CN114032695B - Natural polysaccharide-polyphenol medical protective material and preparation method and application thereof - Google Patents
Natural polysaccharide-polyphenol medical protective material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114032695B CN114032695B CN202111214885.1A CN202111214885A CN114032695B CN 114032695 B CN114032695 B CN 114032695B CN 202111214885 A CN202111214885 A CN 202111214885A CN 114032695 B CN114032695 B CN 114032695B
- Authority
- CN
- China
- Prior art keywords
- tannic acid
- polyphenol
- modified
- medical protective
- polysiloxane
- 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.)
- Active
Links
- 230000001681 protective effect Effects 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 20
- -1 polysiloxane Polymers 0.000 claims abstract description 187
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 102
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 63
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 63
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 63
- 229920002258 tannic acid Polymers 0.000 claims abstract description 63
- 229940033123 tannic acid Drugs 0.000 claims abstract description 63
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical class OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 58
- 229920002558 Curdlan Polymers 0.000 claims abstract description 53
- 239000001879 Curdlan Substances 0.000 claims abstract description 53
- 229940078035 curdlan Drugs 0.000 claims abstract description 53
- 235000019316 curdlan Nutrition 0.000 claims abstract description 53
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 45
- 239000012065 filter cake Substances 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000011253 protective coating Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 230000000844 anti-bacterial effect Effects 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000967 suction filtration Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 14
- 230000003385 bacteriostatic effect Effects 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 238000011010 flushing procedure Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 7
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims description 7
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 5
- 208000015181 infectious disease Diseases 0.000 abstract description 4
- 210000001124 body fluid Anatomy 0.000 abstract description 3
- 239000010839 body fluid Substances 0.000 abstract description 3
- 230000002458 infectious effect Effects 0.000 abstract description 3
- 230000028327 secretion Effects 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- 239000004743 Polypropylene Substances 0.000 description 19
- 229920001155 polypropylene Polymers 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000001914 filtration Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229920002799 BoPET Polymers 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 10
- 239000004745 nonwoven fabric Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 229920006264 polyurethane film Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- KJJPESOHTCIVIS-UHFFFAOYSA-N 2-chloroacetic acid propan-2-ol Chemical compound C(C)(C)O.ClCC(=O)O KJJPESOHTCIVIS-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 244000061456 Solanum tuberosum Species 0.000 description 4
- 235000002595 Solanum tuberosum Nutrition 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000223218 Fusarium Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004750 melt-blown nonwoven Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012676 equilibrium polymerization Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000001965 potato dextrose agar Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- DCGHXSVAHIMIDJ-UHFFFAOYSA-N 3-dimethoxysilyl-N-methylpropan-1-amine Chemical compound CNCCC[SiH](OC)OC DCGHXSVAHIMIDJ-UHFFFAOYSA-N 0.000 description 1
- 241000588813 Alcaligenes faecalis Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229940005347 alcaligenes faecalis Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 244000078885 bloodborne pathogen Species 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000008263 liquid aerosol Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006225 natural substrate Substances 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000012137 tryptone Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
- D06N3/009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin by spraying components on the web
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1607—Degradability
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/18—Medical, e.g. bandage, prostheses or catheter
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a natural polysaccharide-polyphenol medical protective material, a preparation method and application thereof, wherein the natural polysaccharide-polyphenol medical protective material is obtained by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is hydrophilic modified; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the film substrate to the modified tannic acid-amino polysiloxane is 2-4: 2-9; the hydrophilically modified curdlan is carboxymethyl curdlan or quaternized curdlan; the natural polysaccharide-polyphenol medical protective material has excellent protective performance, can block and protect potentially infectious particles, body fluid, secretion and the like, and has good clinical application prospect.
Description
Technical Field
The invention relates to the technical field of medical protective materials, in particular to a natural polysaccharide-polyphenol medical protective material and a preparation method and application thereof.
Background
Medical protective articles, in particular epidemic prevention protective products such as medical protective clothing, operating gowns and the like, are used as effective barriers for people to defend against potentially infectious particulate matters, body fluids, secretions and other harmful substances, and must ensure the protection safety of medical staff under the risk of infection, and must also provide wearing comfort of the protective articles for a long time as far as possible. With the outbreak of new epidemic situation in recent two years, medical workers or workers in public areas need to wear protective clothing and wearing masks for a long time to carry out isolation protection, so that new requirements and challenges are provided for isolation materials. Medical protective articles must be converted to high-grade, reusable, highly comfortable, and easy to use applications to meet the needs of healthcare workers. In addition, on the basis of ensuring the safety and the effectiveness, the functional finishing of medical protection products is becoming urgent, such as antibacterial and bacteriostatic finishing, elastic and flexible finishing, film-covered degradation finishing, flame-retardant and antistatic finishing and the like.
The current medical protective coating material has single performance and can not simultaneously meet the requirements of the protective product on antibiosis and bacteriostasis, barrier protection, compliance, ventilation, safety and comfort. The curdlan is a sexual extracellular polysaccharide formed by beta-1, 3-glycosidic bond through fermentation of alcaligenes faecalis, and the natural biological molecule has the characteristic of solidification after heating, but the curdlan is insoluble in water due to the fact that the molecular structure is a triple helix structure and a large number of hydrogen bonds are contained in the molecule and between the molecules, so that the use of the curdlan is limited; on the other hand, tannic acid is a natural polyphenol composed of a plurality of glucocores of gallic acid dimers linked by ester bonds, the inner core benzene ring of tannic acid is hydrophobic, and the phenolic hydroxyl group is hydrophilic, and when modified alone as a coating, stability is poor due to high water solubility, so that attempts have been made to adjust the hydrophilicity and hydrophobicity of tannic acid by various derivatization reactions to meet practical demands. In conclusion, curdlan and tannic acid are theoretically possible as medical protection, but their own properties determine that curdlan and tannic acid cannot directly prepare medical protection materials.
Disclosure of Invention
The invention aims to solve the problems that the existing medical protective material has single performance and can not simultaneously meet the requirements of antibacterial, barrier protection, compliance and ventilation, safety and comfort of a protective product, and provides a natural polysaccharide-polyphenol medical protective material and a preparation method and application thereof.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
the natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is hydrophilic modified; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2-4: 2 to 9;
the hydrophilic modified curdlan is carboxymethyl curdlan or quaternized curdlan.
The invention also discloses a preparation method of the natural polysaccharide-polyphenol medical protective material, which comprises the following steps:
(1) quaternizing tannic acid to obtain quaternized tannic acid;
(2) adding the quaternized tannic acid and the amino modified polysiloxane obtained in the step (1) into organic alcohol, then adding Tris-HCl solution into the organic alcohol, stirring and reacting for 12-15 hours to obtain reaction liquid, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol in sequence, and carrying out vacuum drying on the filter cake at 50-60 ℃ to obtain the modified tannic acid-amino polysiloxane;
wherein the mass ratio of the quaternized tannic acid to the amino modified polysiloxane to the organic alcohol to the Tris-HCl solution is 1: 5-8: 7-25: 10 to 25;
The organic alcohol is methanol, ethanol or isopropanol;
(3) adding hydrophilic modified curdlan and modified tannic acid-amino polysiloxane obtained in the step (2) into first isopropanol, then adding Tris-HCl solution into the first isopropanol, stirring the mixture for 12 to 15 hours, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol, and then carrying out vacuum drying at 50 to 60 ℃ to obtain a natural polysaccharide-polyphenol medical protective material;
wherein the mass ratio of the hydrophilic modified curdlan to the modified tannic acid-aminopolysiloxane to the first isopropanol to the Tris-HCl solution is 2-4: 2 to 9: 25-35: 10-20 parts;
the hydrophilic modified curdlan is carboxymethyl curdlan or quaternized curdlan.
Preferably, the specific process of the step (1) is as follows:
dissolving tannic acid in water, adding 2, 3-epoxypropyl trimethyl ammonium chloride into the tannic acid, heating to 75-80 ℃, condensing and refluxing the reaction for 20-25 hours, cooling the reaction product to room temperature, carrying out suction filtration, washing a filter cake with water, collecting a supernatant, adding isopropanol for precipitation, centrifuging the precipitate, and carrying out vacuum drying on the precipitate to obtain quaternized tannic acid; wherein the mass ratio of tannic acid to 2, 3-epoxypropyl trimethyl ammonium chloride is 1:0.2 to 5.
Preferably, the specific process of the step (1) is as follows:
A. Adding 1, 6-dibromohexane and N, N-dimethyl N-octylamine into a reaction kettle, reacting for 15-20 hours at 20-30 ℃, adding isopropanol for precipitation, washing a filter cake with isopropanol, and vacuum drying to obtain micromolecular quaternary ammonium salt; dissolving small molecular quaternary ammonium salt and bromodecane in N, N-dimethylamide to obtain a mixed solution for later use;
wherein the mass ratio of the 1, 6-dibromohexane to the N, N-dimethyl N-octylamine is 5-8: 1, a step of;
the mass ratio of the small molecular quaternary ammonium salt to the bromodecane is 10:5 to 10;
B. dissolving and dispersing tannic acid and potassium carbonate in N, N-dimethylamide, slowly adding the mixed solution obtained in the step A under stirring, controlling the temperature of a reaction system to be not higher than 80 ℃ when the mixed solution is added, adding the mixed solution, performing condensation reflux reaction for 24-28 hours, cooling to room temperature, performing suction filtration, washing a filter cake with water, collecting a supernatant, adding isopropyl ether for precipitation, centrifuging the precipitate, and performing vacuum drying on the precipitate to obtain quaternized tannic acid;
the mass ratio of the small molecular quaternary ammonium salt, the tannic acid and the potassium carbonate in the mixed solution is 10: 5-8: 0.2 to 5.
The amino modified polysiloxane is side chain aminopropyl polysiloxane, double-end aminopropyl polysiloxane or side chain N- (2-aminoethyl) -3-aminopropyl polysiloxane.
Preferably, the amino-modified polysiloxane is represented by formula I, formula II or formula III:
n=100 to 650 and m=100 to 800 in the formula I, the formula II or the formula III.
The invention also comprises application of the natural polysaccharide-polyphenol medical protective material in preparation of an antibacterial and bacteriostatic spray or a medical protective coating.
Preferably, the antibacterial and bacteriostatic spray or medical protective coating comprises the following components in parts by weight: 8-12 parts of natural polysaccharide-polyphenol medical protective material and 25-30 parts of deionized water;
the natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is hydrophilically modified curdlan; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2-4: 2 to 9.
Preferably, the antibacterial and bacteriostatic spray or the medical protective coating further comprises a plasticizer, wherein the weight of the plasticizer is 0.05-3% of that of the natural polysaccharide-polyphenol medical protective material;
the plasticizer is one or two of glycerol, stearate or sorbitol.
Compared with the prior art, the invention has the following advantages:
the natural polysaccharide-polyphenol medical protective material has antibacterial compliance and film-forming flame retardant performance, and is suitable for spraying film-forming, adsorbing and loading on the surfaces of various woven fabrics, non-woven fabrics and composite materials thereof to form a flame-retardant compliant and antibacterial film-forming medical protective product. The natural polysaccharide-polyphenol medical protective material is particularly suitable for improving the clinical application performance of disposable or repeatedly-used medical protective clothing, operating gown and mask products, can prevent and protect potentially infectious particles, body fluid, secretion and the like, has good clinical application prospect, adopts natural polysaccharide/polyphenol, has high biocompatibility, can be naturally degraded after disposable or decontaminated treatment, is easy to produce and operate in an environment-friendly way, and has good economic and social benefits.
The natural polysaccharide-polyphenol medical protective material is ingenious in design, and firstly, tannic acid polyphenol is subjected to quaternization derivative modification to prepare the stability and antibacterial property of the tannic acid polyphenol after water dissolution; secondly, the tannic acid derivative is coordinated with amino modified polysiloxane to form a derivative complex, the derivative complex is endowed with the soft and water-resistant performance of the organosilicon polymer, finally, the derivative complex and the hydrophilically modified curdlan are subjected to interweaved hydrogen bond assembly, and a thermally irreversible medical protective coating can be formed through post-treatment, so that the tannic acid derivative has good flame retardance and biocompatibility, can resist high-temperature washing and disinfection or sterilization, and can be prepared to be naturally degraded according to requirements. The functionalized natural substrate coating has universality, can be sprayed to form a film and adsorbed on the surfaces of various woven fabrics (such as cotton fibers and polyester fibers (PET)), non-woven fabrics (such as polypropylene (PP) spun-bonded non-woven fabrics, polypropylene (PP) melt-blown non-woven fabrics and spun-bonded-spun-bonded non-woven fabrics (SMS)), film materials (such as polyethylene films (PE), polyurethane films (PU), polytetrafluoroethylene films (PTFE), thermoplastic polyurethane films (TPU) and polyvinyl alcohol films (PVA)) and composite materials thereof (such as PE/PP, PET/PTFE/PET, PET/PU/PET, PET/TPU/PET, PVA/PP) and sponge products, has wide field of coatable fabrics and high applicability, and can obviously improve the antibacterial property, flame retardance, flexibility and film-covering degradability of the fabrics.
Detailed Description
The invention aims to provide a natural polysaccharide-polyphenol medical protective material and a preparation method and application thereof, and the natural polysaccharide-polyphenol medical protective material is realized by the following technical scheme:
the natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is hydrophilically modified curdlan; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2-4: 2 to 9; the hydrophilic modified curdlan is carboxymethyl curdlan or quaternized curdlan.
The invention also discloses a preparation method of the natural polysaccharide-polyphenol medical protective material, which comprises the following steps:
(1) quaternizing tannic acid to obtain quaternized tannic acid;
(2) adding the quaternized tannic acid and the amino modified polysiloxane obtained in the step (1) into organic alcohol, then adding Tris-HCl solution into the organic alcohol, stirring and reacting for 12-15 hours to obtain reaction liquid, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol in sequence, and carrying out vacuum drying on the filter cake at 50-60 ℃ to obtain the modified tannic acid-amino polysiloxane;
Wherein the mass ratio of the quaternized tannic acid to the amino modified polysiloxane to the organic alcohol to the Tris-HCl solution is 1: 5-8: 7-25: 10 to 25;
the organic alcohol is methanol, ethanol or isopropanol;
(3) adding hydrophilic modified curdlan and modified tannic acid-amino polysiloxane obtained in the step (2) into first isopropanol, then adding Tris-HCl solution into the first isopropanol, stirring the mixture for 12 to 15 hours, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol, and then carrying out vacuum drying at 50 to 60 ℃ to obtain a natural polysaccharide-polyphenol medical protective material;
wherein the mass ratio of the hydrophilic modified curdlan to the modified tannic acid-aminopolysiloxane to the first isopropanol to the Tris-HCl solution is 2-4: 2 to 9: 25-35: 10-20 parts;
the hydrophilic modified curdlan is carboxymethyl curdlan or quaternized curdlan.
Preferably, in the step (1), the tannic acid is quaternized, and the specific process for obtaining the quaternized tannic acid is as follows:
dissolving tannic acid in water, adding 2, 3-epoxypropyl trimethyl ammonium chloride into the tannic acid, heating to 75-80 ℃, condensing and refluxing the reaction for 20-25 hours, cooling the reaction product to room temperature, carrying out suction filtration, washing a filter cake with water, collecting a supernatant, adding isopropanol for precipitation, centrifuging the precipitate, and carrying out vacuum drying on the precipitate to obtain quaternized tannic acid; wherein the mass ratio of tannic acid, water and 2, 3-epoxypropyl trimethyl ammonium chloride is 1:1 to 1.2:0.2 to 5.
In another preferred class, the step (1) of quaternizing tannic acid comprises the following steps:
A. adding 1, 6-dibromohexane and N, N-dimethyl N-octylamine into a reaction kettle, reacting for 15-20 hours at 20-30 ℃, adding isopropanol for precipitation, washing a filter cake with isopropanol, and vacuum drying to obtain a small molecular quaternary ammonium salt of the formula IV;
the reaction equation is:
then, dissolving the small molecular quaternary ammonium salt and bromodecane in N, N-dimethylamide to obtain a mixed solution for later use;
wherein the mass ratio of the 1, 6-dibromohexane to the N, N-dimethyl N-octylamine is 5-8: 1, a step of;
the mass ratio of the small molecular quaternary ammonium salt and the bromodecane in the formula IV is 10:5 to 10;
B. dissolving and dispersing tannic acid and potassium carbonate in N, N-dimethylamide, slowly adding the mixed solution obtained in the step A under stirring, controlling the temperature of a reaction system to be not higher than 80 ℃ when the mixed solution is added, adding the mixed solution, performing condensation reflux reaction for 24-28 hours, cooling to room temperature, performing suction filtration, washing a filter cake with water, collecting a supernatant, adding isopropyl ether for precipitation, centrifuging the precipitate, and performing vacuum drying on the precipitate to obtain quaternized tannic acid;
the mass ratio of the small molecular quaternary ammonium salt, the tannic acid and the potassium carbonate in the mixed solution is 10: 5-8: 0.2 to 5.
Carboxymethyl curdlan can be prepared according to the following steps:
uniformly dispersing curdlan in isopropanol, stirring and dispersing for 30-60 minutes to obtain curdlan dispersion, slowly dripping sodium hydroxide solution with the mass concentration of 25-35% into the curdlan dispersion for a plurality of times, stirring for 1-2 hours, heating to 50-60 ℃, adding chloroacetic acid-isopropanol solution for a plurality of times under stirring, reacting for 8-10 hours, filtering, washing a filter cake by ethanol and acetone for 3 times in sequence, and freeze-drying the filter cake to obtain white flocculent carboxymethyl curdlan;
wherein the mass volume ratio of the curdlan, the isopropanol, the sodium hydroxide solution and the chloroacetic acid-isopropanol solution is 1g: 10-15 ml: 1.2-2 ml: 5-8 g;
wherein the chloroacetic acid-isopropanol solution consists of chloroacetic acid and isopropanol according to a mass volume ratio of 1g: 4-5 ml.
Quaternized cocoa can then be prepared as follows:
uniformly dispersing curdlan in isopropanol, stirring and dispersing for 30-60 minutes to obtain curdlan dispersion, slowly dripping sodium hydroxide with the mass concentration of 25-35% into the curdlan dispersion for a plurality of times, stirring for 1-2 hours, heating to 50-60 ℃, adding 2, 3-epoxypropyl trimethyl ammonium chloride-isopropanol solution for a plurality of times under stirring, reacting for 8-10 hours, filtering, washing a filter cake by ethanol and acetone for 3 times in sequence, and freeze-drying the filter cake to obtain white flocculent quaternized curdlan;
Wherein the mass volume ratio of the curdlan, the isopropanol, the sodium hydroxide solution and the 2, 3-epoxypropyl trimethyl ammonium chloride-isopropanol solution is 1g: 10-15 ml: 1.2-2 ml: 15-20 g;
wherein the 2, 3-epoxypropyl trimethyl ammonium chloride-isopropanol solution is prepared from 2, 3-epoxypropyl trimethyl ammonium chloride and isopropanol according to the mass volume ratio of 1g: 2-3 ml.
Amino-modified polysiloxanes can beIs considered to be the product of polydimethylsiloxane in which the methyl moiety is replaced by an aminoalkyl group, which may be a primary, secondary, tertiary or arylamine group, such as-CH 2 CH 2 CH 2 NH 2 ，-CH 2 CH 2 CH 2 NHCH 2 CH 2 NH 2 ，-CH 2 CH 2 CH 2 OC 6 H 4 NH 2 and-CH 2 CH 2 CH 2 NHC 6 H 11 . Preferably, the amino-modified polysiloxane is a side chain aminopropyl polysiloxane, a double-end aminopropyl polysiloxane or a side chain N- (2-aminoethyl) -3-aminopropyl polysiloxane.
Further preferred, the amino-modified polysiloxane is represented by formula I, formula II or formula III:
n=100 to 650, m=100 to 800 in the formula I, the formula II or the formula III; the molecular weight of the amino-modified polysiloxanes of formula I, formula II or formula III is typically of the order of 10 3 ～10 5 Preferably of the order of magnitude of molecular weight 10 4 。
Preferably, n=220 to 480 and m=110 to 540, and the molecular weight of the material is moderate and the performance is more excellent.
The side chain aminopropyl polysiloxane of formula I can be prepared by the following method:
first kind: from methylaminopropyl dimethoxy silane, octamethyl cyclotetrasiloxane (hereinafter referred to as D) 4 ) The equilibrium reaction is co-catalyzed by hexamethyldisiloxane (hereinafter referred to as MM) with a basic catalyst to give a pendant amino-functional polysiloxane:
second kind:
hydrolyzing methyl aminopropyl dimethoxy silane to obtain hydrolysate, and mixing with D 4 The MM is subjected to a co-catalytic equilibrium reaction by using an alkaline catalyst to obtain side amino-functional polysiloxane, which comprises the following specific steps:
adding methyl aminopropyl dimethoxy silane into deionized water to obtain mixed solution (the mass ratio of the methyl aminopropyl dimethoxy silane to the deionized water is 1:5-10), dropwise adding hydrochloric acid () with the mass of 0.01% -0.8% of the mixed solution as a hydrolysis catalyst, and hydrolyzing at 80 ℃ for 1-2 hours to obtain a hydrolyzed polymer with side chain containing amino propyl groups.
Adding D into a reaction kettle 4 MM and tetramethyl ammonium hydroxide silicon alkoxide (Me 4 NOH silicon alkoxide) is introduced with nitrogen for at least 20 minutes, mechanically stirred and heated to 80-85 ℃, balanced polymerization is carried out for 2-3 hours, a hydrolyzed polymer with an aminopropyl side chain is added, the reaction temperature is controlled to be 95-105 ℃, balanced stirring is carried out for 8-10 hours, and the reaction is completed and is quickly heated to 130-140 ℃ to decompose Me 4 Removing low-boiling substances from NOH silicon alkoxide under reduced pressure to obtain light yellow side chain aminopropyl polysiloxane;
wherein D is 4 The mass ratio of MM, tetramethyl ammonium hydroxide silicon alkoxide and hydrolysis polymer with side chain containing aminopropyl is 40-52: 5 to 9:1: 15-30;
the reaction equation is as follows:
third kind:
cyano groups in the cyanoethyl group-containing side polysiloxane can be reduced by a reducing agent to obtain functional polysiloxane with amino groups in side chains:
the double-end aminopropyl polysiloxane of the formula II can be prepared by the following steps:
first kind:
base catalytic equilibrium method: 1, 3-diaminopropyl-1, 3-tetramethyldisiloxane and D 4 Balanced polymerization under the action of alkali catalystAnd (3) the preparation method comprises the following steps of:
second kind:
silicon-hydrogen addition method: the double-end aminopropyl polysiloxane is obtained by hydrosilylation reaction of hydrogen end socket polysiloxane and allylamine under the catalysis of platinum, and the specific steps are as follows:
d is added into a reaction kettle according to the mass ratio of 7-10:1 4 、MM H (Dihydrotetramethyl disiloxane, wuhan fine chemical Co., ltd.) and nitrogen were introduced for at least 20 minutes, and concentrated H was added dropwise 2 SO 4 (accounting for 2 to 4 percent of the total reactant), heating to 80 to 85 ℃ by mechanical stirring, carrying out equilibrium polymerization for 7 to 8 hours to obtain hydrogen-terminated polysiloxane, and heating to 180 ℃ after the equilibrium is finished to remove low-boiling-point substances.
Taking hydrogen end-capped polysiloxane and allylamine (the mass ratio is 1:2-5), introducing nitrogen for at least 30 minutes, and dropwise adding Pt catalyst (H) 2 PtCl 6 ·6H 2 O, 0.1 to 1.5 percent of the total reactant, stirring and heating to 70 to 75 ℃, balancing and stirring for 2 to 3 hours, and decompressing and removing low-boiling-point substances to obtain light yellow double-end aminopropyl polysiloxane;
the reaction equation is as follows:
the side chain N- (2-aminoethyl) -3-aminopropyl polysiloxane of formula III can be prepared as follows:
silane coupling agent KH550 (3-aminopropyl triethoxysilane), D 4 Basic catalyst for MM (e.g. tetramethyl ammonium hydroxide Me) 4 NOH) co-catalytic equilibrium reaction, the synthetic route is as follows:
reacted byThe process is as follows: adding D into a reaction kettle 4 MM and tetramethyl ammonium hydroxide silicon alkoxide (Me 4 NOH silicon alkoxide) is introduced with nitrogen for at least 20 minutes, mechanically stirred and heated to 80-85 ℃, balanced polymerization is carried out for 2-3 hours, KH550 is added, the reaction temperature is controlled to be 95-105 ℃, balanced stirring is carried out for 8-10 hours, and the reaction is completed and quickly heated to 130-140 ℃ to decompose Me 4 Removing low-boiling substances from NOH silicon alkoxide under reduced pressure to obtain light yellow viscous N-2-aminoethyl-3-aminopropyl methyl dimethoxy polysiloxane;
wherein D is 4 The mass ratio of MM, tetramethyl ammonium hydroxide silicon alkoxide to KH550 is 45-55: 5-8: 1: 20-30 parts;
The invention also comprises application of the natural polysaccharide-polyphenol medical protective material in preparation of an antibacterial and bacteriostatic spray or a medical protective coating.
Preferably, the antibacterial and bacteriostatic spray or medical protective coating comprises the following components in parts by weight: 8-12 parts of natural polysaccharide-polyphenol medical protective material and 25-30 parts of deionized water;
the natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is hydrophilically modified curdlan; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2-4: 2 to 9.
The preparation method of the medical protective coating comprises the steps of uniformly stirring and mixing 8-12 parts by weight of natural polysaccharide-polyphenol medical protective material and 25-30 parts by weight of deionized water, uniformly spraying the mixture on the surface of a fabric, heating the fabric for 20-200 minutes at 50-95 ℃, and drying the fabric by blowing to obtain the medical protective coating.
Preferably, the antibacterial and bacteriostatic spray or the medical protective coating further comprises a plasticizer, wherein the weight of the plasticizer is 0.05-3% of that of the natural polysaccharide-polyphenol medical protective material;
The plasticizer is one or two of glycerol, stearate or sorbitol; the plasticizer can make the film forming property of the antibacterial and bacteriostatic spray or medical protective coating better.
The preparation method of the medical protective coating comprises the steps of uniformly stirring and mixing 8-12 parts by weight of natural polysaccharide-polyphenol medical protective material, 25-30 parts by weight of deionized water and plasticizer, uniformly spraying the mixture on the surface of a fabric, heating the fabric for 20-200 minutes at 50-95 ℃, and drying the fabric by blowing to obtain the medical protective coating;
the weight of the plasticizer is 0.05-3% of the weight of the natural polysaccharide-polyphenol medical protective material;
the plasticizer is one or two of glycerol, stearate or sorbitol.
The fabric of the present invention is a broad range of medical protective products such as woven fabrics (e.g., cotton fibers, polyester fibers (PET)), nonwoven fabrics (e.g., polypropylene (PP) spunbond nonwoven fabrics, polypropylene (PP) meltblown nonwoven fabrics, spunbond-meltblown-spunbond nonwoven fabrics (SMS)), film materials (e.g., polyethylene films (PE), polyurethane films (PU), polytetrafluoroethylene films (PTFE), thermoplastic polyurethane films (TPU), polyvinyl alcohol films (PVA)) and composites thereof (e.g., PE/PP, PET/PTFE/PET, PET/PU/PET, PET/TPU/PET, PVA/PP), even extending to sponge products. The medical protective coating is suitable for medical protective and epidemic prevention products, and is especially suitable for disposable or repeatedly used medical protective clothing, operating gown and mask products.
The invention is further described below in connection with specific embodiments.
The silane coupling agent KH550 in the embodiment of the invention is purchased from Nanjing Yude Heng fine chemical Co., ltd., D 4 Purchased from Zhejiang New England chemical Co., ltd., MM purchased from Zhejiang New England chemical Co., ltd., basic catalyst such as tetramethyl ammonium hydroxide Me 4 NOH, etc. purchased from Beijing Rui Chemie auxiliary Co., ltd., MM H (Dihydrotetramethyldisiloxane) available from Wuhan fine chemical Co., ltd, pt catalyst (H 2 PtCl 6 ·6H 2 O) purchased from Shenyang nonferrous metals institute.
Example 1
A natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is carboxymethyl curdlan; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2:9, a step of performing the process;
the natural polysaccharide-polyphenol medical protective material is prepared by the following steps:
(1) dissolving 1kg of tannic acid in 1kg of water, adding 0.2kg of 2, 3-epoxypropyl trimethyl ammonium chloride into the water, heating to 75 ℃, condensing and refluxing the mixture for reaction for 20 hours, cooling the mixture to room temperature, carrying out suction filtration, washing a filter cake with 600ml of water, collecting a supernatant, adding isopropanol for precipitation, centrifuging the precipitate at 1500rpm for 10 minutes, and then carrying out vacuum drying on the obtained precipitate at 55-65 ℃ to obtain quaternized tannic acid;
(2) Synthesis of aminoethylaminopropyl polysiloxanes
4.5kg of D were added to a reaction vessel 4 0.5kg MM and 0.1kg tetramethylammonium hydroxide silicon alkoxide (Me) 4 NOH silicon alkoxide) is introduced with nitrogen for at least 20 minutes, mechanically stirred and heated to 80-85 ℃, balanced polymerization is carried out for 2-3 hours, 2kg KH550 is added, the reaction temperature is controlled to be 95-105 ℃, balanced stirring is carried out for 8-10 hours, and the reaction is completed and quickly heated to 130-140 ℃ to decompose Me 4 Removing low-boiling substances from NOH silicon alkoxide under reduced pressure to obtain light yellow viscous N-2-aminoethyl-3-aminopropyl methyl dimethoxy polysiloxane with molecular weight of 4.3X10 4 ；
Adding 1kg of quaternized tannic acid obtained in the step (1) and 5kg of N-2-aminoethyl-3-aminopropyl methyl dimethoxy polysiloxane into 7kg of ethanol, then adding 10kg of Tris-HCl solution into the mixture, stirring the mixture for reaction for 12 hours to obtain a reaction solution, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol in sequence, and carrying out vacuum drying on the filter cake at 50 ℃ to obtain modified tannic acid-amino polysiloxane;
(3) uniformly dispersing 1kg of curdlan in 10L of isopropanol, stirring and dispersing for 30 minutes to obtain a curdlan dispersion, slowly dripping 1.2kg of 25% sodium hydroxide solution with mass concentration into the curdlan dispersion for 4 times, stirring for 1 hour, heating to 50 ℃, adding 5kg of chloroacetic acid-isopropanol solution for 4 times under stirring, reacting for 8 hours, filtering, washing a filter cake sequentially by 800ml of ethanol and 800ml of acetone, and freeze-drying the filter cake to obtain white flocculent carboxymethyl curdlan;
Wherein the chloroacetic acid-isopropanol solution consists of chloroacetic acid and isopropanol according to a mass volume ratio of 1g:4 ml;
(4) adding 200g of carboxymethyl curdlan obtained in the step (3) and 900g of modified tannic acid-amino polysiloxane obtained in the step (2) into 3.5kg of isopropanol, then adding 1kg of Tris-HCl solution into the mixture, stirring the mixture for 12 hours, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol, and then carrying out vacuum drying at 50 ℃ to obtain a natural polysaccharide-polyphenol medical protective material;
the hydrophilic modification curdlan is carboxymethyl curdlan.
Example 2
A natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is carboxymethyl curdlan; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 4:9.
the preparation method of the natural polysaccharide-polyphenol medical protective material comprises the following steps:
(1) preparing a small molecule quaternary ammonium salt of formula IV:
200g of 1, 6-dibromohexane and 40g of N, N-dimethyl n-octylamine are weighed and added into a reaction kettle, the mixture is stirred and reacted for 15 hours, 300g of isopropanol is added for precipitation, the mixture is washed, and the mixture is dried in vacuum to obtain the micromolecular quaternary ammonium salt of the formula IV, wherein the reaction equation is as follows:
(2) 200g of the small molecular quaternary ammonium salt of the formula IV obtained in the step (1) and 100g of bromodecane are dissolved in 500g of N, N-dimethylamide to obtain a mixed solution for later use;
(3) dissolving and dispersing 100g of tannic acid and 4g of potassium carbonate in 500g of N, N-dimethylamide, slowly adding the mixed solution obtained in the step (2) under stirring, controlling the temperature of a reaction system to be not higher than 80 ℃ when the mixed solution is added, adding the mixed solution, condensing and refluxing for reaction for 24 hours, cooling to room temperature, carrying out suction filtration, washing a filter cake with 100ml of water, collecting a supernatant, adding 500g of isopropyl ether for precipitation, centrifuging the precipitate, and vacuum drying the precipitate to obtain 276g of quaternized tannic acid;
(4) preparation of double-end aminopropyl polysiloxane by a hydrosilylation method:
3.5kg of D4 and 0.5kg of MM are introduced into a reaction vessel H Introducing nitrogen for at least 20 minutes, dropwise adding concentrated sulfuric acid into a reaction kettle, heating to 80-85 ℃ under mechanical stirring after the dropwise adding, carrying out equilibrium polymerization for 7-8 hours, heating to 180 ℃ after the reaction is finished, and removing low-boiling substances to obtain 3.8kg of hydrogen-terminated polysiloxane;
adding 2kg of hydrogen-terminated polysiloxane and 8kg of allylamine into a reaction kettle, introducing nitrogen for at least 30 minutes, dropwise adding 0.1kg of Pt catalyst, stirring and heating to 70-75 ℃, balancing and stirring for 2-3 hours, and removing low-boiling substances under reduced pressure to obtain 2.6kg of light yellow double-end aminopropyl polysiloxane with the molecular weight Mw=2.3×10 4 ；
(5) 200g of quaternized tannic acid obtained in the step (3) and 1.6kg of double-end aminopropyl polysiloxane obtained in the step (4) are taken and added into 5kg of methanol, then 2kg of Tris-HCl solution is added into the methanol, the reaction is carried out for 12 to 15 hours under stirring, reaction liquid is obtained, suction filtration is carried out, filter cakes are sequentially washed by distilled water and isopropanol, and the filter cakes are dried in vacuum at 50 to 60 ℃ to obtain 1.75kg of modified tannic acid-amino polysiloxane;
(6) uniformly dispersing 1kg of curdlan in 15L of isopropanol, stirring and dispersing for 60 minutes to obtain curdlan dispersion, slowly dripping 2L of 35% sodium hydroxide solution into the curdlan dispersion for 5 times, stirring for 2 hours, heating to 60 ℃, adding 8kg of chloroacetic acid-isopropanol solution for several times under stirring, reacting for 10 hours, filtering, washing a filter cake by 500ml of ethanol and 500ml of acetone in sequence, and freeze-drying the filter cake to obtain 1.1kg of white flocculent carboxymethyl curdlan;
wherein the chloroacetic acid-isopropanol solution consists of chloroacetic acid and isopropanol according to a mass volume ratio of 1g:5 ml;
(7) adding 0.4kg of the hydrophilic modified curdlan obtained in the step (6) and 0.9kg of the modified tannic acid-amino polysiloxane obtained in the step (5) into 3.5kg of isopropanol, then adding 2kg of Tris-HCl solution into the isopropanol, stirring for 12 hours, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol, and then carrying out vacuum drying at 50 ℃ to obtain the natural polysaccharide-polyphenol medical protective material.
Example 3
A natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is quaternized curdlan; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 3:8.
the preparation method of the natural polysaccharide-polyphenol medical protective material comprises the following steps:
(1) dissolving 1kg of tannic acid in 1.2kg of water, adding 5kg of 2, 3-epoxypropyl trimethyl ammonium chloride into the water, heating to 75 ℃, condensing and refluxing the mixture for reaction for 25 hours, cooling the mixture to room temperature, carrying out suction filtration, washing a filter cake with 600ml of water, collecting a supernatant, adding isopropanol for precipitation, centrifuging the precipitate at 1500rpm for 10 minutes, and then carrying out vacuum drying on the obtained precipitate at 55-65 ℃ to obtain quaternized tannic acid;
(2) side chain aminopropyl polysiloxane (molecular weight mw=3.7x10 4 ) Is prepared from the following steps:
adding 2kg of methyl aminopropyl dimethoxy silane and 10kg of deionized water into a reaction kettle, and dropwise adding 1.2g of hydrochloric acid serving as a hydrolysis catalyst, and hydrolyzing at 80 ℃ for 2 hours to obtain a hydrolyzed polymer with side chain containing aminopropyl groups;
Adding 4kg of D into a reaction kettle 4 0.5kg MM and 0.1kg tetramethylammonium hydroxide silicon alkoxide (Me) 4 NOH silicon alkoxide) is introduced with nitrogen for at least 20 minutes, mechanically stirred and heated to 80-85 ℃, balanced polymerization is carried out for 3 hours, 1.5kg of hydrolyzed polymer with amino propyl group on the side chain is added, the reaction temperature is controlled to be 95-105 ℃, balanced stirring is carried out for 10 hours, and the reaction is completed and the temperature is quickly raised to 130-140 DEG CDecomposition of Me 4 Removing low-boiling substances from NOH silicon alkoxide under reduced pressure to obtain light yellow side chain aminopropyl polysiloxane;
(3) adding 0.5kg of quaternized tannic acid obtained in the step (1) and 3kg of side chain aminopropyl polysiloxane obtained in the step (2) into 10kg of isopropanol, then adding 6kg of Tris-HCl solution into the mixture, stirring the mixture for reaction for 13 hours to obtain a reaction solution, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol in sequence, and carrying out vacuum drying on the filter cake at 55 ℃ to obtain modified tannic acid-aminopolysiloxane;
(4) uniformly dispersing 1kg of curdlan in 12L of isopropanol, stirring and dispersing for 40 minutes to obtain curdlan dispersion, slowly dripping 1.5L of sodium hydroxide with the mass concentration of 28% into the curdlan dispersion for a plurality of times, stirring for 1.5 hours, heating to 54 ℃, adding 16kg of 2, 3-epoxypropyl trimethyl ammonium chloride-isopropanol solution for a plurality of times under stirring, reacting for 8-10 hours, filtering, washing a filter cake by ethanol and acetone for 3 times in sequence, and freeze-drying the filter cake to obtain white flocculent quaternized curdlan;
Wherein the 2, 3-epoxypropyl trimethyl ammonium chloride-isopropanol solution is prepared from 2, 3-epoxypropyl trimethyl ammonium chloride and isopropanol according to the mass volume ratio of 1g:2 ml;
(5) adding 0.3kg of quaternized curdlan obtained in the step (4) and 0.8kg of modified tannic acid-amino polysiloxane obtained in the step (2) into 2.8kg of isopropanol, then adding 1.2kg of Tris-HCl solution into the mixture, stirring the mixture for 14 hours, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol, and then carrying out vacuum drying at 54 ℃ to obtain the natural polysaccharide-polyphenol medical protective material.
Example 4
A natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is quaternized curdlan; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 1:2.
a preparation method of a natural polysaccharide-polyphenol medical protective material comprises the following steps:
the preparation steps of the modified tannic acid-amino polysiloxane are obtained according to the method described in example 2, steps (1) to (5);
the quaternization can be obtained according to the following steps:
Uniformly dispersing 1kg of curdlan in 15L of isopropanol, stirring and dispersing for 50 minutes to obtain curdlan dispersion, slowly dripping 2L of sodium hydroxide with the mass concentration of 30% into the curdlan dispersion for 6 times, stirring for 1.5 hours, heating to 55 ℃, adding 20kg of 2, 3-epoxypropyl trimethyl ammonium chloride-isopropanol solution for several times under stirring, reacting for 8-10 hours, filtering, washing a filter cake by ethanol and acetone for 3 times in sequence, and freeze-drying the filter cake to obtain white flocculent quaternized curdlan;
wherein the 2, 3-epoxypropyl trimethyl ammonium chloride-isopropanol solution is prepared from 2, 3-epoxypropyl trimethyl ammonium chloride and isopropanol according to the mass volume ratio of 1g:2.5ml composition;
adding 0.3kg of quaternized curdlan and 0.6kg of modified tannic acid-amino polysiloxane into 3kg of isopropanol, then adding 1.5kg of Tris-HCl solution into the mixture, stirring the mixture for 14 hours, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol, and then carrying out vacuum drying at 50-60 ℃ to obtain the natural polysaccharide-polyphenol medical protective material.
Wherein 80g of the natural polysaccharide-polyphenol medical protective material of the example 1 and 250g of deionized water are adopted to prepare a medical protective coating material 1, and 80g of the natural polysaccharide-polyphenol medical protective material of the example 1, 250g of deionized water and 0.8g of glycerin are adopted to prepare a medical protective coating material 2;
Cutting and taking a piece of reusable medical protective clothing/operating gown (the surface layer and the inner layer are made of polyester fibers, the middle sandwich is made of microporous polyurethane films, and the PET/PU/PET) fabric is 20cm multiplied by 20cm, uniformly spraying the medical protective coating material 1 or the medical protective coating material 2 (the thickness is 0.8 mm) on the PET polyester fiber woven cloth on the surface layer, heating the flat plate to 80 ℃ for 15min, and drying by blowing to obtain the coating-treated reusable medical protective clothing fabric. And cutting the 10cm multiplied by 10cm coated fabric, performing high-temperature wet heat sterilization (134 ℃ for 4 min), and testing the performances of the uncoated, coated and post-coated fabric.
The results of testing the properties of the uncoated, coated and post-sterilized coated fabrics are shown in tables 1-1-1, 1-1-2, 1-2-1 and 1-2-2. Table 1-1-1 and Table 1-1-2 are coated with a medical protective coating material 1, table 1-2-1 and Table 1-2-2 are coated with a medical protective coating material 2, the penetration of blood-borne pathogens is tested according to the method YY/T0689-2008, the penetration of contaminant-resistant liquid aerosols is tested according to the method YY/T1799-2020 annex B, the penetration of microorganisms in a moisture-resistant state is tested according to the method YY/T0506.6-2009, the resistance to water permeation is tested according to the method GB/T4744-2013, the resistance to static electricity is tested according to the method specified by 7.2 in GB/T12703-1991, and the flame resistance is tested according to the method GB/T5455-2014 vertical; the breaking strength-dry state and the breaking strength-wet state are tested according to the GB/T3923.1-2013 method, the abrasion resistance is tested according to the GB/T21196.2-2007 and the GB24539-2009 method, and the flex failure resistance is tested according to the GB/T12586-2003 method.
TABLE 1-1
TABLE 1-1-2
TABLE 1-2-1
TABLE 1-2
As can be seen from the data in tables 1-1-1, 1-1-2 and 1-2-1, 1-2-2, after the PET/PU/PET fabric is sprayed with the natural polysaccharide-polyphenol medical protective material, the total number of the microbial-bacterial colonies is obviously reduced, and the test data of pathogen penetrability resistance, aerosol penetrability resistance of pollution-resistant liquid and penetrability resistance of wet microorganisms show that the pathogen resistance is better, the water impermeability is increased, the antistatic property is increased and the flame retardant property is increased; and the coating still has good germ-preventing capability, water permeability resistance, antistatic property and excellent flame retardant property after being sterilized again after being used, so that the natural polysaccharide-polyphenol medical protective material is not only suitable for disposable medical protective clothing fabric, but also suitable for repeatedly using the medical protective clothing fabric.
As can be seen from a comparison of tables 1-1-1, 1-1-2 and 1-2-1 tables 1-2-2, the coating has significantly improved fabric flexibility and antistatic properties after the addition of glycerol as a plasticizer. Plasticizers such as glycerol weaken the secondary bonds between polymer molecules, i.e., van der Waals forces, thereby increasing the mobility of the polymer chains of the coating, decreasing the crystallinity of the polymer chains of the coating, i.e., increasing the plasticity of the coating, as evidenced by improved properties of the coating in terms of breaking strength in the dry and wet state (including machine direction, transverse direction), abrasion resistance (in terms of number of cycles required to produce damage), flex failure resistance (in terms of number of cycles required to produce damage in the warp and weft directions). Further experiments have found that a similar effect can be achieved by replacing glycerol with stearate or sorbitol.
The medical protective coating material is prepared by adopting 120g of the natural polysaccharide-polyphenol medical protective material of the embodiment 2 and 300g of deionized water, a disposable operating coat/medical protective garment (a polypropylene spun-bonded non-woven fabric material covered with a polyethylene film, PE/PP) fabric is sheared to 15cm multiplied by 15cm, the PE film on the surface layer is uniformly sprayed with the medical protective coating (50 mu m), a flat plate is heated to 79 ℃ for 19min, and the disposable medical protective garment fabric with the coating treatment is obtained after blowing and drying. The properties of the uncoated, coated and post-coated fabrics were tested.
The results of testing the uncoated, coated fabric properties are shown in table 2. Wherein Bacterial Filtration Efficiency (BFE) is tested according to the GB19082-2009 method, non-oily Particle Filtration Efficiency (PFE) is tested according to the GB19082-2009 method, anti-synthetic blood penetration is tested according to the GB19082-2009 method, antistatic property is tested according to the method specified by 7.2 in GB/T12703-1991, and flame retardance is tested according to the GB/T5455-2014 vertical method.
TABLE 2
As can be seen from the results in Table 2, after the natural polysaccharide-polyphenol medical protective material is coated on PE/PP fabric, the bacterial filtration efficiency is improved from 96.41% to 99.95%, the non-oily particle filtration efficiency is improved to 100%, the penetration resistance of the synthetic blood is improved, the antibacterial effect is obvious, and the antibacterial material has better antistatic property and flame retardant property.
The medical protective coating material is prepared by adopting 90g of the natural polysaccharide-polyphenol medical protective material obtained in the example 3 and 260g of deionized water, and the medical protective coating material is prepared by adopting 100g of the natural polysaccharide-polyphenol medical protective material obtained in the example 4 and 280g of deionized water; cutting a disposable medical mask (polypropylene spun-bonded non-woven fabric-polypropylene melt-blown non-woven fabric-polypropylene spun-bonded non-woven fabric, PP-SMS) fabric, wherein 9cm multiplied by 7cm is adopted, the medical protective coating material (0.5 mm) is uniformly sprayed on the PP spun-bonded non-woven fabric on the blue surface layer, the flat plate is heated to 69 ℃ for 16min, and the surgical mask fabric with the coating treatment is obtained after blowing and drying.
The performance of the surgical mask before and after coating was tested and the results are shown in table 3. The detection method is the same as the detection method of the detection item in Table 2.
TABLE 3 Table 3
As can be seen from the results in table 3, after the natural polysaccharide-polyphenol medical protective material is coated on the PP-SMS fabric, the bacterial filtration efficiency is obviously improved, the non-oily particle filtration efficiency is improved, the penetration resistance of the synthetic blood is improved, the antibacterial effect is obvious, and the antistatic property and the flame retardant property are better, so that the natural polysaccharide-polyphenol medical protective material has excellent protective performance and application prospect.
The natural polysaccharide-polyphenol medical protective material is prepared into an antibacterial and bacteriostatic spray for antibacterial performance detection. The process is as follows:
preparation of LB (Luria-Bertani) medium, namely adding 10.0g of tryptone, 5.0g of yeast extract, 10.0g of sodium chloride and 20.0g of agar powder into 1000mL of distilled water, fully mixing, adjusting the pH of the medium to 7.2+/-0.1, heating to fully dissolve, subpackaging into conical flasks, adding a plug, sealing, and sterilizing at 121 ℃ for 25min.
The preparation of potato dextrose agar culture medium comprises cleaning potato, peeling, cutting, weighing 200g potato small blocks, adding 1000mL distilled water, boiling for 0.5h until the potato small blocks can be broken by a glass rod, filtering, adding distilled water into the filtrate to make up 1000mL, respectively adding 20.0g agar and 20.0g glucose, subpackaging into conical flasks, adding plugs, sealing, and sterilizing at 121 ℃ for 25min. Cooling to 60deg.C, pouring into a sterile workbench, cooling to solidify, and applying activated bacteria liquid (such as Escherichia coli, staphylococcus aureus and Fusarium bacteria liquid), and performing self-made culture in laboratory.
The natural polysaccharide-polyphenol medical protective materials of examples 1-4 are adopted to prepare antibacterial and bacteriostatic spray, and the compositions are shown in table 4:
TABLE 4 Table 4
The spray 1-8 was made into a film (thickness is 0.55 mm), the film was punched out into a circular film sheet with a diameter of 6mm by a punch, sterilized and dried, the three test bacteria were uniformly spread on a dish containing LB medium and potato dextrose agar medium, respectively, and the spare film sheet sample and blank sample were attached to the above-mentioned spread bacteria medium by using sterile ophthalmic tweezers, the LB medium was cultured at 37℃for 24 hours, the potato medium was cultured at 30℃for 36 hours, and the size of the inhibition zone was observed, measured and recorded, and the test results are shown in Table 5 below.
TABLE 5
From the results shown in Table 5, the spray film has a certain antibacterial effect on all of Escherichia coli, staphylococcus aureus and Fusarium, and the antibacterial effect on Fusarium and Staphylococcus aureus is slightly higher than that of Escherichia coli.
Claims (4)
1. A natural polysaccharide-polyphenol medical protective material is characterized in that: the natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is hydrophilic modified; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the film substrate to the modified tannic acid-amino polysiloxane is 2-4: 2-9;
the hydrophilically modified curdlan is carboxymethyl curdlan or quaternized curdlan;
the natural polysaccharide-polyphenol medical protective material is prepared by the following steps:
(1) quaternizing tannic acid to obtain quaternized tannic acid;
(2) adding the quaternized tannic acid and the amino modified polysiloxane obtained in the step (1) into organic alcohol, then adding Tris-HCl solution into the organic alcohol, stirring and reacting for 12-15 hours to obtain reaction liquid, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol in sequence, and carrying out vacuum drying on the filter cake at 50-60 ℃ to obtain the modified tannic acid-amino polysiloxane;
Wherein the mass ratio of the quaternized tannic acid to the amino modified polysiloxane to the organic alcohol to the Tris-HCl solution is 1: 5-8: 7-25: 10-25 parts of a base;
the organic alcohol is methanol, ethanol or isopropanol;
(3) adding hydrophilic modified curdlan and modified tannic acid-amino polysiloxane obtained in the step (2) into first isopropanol, then adding Tris-HCl solution into the first isopropanol, stirring for 12-15 hours, carrying out suction filtration, flushing a filter cake with distilled water and isopropanol, and then carrying out vacuum drying at 50-60 ℃ to obtain a natural polysaccharide-polyphenol medical protective material;
the hydrophilic modified curdlan, modified tannic acid-aminopolysiloxane, first isopropanol and Tris-HCl solution are in a mass ratio of 2-4: 2-9: 25-35: 10-20 parts of a base;
the specific process of the step (1) is as follows:
dissolving tannic acid in water, adding 2, 3-epoxypropyl trimethyl ammonium chloride into the tannic acid, heating to 75-80 ℃, condensing and refluxing the reaction for 20-25 hours, cooling the reaction product to room temperature, carrying out suction filtration, washing a filter cake with water, collecting a supernatant, adding isopropanol for precipitation, centrifuging the precipitate, and carrying out vacuum drying on the precipitate to obtain quaternized tannic acid; wherein the mass ratio of tannic acid to 2, 3-epoxypropyl trimethyl ammonium chloride is 1: 0.2-5;
Or the specific process of the step (1) is as follows:
A. adding 1, 6-dibromohexane and N, N-dimethyl N-octylamine into a reaction kettle, reacting for 15-20 hours at 20-30 ℃, adding isopropanol for precipitation, washing a filter cake with isopropanol, and vacuum drying to obtain micromolecular quaternary ammonium salt; dissolving small molecular quaternary ammonium salt and bromodecane in N, N-dimethylamide to obtain a mixed solution for later use;
wherein the mass ratio of the 1, 6-dibromohexane to the N, N-dimethyl N-octylamine is 5-8: 1, a step of;
the mass ratio of the small molecular quaternary ammonium salt to the bromodecane is 10: 5-10;
B. dissolving and dispersing tannic acid and potassium carbonate in N, N-dimethylamide, slowly adding the mixed solution obtained in the step A under stirring, controlling the temperature of a reaction system to be not higher than 80 ℃ when the mixed solution is added, adding the mixed solution, performing condensation reflux reaction for 24-28 hours, cooling to room temperature, performing suction filtration, washing a filter cake with water, collecting a supernatant, adding isopropyl ether for precipitation, centrifuging the precipitate, and performing vacuum drying on the precipitate to obtain quaternized tannic acid;
the mass ratio of the small molecular quaternary ammonium salt, the tannic acid and the potassium carbonate in the mixed solution is 10: 5-8: 0.2-5;
the amino modified polysiloxane is shown as a formula I, a formula II or a formula III:
n=100 to 650, m=100 to 800 in the formula I, the formula II or the formula III.
2. The use of a natural polysaccharide-polyphenol medical protective material according to claim 1, characterized in that: the application in preparing antibacterial and bacteriostatic spray or medical protective coating.
3. The use of a natural polysaccharide-polyphenol medical protective material according to claim 2, wherein: the antibacterial and bacteriostatic spray or medical protective coating comprises the following components in parts by weight: 8-12 parts of natural polysaccharide-polyphenol medical protective material and 25-30 parts of deionized water;
the natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaving hydrogen bonds; the membranous matrix is hydrophilically modified curdlan; the modified tannic acid-amino polysiloxane is amino polysiloxane coordinated by quaternized tannic acid polyphenol; the mass ratio of the film substrate to the modified tannic acid-amino polysiloxane is 2-4: 2-9.
4. The use of a natural polysaccharide-polyphenol medical protective material according to claim 3, wherein: the antibacterial and bacteriostatic spray or the medical protective coating further comprises a plasticizer, wherein the weight of the plasticizer is 0.05-3% of that of the natural polysaccharide-polyphenol medical protective material;
The plasticizer is one or two of glycerol, stearate or sorbitol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111214885.1A CN114032695B (en) | 2021-10-19 | 2021-10-19 | Natural polysaccharide-polyphenol medical protective material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111214885.1A CN114032695B (en) | 2021-10-19 | 2021-10-19 | Natural polysaccharide-polyphenol medical protective material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114032695A CN114032695A (en) | 2022-02-11 |
| CN114032695B true CN114032695B (en) | 2023-07-14 |
Family
ID=80141661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111214885.1A Active CN114032695B (en) | 2021-10-19 | 2021-10-19 | Natural polysaccharide-polyphenol medical protective material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114032695B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5357636A (en) * | 1992-06-30 | 1994-10-25 | Dresdner Jr Karl P | Flexible protective medical gloves and methods for their use |
| CN102040670A (en) * | 2010-11-29 | 2011-05-04 | 青蛙王子(中国)日化有限公司 | Carboxymethyl chitosan quaternary ammonium salt as well as preparation and application thereof in preparing natural cosmetic antibacterial agent |
| CN111153815A (en) * | 2020-03-10 | 2020-05-15 | 北京化工大学 | A kind of antibacterial polyphenol material and application |
| CN111592668A (en) * | 2020-06-23 | 2020-08-28 | 齐鲁工业大学 | Crosslinking modification method of antibacterial gelatin |
| CN112175210A (en) * | 2020-09-30 | 2021-01-05 | 山东大学 | Preparation method of organic silicon elastomer based on polyphenol compound crosslinking |
| CN112759670A (en) * | 2020-12-17 | 2021-05-07 | 中国石油大学(华东) | Mussel bionic functionalized hydrophilic polymer and hydrophilic polymer network modified super-hydrophilic net membrane as well as preparation method and application thereof |
| CN113337128A (en) * | 2021-05-31 | 2021-09-03 | 福建臻璟新材料科技有限公司 | High-weather-resistance heat-conducting gel composition and preparation method thereof |
| CN113336950A (en) * | 2021-06-28 | 2021-09-03 | 山东大学 | Preparation method of high-strength organic silicon elastomer based on modified polyphenol crosslinking |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10731040B2 (en) * | 2016-07-12 | 2020-08-04 | The University Of Massachusetts | Crosslinked phenolic compound, method of forming, and polymer composition containing the same |
-
2021
- 2021-10-19 CN CN202111214885.1A patent/CN114032695B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5357636A (en) * | 1992-06-30 | 1994-10-25 | Dresdner Jr Karl P | Flexible protective medical gloves and methods for their use |
| CN102040670A (en) * | 2010-11-29 | 2011-05-04 | 青蛙王子(中国)日化有限公司 | Carboxymethyl chitosan quaternary ammonium salt as well as preparation and application thereof in preparing natural cosmetic antibacterial agent |
| CN111153815A (en) * | 2020-03-10 | 2020-05-15 | 北京化工大学 | A kind of antibacterial polyphenol material and application |
| CN111592668A (en) * | 2020-06-23 | 2020-08-28 | 齐鲁工业大学 | Crosslinking modification method of antibacterial gelatin |
| CN112175210A (en) * | 2020-09-30 | 2021-01-05 | 山东大学 | Preparation method of organic silicon elastomer based on polyphenol compound crosslinking |
| CN112759670A (en) * | 2020-12-17 | 2021-05-07 | 中国石油大学(华东) | Mussel bionic functionalized hydrophilic polymer and hydrophilic polymer network modified super-hydrophilic net membrane as well as preparation method and application thereof |
| CN113337128A (en) * | 2021-05-31 | 2021-09-03 | 福建臻璟新材料科技有限公司 | High-weather-resistance heat-conducting gel composition and preparation method thereof |
| CN113336950A (en) * | 2021-06-28 | 2021-09-03 | 山东大学 | Preparation method of high-strength organic silicon elastomer based on modified polyphenol crosslinking |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114032695A (en) | 2022-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Emam | Antimicrobial cellulosic textiles based on organic compounds | |
| Buşilă et al. | Synthesis and characterization of antimicrobial textile finishing based on Ag: ZnO nanoparticles/chitosan biocomposites | |
| Mahltig et al. | Functionalisation of textiles by inorganic sol–gel coatings | |
| Gargoubi et al. | Enhancing the functionality of cotton fabric by physical and chemical pre-treatments: A comparative study | |
| WO2008009651A1 (en) | Anti-viral face mask and filter material | |
| EP1830639B1 (en) | Antimicrobial and antiviral product | |
| CN114032695B (en) | Natural polysaccharide-polyphenol medical protective material and preparation method and application thereof | |
| WO2021181345A1 (en) | Air filtration system and manufacturing method thereof | |
| CN105615053A (en) | Highly-antibacterial novel slightly-soluble anti-haze healthcare mask capable of adsorbing heavy metal particles | |
| US12193532B2 (en) | Antibacterial and antiviral degradable mask and manufacturing method thereof | |
| CN104975504B (en) | The method that a kind of carboxymethyl chitosan grafted branch nylon66 fiber fabric of O prepares footwear antibacterial synthetic leather base material and back boxing | |
| CN105624920B (en) | A kind of high antibacterial, the novel slightly soluble non-woven fabrics for adsorbing heavy metal molecule | |
| CN109320999B (en) | Quaternized nano taiji stone, preparation method thereof and modified polypropylene fiber | |
| CN102061614A (en) | Dual mode high-efficiency antibacterial and antiviral adsorbing material | |
| CN111286121A (en) | Antibacterial protection environment-friendly composite polymer material and preparation method and application thereof | |
| CN111235871A (en) | Antiviral filter layer prepared from copper-containing chitosan fiber and application thereof | |
| CN105755673A (en) | Manufacturing method for antibacterial high selectivity nanofiber membrane | |
| CN112941721B (en) | High-strength antibacterial non-woven fabric and preparation method thereof | |
| KR20160050468A (en) | Antibiotic medical fabric with violacein supported particle and making process therof | |
| CN111155177B (en) | Electrostatic spinning antiviral thin layer and application thereof in antiviral field | |
| CN113087883B (en) | Antiviral polylactic acid melt-blown material and preparation method and application thereof | |
| CN112522862B (en) | Visible light driven antibacterial nanofiber and preparation method and application thereof | |
| JP2022177994A (en) | Protective non-woven and woven fabric manufacturing methods and protective articles | |
| WO2012065610A1 (en) | Method and substrate with a quat coating | |
| CN113840552A (en) | Method for manufacturing antiviral fiber product and antiviral mask manufactured by using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |