and containing no quaternary ammonium salt chitosan template in the thiourea solution added dropwise in the step (3) are irradiated for 10min, the fabric surface temperature T1 and the sterilization rate are respectively lower than those of the samples of the examples 1 and 2; the result shows that thiourea can not be adsorbed to the surface of the fiber along with the quaternary ammonium salt chitosan when the quaternary ammonium salt chitosan template is not used, so that the quantity of sulfur sources enriched on the surface of the fiber is reduced, and the quantity of deposited nano copper sulfide particles and the photo-thermal effect are reduced; in addition, the difference between the surface temperature T2 of the fiber product measured again after the fiber product is stored for half a year and the initial temperature T1 is not great, which indicates that the prepared fiber product has a lasting and stable photo-thermal effect.
Claims (10)
1. A fiber product finishing method for realizing photo-thermal rapid sterilization based on in-situ deposited nanoparticles is characterized by comprising the following steps:
(1) Introduction of sulfydryl on fiber
Soaking the natural fiber product in cystamine water solution; adding laccase to catalyze and oxidize phenolic hydroxyl of tyrosine in the natural fiber to react with terminal amino in cystamine, and grafting cystamine with an enzymatic fiber product; then taking out the fiber product, soaking the fiber product in sodium bisulfite solution, and reducing the cystamine grafted on the fiber to obtain a fiber product containing sulfydryl;
(2) Lipoic acid graft polymerization
Dipping the fiber product containing the sulfydryl obtained in the step (1) in a lipoic acid solution, and performing graft polymerization on the surface of the fiber to form poly lipoic acid through the reaction of the sulfydryl on the fiber and a lipoic acid free radical and the mutual reaction of lipoic acid free radicals;
(3) Deposition of nano-copper sulfide particles
Soaking the fiber product treated in the step (2) in a copper ammonia solution after washing, treating for 15-30 min at 30-40 ℃, dropwise adding a solution of quaternary ammonium salt chitosan template loaded with thiourea, continuing to react for 15-30 min after dropwise adding, and depositing in situ on the surface of the fiber to obtain nano copper sulfide particles;
(4) Nanoparticle oxidation resistant packaging
And (4) soaking the fiber product treated in the step (3) in an ethanol solution of polydimethylsilane, drying at room temperature, and baking to obtain the fiber product.
2. The method of claim 1, wherein the treatment conditions of the step (1) of grafting cystamine to the fiber product are as follows: laccase of 2-5U/mL, cystamine of 5-10 g/L, bath ratio of 1.
3. The method according to claim 1, wherein the cystamine reduction of step (1) is performed under the following conditions: sodium bisulfite 10-20 g/L, bath ratio 1.
4. The method of claim 1, wherein the lipoic acid graft polymerization of step (2) is performed under the following conditions: the thioctic acid solution is prepared by 20-30% ethanol solution, the mass concentration of the thioctic acid is 5-10 g/L, the bath ratio is 1.
5. The method according to claim 1, wherein the natural fiber product is a composite fiber, yarn or fabric comprising silk, pressed silk, wool and cashmere.
6. The method according to claim 1, wherein the copper ammonia solution in the step (3) is a copper ammonia solution of copper tetraammine complex ions, and the concentration of the copper ammonia solution is 0.1-0.2 mol/L.
7. The method according to claim 1, wherein the mass concentration of the quaternary ammonium salt chitosan in the solution of the quaternary ammonium salt chitosan template loaded with thiourea in the step (3) is 5-10 g/L, and the mass concentration of the thiourea is 3-5 g/L.
8. The method as claimed in claim 1, wherein the baking temperature in step (4) is 100-105 ℃ for 10-20 min.
9. The photothermal fast germicidal fiber product prepared by the method of any of claims 1-8.
10. Use of the photothermal rapidly sterilized fiber product of claim 9 for the preparation of functional textiles.
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| CN109487554A (en) * | 2018-11-17 | 2019-03-19 | 赵兵 | A kind of antibacterial cotton fabric based on Chitosan-Thiolated Polymers in-situ reducing nano silver |
| CN113073464A (en) * | 2021-03-29 | 2021-07-06 | 江南大学 | Processing method of cellulose fiber product with photothermal effect |
| WO2021164408A1 (en) * | 2020-02-21 | 2021-08-26 | 江南大学 | Formaldehyde-free and strength loss-free crease-resistant finishing method for cotton fabrics |
| CN114672995A (en) * | 2022-04-19 | 2022-06-28 | 江南大学 | Fiber product with continuous antibacterial and rapid sterilization functions and preparation method thereof |
| CN114941239A (en) * | 2022-06-16 | 2022-08-26 | 江苏大同宝富纺织科技有限公司 | Photo-thermal polyester fiber product finishing method based on in-situ deposition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109487554A (en) * | 2018-11-17 | 2019-03-19 | 赵兵 | A kind of antibacterial cotton fabric based on Chitosan-Thiolated Polymers in-situ reducing nano silver |
| WO2021164408A1 (en) * | 2020-02-21 | 2021-08-26 | 江南大学 | Formaldehyde-free and strength loss-free crease-resistant finishing method for cotton fabrics |
| CN113073464A (en) * | 2021-03-29 | 2021-07-06 | 江南大学 | Processing method of cellulose fiber product with photothermal effect |
| CN114672995A (en) * | 2022-04-19 | 2022-06-28 | 江南大学 | Fiber product with continuous antibacterial and rapid sterilization functions and preparation method thereof |
| CN114941239A (en) * | 2022-06-16 | 2022-08-26 | 江苏大同宝富纺织科技有限公司 | Photo-thermal polyester fiber product finishing method based on in-situ deposition |
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