CN113802382A - Antibacterial agent and preparation method and application thereof - Google Patents
Antibacterial agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN113802382A CN113802382A CN202111114491.9A CN202111114491A CN113802382A CN 113802382 A CN113802382 A CN 113802382A CN 202111114491 A CN202111114491 A CN 202111114491A CN 113802382 A CN113802382 A CN 113802382A
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- CN
- China
- Prior art keywords
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- antibacterial agent
- quaternary ammonium
- ammonium salt
- chitosan quaternary
- Prior art date
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001661 Chitosan Polymers 0.000 claims abstract description 62
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 42
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 27
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 23
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 21
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 15
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000004753 textile Substances 0.000 claims abstract description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052625 palygorskite Inorganic materials 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000007900 aqueous suspension Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000004599 antimicrobial Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 44
- 230000000694 effects Effects 0.000 abstract description 16
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 206010059866 Drug resistance Diseases 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052751 metal Chemical class 0.000 description 3
- 239000002184 metal Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000222122 Candida albicans Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 240000005308 Juniperus chinensis Species 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OMRXVBREYFZQHU-UHFFFAOYSA-N 2,4-dichloro-1,3,5-triazine Chemical class ClC1=NC=NC(Cl)=N1 OMRXVBREYFZQHU-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- 244000306301 Caesalpinia sappan Species 0.000 description 1
- 235000015162 Caesalpinia sappan Nutrition 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000721662 Juniperus Species 0.000 description 1
- BWKZWWVOAKQPIO-UHFFFAOYSA-M [Cl-].C(CC)[N+](OC)(OC)OC Chemical compound [Cl-].C(CC)[N+](OC)(OC)OC BWKZWWVOAKQPIO-UHFFFAOYSA-M 0.000 description 1
- IDWOCGJHKZFFKC-UHFFFAOYSA-N [N+](=O)(O)[O-].[Cu].[Ag] Chemical compound [N+](=O)(O)[O-].[Cu].[Ag] IDWOCGJHKZFFKC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 150000004283 biguanides Chemical group 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- 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
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
- D06M11/65—Salts of oxyacids of nitrogen
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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
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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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- 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)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of antibacterial products, and relates to an antibacterial agent, a preparation method and application thereof, wherein the antibacterial agent comprises the following components in parts by mass: 30-60 parts of chitosan quaternary ammonium salt, 2.5-10 parts of polyacrylic acid, 0.5-1 part of copper sulfate/silver nitrate and 10-30 parts of nano titanium dioxide particles; the chitosan quaternary ammonium salt is grafted with carboxyl groups. The antibacterial agent disclosed by the invention has the advantages of good sterilization effect, washing resistance and the like when being applied to the field of textiles.
Description
Technical Field
The invention belongs to the technical field of antibacterial products, and relates to an antibacterial agent, and a preparation method and application thereof.
Background
Various microorganisms such as bacteria and fungi exist in the daily living environment of people, and the microorganisms can propagate on textiles in large quantity, decompose human secretion, generate substances with peculiar smell such as ammonia and the like, or generate bacterial plaque on fabrics, so that discomfort or adverse effects are generated on human bodies in the wearing or application process. The antibacterial textile has attracted extensive attention in the aspects of human health protection and medical care because of inhibiting the growth and reproduction of microorganisms such as bacteria, fungi and the like.
Patent 202011232809.9 discloses a textile antimicrobial agent and its use. Adding Chinese juniper into sodium chloride solution, distilling to obtain Chinese juniper oil, mashing and decocting dry heartwood of lignum sappan, and extracting with ethanol solution; extracting, centrifuging, and concentrating the supernatant to obtain lignum sappan extract. Finally, mixing the water-soluble chitosan into water, then adding the juniper oil and the sappan wood extract, stirring uniformly, and then adding a pH regulator; stirring evenly at room temperature to obtain the textile antibacterial agent. The antibacterial agent has broad-spectrum antibacterial effect and is not easy to generate drug resistance. However, the chitosan natural antibacterial agent has low antibacterial activity and cannot be directly dissolved in water and common organic solvents, so that the application range of the chitosan natural antibacterial agent is greatly limited.
Patent 201610843665.8 discloses chitosan quaternary ammonium salt antibacterial agent, antibacterial liquid and preparation process thereof. The chitosan quaternary ammonium salt with the substitution degree is prepared from chitosan and epoxy propyl trimethoxy ammonium chloride, and then the chitosan quaternary ammonium salt reacts with isocyanate closed by methyl ethyl ketoxime to obtain the reactive chitosan quaternary ammonium salt antibacterial agent. The antibacterial agent has improved water solubility, improved substitution degree, better antibacterial property than chitosan, and good crosslinking effect with fabric. However, the quaternary ammonium salt chitosan as an organic polymer material has insufficient self thermal property and limited antibacterial application.
Patent 202011232809.9 discloses a high-efficiency composite inorganic antibacterial agent and its preparation method. The method is characterized in that the palygorskite with a porous structure is used as a carrier, the palygorskite and graphene are subjected to microscopic nano-compounding, so that the palygorskite carrier and the graphene can keep a high dispersion state in the processing and using processes, and meanwhile, a photocatalytic material with an antibacterial effect, a metal oxide and a metal salt are added, so that the novel composite inorganic antibacterial material with the photocatalytic effect, the electron migration wall breaking function and the synergistic effect of multiple functions of metal ion antibiosis is prepared. The contact area of the antibacterial active ingredients and bacteria can be increased through the good dispersibility of the antibacterial active ingredients, and the antibacterial effect can be synergistically exerted through the antibacterial ingredients, so that the effects of killing bacteria and efficiently inhibiting the propagation of the bacteria are achieved. However, the antibacterial agent contains graphene, is high in cost, contains a large amount of metal ions, and affects human health after long-term use.
Patent 201911396305.8 discloses a method for preparing a guanidino chitosan quaternary ammonium salt antibacterial agent, which comprises the steps of reacting chitosan with epoxypropyl trimethyl ammonium chloride to prepare a chitosan quaternary ammonium salt, reacting the chitosan quaternary ammonium salt with polyalminopropyl biguanide substituted dichloro-s-triazine, and performing ultrafiltration concentration to obtain the guanidino chitosan quaternary ammonium salt antibacterial agent. The synthesized guanidine chitosan quaternary ammonium salt antibacterial agent has good water solubility and high antibacterial activity, is higher than chitosan and chitosan quaternary ammonium salt, has simple preparation method and convenient raw material source, and is easy for industrial production. However, the guanidine chitosan quaternary ammonium salt antibacterial agent has irritation to skin, low safety and poor antibacterial durability.
Patent 202010808444.3 discloses a method for preparing silver copper metal colloid active carbon antibacterial agent and its organic artificial stone. Firstly, preparing an aqueous solution containing silver nitrate and copper nitrate to prepare a silver-copper nitric acid solution, then adding activated carbon micro powder, uniformly stirring to prepare an activated carbon micro powder adsorption solution, then drying, putting the activated carbon micro powder adsorption solution into a graphite sagger, sending the graphite sagger into a reduction sintering furnace, adding hydrogen, and carrying out reduction reaction to prepare activated carbon micro powder adsorption baking powder; and finally, sieving the activated carbon micro powder adsorption roasting powder to prepare the silver-copper metal colloid activated carbon antibacterial agent. The antibacterial agent has the characteristics of good heat resistance, broad-spectrum antibacterial property, good slow release property and the like. However, the antibacterial agent uses silver, the cost of the copper antibacterial agent is high, the antibacterial effect is slow, and the risk of heavy metal pollution exists.
Antimicrobial agents are key factors in determining the performance of antimicrobial textiles. The antibacterial agents currently used in the market mainly include three major classes, organic antibacterial agents, inorganic antibacterial agents and natural antibacterial agents. The organic antibacterial agent has the advantages of low price, easy modification and wide application, but has the limitations of poor washing fastness, easy dissolution, toxicity, drug resistance and the like. The inorganic antibacterial agent mainly comprises metal ions and metal oxides, has low toxicity and is not easy to generate drug resistance. But it is not firmly combined with the fiber, so that it has poor washing fastness and may cause harm to human body after long-term application. The natural antibacterial agent has the advantages of stable chemical property, good biocompatibility, biodegradability, no toxicity and the like, but has limited antibacterial action, poorer heat resistance and low sterilization rate, and cannot be used for a long term with broad spectrum. The existing antibacterial agent research shows that the antibacterial material has defects when being used alone.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention of the antibacterial agent which can realize long-acting antibacterial effect and is excellent in washing fastness and harmless to human bodies is urgently needed. In order to solve the problems, the invention provides an antibacterial agent, a preparation method and application thereof, and the antibacterial agent has the advantages of good sterilization effect, washing resistance and the like.
The technical scheme provided by the invention is as follows:
the antibacterial agent comprises the following raw materials in parts by mass: 30-60 parts of chitosan quaternary ammonium salt, 2.5-10 parts of polyacrylic acid, 0.5-1 part of copper sulfate/silver nitrate and 10-30 parts of nano titanium dioxide particles; the chitosan quaternary ammonium salt is grafted with carboxyl groups.
Further, the mass ratio of the chitosan quaternary ammonium salt grafted with carboxyl groups to the polyacrylic acid to the copper sulfate/silver nitrate to the nano titanium dioxide particles is 45:5:0.8: 20.
The invention also provides a preparation method of the antibacterial agent, which comprises the following steps:
adding the chitosan quaternary ammonium salt grafted with carboxyl groups into deionized water, adding polyacrylic acid, performing ultrasonic treatment, then adding copper sulfate or silver nitrate, uniformly stirring, adding nano titanium dioxide particles, and stirring to finally obtain the antibacterial agent.
Further, after adding the nano titanium dioxide particles, stirring for 30-40 min at 50 ℃.
Further, the nano titanium dioxide particles are prepared from the following raw materials in parts by mass:
130-150 parts of mixed solvent, 30-50 parts of tetrabutyl titanate, 20-23 parts of water, 18-22 parts of mixed monomer, 10-12 parts of additive particles, 9-12 parts of auxiliary agent and 6-9 parts of initiator; the mixed solvent is formed by mixing absolute ethyl alcohol and oleic acid according to the volume ratio of 12: 2-4; the mixed monomer is formed by mixing methyl methacrylate and maleic anhydride according to a mass ratio of 7: 1-3; the additive particles are formed by mixing strontium sulfate and sodium carbonate according to a mass ratio of 7: 3-5; the auxiliary agent is any one of sodium bicarbonate and ammonium bicarbonate; the initiator is any one of sodium persulfate and ammonium persulfate.
Further, the nano titanium dioxide particles are prepared from the following raw materials in parts by mass:
140 parts of mixed solvent, 40 parts of tetrabutyl titanate, 22 parts of water, 20 parts of mixed monomer, 11 parts of added particles, 10 parts of auxiliary agent and 8 parts of initiator; the mixed solvent is formed by mixing absolute ethyl alcohol and oleic acid according to the volume ratio of 12: 3; the mixed monomer is formed by mixing methyl methacrylate and maleic anhydride according to the mass ratio of 7: 2; the additive particles are formed by mixing strontium sulfate and sodium carbonate according to the mass ratio of 7: 4; the auxiliary agent is any one of sodium bicarbonate and ammonium bicarbonate; the initiator is any one of sodium persulfate and ammonium persulfate.
Further, the preparation method of the nano titanium dioxide particles comprises the following steps:
putting the mixed solvent, tetrabutyl titanate and the added particles into a reaction kettle, and preheating for 30-40 min at 50-60 ℃ under the protection of nitrogen;
adding a mixed monomer and an initiator, heating to 133-140 ℃, stirring for reacting for 4-6 h, cooling to 45-48 ℃, adding an auxiliary agent, uniformly mixing, standing for 3-5 h, discharging, freeze-drying, and collecting a dried substance;
and (3) putting the freeze-dried material into a calcining furnace, calcining for 2 hours at 400-550 ℃, fully grinding, and collecting ground particles to obtain the nano titanium dioxide particles.
Further, the preheating temperature is a specific value between 50 ℃ and 60 ℃, such as 50 ℃, 55 ℃ or 60 ℃.
Furthermore, the calcination temperature is a specific value between 400 ℃ and 550 ℃, such as 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃ or 450 ℃.
Further, the preparation method of the chitosan quaternary ammonium salt grafted with carboxyl groups comprises the following steps: adding the palygorskite and chitosan quaternary ammonium salt mixed powder into deionized water to prepare aqueous suspension, then adding an initiator, stirring, dropwise adding polyacrylic acid or acrylic acid, carrying out ultrasonic treatment and adjusting the pH value, precipitating with excessive ethanol, filtering and washing the precipitate, drying, and then carrying out constant weight to obtain the chitosan quaternary ammonium salt grafted with carboxyl groups.
Further, the mass ratio of the palygorskite to the chitosan quaternary ammonium salt to the polyacrylic acid/acrylic acid is 1:1: 2.
Further, the preparation method of the aqueous suspension comprises the following steps: adding 2-8 parts of palygorskite and 2-8 parts of chitosan quaternary ammonium salt mixed powder into 100 parts of deionized water to prepare aqueous suspension.
Further, cooling and adjusting the pH value to 6-7; precipitating with excessive ethanol, filtering and washing, dissolving the precipitate with deionized water, precipitating with ethanol, filtering and washing, repeating for several times until the precipitate is dried and has constant weight, and obtaining the chitosan quaternary ammonium salt grafted with carboxyl groups.
The invention also provides application of the antibacterial agent in textile fabrics.
The existing antibacterial agent research shows that the antibacterial material has defects when being used alone. Aiming at the defects and shortcomings in the prior art, the organic/inorganic composite antibacterial agent is prepared from methyl methacrylate, maleic anhydride, sodium persulfate, oleic acid, ethanol, sodium bicarbonate, sodium carbonate, tetrabutyl titanate, chitosan quaternary ammonium salt, palygorskite, copper sulfate/silver nitrate and polyacrylic acid, has a certain synergistic effect, and has the advantages of long-acting antibacterial property and water washing resistance. The preparation method comprises the following steps:
(1) taking 140 parts of a mixed solvent (the mixed solvent is formed by mixing absolute ethyl alcohol and oleic acid according to a volume ratio of 12: 3), 40 parts of tetrabutyl titanate, 22 parts of water, 20 parts of a mixed monomer (formed by mixing methyl methacrylate and maleic anhydride according to a mass ratio of 7: 1-3), 11 parts of added particles (formed by mixing strontium sulfate and sodium carbonate according to a mass ratio of 7: 3-5), 10 parts of an auxiliary agent (any one of sodium bicarbonate and ammonium bicarbonate) and 8 parts of an initiator (any one of sodium persulfate and ammonium persulfate), firstly putting the mixed solvent and the tetrabutyl titanate into a reaction kettle, using nitrogen for protection, and preheating for 30-40 min at 50-60 ℃.
(2) After preheating is finished, adding a mixed monomer, added particles and an initiator (any one of sodium persulfate or ammonium persulfate), heating to 133-140 ℃, stirring for reaction for 4-6 h, cooling to 45-48 ℃, adding an auxiliary agent (any one of sodium bicarbonate and ammonium bicarbonate), uniformly mixing, standing for 3-5 h, discharging, freeze-drying, and collecting a dried substance.
(3) And (3) putting the freeze-dried substance into a calcining furnace, calcining for 2 hours at 400-550 ℃, crushing, fully grinding, and collecting ground particles to obtain the high-activity nano titanium dioxide particles.
(4) Grafting carboxyl group on chitosan quaternary ammonium salt: respectively adding 2-8 parts of palygorskite and 2-8 parts of chitosan quaternary ammonium salt mixed powder into 100 parts of deionized water to prepare a water suspension, stirring at 65 ℃ for 30-40 min, then adding an initiator (any one of sodium persulfate and ammonium persulfate), stirring for 10min, slowly dropwise adding 2.5-10 parts of any one of polyacrylic acid or acrylic acid, and carrying out ultrasonic treatment for 2-4 hours; after cooling, adjusting the pH value of the product to 6-7 by using a NaOH solution with the mass fraction of 10%; precipitating with excessive ethanol, filtering and washing, dissolving the precipitate with deionized water, precipitating with ethanol, filtering and washing, repeating for several times until the precipitate is dried and has constant weight, and obtaining the chitosan quaternary ammonium salt grafted with carboxyl groups.
(5) And (3) adding 30-60 parts of the chitosan quaternary ammonium salt grafted with carboxyl groups prepared in the step (4) into 100 parts of deionized water, adding 3 parts of polyacrylic acid dispersant, performing ultrasonic treatment for 30-40 min, then adding 0.5-1 part of copper sulfate or silver nitrate, uniformly stirring, finally adding 10-30 parts of high-activity nano titanium dioxide particles prepared in the step (3), stirring at 50 ℃ for 30-40 min, and finally preparing the long-acting antibacterial washable antibacterial agent.
The method comprises the steps of firstly, using mixed monomers as raw materials, carrying out polymerization under the action of an initiator to form microspheres, using tetrabutyl titanate as a base material, reacting under a certain action to form nano titanium dioxide to be deposited on the surfaces of the microspheres, then using oleic acid to wrap the nano titanium dioxide to improve the dispersibility, and then calcining to form high-activity titanium dioxide particles with porous surfaces and hollow interiors. And then, grafting polyacrylic acid or acrylic acid on the chitosan quaternary ammonium salt to ensure that the surface of the chitosan quaternary ammonium salt is rich in carboxyl groups, and uniformly stirring the chitosan quaternary ammonium salt, the high-activity titanium dioxide particles and the mixed solution of silver nitrate or copper sulfate by taking the polyacrylic acid as a dispersing agent to prepare the long-acting antibacterial washable antibacterial agent.
Advantageous effects
According to the invention, firstly, the high-activity titanium dioxide particles with porous surfaces and hollow interiors are prepared from methyl methacrylate, maleic anhydride, sodium persulfate, oleic acid, ethanol, sodium bicarbonate, sodium carbonate and nano titanium dioxide, so that the adhesion and the adsorption properties and the antibacterial performance of the antibacterial agent are improved. Then, the chitosan quaternary ammonium salt is grafted with polyacrylic acid to load copper ions, so that the antibacterial performance of the antibacterial agent is improved. The palygorskite has excellent colloid performance, adsorption performance and catalytic performance, and can greatly improve the adsorption capacity and antibacterial performance of copper sulfate. Polyacrylic acid is colloidal, has excellent adhesion performance, is rich in a large number of carboxyl groups, can improve the adhesion of titanium dioxide, and can be used as a good dispersing agent for titanium dioxide and silver nitrate or copper sulfate to improve the antibacterial performance and the water washing resistance.
The prepared antibacterial agent is added into the blended fabric according to the addition of 5-10% to prepare the textile fabric, antibacterial detection is carried out according to the antibacterial knitwear standard of FZ/T73023-2006 in textile industry, and the antibacterial rate of Escherichia coli, staphylococcus aureus and Candida albicans can reach 99% after washing for 50 times.
Detailed Description
Examples 1 to 3
The antibacterial agent comprises the following raw materials in parts by mass:
| example 1 | Example 2 | Example 3 | |
| Chitosan quaternary ammonium salt grafted with carboxyl group | 30 | 45 | 60 |
| Polyacrylic acid | 2.5 | 5 | 10 |
| Copper sulfate/silver nitrate | 0.5 | 0.8 | 1 |
| High activity nano titanium dioxide particles | 15 | 20 | 30 |
The preparation method comprises the following steps:
(1) according to the parts by weight, 140 parts of mixed solvent, 40 parts of tetrabutyl titanate, 22 parts of water, 20 parts of mixed monomer, 11 parts of added particles, 10 parts of auxiliary agent and 8 parts of initiator are taken. Firstly, putting a mixed solvent and tetrabutyl titanate into a reaction kettle, and preheating for 35min at 55 ℃ under the protection of nitrogen.
(2) After preheating is finished, adding the mixed monomer, the added particles and an initiator (any one of sodium persulfate or ammonium persulfate), heating to 133 ℃, stirring for reaction for 5 hours, cooling to 48 ℃, adding an auxiliary agent (any one of sodium bicarbonate and ammonium bicarbonate) sodium bicarbonate, uniformly mixing, standing for 4 hours, discharging, freeze-drying, and collecting a dried product.
(3) And putting the freeze-dried substance into a calcining furnace, calcining for 2 hours at 450 ℃, fully grinding, and collecting ground particles to obtain the high-activity nano titanium dioxide particles.
(4) Grafting carboxyl group on chitosan quaternary ammonium salt: respectively adding 2-8 parts of palygorskite and 2-8 parts of chitosan quaternary ammonium salt mixed powder into 100 parts of deionized water to prepare a water suspension, stirring at 65 ℃ for 30-40 min, then adding an initiator (any one of sodium persulfate and ammonium persulfate), stirring for 10min, slowly dropwise adding 2.5-10 parts of any one of polyacrylic acid or acrylic acid, and carrying out ultrasonic treatment for 2-4 hours; after cooling, adjusting the pH value of the product to 6-7 by using a NaOH solution with the mass fraction of 10%; precipitating with excessive ethanol, filtering and washing, dissolving the precipitate with deionized water, precipitating with ethanol, filtering and washing, repeating for several times until the precipitate is dried and has constant weight, and obtaining the chitosan quaternary ammonium salt grafted with carboxyl groups.
(5) And (3) adding 30-60 parts of the chitosan quaternary ammonium salt grafted with carboxyl groups prepared in the step (4) into 100 parts of deionized water, adding 2.5-10 parts of polyacrylic acid dispersant, performing ultrasonic treatment for 30-40 min, then adding 0.5-1 part of copper sulfate or silver nitrate, uniformly stirring, finally adding 10-30 parts of the high-activity nano titanium dioxide particles prepared in the step (3), and stirring at 50 ℃ for 30-40 min to finally prepare the long-acting antibacterial water-fast antibacterial agent.
Comparative example 1
This comparative example provides a method for producing an antibacterial agent, except that the step of grafting carboxyl groups to chitosan quaternary ammonium salt in step (4) was removed, and "chitosan quaternary ammonium salt grafted with carboxyl groups" added in step (5) was replaced with "chitosan quaternary ammonium salt", and the other conditions were exactly the same as in example 1.
Comparative example 2
This comparative example provides a method for producing an antibacterial agent, except that the step of grafting carboxyl groups to chitosan quaternary ammonium salt in step (4) was removed, and "chitosan quaternary ammonium salt grafted with carboxyl groups" added in step (5) was replaced with "chitosan", and the other conditions were exactly the same as in example 1.
Comparative example 3
This example provides a process for producing an antibacterial agent, which is identical to example 1 except that copper sulfate/silver sulfate is not added in step (5).
Comparative example 4
This example provides a method for producing an antibacterial agent, which is identical to example 1 except that polyacrylic acid is not used as a dispersant in step (5).
Comparative example 5
This example provides a method for producing an antibacterial agent, which is identical to example 1 except that no palygorskite is used in step (4).
Comparative example 6
This example provides a method for producing an antibacterial agent, which is identical to example 1 except that steps (1) to (3) are eliminated, and the "highly active nano titanium dioxide particles" added in step (5) are changed to commercially available ordinary 25nm "nano titanium dioxide".
Comparative example 7
This example provides a method for producing an antibacterial agent, which is identical to example 1 except that steps (1) to (3) are eliminated and nano titanium dioxide particles are not used in step (5).
The antibacterial agents in the examples and the comparative examples are added into the textile fabric according to the addition amount of 5%, and antibacterial detection is carried out according to the antibacterial knitwear standard FZ/T73023-2006, and the results are as follows:
the antibacterial agents in the examples and the comparative examples are added into the textile fabric according to the addition amount of 5%, after being washed by water for 50 times, and antibacterial detection is carried out according to the antibacterial knitwear standard FZ/T73023-2006, and the results are as follows:
according to the data, the antibacterial agent is added into the textile fabric, and the antibacterial rate of the antibacterial agent on escherichia coli, staphylococcus aureus and candida albicans can reach 99% after the textile fabric is washed for 50 times.
As can be seen from comparison of examples 1-3 and comparative examples 1-4, the antibacterial performance of the antibacterial agent is improved by grafting polyacrylic acid with copper/silver ions on the chitosan quaternary ammonium salt grafted with the carboxyl groups relative to the chitosan quaternary ammonium salt. The palygorskite has excellent colloid performance, adsorption performance and catalytic performance, and can greatly improve the adsorption capacity and antibacterial performance of copper sulfate. Polyacrylic acid is colloidal, has excellent adhesion performance, is rich in a large number of carboxyl groups, can improve the adhesion of titanium dioxide, and improves the antibacterial performance and the water washing resistance. The raw materials and the steps of the invention can ensure that the antibacterial effect of the textile product after washing can achieve the best effect. As can be seen from comparison between examples 1 to 3 and comparative examples 6 to 7, the preparation method provided by the invention can be used for obtaining the titanium dioxide particles with hollow interiors and high activity, and the adhesion and the antibacterial performance of the antibacterial agent are improved, so that the antibacterial agent provided by the invention still has good adsorption under the condition of multiple times of water washing, and a lasting antibacterial effect is obtained.
Claims (10)
1. The antibacterial agent is characterized by comprising the following raw materials in parts by mass: 30-60 parts of chitosan quaternary ammonium salt, 2.5-10 parts of polyacrylic acid, 0.5-1 part of copper sulfate/silver nitrate and 10-30 parts of nano titanium dioxide particles; the chitosan quaternary ammonium salt is grafted with carboxyl groups.
2. The method of producing an antibacterial agent according to claim 1, characterized by comprising the steps of:
adding the chitosan quaternary ammonium salt grafted with carboxyl groups into deionized water, adding a dispersant polyacrylic acid, performing ultrasonic treatment, then adding copper sulfate or silver nitrate, uniformly stirring, adding nano titanium dioxide particles, and stirring to obtain the antibacterial agent.
3. The method for preparing an antibacterial agent according to claim 2, wherein the nano titanium dioxide particles are added and stirred at 50 ℃ for 30-40 min.
4. The preparation method of the antibacterial agent according to claim 2, wherein the nano titanium dioxide particles are prepared from the following raw materials in parts by mass:
130-150 parts of mixed solvent, 30-50 parts of tetrabutyl titanate, 20-23 parts of water, 18-22 parts of mixed monomer, 10-12 parts of additive particles, 9-12 parts of auxiliary agent and 6-9 parts of initiator; the mixed solvent is formed by mixing absolute ethyl alcohol and oleic acid according to the volume ratio of 12: 2-4; the mixed monomer is formed by mixing methyl methacrylate and maleic anhydride according to a mass ratio of 7: 1-3; the additive particles are formed by mixing strontium sulfate and sodium carbonate according to a mass ratio of 7: 3-5; the auxiliary agent is any one of sodium bicarbonate and ammonium bicarbonate; the initiator is any one of sodium persulfate and ammonium persulfate.
5. The method for preparing an antibacterial agent according to claim 4, wherein the method for preparing the nano titanium dioxide particles comprises the following steps:
putting the mixed solvent and tetrabutyl titanate into a reaction kettle, and preheating for 30-40 min at 50-60 ℃ under the protection of nitrogen;
adding a mixed monomer, adding particles and an initiator, heating to 133-140 ℃, stirring for reaction for 4-6 h, cooling to 45-48 ℃, adding an auxiliary agent, uniformly mixing, standing for 3-5 h, discharging, freeze-drying, and collecting a dried substance;
and (3) putting the freeze-dried material into a calcining furnace, calcining for 2 hours at 400-550 ℃, fully grinding, and collecting ground particles to obtain the nano titanium dioxide particles.
6. The method for preparing the antibacterial agent according to claim 2, wherein the chitosan quaternary ammonium salt grafted with carboxyl groups is prepared by: adding the palygorskite and chitosan quaternary ammonium salt mixed powder into deionized water to prepare aqueous suspension, then adding an initiator, stirring, dropwise adding polyacrylic acid or acrylic acid, carrying out ultrasonic treatment and adjusting the pH value, precipitating with excessive ethanol, filtering and washing the precipitate, drying, and then carrying out constant weight to obtain the chitosan quaternary ammonium salt grafted with carboxyl groups.
7. The method for producing an antibacterial agent according to claim 6, wherein the mass ratio of palygorskite, chitosan quaternary ammonium and polyacrylic acid/acrylic acid is 1:1: 2.
8. The method for producing an antibacterial agent according to claim 6, wherein the aqueous suspension is prepared by: adding 2-8 parts of palygorskite and 2-8 parts of chitosan quaternary ammonium salt mixed powder into 100 parts of deionized water to prepare aqueous suspension.
9. The method for preparing an antibacterial agent according to claim 6, wherein after cooling and adjusting the pH to 6 to 7; precipitating with excessive ethanol, filtering and washing, dissolving the precipitate with deionized water, precipitating with ethanol, filtering and washing, repeating for several times until the precipitate is dried and has constant weight, and obtaining the chitosan quaternary ammonium salt grafted with carboxyl groups.
10. Use of the antimicrobial agent of claim 1 in textile fabrics.
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| CN117051606A (en) * | 2023-08-15 | 2023-11-14 | 波司登羽绒服装有限公司 | Antibacterial dyeing finishing liquid and preparation method and application thereof |
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