CN117306262A - Aramid fiber with antifouling and antibacterial functions and preparation method thereof - Google Patents
Aramid fiber with antifouling and antibacterial functions and preparation method thereof Download PDFInfo
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- CN117306262A CN117306262A CN202311566538.4A CN202311566538A CN117306262A CN 117306262 A CN117306262 A CN 117306262A CN 202311566538 A CN202311566538 A CN 202311566538A CN 117306262 A CN117306262 A CN 117306262A
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- aramid fiber
- antibacterial
- layer
- antifouling
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 202
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 153
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- 239000011159 matrix material Substances 0.000 claims abstract description 92
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 54
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims abstract description 24
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 230000003115 biocidal effect Effects 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 86
- 239000008367 deionised water Substances 0.000 claims description 57
- 229910021641 deionized water Inorganic materials 0.000 claims description 57
- 229910000077 silane Inorganic materials 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 30
- 230000001105 regulatory effect Effects 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 26
- 238000002791 soaking Methods 0.000 claims description 26
- CEAZRRDELHUEMR-URQXQFDESA-N Gentamicin Chemical compound O1[C@H](C(C)NC)CC[C@@H](N)[C@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](NC)[C@@](C)(O)CO2)O)[C@H](N)C[C@@H]1N CEAZRRDELHUEMR-URQXQFDESA-N 0.000 claims description 23
- 229930182566 Gentamicin Natural products 0.000 claims description 22
- 239000003242 anti bacterial agent Substances 0.000 claims description 22
- 229960002518 gentamicin Drugs 0.000 claims description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 20
- -1 silane compound Chemical class 0.000 claims description 18
- RDEIXVOBVLKYNT-VQBXQJRRSA-N (2r,3r,4r,5r)-2-[(1s,2s,3r,4s,6r)-4,6-diamino-3-[(2r,3r,6s)-3-amino-6-(1-aminoethyl)oxan-2-yl]oxy-2-hydroxycyclohexyl]oxy-5-methyl-4-(methylamino)oxane-3,5-diol;(2r,3r,4r,5r)-2-[(1s,2s,3r,4s,6r)-4,6-diamino-3-[(2r,3r,6s)-3-amino-6-(aminomethyl)oxan-2-yl]o Chemical compound OS(O)(=O)=O.O1C[C@@](O)(C)[C@H](NC)[C@@H](O)[C@H]1O[C@@H]1[C@@H](O)[C@H](O[C@@H]2[C@@H](CC[C@@H](CN)O2)N)[C@@H](N)C[C@H]1N.O1C[C@@](O)(C)[C@H](NC)[C@@H](O)[C@H]1O[C@@H]1[C@@H](O)[C@H](O[C@@H]2[C@@H](CC[C@H](O2)C(C)N)N)[C@@H](N)C[C@H]1N.O1[C@H](C(C)NC)CC[C@@H](N)[C@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](NC)[C@@](C)(O)CO2)O)[C@H](N)C[C@@H]1N RDEIXVOBVLKYNT-VQBXQJRRSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 16
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 16
- 229920003235 aromatic polyamide Polymers 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 10
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 241000894006 Bacteria Species 0.000 abstract description 26
- 210000000170 cell membrane Anatomy 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 7
- 239000004760 aramid Substances 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 211
- 239000000203 mixture Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 241000588724 Escherichia coli Species 0.000 description 19
- 241000191967 Staphylococcus aureus Species 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000005406 washing Methods 0.000 description 12
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000001580 bacterial effect Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000008041 oiling agent Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003385 bacteriostatic effect Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 238000000707 layer-by-layer assembly Methods 0.000 description 3
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 2
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 210000002744 extracellular matrix Anatomy 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FBUZNPORDKVYFD-AATRIKPKSA-N (e)-1-bromohex-1-ene Chemical compound CCCC\C=C\Br FBUZNPORDKVYFD-AATRIKPKSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- IMAMKGXMSYGEGR-UHFFFAOYSA-N triethoxy(tridecyl)silane Chemical compound CCCCCCCCCCCCC[Si](OCC)(OCC)OCC IMAMKGXMSYGEGR-UHFFFAOYSA-N 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/01—Stain or soil resistance
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the technical field of aramid fibers, in particular to an aramid fiber with antifouling and antibacterial functions and a preparation method thereof, wherein the aramid fiber comprises an aramid fiber matrix, the surface of the aramid fiber matrix is provided with an antibacterial coating, and the outer surface of the antibacterial coating is provided with a hydrophobic coating; the antibacterial coating comprises at least one quaternized polyethylenimine layer and at least one antibiotic layer, and a polystyrene sulfonic acid layer is arranged between the quaternized polyethylenimine layer and the antibiotic layer. The aramid fiber can be used for effectively sterilizing in a reversible adhesion stage of bacteria, can be used for further sterilizing irreversible adhesion or bacteria with mature cell membranes, has self-cleaning performance, can reduce cleaning times and prolongs the service life of the fiber.
Description
Technical Field
The invention relates to an aramid fiber with antifouling and antibacterial functions and a preparation method thereof, belonging to the technical field of aramid fibers.
Background
Bacteria are widely present in various environments of the earth and pose a serious threat to human life safety. In general, bacteria can be reversibly adsorbed on the surface of a material by non-covalent interactions (van der waals forces or hydrogen bonding), and as the bacteria aggregate and begin to secrete extracellular matrix (ECM) to achieve irreversible adhesion to the surface of the material, migration and proliferation of the bacteria is achieved.
The aramid fiber is a novel high-tech synthetic fiber, has excellent performances of ultrahigh strength, high modulus, high temperature resistance, acid and alkali resistance, light weight, insulation, aging resistance, long life cycle and the like, and is widely applied to the fields of composite materials, bulletproof products, building materials, special protective clothing, electronic equipment and the like. However, the aramid fiber has a molecular structure containing amide bonds, which can absorb water molecules, especially the crystal area and the micropore structure are not easy to fall off after absorbing water, so that the moisture regain of the fiber is high, and the fiber fabric with high water content is easy to be affected by bacteria, and the appearance and the internal performance of the fabric are affected.
At present, two modes are commonly adopted to reduce the adhesion strength of bacteria on the surface of a material, one is to modify the surface of the material by a physical method, and the interface with low surface energy can effectively prevent the reversible adhesion of bacteria on the surface and enable the adhered bacteria to gradually release and fall off under the action of low shear stress so as to achieve the effect of preventing bacterial pollution; the other is to sterilize bacteria having mature cell membranes or irreversibly attached by chemical methods such as adding an antibacterial agent. The commonly used antibacterial agents are classified into metal particles or metal oxide inorganic antibacterial agents, natural organic antibacterial agents, and organic synthetic antibacterial agents. Wherein, inorganic metal antibacterial agents such as nano silver, titanium dioxide and the like have poor dispersibility and are easy to agglomerate, and toxicity da Yi is enriched in organisms, so that liver and kidney are irreversibly damaged; the natural organic antibacterial agent has poor heat resistance and is easy to decompose; organic synthetic antibacterial agents, especially organic cationic antibacterial agents, are of great interest due to their stable properties and their wide sources.
Chinese patent application CN115652460A discloses a polyacrylonitrile fiber containing a cationic guanidyl antibacterial agent and a preparation method thereof, which endows the polyacrylonitrile fiber with long-acting antibacterial performance and is better applied to medical and health products, antibacterial and mildew-proof underwear fabrics and other products. Chinese patent application CN108411626A discloses a preparation method and application of quaternary ammonium salt-N-halamine type nano antibacterial fiber, has strong antibacterial property and has wide prospect in the field of medical supplies. However, these methods involve complicated synthetic processes, and most of the methods focus on killing bacteria with mature cell membranes, and cannot take into account the degerming effect of different bacteria in the development stages, so that the development of an aramid fiber with both the functions of preventing bacterial contamination and sterilizing is a problem to be solved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the aramid fiber with the functions of both antifouling and antibacterial, which not only can effectively sterilize in the reversible adhesion stage of bacteria, but also can further sterilize bacteria which are irreversibly adhered or have mature cell membranes, and the aramid fiber has self-cleaning performance, so that the cleaning times can be reduced, and the service life of the fiber can be prolonged.
The technical scheme for solving the technical problems is as follows: the aramid fiber with the functions of antifouling and antibacterial is characterized by comprising an aramid fiber matrix, wherein the surface of the aramid fiber matrix is provided with an antibacterial coating, and the outer surface of the antibacterial coating is provided with a hydrophobic coating;
the antibacterial coating comprises at least one quaternized polyethylenimine layer and at least one antibiotic layer, and a polystyrene sulfonic acid layer is arranged between the quaternized polyethylenimine layer and the antibiotic layer.
Further, the aramid fiber matrix is meta-aramid fiber or para-aramid fiber.
Further, the quaternized polyethyleneimine layer is formed by using a quaternized polyethyleneimine-based cationic antibacterial agent as a raw material; the antibiotic layer is formed by using gentamicin or gentamicin sulfate as a raw material; the polystyrene sulfonic acid layer is formed by using polystyrene sulfonic acid or polystyrene sulfonate as a raw material.
Further, the hydrophobic coating layer is formed by using a silane compound as a raw material, the silane compound being one or a combination of two of tridecafluorooctyltriethoxysilane and trifluoropropyltrimethoxysilane.
The invention also discloses a preparation method of the aramid fiber with the functions of antifouling and antibacterial, which comprises the following steps:
s1, fiber surface treatment: modifying the surface of the aramid fiber matrix, and increasing the number of active functional groups and the surface roughness of the surface of the aramid fiber matrix to obtain the surface-modified aramid fiber matrix;
s2, preparation of an antibacterial layer:
preparation of solution A: dispersing and dissolving quaternized polyethyleneimine in deionized water, and regulating pH to be alkalescent to obtain solution A;
preparation of solution B: dispersing and dissolving polystyrene sulfonic acid or polystyrene sulfonate in deionized water, and regulating the pH to be neutral or weak acidity to obtain a solution B;
preparation of solution C: dispersing and dissolving gentamicin or gentamicin sulfate in deionized water, and regulating the pH value to be slightly alkaline to obtain a solution C;
and assembling antibacterial layers layer by layer: sequentially removing the solution A and the solution C from the surface-modified aramid fiber matrix, or sequentially removing the solution C and the solution A from the surface-modified aramid fiber matrix, wherein the solution B is required to be soaked between the solution A and the solution C which are soaked in a non-sequential manner;
The process of assembling the antibacterial layers layer by layer can be circularly carried out once or more times, and finally drying treatment is carried out;
s3, preparation of a hydrophobic layer: and (2) soaking the aramid fiber matrix subjected to the drying treatment in the step (S2) in a silane solution, and then drying to obtain the aramid fiber with the antifouling and antibacterial functions.
In step S1, the aramid fiber substrate is first cleaned to remove the surface oil and dirt, and then subjected to surface modification treatment.
Further, in step S1, the surface modification method includes: any one or more of plasma modification, high-energy ray radiation modification and inorganic etching surface modification.
Further, in the step S2, the pH of the solution A is 10-11, and the concentration of the solution A is 10-15g/L;
the pH of the solution B is 5-7, and the concentration of the solution B is 10-30g/L;
the pH of the solution C is 8-9, and the concentration of the solution C is 10-15g/L.
Preferably, in the step S2 of assembling the antibacterial layer by layer, the solution A and the solution C are sequentially soaked in the surface-modified aramid fiber matrix, and the solution B is needed to be soaked between the solution A and the solution C at intervals.
The surface-modified aramid fiber matrix is soaked in the sequence of the solution A and the solution C, so that the surface of the aramid fiber matrix is directly contacted with the quaternized polyethyleneimine, and the quaternized polyethyleneimine has more positive charges, so that the adhesive force on the aramid fiber matrix is stronger, and the construction of an antibacterial layer is facilitated.
Further, the silane solution is a solution obtained by dispersing a silane compound in an organic solvent and water;
the volume ratio of the silane compound, the organic solvent and the water is 1: (10-20): (80-100).
Further, the silane compound is one or two of tridecafluorooctyl triethoxysilane and trifluoropropyl trimethoxysilane;
the organic solvent is one or more of isopropanol, ethanol, n-hexane, propanol, xylene and ethyl acetate.
The beneficial effects of the invention are as follows:
in the aramid fiber with both antifouling and antibacterial functions, the antibacterial layer mainly comprises quaternized polyethylenimine, polystyrene sulfonic acid/polystyrene sulfonate and gentamicin or gentamicin sulfate in a layer-by-layer assembly mode. Wherein, the quaternized polyethyleneimine and gentamicin or gentamicin sulfate can interact with bacterial cell membranes so as to kill bacteria, and the polystyrene sulfonic acid/polystyrene sulfonate can be used as a bridge to connect two antibacterial agents. The quaternized polyethyleneimine in the antibacterial coating has positive charges, and is assembled with polystyrene sulfonic acid/polystyrene sulfonate with negative charges through intermolecular electrostatic attraction interaction, and the positively charged gentamicin or gentamicin sulfate is also assembled with polystyrene sulfonic acid/polystyrene sulfonate through intermolecular interaction, so that the three-component layer-by-layer assembly is realized, and the multiple antibacterial effect is realized.
The process of bacterial growth on the surface of a material comprises the following steps: the initial adhesion (reversible adhesion) of the bacteria is achieved on the surface of the material by non-covalent interactions with surface molecules, and then the reversible adhesion is converted into irreversible adhesion and the bacteria with mature cell membranes undergo diffusion migration and multiplication with progressive maturation of the bacterial biofilm. The surface energy of the hydrophobic layer on the aramid fiber is low, so that the adhesion of bacteria on the surface of the aramid fiber can be effectively reduced, and the bacteria which are reversibly adhered on the surface of the aramid fiber can be easily removed. Bacteria with irreversible adhesion and mature cell membranes can be subjected to antibacterial treatment by the double sterilization effect of quaternized polyethyleneimine cationic antibacterial agent and gentamicin antibiotic, and the cationic antibacterial agent can be adsorbed on negatively charged bacterial cell walls and spread into bacterial bodies, so that the membrane is damaged, cytoplasm leaks and the bacteria die. According to the invention, the cationic antibacterial agent and the antibiotics are assembled on the surface of the fiber together by a layer-by-layer assembly method, so that the antibacterial property of the fiber is improved, meanwhile, the generation of bacterial drug resistance is slowed down, the adhesion of bacteria on the surface of the fiber is further reduced by the hydrophobic layer on the surface, and the aramid fiber with the antifouling and antibacterial effects is prepared by utilizing the synergistic effect of a physical method and a chemical method.
The hydrophobic layer on the surface of the aramid fiber with both the antifouling and antibacterial functions can effectively prevent bacteria from attaching, can also endow the fiber with self-cleaning performance, and prolongs the service life of the fiber.
The contact angle between the aramid fiber with the antifouling and antibacterial functions and water reaches 155-160 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli can reach more than 96 percent, even more than 98 percent. In addition, the aramid fiber has antibacterial performance in a surface treatment mode of the aramid fiber, the treatment mode is simpler and more convenient, compared with the conventional method for preparing the fiber with antibacterial effect by adding the antibacterial agent into the aramid polymer, the method disclosed by the invention does not influence the strength performance of the aramid fiber, the aramid fiber with both the antifouling and antibacterial functions has good strength performance, and the whole preparation process does not cause great loss of antibacterial raw materials, so that the preparation cost is low.
Drawings
FIG. 1 is a schematic diagram of the antimicrobial assembly described in example 6.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The aramid fiber with the functions of antifouling and antibacterial comprises an aramid fiber matrix, wherein the surface of the aramid fiber matrix is provided with an antibacterial coating, and the outer surface of the antibacterial coating is provided with a hydrophobic coating;
the antibacterial coating comprises at least one quaternized polyethylenimine layer and at least one antibiotic layer, and a polystyrene sulfonic acid layer is arranged between the quaternized polyethylenimine layer and the antibiotic layer.
Specifically, the aramid fiber matrix is meta-aramid fiber or para-aramid fiber.
More specifically, the para-aramid fiber used in the embodiment of the invention is: the strength is between 19 and 23cN/dtex, the modulus is between 80 and 100GPa, and the elongation at break is between 3 and 4 percent. The meta-aramid fiber used in the embodiment of the invention is: the strength is 3-4cN/dtex, the modulus is 50-80cN/dtex, and the elongation at break is 25-30%. But are not limited to these several aramid fiber matrices.
Specifically, the quaternized polyethyleneimine layer is formed by using a quaternized polyethyleneimine-based cationic antibacterial agent as a raw material; the antibiotic layer is formed by using gentamicin or gentamicin sulfate as a raw material; the polystyrene sulfonic acid layer is formed by using polystyrene sulfonic acid or polystyrene sulfonate as a raw material.
The polystyrene sulfonate is sodium polystyrene sulfonate or ammonium polystyrene sulfonate.
In the embodiment of the invention, the structural formula of the quaternized polyethyleneimine cationic antibacterial agent is as follows:
；
the synthesis method of the quaternized polyethyleneimine cationic antibacterial agent comprises the following steps:
obtained by reacting Polyethylenimine (PEI) with halogenated hydrocarbons (bromoethane, 1-bromobutane, 1-bromohexene or 1-bromoheptane), respectively. Adding PEI and halogenated hydrocarbon into absolute ethyl alcohol, stirring and refluxing for 24 hours at 70 ℃, dialyzing the obtained mixture in ethanol for 48 hours to obtain the quaternized polyethyleneimine, wherein the molar ratio of the polyethyleneimine to the halogenated hydrocarbon is 1:10, x is 0, 1, 3 or 5 in the structural formula, and the molecular weight of the quaternized polyethyleneimine is 700-10000.
The polyethyleneimine has CAS number 9002-98-6 and can be directly purchased for use.
Polystyrene sulfonic acid: CAS number 28210-41-5, and can be directly purchased for use.
Sodium polystyrene sulfonate: the CAS number is 25704-18-1, and can be directly purchased for use.
Ammonium polystyrene sulfonate: the CAS number is 29965-34-2, and can be directly purchased for use.
Gentamicin: the CAS number is 1403-66-3, and can be directly purchased for use.
Gentamicin sulfate: CAS number 1405-41-0, which can be purchased directly.
Specifically, the hydrophobic coating is formed by using a silane compound as a raw material, which is one or a combination of two of tridecafluorooctyltriethoxysilane and trifluoropropyltrimethoxysilane.
Tridecafluorooctyltriethoxysilane: CAS number 51851-37-7, which can be directly purchased for use.
Trifluoropropyl trimethoxysilane: CAS number is 429-60-7, and can be directly purchased for use.
A preparation method of aramid fiber with antifouling and antibacterial functions comprises the following steps:
s1, fiber surface treatment: modifying the surface of the aramid fiber matrix, and increasing the number of active functional groups and the surface roughness of the surface of the aramid fiber matrix to obtain the surface-modified aramid fiber matrix;
s2, preparation of an antibacterial layer:
preparation of solution A: dispersing and dissolving quaternized polyethyleneimine in deionized water, and regulating pH to be alkalescent to obtain solution A;
Preparation of solution B: dispersing and dissolving polystyrene sulfonic acid or polystyrene sulfonate in deionized water, and regulating the pH to be neutral or weak acidity to obtain a solution B;
preparation of solution C: dispersing and dissolving gentamicin or gentamicin sulfate in deionized water, and regulating the pH value to be slightly alkaline to obtain a solution C;
and assembling antibacterial layers layer by layer: sequentially removing the solution A and the solution C from the surface-modified aramid fiber matrix, or sequentially removing the solution C and the solution A from the surface-modified aramid fiber matrix, wherein the solution B is required to be soaked between the solution A and the solution C which are soaked in a non-sequential manner;
the process of assembling the antibacterial layer by layer can be circularly carried out once or more times; the surface-modified aramid fiber matrix is circularly soaked in the sequence of A solution-B solution-C solution or in the sequence of C solution-B solution-A solution, the B solution is soaked once between each soaking cycle, the B solution is ensured to be separated between the soaking A solution and the C solution, and finally drying treatment is carried out.
S3, preparation of a hydrophobic layer: and (2) soaking the aramid fiber matrix subjected to the drying treatment in the step (S2) in a silane solution, and then drying to obtain the aramid fiber with the antifouling and antibacterial functions.
Specifically, in step S1, the aramid fiber substrate is first cleaned to remove the surface oil and dirt, and then subjected to surface modification treatment.
In this embodiment, the method for cleaning the aramid fiber substrate includes: and (3) placing the aramid fiber matrix in an acetone solvent for ultrasonic treatment for 2-5 minutes, washing with deionized water, drying, and removing oiling agent and dirt on the surface.
Specifically, in step S1, the surface modification method includes: any one or more of plasma modification, high-energy ray radiation modification and inorganic etching surface modification.
More specifically, the plasma modification process method comprises the following steps: and (3) performing plasma modification by using a DT-02 type low-temperature plasma treatment instrument through gases such as oxygen, nitrogen, argon and the like, wherein the air flow is set to be 1.5L/min, the treatment pressure is 40Pa, the treatment power is 4 kW, and the treatment time is 0-120 s.
The high-energy ray radiation modification process method comprises the following steps: the para-aramid fiber is irradiated and modified in the air by laser, gamma rays, X rays, ultraviolet radiation and the like for 1-10 seconds/meter.
The process method for modifying the inorganic etched surface comprises the following steps: the aramid fiber matrix is soaked in 10% sodium hydroxide aqueous solution for 2 hours, washed clean by deionized water, dried in an oven at 80 ℃, and ion-exchanged after being soaked in 30% hydrochloric acid solution for 10 seconds, washed clean by deionized water and dried for later use.
Or the process method for modifying the inorganic etched surface comprises the following steps: the aramid fiber matrix is soaked in 10% phosphoric acid solution, sodium hydroxide solution or calcium chloride solution for 2 hours, washed clean by deionized water and dried in an oven at 80 ℃ for standby.
Specifically, in the step S2, the pH of the solution A is 10-11, and the concentration of the solution A is 10-15g/L;
the pH of the solution B is 5-7, and the concentration of the solution B is 10-30g/L;
the pH of the solution C is 8-9, and the concentration of the solution C is 10-15g/L.
More specifically, in step S2, the soaking time of the surface-modified aramid fiber in the solution a, the solution B and the solution C is not less than 10min each time, and in the embodiment of the present invention, the soaking time is 10min. In addition, in order to avoid cross contamination among solutions, after each soaking of the aramid fiber matrix, the aramid fiber matrix is taken out, washed with deionized water, and then soaked in the next solution.
More specifically, in the embodiment of the present invention, the drying temperature in step S2 is 60 ℃.
More specifically, in step S2, the pH of the solution a, the solution B, and the solution C is adjusted using hydrochloric acid or sodium hydroxide.
Specifically, the silane solution is a solution obtained by dispersing a silane compound in an organic solvent and water;
The volume ratio of the silane compound, the organic solvent and the water is 1: (10-20): (80-100).
Specifically, the silane compound is one or two of tridecafluorooctyl triethoxysilane and trifluoropropyl trimethoxysilane;
the organic solvent is one or more of isopropanol, ethanol, n-hexane, propanol, xylene and ethyl acetate.
Example 1
An aramid fiber with antifouling and antibacterial functions is prepared by the following steps:
(1) And (3) fiber surface treatment:
taking para-aramid fiber as an aramid fiber matrix, carrying out ultrasonic treatment on the aramid fiber matrix in an acetone solvent for 2 minutes, washing with deionized water, and then drying to remove oiling agents and dirt on the surface;
modifying the surface of an aramid fiber matrix: soaking an aramid fiber matrix in 10 mass percent aqueous solution of sodium hydroxide for 2 hours, washing with deionized water, drying in an oven at 80 ℃, soaking the dried aramid fiber matrix in 30 mass percent aqueous solution of hydrochloric acid for 10 seconds for ion exchange, washing with deionized water, and drying for later use to obtain the surface modified aramid fiber matrix.
(2) Preparation of an antibacterial layer:
Preparation of solution A: dispersing and dissolving quaternized polyethyleneimine (prepared by synthesizing PEI and bromoethane) in deionized water, regulating the pH to 11, and stirring the mixture for 1 hour to obtain solution A, wherein the concentration of the solution A is 12.5g/L;
preparation of solution B: dispersing and dissolving sodium polystyrene sulfonate in deionized water, regulating the pH to 5, and stirring the mixture for 1 hour by using a magnet to obtain a solution B, wherein the concentration of the solution B is 20g/L;
preparation of solution C: dispersing and dissolving gentamicin in deionized water, regulating the pH value to 9, and stirring the mixture for 1 hour to obtain a C solution, wherein the concentration of the C solution is 12.5g/L;
and assembling antibacterial layers layer by layer: the aramid fiber matrix with the surface modified is circularly soaked according to the sequence of the solution A, the solution B and the solution C, the total circulation is 5 times, the solution B is soaked once between each soaking circulation, and the solution B is ensured to be arranged between the solution A and the solution C. Each solution was soaked for 10 minutes, and after each soak, the surface was rinsed with deionized water and dried in an oven at 60 ℃.
(3) Preparation of a hydrophobic layer:
tridecafluorooctyltriethoxysilane, methanol and water were combined at 1:20:80 volume ratio is prepared into a silane solution, the aramid fiber matrix treated in the step (2) is placed into the silane solution to be soaked for 2 hours, and is heated in a baking oven at 100 ℃ for 24 hours to be dried, so that the aramid fiber with the functions of both antifouling and antibacterial is obtained.
The contact angle between the aramid fiber with the antifouling and antibacterial functions and water is 158 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 98.7 percent according to GB/T20944.3-2008.
Example 2
An aramid fiber with antifouling and antibacterial functions is prepared by the following steps:
(1) And (3) fiber surface treatment:
taking para-aramid fiber as an aramid fiber matrix, carrying out ultrasonic treatment on the aramid fiber matrix in an acetone solvent for 2 minutes, washing with deionized water, and then drying to remove oiling agents and dirt on the surface;
modifying the surface of an aramid fiber matrix: the aramid fiber matrix is subjected to a plasma treatment to increase the surface roughness and the number of active functional groups.
(2) Preparation of an antibacterial layer:
preparation of solution A: dispersing and dissolving quaternized polyethyleneimine (prepared by synthesizing PEI and 1-bromobutane) in deionized water, regulating the pH value to 10, and stirring the mixture for 1 hour to obtain solution A, wherein the concentration of the solution A is 10g/L;
preparation of solution B: dispersing and dissolving polystyrene sulfonic acid in deionized water, regulating the pH to 5, and stirring the mixture for 1 hour by using a magnet to obtain a solution B, wherein the concentration of the solution B is 15g/L;
Preparation of solution C: dispersing and dissolving gentamicin sulfate in deionized water, regulating the pH value to 8, and stirring the mixture for 1 hour to obtain a C solution, wherein the concentration of the C solution is 12.5g/L;
and assembling antibacterial layers layer by layer: the aramid fiber matrix with the surface modified is circularly soaked according to the sequence of the solution A, the solution B and the solution C, the total circulation is 5 times, the solution B is soaked once between each soaking circulation, and the solution B is ensured to be arranged between the solution A and the solution C. Each solution was soaked for 10 minutes, and after each soak, the surface was rinsed with deionized water and dried in an oven at 60 ℃.
(3) Preparation of a hydrophobic layer:
fluoropropyl trimethoxysilane, isopropanol and water were mixed in an amount of 1:10:90 volume ratio is prepared into silane solution, the aramid fiber matrix treated in the step (2) is put into the silane solution for soaking for 2 hours, and is heated in a baking oven at 100 ℃ for 24 hours for drying treatment, so that the aramid fiber with the functions of both antifouling and antibacterial is obtained.
The contact angle between the aramid fiber with the antifouling and antibacterial functions and water is 155 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 98.2 percent according to GB/T20944.3-2008.
Example 3
An aramid fiber with antifouling and antibacterial functions is prepared by the following steps:
(1) And (3) fiber surface treatment:
taking para-aramid fiber as an aramid fiber matrix, carrying out ultrasonic treatment on the aramid fiber matrix in an acetone solvent for 2 minutes, washing with deionized water, and then drying to remove oiling agents and dirt on the surface;
modifying the surface of an aramid fiber matrix: the aramid fiber matrix is soaked in 10% phosphoric acid solution for 2 hours, washed clean by deionized water and dried in an oven at 80 ℃ for standby.
(2) Preparation of an antibacterial layer:
preparation of solution A: dispersing and dissolving quaternized polyethyleneimine (prepared by synthesizing PEI and 1-bromohexane) in deionized water, regulating the pH value to 10.5, and stirring the mixture for 1 hour to obtain solution A, wherein the concentration of the solution A is 15g/L;
preparation of solution B: dispersing and dissolving polystyrene sulfonic acid in deionized water, regulating the pH to 5, and stirring the mixture for 1 hour by using a magnet to obtain a solution B, wherein the concentration of the solution B is 17.5g/L;
preparation of solution C: dispersing and dissolving gentamicin sulfate in deionized water, regulating the pH value to 8.5, and stirring the mixture for 1 hour to obtain a solution C, wherein the concentration of the solution C is 15g/L;
and assembling antibacterial layers layer by layer: the aramid fiber matrix with the surface modified is circularly soaked according to the sequence of the solution A, the solution B and the solution C, the total circulation is 5 times, the solution B is soaked once between each soaking circulation, and the solution B is ensured to be arranged between the solution A and the solution C. Each solution was soaked for 10 minutes, and after each soak, the surface was rinsed with deionized water and dried in an oven at 60 ℃.
(3) Preparation of a hydrophobic layer:
fluoropropyl trimethoxysilane, tridecyl triethoxysilane, ethanol and water at 0.5:0.5:10:90 volume ratio is prepared into silane solution, the aramid fiber matrix treated in the step (2) is put into the silane solution for soaking for 2 hours, and is heated in a baking oven at 100 ℃ for 24 hours for drying treatment, so that the aramid fiber with the functions of both antifouling and antibacterial is obtained.
The contact angle between the aramid fiber with the antifouling and antibacterial functions and water is 157 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 98.4 percent according to GB/T20944.3-2008.
Example 4
An aramid fiber with antifouling and antibacterial functions is prepared by the following steps:
(1) And (3) fiber surface treatment:
taking para-aramid fiber as an aramid fiber matrix, carrying out ultrasonic treatment on the aramid fiber matrix in an acetone solvent for 2 minutes, washing with deionized water, and then drying to remove oiling agents and dirt on the surface;
modifying the surface of an aramid fiber matrix: the aramid fiber matrix is subjected to a plasma treatment to increase the surface roughness and the number of active functional groups.
(2) Preparation of an antibacterial layer:
preparation of solution A: dispersing and dissolving quaternized polyethyleneimine (prepared by synthesizing PEI and 1-bromoheptane) in deionized water, adjusting pH to 11, and stirring the mixture for 1 hour to obtain solution A, wherein the concentration of the solution A is 12.5g/L;
preparation of solution B: dispersing and dissolving polystyrene ammonium sulfonate in deionized water, regulating the pH to 5, and stirring the mixture for 1 hour by using a magnet to obtain a solution B, wherein the concentration of the solution B is 20g/L;
preparation of solution C: dispersing and dissolving gentamicin in deionized water, regulating the pH value to 9, and stirring the mixture for 1 hour to obtain a C solution, wherein the concentration of the C solution is 30g/L;
and assembling antibacterial layers layer by layer: and soaking the surface-modified aramid fiber matrix once according to the sequence of the solution A, the solution B and the solution C. Each solution was soaked for 10 minutes, and after each soak, the surface was rinsed with deionized water and dried in an oven at 60 ℃.
(3) Preparation of a hydrophobic layer:
tridecafluorooctyltriethoxysilane, methanol and water were combined at 1:20:80 volume ratio is prepared into a silane solution, the aramid fiber matrix treated in the step (2) is placed into the silane solution to be soaked for 2 hours, and is heated in a baking oven at 100 ℃ for 24 hours to be dried, so that the aramid fiber with the functions of both antifouling and antibacterial is obtained.
The contact angle between the aramid fiber with the antifouling and antibacterial functions and water is 155 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 98.1 percent according to GB/T20944.3-2008.
Example 5
An aramid fiber with antifouling and antibacterial functions is prepared by the following steps:
(1) And (3) fiber surface treatment:
taking meta-aramid fiber as an aramid fiber matrix, carrying out ultrasonic treatment on the aramid fiber matrix in an acetone solvent for 2 minutes, washing with deionized water, and then drying to remove oiling agents and dirt on the surface;
modifying the surface of an aramid fiber matrix: the aramid fiber matrix is modified by high-energy ray radiation to increase the surface roughness and the number of active functional groups.
(2) Preparation of an antibacterial layer:
preparation of solution A: dispersing and dissolving quaternized polyethyleneimine (prepared by synthesizing PEI and 1-bromohexane) in deionized water, regulating the pH value to 10, and stirring the mixture for 1 hour to obtain solution A, wherein the concentration of the solution A is 15g/L;
preparation of solution B: dispersing and dissolving polystyrene sulfonic acid in deionized water, regulating the pH value to 7, and stirring the mixture for 1 hour by using a magnet to obtain a solution B, wherein the concentration of the solution B is 10g/L;
Preparation of solution C: dispersing and dissolving gentamicin sulfate in deionized water, regulating the pH value to 9, and stirring the mixture for 1 hour to obtain a C solution, wherein the concentration of the C solution is 15g/L;
and assembling antibacterial layers layer by layer: the aramid fiber matrix with the surface modified is circularly soaked according to the sequence of the solution A, the solution B and the solution C, the total circulation is 5 times, the solution B is soaked once between each soaking circulation, and the solution B is ensured to be arranged between the solution A and the solution C. Each solution was soaked for 10 minutes, and after each soak, the surface was rinsed with deionized water and dried in an oven at 60 ℃.
(3) Preparation of a hydrophobic layer:
fluoropropyl trimethoxysilane, n-hexane and water were combined at 1:10:100 volume ratio is prepared into a silane solution, the aramid fiber matrix treated in the step (2) is put into the silane solution for soaking for 2 hours, and is heated in a baking oven at 100 ℃ for 24 hours for drying treatment, so that the aramid fiber with the functions of both antifouling and antibacterial is obtained.
The contact angle between the aramid fiber with the antifouling and antibacterial functions and water is 156 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 98.4 percent according to GB/T20944.3-2008.
Example 6
An aramid fiber with antifouling and antibacterial functions is prepared by the following steps:
(1) And (3) fiber surface treatment:
taking meta-aramid fiber as an aramid fiber matrix, carrying out ultrasonic treatment on the aramid fiber matrix in an acetone solvent for 2 minutes, washing with deionized water, and then drying to remove oiling agents and dirt on the surface;
modifying the surface of an aramid fiber matrix: the aramid fiber matrix is subjected to a plasma treatment to increase the surface roughness and the number of active functional groups.
(2) Preparation of an antibacterial layer:
preparation of solution A: dispersing and dissolving quaternized polyethyleneimine (prepared by synthesizing PEI and 1-bromobutane) in deionized water, regulating the pH value to 10, and stirring the mixture for 1 hour to obtain solution A, wherein the concentration of the solution A is 10g/L;
preparation of solution B: dispersing and dissolving sodium polystyrene sulfonate in deionized water, regulating the pH to 6, and stirring the mixture for 1 hour by using a magnet to obtain a solution B, wherein the concentration of the solution B is 30g/L;
preparation of solution C: dispersing and dissolving gentamicin sulfate in deionized water, regulating the pH value to 9, and stirring the mixture for 1 hour by using a magnet to obtain a solution C, wherein the concentration of the solution C is 10g/L;
and assembling antibacterial layers layer by layer: the aramid fiber matrix with the surface modified is circularly soaked according to the sequence of the solution A, the solution B and the solution C, the total circulation is 5 times, the solution B is soaked once between each soaking circulation, and the solution B is ensured to be arranged between the solution A and the solution C. Each solution was soaked for 10 minutes, and after each soak, the surface was rinsed with deionized water and dried in an oven at 60 ℃. The antibacterial layer assembly schematic diagram is shown in figure 1.
(3) Preparation of a hydrophobic layer:
fluoropropyl trimethoxysilane, ethyl acetate and water were combined at 1:20:100 volume ratio is prepared into a silane solution, the aramid fiber matrix treated in the step (2) is put into the silane solution for soaking for 2 hours, and is heated in a baking oven at 100 ℃ for 24 hours for drying treatment, so that the aramid fiber with the functions of both antifouling and antibacterial is obtained.
The contact angle between the aramid fiber with the antifouling and antibacterial functions and water is 157 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 98.2 percent according to GB/T20944.3-2008.
Example 7
An aramid fiber with antifouling and antibacterial functions is prepared by the following steps:
(1) And (3) fiber surface treatment:
taking para-aramid fiber as an aramid fiber matrix, carrying out ultrasonic treatment on the aramid fiber matrix in an acetone solvent for 2 minutes, washing with deionized water, and then drying to remove oiling agents and dirt on the surface;
modifying the surface of an aramid fiber matrix: soaking an aramid fiber matrix in 10 mass percent aqueous solution of sodium hydroxide for 2 hours, washing with deionized water, drying in an oven at 80 ℃, soaking the dried aramid fiber matrix in 30 mass percent aqueous solution of hydrochloric acid for 10 seconds for ion exchange, washing with deionized water, and drying for later use to obtain the surface modified aramid fiber matrix.
(2) Preparation of an antibacterial layer:
preparation of solution A: dispersing and dissolving quaternized polyethyleneimine (prepared by synthesizing PEI and bromoethane) in deionized water, regulating the pH to 11, and stirring the mixture for 1 hour to obtain solution A, wherein the concentration of the solution A is 12.5g/L;
preparation of solution B: dispersing and dissolving sodium polystyrene sulfonate in deionized water, regulating the pH to 5, and stirring the mixture for 1 hour by using a magnet to obtain a solution B, wherein the concentration of the solution B is 20g/L;
preparation of solution C: dispersing and dissolving gentamicin in deionized water, regulating the pH value to 9, and stirring the mixture for 1 hour to obtain a C solution, wherein the concentration of the C solution is 12.5g/L;
and assembling antibacterial layers layer by layer: the aramid fiber matrix with the surface modified is circularly soaked according to the sequence of the solution C, the solution B and the solution A, the total circulation is 5 times, the solution B is soaked once between each soaking circulation, and the solution B is ensured to be arranged between the solution A and the solution C. Each solution was soaked for 10 minutes, and after each soak, the surface was rinsed with deionized water and dried in an oven at 60 ℃.
(3) Preparation of a hydrophobic layer:
tridecafluorooctyltriethoxysilane, methanol and water were combined at 1:20:80 volume ratio is prepared into a silane solution, the aramid fiber matrix treated in the step (2) is placed into the silane solution to be soaked for 2 hours, and is heated in a baking oven at 100 ℃ for 24 hours to be dried, so that the aramid fiber with the functions of both antifouling and antibacterial is obtained.
The contact angle between the aramid fiber with the antifouling and antibacterial functions and water is 155 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 96.2 percent according to GB/T20944.3-2008.
The experimental difference between this example 7 and example 1 is that: when the antibacterial layer is assembled layer by layer, the soaking sequence of example 1 is A solution-B solution-C solution, and the soaking sequence of example 7 is C solution-B solution-A solution. Both modes of operation can give aramid fiber having both anti-fouling and antibacterial functions, but compared with the former, example 1 has better antibacterial effect, which means that the adhesion between the quaternized polyethylenimine and the aramid fiber matrix is stronger, which is more favorable for construction of the antibacterial layer.
Comparative example 1
An aramid fiber having both anti-fouling and antibacterial functions was prepared by the same method as in example 1, except that sodium polystyrene sulfonate was not used in this comparative example, i.e., the solution B was not used in the whole preparation process.
The contact angle between the aramid fiber with the antifouling and antibacterial functions prepared in the comparative example and water is 150 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 78.3 percent according to GB/T20944.3-2008.
Comparison of experimental data of this comparative example 1 with that of example 1 shows that if sodium polystyrene sulfonate is not used, the antibacterial rate of the aramid fiber is reduced. Because sodium polystyrene sulfonate can be used as a bridge to connect two antibacterial agents, namely quaternized polyethylenimine and gentamicin. If sodium polystyrene sulfonate is not used in the preparation process, the adhesiveness of the quaternized polyethyleneimine and gentamicin on the aramid fiber matrix is poor, and the antibacterial layer cannot be assembled layer by layer well, so that the antibacterial performance of the aramid fiber is finally affected.
Comparative example 2
An aramid fiber having both antifouling and antibacterial functions was prepared by the same method as in example 1 except that the quaternized polyethyleneimine was not used in this comparative example, that is, the solution a was not used in the entire preparation process, and the surface-modified aramid fiber matrix was subjected to cyclic soaking in the order of the solution B-C for a total of 5 times in the course of assembling the antibacterial layer by layer.
The contact angle between the aramid fiber with the antifouling and antibacterial functions prepared in the comparative example and water is 152 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 82.0 percent according to GB/T20944.3-2008.
Comparative example 3
An aramid fiber having both antifouling and antibacterial functions was prepared by the same method as in example 1, except that gentamicin was not used in this comparative example, that is, no solution C was used in the entire preparation process, and the surface-modified aramid fiber matrix was cyclically immersed in the order of solution a to solution B for a total of 5 times in the course of assembling the antibacterial layer by layer.
The contact angle between the aramid fiber with the antifouling and antibacterial functions prepared in the comparative example and water is 152 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 81.5 percent according to GB/T20944.3-2008.
From the comparison of experimental data of comparative examples 2-3 and example 1, it can be seen that: the lack of either of the quaternized polyethylenimine and gentamicin results in a decrease in the antibacterial properties of the aramid fibers. Example 1 by the method defined by the invention, the obtained aramid fiber has better antibacterial effect, because the quaternized polyethylenimine and gentamicin or gentamicin sulfate can interact with bacterial cell membranes, thereby killing bacteria.
Comparative example 4
An aramid fiber having both antifouling and antibacterial functions was prepared by the same method as in example 1, except that the solutions a, B, and C were prepared without pH adjustment. In the comparative example, the solution A used in the comparative example is prepared by dispersing and dissolving quaternized polyethyleneimine in deionized water; dispersing and dissolving sodium polystyrene sulfonate in deionized water to obtain a solution B used in the comparative example; dispersing and dissolving gentamicin in deionized water to obtain the C solution used in the comparative example.
The contact angle between the aramid fiber with the antifouling and antibacterial functions prepared in the comparative example and water is 150 degrees, and the antibacterial rate of the aramid fiber with the antifouling and antibacterial functions on staphylococcus aureus and escherichia coli reaches 77.4 percent according to GB/T20944.3-2008.
From comparison of experimental data of the present comparative example 4 and example 1, it can be seen that if the solutions a, B and C are not adjusted to the respective pH, the antibacterial performance of the aramid fiber is also reduced. Because the positively charged quaternized polyethylenimine is assembled with the negatively charged and negatively charged polystyrene sulfonic acid/polystyrene sulfonate by intermolecular electrostatic attraction, and the positively charged gentamicin or gentamicin sulfate is also assembled with the polystyrene sulfonic acid/polystyrene sulfonate by intermolecular interaction, the assembly of multiple antibacterial efficacy is achieved. However, the quaternized polyethyleneimine and gentamicin or gentamicin sulfate can show more positive charges under alkaline conditions, and the polystyrene sulfonic acid/polystyrene sulfonate can show more negative charges under acidic conditions, so that interaction of intermolecular electrostatic attraction is facilitated, if the pH is not regulated, the intermolecular electrostatic attraction is caused to be smaller, thus the construction of a bacteriostatic layer is affected, and finally the bacteriostatic performance of the aramid fiber is affected.
In conclusion, from the experimental data of examples 1-7, it can be seen that the aramid fiber with both the antifouling and antibacterial functions prepared by the preparation method of the invention can effectively prevent bacteria from attaching, has good self-cleaning performance, and can prolong the service life of the aramid fiber. In particular, the aramid fibers of examples 1-6 have a contact angle with water of 155-160 degrees, and the antibacterial rate against staphylococcus aureus and escherichia coli is more than 98%.
In addition, the aramid fiber with the functions of antifouling and antibacterial prepared by the invention also has good strength performance, such as:
the para-aramid fiber (aramid fiber matrix) used in example 1 had a strength of 21 cN/dtex and a bacteriostatic rate against staphylococcus aureus and escherichia coli of 67%; the aramid fiber with both antifouling and antibacterial functions finally prepared in the step (3) of example 1 has the strength of 20.8 cN/dtex and the antibacterial rate to staphylococcus aureus and escherichia coli of 98.7 percent.
The para-aramid fiber (aramid fiber matrix) used in example 2 had a strength of 23 cN/dtex and a bacteriostatic rate against staphylococcus aureus and escherichia coli of 66.7%; the aramid fiber with both antifouling and antibacterial functions finally prepared in the step (3) of example 2 has the strength of 22.9cN/dtex and the antibacterial rate to staphylococcus aureus and escherichia coli of 98.2 percent.
The meta-aramid fiber (aramid fiber matrix) used in example 5 had a strength of 4cN/dtex and a bacteriostatic rate of 68% against staphylococcus aureus and escherichia coli; the aramid fiber with both antifouling and antibacterial functions finally prepared in the step (3) of example 5 has the strength of still 4cN/dtex and the antibacterial rate to staphylococcus aureus and escherichia coli of 98.4 percent.
Therefore, the aramid fiber prepared by the method can greatly improve the antibacterial performance and hardly influence the strength performance.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (10)
1. The aramid fiber with the functions of antifouling and antibacterial is characterized by comprising an aramid fiber matrix, wherein the surface of the aramid fiber matrix is provided with an antibacterial coating, and the outer surface of the antibacterial coating is provided with a hydrophobic coating;
The antibacterial coating comprises at least one quaternized polyethylenimine layer and at least one antibiotic layer, and a polystyrene sulfonic acid layer is arranged between the quaternized polyethylenimine layer and the antibiotic layer.
2. The aramid fiber with both antifouling and antibacterial functions according to claim 1, wherein the aramid fiber matrix is meta-aramid fiber or para-aramid fiber.
3. An aramid fiber having both antifouling and antibacterial functions according to claim 1, wherein the quaternized polyethyleneimine layer is formed by using a quaternized polyethyleneimine-based cationic antibacterial agent as a raw material; the antibiotic layer is formed by using gentamicin or gentamicin sulfate as a raw material; the polystyrene sulfonic acid layer is formed by using polystyrene sulfonic acid or polystyrene sulfonate as a raw material.
4. An aramid fiber having both antifouling and antibacterial functions according to claim 1, wherein the hydrophobic coating layer is formed by using a silane compound as a raw material, the silane compound being one or a combination of two of tridecafluorooctyltriethoxysilane and trifluoropropyltrimethoxysilane.
5. A method for preparing an aramid fiber having both antifouling and antibacterial functions according to any one of claims 1 to 4, wherein the method comprises the steps of:
s1, fiber surface treatment: modifying the surface of the aramid fiber matrix, and increasing the number of active functional groups and the surface roughness of the surface of the aramid fiber matrix to obtain the surface-modified aramid fiber matrix;
s2, preparation of an antibacterial layer:
preparation of solution A: dispersing and dissolving quaternized polyethyleneimine in deionized water, and regulating pH to be alkalescent to obtain solution A;
preparation of solution B: dispersing and dissolving polystyrene sulfonic acid or polystyrene sulfonate in deionized water, and regulating the pH to be neutral or weak acidity to obtain a solution B;
preparation of solution C: dispersing and dissolving gentamicin or gentamicin sulfate in deionized water, and regulating the pH value to be slightly alkaline to obtain a solution C;
and assembling antibacterial layers layer by layer: sequentially removing the solution A and the solution C from the surface-modified aramid fiber matrix, or sequentially removing the solution C and the solution A from the surface-modified aramid fiber matrix, wherein the solution B is required to be soaked between the solution A and the solution C which are soaked in a non-sequential manner;
The process of assembling the antibacterial layers layer by layer can be circularly carried out once or more times, and finally drying treatment is carried out;
s3, preparation of a hydrophobic layer: and (2) soaking the aramid fiber matrix subjected to the drying treatment in the step (S2) in a silane solution, and then drying to obtain the aramid fiber with the antifouling and antibacterial functions.
6. The method for producing an aramid fiber having both anti-fouling and antibacterial functions according to claim 5, wherein in step S1, the aramid fiber substrate is subjected to surface modification treatment after being cleaned to remove the surface oil and the dirt.
7. The method for preparing aramid fiber having both antifouling and antibacterial functions according to claim 5, wherein in step S1, the surface modification method is as follows: any one or more of plasma modification, high-energy ray radiation modification and inorganic etching surface modification.
8. The method for producing an aramid fiber having both anti-fouling and antibacterial functions according to claim 5, wherein in step S2, the pH of the a solution is 10-11 and the concentration of the a solution is 10-15g/L;
the pH of the solution B is 5-7, and the concentration of the solution B is 10-30g/L;
the pH of the solution C is 8-9, and the concentration of the solution C is 10-15g/L.
9. The method for producing an aramid fiber having both an antifouling and an antibacterial function according to claim 5, wherein the silane solution is a solution obtained by dispersing a silane compound in an organic solvent and water;
the volume ratio of the silane compound, the organic solvent and the water is 1: (10-20): (80-100).
10. The method for preparing an aramid fiber having both antifouling and antibacterial functions according to claim 9, wherein the silane compound is one or a combination of two of tridecafluorooctyltriethoxysilane and trifluoropropyltrimethoxysilane;
the organic solvent is one or more of isopropanol, ethanol, n-hexane, propanol, xylene and ethyl acetate.
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