CN116876215A - Hydrophilic antibacterial functional material and preparation method and application thereof - Google Patents
Hydrophilic antibacterial functional material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116876215A CN116876215A CN202310773951.1A CN202310773951A CN116876215A CN 116876215 A CN116876215 A CN 116876215A CN 202310773951 A CN202310773951 A CN 202310773951A CN 116876215 A CN116876215 A CN 116876215A
- Authority
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- China
- Prior art keywords
- antibacterial
- hydrophilic
- quaternary ammonium
- ammonium salt
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 39
- 239000010703 silicon Substances 0.000 claims abstract description 39
- -1 silicon quaternary ammonium salt Chemical class 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 241000191967 Staphylococcus aureus Species 0.000 claims abstract description 9
- 239000004753 textile Substances 0.000 claims abstract description 9
- 241000222122 Candida albicans Species 0.000 claims abstract description 8
- 229940095731 candida albicans Drugs 0.000 claims abstract description 8
- 241000588724 Escherichia coli Species 0.000 claims abstract description 7
- 239000002657 fibrous material Substances 0.000 claims abstract description 7
- 238000009736 wetting Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 26
- 229920005862 polyol Polymers 0.000 claims description 22
- 150000003077 polyols Chemical class 0.000 claims description 22
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000004743 Polypropylene Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 230000000845 anti-microbial effect Effects 0.000 claims description 16
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910002808 Si–O–Si Inorganic materials 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000004809 thin layer chromatography Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003242 anti bacterial agent Substances 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Chemical group 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 229910052740 iodine Chemical group 0.000 claims description 5
- 239000011630 iodine Chemical group 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 229920006052 Chinlon® Polymers 0.000 claims description 4
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002334 Spandex Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229920004933 Terylene® Polymers 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 229920005615 natural polymer Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000004759 spandex Substances 0.000 claims description 4
- OXKAXHPVFLEQHV-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropan-1-amine Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCN OXKAXHPVFLEQHV-UHFFFAOYSA-N 0.000 claims description 3
- UAHAMNBFDHWCPU-UHFFFAOYSA-N 3-tributoxysilylpropan-1-amine Chemical compound CCCCO[Si](CCCN)(OCCCC)OCCCC UAHAMNBFDHWCPU-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- XUZVALKTSQQLCH-UHFFFAOYSA-N 3-tripropoxysilylpropan-1-amine Chemical compound CCCO[Si](CCCN)(OCCC)OCCC XUZVALKTSQQLCH-UHFFFAOYSA-N 0.000 claims description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 3
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229940072056 alginate Drugs 0.000 claims description 3
- 229920000615 alginic acid Polymers 0.000 claims description 3
- 235000010443 alginic acid Nutrition 0.000 claims description 3
- 235000009120 camo Nutrition 0.000 claims description 3
- 235000005607 chanvre indien Nutrition 0.000 claims description 3
- 239000011487 hemp Substances 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000008204 material by function Substances 0.000 claims description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 72
- 150000001875 compounds Chemical class 0.000 description 40
- 239000004745 nonwoven fabric Substances 0.000 description 27
- 238000001228 spectrum Methods 0.000 description 24
- 238000012360 testing method Methods 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 239000000523 sample Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 7
- 230000002401 inhibitory effect Effects 0.000 description 7
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 7
- 229940126062 Compound A Drugs 0.000 description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- DZRJLJPPUJADOO-UHFFFAOYSA-N chaetomin Natural products CN1C(=O)C2(Cc3cn(C)c4ccccc34)SSC1(CO)C(=O)N2C56CC78SSC(CO)(N(C)C7=O)C(=O)N8C5Nc9ccccc69 DZRJLJPPUJADOO-UHFFFAOYSA-N 0.000 description 5
- DIUIQJFZKRAGBZ-UHFFFAOYSA-N chetoseminudin A Natural products O=C1C(SSS2)(CO)N(C)C(=O)C32CC2(N4C5=CC=CC=C5C(CC56C(N(C)C(CO)(SS5)C(=O)N6C)=O)=C4)C4=CC=CC=C4NC2N31 DIUIQJFZKRAGBZ-UHFFFAOYSA-N 0.000 description 5
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 5
- CCPHAMSKHBDMDS-UHFFFAOYSA-N Chetoseminudin B Natural products C=1NC2=CC=CC=C2C=1CC1(SC)NC(=O)C(CO)(SC)N(C)C1=O CCPHAMSKHBDMDS-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000002815 broth microdilution Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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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
- 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
-
- 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
- D06M15/53—Polyethers
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention belongs to the technical field of antibacterial modification of fiber materials, and relates to a synthetic method of hydrophilic antibacterial organic silicon quaternary ammonium salt and application of the functional material with hydrophilic antibacterial performance in the fields of medical protection articles, medical dressing, household textile, sanitary articles and the like, which are prepared from the functional material. The preparation method of the hydrophilic antibacterial organosilicon quaternary ammonium salt is simple, the antibacterial performance is good, a polymer with a three-dimensional interpenetrating network structure can be formed on the surface of a substrate through self-polymerization reaction, the polymer does not fall off freely, the substrate has super-hydrophilic and long-acting antibacterial functions, and the antibacterial rate of the substrate to escherichia coli, staphylococcus aureus and candida albicans is maintained to be more than 99% after the substrate is washed for 50 times; has excellent hydrophilicity, and the time for wetting the material by water drops is less than 0.1s. The use method is simple and is easy for industrial production. The post-treatment dosage is small, and the hydrophilic antibacterial modification of the base material can be realized when the molar concentration is 0.1-1 mmol/L, so that the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of antibacterial modification of fiber materials, and relates to a synthesis method of a hydrophilic antibacterial organic silicon quaternary ammonium salt compound and application of the compound serving as a raw material to preparation of a functional material with hydrophilic antibacterial performance in the fields of medical protection articles, medical dressings, household textiles, sanitary articles and the like.
Background
Textile products are closely related to our lives, and the common materials of the textile products such as clothes, bedclothes and the like are cellulose (cotton, hemp and the like), chemical fiber (terylene, polypropylene, chinlon, spandex, acrylon and the like) and natural silk. Over the years, the broad sense of woven products has not been as simple as traditional clothing, bedding and the like, and it has also included nonwoven products, i.e. products produced by nonwoven technology. The non-woven fabric is also called as non-woven fabric or non-woven fabric, is formed by needling or hydroentangling directional or random fibers, is a new generation environment-friendly material, and has the characteristics of moisture resistance, ventilation, flexibility, light weight, no toxicity or irritation, rich color, low price, recycling and the like, and is widely applied to our daily life. The non-woven fabric is called cloth because of the appearance and certain properties of the cloth, and the components of the non-woven fabric can be one or more of the following materials according to the application, such as polyolefin materials (polypropylene, polyethylene, polyvinyl chloride, polyesters, etc.), chemical fiber materials (terylene, spandex, chinlon, acrylon, nylon, etc.), natural polymer materials (chitosan, alginate, etc.), etc. Such as paper diapers, urine-insulating pads, diaper, sanitary napkins (sanitary products) and the like, which lack hydrophilic groups and thus cause poor hydrophilic properties of nonwoven fabrics, hydrophilic treatment of the nonwoven fabrics is required in production. Most of the hydrophilizing agents used in the current industrial production are substances of fatty alcohol polyoxyethylene ethers, and the substances are easy to fall off from non-woven fabrics by a simple dipping and drying process during use, so that the substances have certain biotoxicity and cause certain environmental pollution during preparation and use.
At present, most of the antibacterial products (such as antibacterial clothes, antibacterial bedding and the like) on the market use zinc ion antibacterial products, zinc ions are heavy metal salts, and most of the antibacterial products use a dipping and drying process, so that the zinc ion antibacterial agent is easy to dissolve out and fall off, and the antibacterial property of the antibacterial product is gradually weakened after long-term use. In addition, the non-woven fabric is firstly subjected to hydrophilic treatment during production, so that the hydrophilicity of the non-woven fabric is increased, and if the non-woven fabric is subjected to antibacterial treatment by using a dipping method, the hydrophilicity of the non-woven fabric is greatly weakened. There are also reports of hydrophilic treatment of materials using PVA crosslinked with glutaraldehyde, which makes the hydrophilic agent not easily detached, but changes some properties of the materials such as softness, comfort, etc. due to the presence of the coating, and glutaraldehyde is a toxic chemical substance, which causes environmental pollution, and glutaraldehyde remaining in the treated coating is harmful to health.
In view of the above, there is a need to develop a safe, nontoxic, low-cost, self-polymerizable treatment agent with hydrophilic and antibacterial functions suitable for medical, household, sanitary and other fields, and as a main raw material to prepare a functional material with hydrophilic and antibacterial properties for medical protection articles, medical dressings, household textiles, sanitary articles and other fields.
Disclosure of Invention
Based on the above, the invention aims to provide a hydrophilic antibacterial organic silicon quaternary ammonium salt compound and a preparation method thereof, and further provides a hydrophilic antibacterial functional material which is subjected to antibacterial treatment by utilizing the quaternary ammonium salt.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a hydrophilic antibacterial organic silicon quaternary ammonium salt, which has the following structural general formula, wherein R is 1 Is- (OCH) 2 CH 2 ) n OH、-(CH 2 CHOH) n Wherein n is a positive integer of 1 to 30 or CHOH (CH) 2 OH) 2 Any one of them; r is R 2 Saturated alkane with carbon chain of 1-16; x is fluorine, chlorine, bromine or iodine;
further, the invention provides a preparation method of hydrophilic antibacterial organic silicon quaternary ammonium salt, which mainly comprises the following steps:
step A: placing a certain amount of polyol in a reaction container, and adding a solvent to form a polyol solution; weighing a certain amount of chloride, adding the chloride into the polyol solution, heating to a certain temperature, reacting for a period of time, determining the reaction progress through thin layer chromatography, removing the solvent after the reaction is complete, and obtaining the polyol substituted by chlorine atoms through a sedimentation method; the addition ratio of the polyol, the solvent and the chloride is 1:10-15:0.9-1; the reaction temperature is set to 70-110 ℃, and the reaction time is set: 4-8 h.
The polyalcohol comprises any one of polyethylene glycol, polyvinyl alcohol and glycerol; the solvent comprises any one of tetrahydrofuran and toluene; the chloro compound comprises phosphorus oxychloride POCl 3 Phosphorus trichloride PCl 3 Any one of N-chlorosuccinimide NClS.
And (B) step (B): placing a certain amount of silane coupling agent into a reaction container, adding a solvent, alkali and a certain amount of the polyol substituted by chlorine atoms prepared in the step A, heating to a certain temperature, reacting for a period of time, determining the reaction progress through thin layer chromatography, removing the solvent after the reaction is complete, and obtaining the organosilicon compound containing the polyol through a sedimentation method; the addition ratio of the silane coupling agent, the solvent, the alkali and the polyol substituted by chlorine atoms is 1:10-15:2-6:2-4; the reaction temperature is set to 70-110 ℃ and the reaction time is set to 6-10 h.
The silane coupling agent comprises any one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl tripropoxysilane, 3-aminopropyl tributoxysilane and 3-aminopropyl triisopropoxysilane; the solvent comprises any one of tetrahydrofuran and toluene; the alkali comprises any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate.
Step C: placing a certain amount of the organic silicon compound containing the polyol prepared in the step B into a reaction container, adding a solvent, alkali and a certain amount of halogenated alkane, heating to a certain temperature, reacting for a period of time, determining the reaction progress through thin layer chromatography, removing the solvent after the reaction is complete, and obtaining the hydrophilic antibacterial organic silicon quaternary ammonium salt through a sedimentation method; the hydrophilic antibacterial organic silicon compound, the solvent, the alkali and the halogenated alkane are added in the proportion of 1:10-15:1-3:1-3; the reaction temperature is set to 70-110 ℃ and the reaction time is set to 6-10 h.
The solvent comprises any one of tetrahydrofuran, toluene and acetonitrile; the alkali comprises any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate; the halogenated alkane comprises any one of saturated halogenated hydrocarbons with the carbon number of 1-16. Wherein the polyol-containing organosilicon compound in step B has the structural formula, wherein R 1 Is- (OCH) 2 CH 2 ) n OH、-(CH 2 CHOH) n N is a positive integer of 1-30 or CHOH (CH) 2 OH) 2 Any one of them;
the invention provides a hydrophilic antibacterial functional material, which has lasting antibacterial performance, and the antibacterial rate of the material to escherichia coli, staphylococcus aureus and candida albicans after 50 times of washing is maintained to be more than 99 percent; has excellent hydrophilicity, and the time for wetting the material by water drops is less than 0.1s.
As shown in fig. 1 and 2, preparing hydrophilic antibacterial organosilicon quaternary ammonium salt with concentration of 0.1-1 mmol/L, standing for a period of time under an acidic condition, soaking a substrate into the solution, drying at 100-150 ℃ and forming a Si-O-Si three-dimensional interpenetrating network on the surface of the substrate; the acidic solution is any one of hydrochloric acid, sulfuric acid or acetic acid.
The hydrophilic antibacterial organic silicon quaternary ammonium salt is kept stand for 1-6 h under the acidic condition with the pH value of 4-6 to hydrolyze to form organic silicon quaternary ammonium salt containing silicon hydroxyl, and the organic silicon quaternary ammonium salt containing silicon hydroxyl is polymerized by heating reaction to form a Si-O-Si three-dimensional interpenetrating network on the surface of the substrate; the organosilicon quaternary ammonium salt containing silicon hydroxyl has the following structural formula, wherein R 1 Is- (OCH) 2 CH 2 ) n OH、-(CH 2 CHOH) n N is a positive integer of 1-30 or CHOH (CH) 2 OH) 2 Any one of them; r is R 2 Saturated alkane with carbon chain of 1-16; x is fluorine, chlorine, bromine or iodine;
as shown in figure 1, the process of forming the high molecular polymer of the Si-O-Si three-dimensional interpenetrating network on the surface of the substrate after the organosilicon quaternary ammonium salt compound containing the silicon hydroxyl is polymerized by heating reaction is realized in situ by one-step reaction of self-polymerization of the silicon hydroxyl, because the silicon hydroxyl has higher reactivity, condensation reaction occurs between the silicon hydroxyl under the heating condition, and OH groups and H ions in the two silicon hydroxyl can be separated in the condensation reaction process to form Si-O-Si bonds and release a water molecule. Since the hydroxyl-containing organosilicon quaternary ammonium salt contains a plurality of silicon hydroxyl groupsAnd the base, so that the silicon hydroxyl and the silicon hydroxyl are subjected to condensation reaction to finally form the Si-O-Si-containing three-dimensional interpenetrating network high polymer. The structural formula of the polymer is shown as follows, wherein R 1 Is- (OCH) 2 CH 2 ) n OH、-(CH 2 CHOH) n N is a positive integer of 1-30, CHOH (CH) 2 OH) 2 One of the following; r is R 2 Saturated alkane with carbon chain of 1-16; x is fluorine, chlorine, bromine or iodine;
further, the base material comprises any one or more of polyolefin materials, chemical fiber materials or natural high polymer materials; the polyolefin material comprises any one of polypropylene, polyethylene, polyvinyl chloride or polyester; the chemical fiber material comprises any one of terylene, spandex, chinlon, acrylon or nylon; the natural polymer material comprises any one of chitosan, cotton, hemp, alginate and the like.
The invention further provides application of the functional material serving as a raw material in the fields of medical protection articles, medical dressings, household textiles, sanitary articles and the like.
The beneficial effects of the invention are as follows:
1. the invention provides a hydrophilic antibacterial functional material, which has lasting antibacterial performance, and the antibacterial rate of the material to escherichia coli, staphylococcus aureus and candida albicans after 50 times of washing is maintained to be more than 99 percent; and has excellent hydrophilicity, water drops on the treated material, and the water drops instantly wet the material for less than 0.1s. The material has good application prospect in the fields of medical protection articles, medical dressings, household textiles, sanitary articles and the like.
2. The invention provides a hydrophilic antibacterial organic silicon quaternary ammonium salt compound for preparing a hydrophilic antibacterial functional material, which has good antibacterial performance. The Si-O-Si three-dimensional interpenetrating network polymer can be formed by self-polymerization reaction and is connected to the base material, and the generated polymer can not be released and fall off freely, so that the base material has super-hydrophilic and long-acting antibacterial functions. The use method is simple and is easy for industrial production. The post-treatment dosage is small, and the hydrophilic antibacterial modification of the base material can be realized when the molar concentration is 0.1-1 mmol/L, so that the production cost is reduced.
3. The invention provides a preparation method of a hydrophilic antibacterial organic silicon quaternary ammonium salt compound for preparing a hydrophilic antibacterial functional material, which has the advantages of abundant raw materials, simplicity and easiness in operation and batch preparation.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram showing the hydrophilic antibacterial effect of a hydrophilic antibacterial organosilicon quaternary ammonium salt polymer intermediate in a hydrophilic antibacterial functional material acting on the surface of a substrate, so that the surface of the substrate is entangled by Si-O-Si bonds.
FIG. 2 is a schematic diagram of the route from the preparation of hydrophilic antimicrobial silicone quaternary ammonium salt to the hydrolysis to intermediate.
FIG. 3 is a graph showing the hydrophilic property test of polypropylene nonwoven fabrics, wherein (a) (B) (C) (d) are water contact angles of PP, PP-A, PP-B and PP-C, respectively.
FIG. 4 is se:Sup>A graph showing the hydrophilic property test of chitosan nonwoven fabrics, wherein (se:Sup>A) (B) (C) (d) are water contact angles of CS, CS-A, CS-B and CS-C, respectively.
FIG. 5 shows the hydrogen spectrum of the compound PEG-200-Cl.
FIG. 6 is a carbon spectrum of the compound PEG-200-Cl.
FIG. 7 shows the hydrogen spectrum of the compound PEG-600-Cl.
FIG. 8 is a carbon spectrum of the compound PEG-600-Cl.
FIG. 9 shows the hydrogen spectrum of the compound PEG-1000-Cl.
FIG. 10 is a carbon spectrum of the compound PEG-1000-Cl.
FIG. 11 shows the hydrogen spectrum of the compound Si-PEG-200.
FIG. 12 is a carbon spectrum of the compound Si-PEG-200.
FIG. 13 is a hydrogen spectrum of the compound Si-PEG-600.
FIG. 14 is a carbon spectrum of the compound Si-PEG-600.
FIG. 15 is a hydrogen spectrum of the compound Si-PEG-1000.
FIG. 16 is a carbon spectrum of the compound Si-PEG-1000.
FIG. 17 is a hydrogen spectrum of a hydrophilic antimicrobial silicone quaternary ammonium salt compound A.
FIG. 18 is a carbon spectrum of a hydrophilic antimicrobial silicone quaternary ammonium salt compound A.
FIG. 19 is a hydrogen spectrum of a hydrophilic antimicrobial silicone quaternary ammonium salt compound B.
FIG. 20 is a carbon spectrum of a hydrophilic antimicrobial silicone quaternary ammonium salt compound B.
FIG. 21 is a graph of the C hydrogen spectrum of a hydrophilic antimicrobial silicone quaternary ammonium compound.
FIG. 22 is a C carbon spectrum of a hydrophilic antimicrobial silicone quaternary ammonium salt compound.
FIG. 23 is a hydrogen spectrum of a hydrophilic antimicrobial silicone quaternary ammonium compound D.
FIG. 24 is a carbon spectrum of a hydrophilic antimicrobial silicone quaternary ammonium compound D.
FIG. 25 is a hydrogen spectrum of a hydrophilic antimicrobial silicone quaternary ammonium compound E.
FIG. 26 is a carbon spectrum of a hydrophilic antimicrobial silicone quaternary ammonium compound E.
FIG. 27 is a hydrogen spectrum of a hydrophilic antimicrobial silicone quaternary ammonium salt compound F.
FIG. 28 is a carbon spectrum of a hydrophilic antimicrobial silicone quaternary ammonium salt compound F.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. The embodiments are all implemented on the premise of the technical scheme of the invention, and detailed implementation process is given, but it is to be stated that the protection scope of the invention is not limited to the following embodiments.
Examples
1. Preparing chlorine atom substituted polyethylene glycol:
taking a Smick bottle, adding 50 mL dry tetrahydrofuran, adding PEG-200 and phosphorus oxychloride, and controlling the molar ratio of polyethylene glycol to phosphorus oxychloride to be 1:0.9, heating to 80 ℃, reacting 4 and h, adding ice water to quench the reaction after the reaction is finished, generating white solid in a reaction bottle, and recrystallizing the white solid by using ethanol to obtain a final product PEG-200-Cl with the yield of 90 percent.
The PEG-600 and PEG-1000 were modified in the same manner to give PEG-600-Cl and PEG-1000-Cl, respectively. The reaction process is schematically shown below:
the structural characterization is as follows:
compound PEG-200-Cl (C) 8 H 17 ClO 4 )
1H NMR (400 MHz, DMSO) δ5.4(s, 1 H),3.8(t, 2 H), δ3.7(t, 2 H), 3.53(m, 12H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 69.6, 69.2, 61.3, 43.3
HRMS(ESI) m/z: calc for[C 8 H 18 ClO 4 ]+ :213.0984;Found:213.0988.
Compound PEG-600-Cl (C) 28 H 57 ClO 14 )
1H NMR (400 MHz, DMSO) δ5.4(s, 1 H),δ3.83(t, 2 H), δ3.7(t, 2 H), 3.53(m, 32H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 69.6, 69.2, 61.3, 43.3
HRMS(ESI) m/z: calc for[C 28 H 58 ClO 14 ]+ :653.3515;Found:653.3518.
Compound PEG-1000-Cl (C) 46 H 93 ClO 23 )
1H NMR (400 MHz, DMSO) δ5.4(s, 1 H),δ3.83(t, 2 H), δ3.7(t, 2 H), 3.53(m, 88H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 69.6, 69.2, 61.3, 43.3
HRMS(ESI) m/z: calc for[C 46 H 94 ClO 23 ]+ :1049.5874;Found:1049.5877.
When phosphorus oxychloride is replaced with PCl 3 Or NClS, the above-mentioned compounds can be prepared under the same conditions.
2. Preparing an organosilicon compound containing a polyol:
a smith flask was taken, 50 mL dry tetrahydrofuran was added, and a quantity of 3-aminopropyl triethoxysilane and PEG-200-Cl were added in a molar ratio of 1:3, adding potassium carbonate, wherein the adding amount is 4 times of that of 3-aminopropyl triethoxysilane, heating to 80 ℃, and reacting 8 h. The reaction progress was determined by thin layer chromatography, and after the completion of the reaction, the solvent was removed, and the organosilicon compound containing the polyhydric alcohol was obtained by sedimentation, which was designated as compound Si-PEG-200.
Organosilicon compounds comprising PEG-600, PEG-1000, designated as compound Si-PEG-600 and compound Si-PEG-1000, respectively, were prepared in the same manner. The structural formula is shown in the following figures:
the structural characterization is as follows:
compound Si-PEG-200 (C) 21 H 47 NO 9 Si)
1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m, 16 H), 2.48(m, 6H), 1.35(f, 2 H), 1.21(t,9 H), 0.56(t, 2 H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4 58.4, 18.4, 14.4.
HRMS(ESI) m/z: calc for[C 21 H 48 NO 9 Si]+ :486.3098;Found:486.3095.
Compound Si-PEG-600 (C) 66 H 137 NO 31 Si)
1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m,106 H), 2.48(m, 6H), 1.35(m, 2 H), 1.21(t,9 H), 0.56(t, 2 H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4 58.4, 18.4, 14.4.
HRMS(ESI) m/z: calc for[C 66 H 138 NO 31 Si]+ :1468.9022;Found:1468.9027.
Compound Si-PEG-1000 (C) 103 H 211 NO 49 Si)
1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m,180 H), 2.48(m, 6H), 1.35(m, 2 H), 1.21(t,9 H), 0.56(t, 2 H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4 58.4, 18.4, 14.4.
HRMS(ESI) m/z: calc for[C 103 H 212 NO 49 Si]+ :1468.9022;Found:1468.9027.
When 3-aminopropyl triethoxysilane is replaced with 3-aminopropyl trimethoxysilane, 3-aminopropyl tripropoxysilane, 3-aminopropyl triisopropoxysilane or 3-aminopropyl tributoxysilane, the reaction can also take place under the same conditions, to prepare the corresponding organosilicon compounds.
3. Preparation of hydrophilic antibacterial organosilicon quaternary ammonium salt compound:
the compound Si-PEG-200 (1 mmol,619 mg) was weighed into a round bottom flask and acetonitrile 30 mL was added. Chlorohexadecane (1.2 mmol) was weighed into a round bottom flask. The reaction was run by thin layer chromatography with reflux 6 h. After the reaction is finished, the solvent is removed, and a sedimentation method is used to obtain the hydrophilic organic silicon quaternary ammonium salt, and the yield is as high as 94%. Designated compound a.
In the same manner, organosilicon quaternary ammonium salts containing PEG-600 and PEG-1000 were prepared, respectively, and named Compound B and Compound C, respectively.
The structural characterization is as follows:
compound A (C) 37 H 80 ClNO 9 Si)
1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m, 16 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t, 12 H), 0.56(t, 2 H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4 58.4, 18.4, 14.4.
HRMS(ESI) m/z: calc for[C 37 H 80 ClNO 9 Si] :745.5291;Found: 745.5296.
Compound B (C) 82 H 170 ClNO 31 Si)
1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m,106 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t,12 H), 0.56(t, 2 H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4 58.4, 18.4, 14.4.
HRMS(ESI) m/z: calc for[C 82 H 170 ClNO 31 Si] :1728.1215;Found:1728.1219.
Compound C (C) 119 H 244 ClNO 49 Si)
1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m,180 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t, 12 H), 0.56(t, 2 H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4 58.4, 18.4, 14.4.
HRMS(ESI) m/z: calc for[C 119 H 244Cl NO 49 Si] :2534.6090;Found:2534.6096
When the chlorohexadecane is replaced by chlorododecane, the compounds D, E and F are respectively prepared by the same method, and the structural formula is shown in the following figure:
the structural characterization is as follows:
compound D (C) 33 H 72 ClNO 9 Si)
1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m, 8 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t, 12 H), 0.56(t, 2 H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4 58.4, 18.4, 14.4.
HRMS(ESI) m/z: calc for[C 33 H 72 ClNO 9 Si] :689.4665;Found: 745.5296.689.4668
Compound E (C) 78 H 162 ClNO 31 Si)
1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m,98 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t,12 H), 0.56(t, 2 H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4 58.4, 18.4, 14.4.
HRMS(ESI) m/z: calc for[C 78 H 162 ClNO 31 Si] :1672.0589;Found:1672.0693.
Compound F (C) 115 H 236 ClNO 49 Si)
1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m,172 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t, 12 H), 0.56(t, 2 H).
13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4 58.4, 18.4, 14.4.
HRMS(ESI) m/z: calc for[C 115 H 236 ClNO 49 Si] :2478.5464;Found:2478.5468
Hydrophilic antibacterial organic silicon quaternary ammonium salt compound performance test:
the compound A, B, C, D, E, F synthesized in the examples was tested for minimal inhibitory concentration, as follows:
the testing steps are as follows: staphylococcus aureus was tested according to the second section of the disinfection technical Specification (2002 edition of the Ministry of health) 2.1.8.4 minimum inhibitory concentration assay (nutrient broth dilution method).
The minimum inhibitory concentration of each compound is shown in table 1.
TABLE 1
Compounds of formula (I) | Minimum inhibitory concentration MIC (mg/L) of Staphylococcus aureus |
A | 45.3 |
B | 78.6 |
C | 146.8 |
D | 98.6 |
E | 128.6 |
F | 184.5 |
The minimum inhibitory concentration of the compound was tested, and found that the minimum inhibitory concentration of the compound containing hexadecane was superior to that of the compound containing dodecaalkane, so that the sample was subsequently treated with the compound A, B, C containing hexadecane as a preferred sample, and the hydrophilic and antibacterial properties of the sample were tested.
4. Preparation of hydrophilic antibacterial functional material
Bacterial and fungal test subjects included: staphylococcus aureus, escherichia coli and candida albicans, and the experiment is carried out according to the section 3 of the evaluation of the antibacterial property of textiles of GB/T20944.3-2008: the oscillation method. Wherein, E.coli 8099, staphylococcus aureus ATCC 6538 and candida albicans ATCC 10231 are purchased from American type culture Collection ATCC, the culture medium for test is purchased from Qingdao sea Bo biotechnology Co., ltd, and other reagents are all analytically pure.
Taking a compound A, preparing 0.25 mmol/L aqueous solution, adding a certain amount of hydrochloric acid, adjusting the pH of the solution to 6, and standing at room temperature for 1 h. Immersing non-woven fabric of PP material (polypropylene) into the solution, extruding redundant liquid, and drying at 120 ℃, wherein the material is named as PP-A. The compound B, C was taken and treated in the same manner to obtain samples PP-B and PP-C, respectively.
The functional chitosan materials are prepared by the same method and are named CS-A, CS-B and CS-C respectively.
Testing the performance of hydrophilic antibacterial functional materials: the samples PP-A, PP-B, PP-C, CS-A, CS-B, CS-C prepared in the examples were tested for hydrophilicity and antimicrobial properties:
first, the results of the hydrophilic performance test are shown in fig. 3 and 4:
by performing water contact angle tests on blank sample PP non-woven fabric, blank CS non-woven fabric, and PP non-woven fabric and CS non-woven fabric samples PP-A, PP-B, PP-C, CS-A, CS-B, CS-C treated by the compounds A, B and C respectively, the test shows that the water contact angles of the untreated PP non-woven fabric and CS non-woven fabric samples respectively reach 117 DEG and 106 DEG, because PP and CS are hydrophobic materials, the water contact angles are larger. When the PP non-woven fabrics and the CS non-woven fabrics are treated by using the compounds A, B and C, water contact angle tests are carried out on the PP non-woven fabrics and the CS non-woven fabrics, the water contact angles of the PP non-woven fabrics after treatment are respectively 82 degrees, 61 degrees, 32 degrees, 35 degrees, 56 degrees, 85 degrees, 72 degrees, 57 degrees, 23 degrees, 34 degrees, 49 degrees and 83 degrees. It can be found through the water contact angle experiment that the water contact angle of the treated sample gradually becomes smaller and the hydrophilicity of the sample gradually increases with the increase of the molecular weight of PEG.
Secondly, antibacterial performance test:
sample treatment: PP-A, PP-B, PP-C, CS-A, CS-B, CS-C6 samples (0.75+ -0.05 g of each sample was weighed), washed 50 times according to the test conditions of GB/T209444.3-2008, and dried at 50deg.C for use. Control samples PP, CS were prepared in the same manner.
The testing steps are as follows: after the sample is sterilized, the sample is put into an Erlenmeyer flask, PBS buffer solution is added and escherichia coli, staphylococcus aureus or candida albicans liquid is inoculated, and after the sample is subjected to shaking culture on a constant-temperature oscillator for 18 hours, 1 mL bacterial suspension is taken and subjected to gradient dilution sequentially. And (3) adding a proper gradient bacterial suspension into a culture dish, adding trypticase soy agar 15-20 and ml into the culture dish, performing inverted culture after room temperature solidification, performing culture at 37+/-1 ℃ for 24-48 hours (candida albicans 48-72 hours), recording the colony number in each plate, and calculating the bacteriostasis rate according to a formula in a standard. The bacteriostasis rate is shown in table 2.
TABLE 2
From the results of the minimum inhibitory concentration test for each compound in table 1, the results of the inhibition rate test for each sample in table 2 can be combined:
the hydrophilic organosilicon quaternary ammonium salt compound provided by the invention has excellent antibacterial performance. The PP non-woven fabric treated by the compound also has good antibacterial performance, and has good antibacterial effect after 50 times of washing. The antibacterial agent has a good antibacterial effect, and the silicon hydroxyl groups have high reactivity, and under the heating condition, condensation reaction occurs between the silicon hydroxyl groups, and in the condensation reaction, OH groups and H ions in the two silicon hydroxyl groups can be combined to be separated, so that a Si-O-Si bond is formed and a water molecule is released. The condensation reaction between the silicon hydroxyl groups is not limited to the reaction of two silicon hydroxyl groups, but can also occur among a plurality of silicon hydroxyl groups, and finally formed Si-O-Si chains can be mutually crosslinked with other Si-O-Si chains, so that a three-dimensional interpenetrating network structure of the silicon oxygen compound is formed. Therefore, the modified material provided by the invention has long-acting hydrophilic antibacterial performance.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A hydrophilic antibacterial functional material is characterized in that the material is prepared by soaking a substrate in a hydrophilic antibacterial organic silicon quaternary ammonium salt solution subjected to acid hydrolysis with a certain concentration, fully soaking the substrate, drying at a certain temperature, and forming a Si-O-Si three-dimensional interpenetrating network on the surface of the substrate; the antibacterial agent has lasting antibacterial performance, and the antibacterial rate of the antibacterial agent to escherichia coli, staphylococcus aureus and candida albicans is maintained to be more than 99% after the antibacterial agent is washed for 50 times; the material has excellent hydrophilicity, and the time for wetting the material by water drops is less than 0.1s; wherein the hydrophilic antibacterial organic silicon quaternary ammonium salt has the following structural general formula, wherein R 1 Is- (OCH) 2 CH 2 ) n OH、-(CH 2 CHOH) n N is a positive integer of 1-30 or CHOH (CH) 2 OH) 2 Any one of them; r is R 2 Saturated alkane with carbon chain of 1-16; x is fluorine, chlorine, bromine or iodine;
2. the hydrophilic antibacterial functional material according to claim 1, wherein the base material comprises any one or more of polyolefin materials, chemical fiber materials, or natural polymer materials; the polyolefin material comprises any one of polypropylene, polyethylene, polyvinyl chloride or polyester; the chemical fiber material comprises any one of terylene, spandex, chinlon, acrylon or nylon; the natural polymer material comprises any one of chitosan, cotton, hemp and alginate; the hydrophilic antibacterial organosilicon quaternary ammonium salt solution is an aqueous solution with the concentration of 0.1-1 mmol/L, the soaking time is 10s-60s, and the drying temperature is 100-150 ℃.
3. The hydrophilic antibacterial functional material according to claim 1, wherein the hydrophilic antibacterial organic materialAfter the silicon quaternary ammonium salt is hydrolyzed under an acidic condition, forming organic silicon quaternary ammonium salt containing silicon hydroxyl, and heating, reacting and polymerizing the organic silicon quaternary ammonium salt containing silicon hydroxyl to form a Si-O-Si three-dimensional interpenetrating network on the surface of the substrate; the organosilicon quaternary ammonium salt containing the silicon hydroxyl has the following structural formula, wherein R 1 Is- (OCH) 2 CH 2 ) n OH、-(CH 2 CHOH) n N is a positive integer of 1-30 or CHOH (CH) 2 OH) 2 Any one of them; r is R 2 Saturated alkane with carbon chain of 1-16; x is fluorine, chlorine, bromine or iodine;
4. a hydrophilic antimicrobial functional material according to claim 3, wherein the acidic conditions comprise an acidic solution having a pH of 4-6, and wherein the hydrophilic antimicrobial silicone quaternary ammonium salt is hydrolyzed by standing 1-6 h in the acidic solution; the acidic solution is any one of hydrochloric acid, sulfuric acid or acetic acid.
5. A method for preparing a hydrophilic antibacterial silicone quaternary ammonium salt for preparing the hydrophilic antibacterial functional material according to claims 1-4, which is characterized by comprising the following steps:
step A: placing a certain amount of polyol in a reaction container, and adding a solvent to form a polyol solution; weighing a certain amount of chloride, adding the chloride into the polyol solution, heating to a certain temperature, reacting for a period of time, determining the reaction progress through thin layer chromatography, removing the solvent after the reaction is complete, and obtaining the polyol substituted by chlorine atoms through a sedimentation method; the addition ratio of the polyol, the solvent and the chloride is 1:10-15:0.9-1; the reaction temperature is set to 70-110 ℃, and the reaction time is set: 4-8 h;
and (B) step (B): placing a certain amount of silane coupling agent into a reaction container, adding a solvent, alkali and a certain amount of the polyol substituted by chlorine atoms prepared in the step A, heating to a certain temperature, reacting for a period of time, determining the reaction progress through thin layer chromatography, removing the solvent after the reaction is complete, and obtaining the organosilicon compound containing the polyol through a sedimentation method; the addition ratio of the silane coupling agent, the solvent, the alkali and the polyol substituted by chlorine atoms is 1:10-15:2-6:2-4; the reaction temperature is set to 70-110 ℃ and the reaction time is set to 6-10 h;
step C: placing a certain amount of the organic silicon compound containing the polyol prepared in the step B into a reaction container, adding a solvent, alkali and a certain amount of halogenated alkane, heating to a certain temperature, reacting for a period of time, determining the reaction progress through thin layer chromatography, removing the solvent after the reaction is complete, and obtaining the hydrophilic antibacterial organic silicon quaternary ammonium salt through a sedimentation method; the hydrophilic antibacterial organic silicon compound, the solvent, the alkali and the halogenated alkane are added in the proportion of 1:10-15:1-3:1-3; the reaction temperature is set to 70-110 ℃ and the reaction time is set to 6-10 h.
6. The method according to claim 5, wherein the polyol in the step A comprises any one of polyethylene glycol, polyvinyl alcohol, and glycerol; the solvent comprises any one of tetrahydrofuran and toluene; the chloro compound comprises phosphorus oxychloride POCl 3 Phosphorus trichloride PCl 3 Any one of N-chlorosuccinimide NClS.
7. The method according to claim 5, wherein the silane coupling agent in the step B comprises any one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl tripropoxysilane, 3-aminopropyl tributoxysilane, and 3-aminopropyl triisopropoxysilane; the solvent comprises any one of tetrahydrofuran and toluene; the alkali comprises any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate.
8. The preparation method according to claim 5, wherein the solvent in the step C comprises any one of tetrahydrofuran, toluene and acetonitrile; the alkali comprises any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate; the halogenated alkane comprises any one of saturated halogenated hydrocarbons with the carbon number of 1-16.
9. The method according to any one of claims 6 to 8, wherein the polyol-containing organosilicon compound in step B has the structural formula wherein R 1 Is- (OCH) 2 CH 2 ) n OH、-(CH 2 CHOH) n N is a positive integer of 1-30 or CHOH (CH) 2 OH) 2 Any one of them;
10. use of any one of the functional materials according to claims 1-4 as a raw material in the fields of medical protection articles, medical dressings, household textiles, hygiene articles and the like.
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