CN114032695A - 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
- CN114032695A CN114032695A CN202111214885.1A CN202111214885A CN114032695A CN 114032695 A CN114032695 A CN 114032695A CN 202111214885 A CN202111214885 A CN 202111214885A CN 114032695 A CN114032695 A CN 114032695A
- Authority
- CN
- China
- Prior art keywords
- polyphenol
- medical protective
- polysiloxane
- tannic acid
- protective material
- 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.)
- Granted
Links
- 230000001681 protective effect Effects 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title abstract description 16
- -1 polysiloxane Polymers 0.000 claims abstract description 146
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 106
- 239000011159 matrix material Substances 0.000 claims abstract description 33
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 24
- 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
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 16
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 15
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 229920001864 tannin Polymers 0.000 claims abstract description 14
- 235000018553 tannin Nutrition 0.000 claims abstract description 14
- 239000001648 tannin Substances 0.000 claims abstract description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 112
- 238000006243 chemical reaction Methods 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 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 description 50
- 239000001263 FEMA 3042 Substances 0.000 claims description 50
- 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 description 50
- 235000015523 tannic acid Nutrition 0.000 claims description 50
- 229920002258 tannic acid Polymers 0.000 claims description 50
- 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 50
- 229940033123 tannic acid Drugs 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 45
- 239000012065 filter cake Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 31
- 239000011253 protective coating Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000967 suction filtration Methods 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 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
- 230000000844 anti-bacterial effect Effects 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 230000003385 bacteriostatic effect Effects 0.000 claims description 16
- 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
- 150000003242 quaternary ammonium salts Chemical class 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
- 239000007921 spray Substances 0.000 claims description 14
- 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
- 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
- 238000001035 drying Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 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
- 150000004676 glycans Chemical class 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
- 229920001282 polysaccharide Polymers 0.000 claims description 7
- 239000005017 polysaccharide Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 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
- 230000008569 process Effects 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
- 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
- 230000028327 secretion Effects 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000010408 film Substances 0.000 description 21
- 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
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 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
- 239000006185 dispersion Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000005445 natural material Substances 0.000 description 10
- 239000004745 nonwoven fabric Substances 0.000 description 10
- 229920006264 polyurethane film Polymers 0.000 description 9
- 239000001963 growth medium Substances 0.000 description 8
- 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
- 238000012676 equilibrium polymerization Methods 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 238000011282 treatment Methods 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
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 6
- 238000004108 freeze drying Methods 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
- 230000001954 sterilising effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- DCGHXSVAHIMIDJ-UHFFFAOYSA-N 3-dimethoxysilyl-N-methylpropan-1-amine Chemical compound CNCCC[SiH](OC)OC DCGHXSVAHIMIDJ-UHFFFAOYSA-N 0.000 description 5
- 244000061456 Solanum tuberosum Species 0.000 description 5
- 235000002595 Solanum tuberosum Nutrition 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- AKPUJVVHYUHGKY-UHFFFAOYSA-N hydron;propan-2-ol;chloride Chemical compound Cl.CC(C)O AKPUJVVHYUHGKY-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 239000002759 woven fabric Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 239000001879 Curdlan Substances 0.000 description 3
- 229920002558 Curdlan Polymers 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000223218 Fusarium Species 0.000 description 3
- 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 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- OZMCWWGXJZFBLQ-UHFFFAOYSA-N azanium;propan-2-ol;chloride Chemical compound [NH4+].[Cl-].CC(C)O OZMCWWGXJZFBLQ-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 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
- 229940078035 curdlan Drugs 0.000 description 3
- 235000019316 curdlan Nutrition 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 239000004750 melt-blown nonwoven Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- 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 2
- 229920000742 Cotton Polymers 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000008263 liquid aerosol Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000005303 weighing 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
- IIKPYSNAHDRJSM-UHFFFAOYSA-N 1-[dimethylsilyloxy(dimethyl)silyl]propane-1,3-diamine Chemical compound C[SiH](C)O[Si](C)(C)C(N)CCN IIKPYSNAHDRJSM-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 241000588813 Alcaligenes faecalis Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 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
- 125000005264 aryl amine group Chemical group 0.000 description 1
- 230000005540 biological transmission 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
- 238000009835 boiling Methods 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009795 derivation 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
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 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
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 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
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 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
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000012137 tryptone Substances 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 and a preparation method and application thereof, wherein the natural polysaccharide-polyphenol medical protective material is prepared by assembling a membranous matrix and modified tannic acid-amino polysiloxane through interweaved hydrogen bonds; the membranous matrix is obtained by hydrophilic modification; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2-4: 2-9; the hydrophilic modification may be either carboxymethyl or quaternized; the natural polysaccharide-polyphenol medical protective material has excellent protective performance, can prevent and protect particles, body fluid, secretion and the like with potential infection, 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 clothing and the like, are used as effective barriers for defending people against harmful substances such as potential infectious particulate matters, body fluids, secretions and the like, and the medical care personnel must be ensured to be protected and safe under the infection risk and must provide the long-time wearing comfort of the protective articles as much as possible. In recent two years, with the outbreak of new crown epidemic situations, medical workers or workers in public areas need to wear protective clothing and masks for a long time to carry out isolation protection, so that new requirements and challenges are brought to isolation materials. Medical protective articles must be converted to high-grade, reusable, highly comfortable and easy-to-use products to meet the needs of medical care workers. In addition, on the basis of ensuring the safety and the effectiveness, functional finishing of medical protective products is urgently needed, such as antibacterial finishing, elastic soft finishing, film-coated degradation finishing, flame-retardant antistatic finishing and the like.
The performance of the existing medical protective coating material is single, and the requirements of the protective product on antibiosis, bacteriostasis, barrier protection, smoothness, ventilation, safety and comfort cannot be met simultaneously. The curdlan is naturally extracellular polysaccharide which is fermented by the alcaligenes faecalis and consists of beta-1, 3-glycosidic bond glycosidic bonds, the natural biomolecule has the characteristic of being capable of solidifying after being heated, but the molecular structure is a triple helix structure, and a large amount of hydrogen bonds are contained in the molecule and among the molecules, so that the curdlan is insoluble in water, and the use of the curdlan is limited; on the other hand, tannic acid is a natural polyphenol consisting of glucose cores connected by ester bonds through a plurality of gallic acid dimers, the benzene ring of the inner core of tannic acid is hydrophobic, the phenolic hydroxyl group is hydrophilic, and when the tannic acid is singly used as a coating for modification, the stability is poor due to high water solubility, so that people try to adjust the hydrophilicity and hydrophobicity of tannic acid through various derivatization reactions to meet the actual requirement. In conclusion, although the acquirable tannic acid has the possibility of being used as medical protection in theory, the nature of the acquirable tannic acid determines that the acquirable tannic acid cannot be directly used for preparing medical protection materials.
Disclosure of Invention
The invention aims to solve the problems that the existing medical protective material has single performance and cannot simultaneously meet the requirements of a protective product on antibiosis, bacteriostasis, barrier protection, smoothness, ventilation, safety and comfort, and the invention aims to provide a natural polysaccharide-polyphenol medical protective material and a preparation method and application thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
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 obtained by hydrophilic modification; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2-4: 2-9;
the hydrophilic modification may be either carboxymethyl or quaternized.
The invention also comprises a preparation method of the natural polysaccharide-polyphenol medical protective material, which comprises the following steps:
quaternizing tannic acid to obtain quaternized tannic acid;
adding the quaternized tannic acid and amino modified polysiloxane obtained in the step one into organic alcohol, adding a Tris-HCl solution into the organic alcohol, stirring the mixture to react for 12 to 15 hours to obtain a reaction solution, performing suction filtration, washing a filter cake with distilled water and isopropanol in sequence, and performing vacuum drying on the filter cake at the temperature of between 50 and 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;
the organic alcohol is methanol, ethanol or isopropanol;
thirdly, adding the modified tannic acid-amino polysiloxane obtained in the second step into first isopropanol, then adding a Tris-HCl solution into the first isopropanol, stirring the mixture for 12 to 15 hours, carrying out suction filtration, washing 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 hydrophilic modified polysiloxane, modified tannin-amino polysiloxane, first isopropanol and Tris-HCl solution is (2-4): 2-9: 25-35: 10-20;
the hydrophilic modification may be either carboxymethyl or quaternized.
Preferably, the specific process of the step (i) is as follows:
dissolving tannic acid in water, adding 2, 3-epoxypropyl trimethyl ammonium chloride, heating to 75-80 ℃, condensing, refluxing and reacting for 20-25 hours, cooling to room temperature, performing suction filtration, washing a filter cake with water, collecting a lower clear liquid, adding isopropanol for precipitation, performing centrifugal separation on a precipitate, and performing vacuum drying on the precipitate to obtain quaternized tannic acid; wherein the mass ratio of the tannic acid to the 2, 3-epoxypropyltrimethylammonium chloride is 1: 0.2 to 5.
Preferably, the specific process of the step (i) 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 drying in vacuum to obtain micromolecular quaternary ammonium salt; dissolving small molecular quaternary ammonium salt and bromodecane in N, N-dimethyl amide 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;
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-dimethyl amide, stirring, slowly adding the mixed solution obtained in the step A, controlling the temperature of a reaction system to be not more than 80 ℃ when 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 lower clear solution, adding isopropyl ether for precipitation, performing centrifugal separation on the precipitate, and performing vacuum drying on the precipitate to obtain quaternized tannic acid;
the mass ratio of the micromolecular 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, bi-terminal 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:
in the formula I, the formula II or the formula III, n is 100-650, and m is 100-800.
The invention also comprises the application of the natural polysaccharide-polyphenol medical protective material in preparing antibacterial and bacteriostatic spray or medical protective coating.
Preferably, the antibacterial and bacteriostatic spray or the medical protective coating comprises the following components in parts by weight: 8-12 parts of a 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 hydrophilic modified natural polysaccharide; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin 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 the weight 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, softening and film-forming flame retardant properties, and is suitable for being sprayed to form a film, adsorbed and loaded on the surfaces of various woven fabrics, non-woven fabrics and composite materials thereof, so as to form a flame-retardant, flexible 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 clothing and mask products, can prevent and protect particles, body fluid, secretion and the like with potential infection, has good clinical application prospect, adopts natural polysaccharide/polyphenol, has high biocompatibility, can be naturally degraded after disposable use or decontamination treatment, is easy for environment-friendly production operation, and has good economic benefit and social benefit.
The natural polysaccharide-polyphenol medical protective material is ingenious in design, firstly, tannin polyphenol is subjected to quaternization derivation modification, and the stability and the antibacterial property of the tannin polyphenol after water dissolution are adjusted; secondly, the tannin derivative is coordinated with amino modified polysiloxane to form a derivative complex, the derivative complex is endowed with the soft and smooth water resistance of an organic silicon polymer, finally the derivative complex and hydrophilic modified polysiloxane are subjected to interweaving hydrogen bond assembly, and a thermal irreversible medical protective coating can be formed through post-treatment, has good flame retardance and biocompatibility, can resist high-temperature washing sterilization or sterilization, and can be formulated to be naturally degraded according to requirements. The functionalized natural substrate coating has universality, can be sprayed to form a film, and can be adsorbed and loaded on the surfaces of various woven fabrics (such as cotton fibers, polyester fibers (PET)), non-woven fabrics (such as polypropylene (PP) spun-bonded non-woven fabric, polypropylene (PP) melt-blown non-woven fabric, spun-bonded-melt-blown-spun-bonded non-woven fabric (SMS)), film materials (such as polyethylene film (PE), polyurethane film (PU), polytetrafluoroethylene film (PTFE), thermoplastic polyurethane film (TPU), polyvinyl alcohol film (PVA)) and composite materials thereof (such as PE/PP, PET/PTFE/PET, PET/PU/PET, PET/TPU/PET, PVA/PP) and sponge products, the coated fabric has wide field and high applicability, and can obviously improve the antibacterial property, the flame retardance, the flexibility and the degradable performance of the coated film.
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:
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 hydrophilic modified natural polysaccharide; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2-4: 2-9; the hydrophilic modification may be either carboxymethyl or quaternized.
The invention also comprises a preparation method of the natural polysaccharide-polyphenol medical protective material, which comprises the following steps:
quaternizing tannic acid to obtain quaternized tannic acid;
adding the quaternized tannic acid and amino modified polysiloxane obtained in the step one into organic alcohol, adding a Tris-HCl solution into the organic alcohol, stirring the mixture to react for 12 to 15 hours to obtain a reaction solution, performing suction filtration, washing a filter cake with distilled water and isopropanol in sequence, and performing vacuum drying on the filter cake at the temperature of between 50 and 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;
the organic alcohol is methanol, ethanol or isopropanol;
thirdly, adding the modified tannic acid-amino polysiloxane obtained in the second step into first isopropanol, then adding a Tris-HCl solution into the first isopropanol, stirring the mixture for 12 to 15 hours, carrying out suction filtration, washing 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 hydrophilic modified polysiloxane, modified tannin-amino polysiloxane, first isopropanol and Tris-HCl solution is (2-4): 2-9: 25-35: 10-20;
the hydrophilic modification may be either carboxymethyl or quaternized.
Preferably, the quaternization treatment of the tannic acid in the step (i) to obtain the quaternized tannic acid comprises the following specific steps:
dissolving tannic acid in water, adding 2, 3-epoxypropyl trimethyl ammonium chloride, heating to 75-80 ℃, condensing, refluxing and reacting for 20-25 hours, cooling to room temperature, performing suction filtration, washing a filter cake with water, collecting a lower clear liquid, adding isopropanol for precipitation, performing centrifugal separation on a precipitate, and performing vacuum drying on the precipitate to obtain quaternized tannic acid; wherein the mass ratio of the tannic acid to the water to the 2, 3-epoxypropyltrimethylammonium chloride is 1: 1-1.2: 0.2 to 5.
In another preferred embodiment, in step (i), the tannic acid is quaternized, and the quaternized tannic acid is obtained by 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 drying in vacuum to obtain micromolecular quaternary ammonium salt shown in formula IV;
the reaction equation is:
then dissolving the micromolecular quaternary ammonium salt and bromodecane shown in the formula IV in N, N-dimethyl amide 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;
the mass ratio of the micromolecular quaternary ammonium salt of the formula IV to the bromodecane is 10: 5-10;
B. dissolving and dispersing tannic acid and potassium carbonate in N, N-dimethyl amide, stirring, slowly adding the mixed solution obtained in the step A, controlling the temperature of a reaction system to be not more than 80 ℃ when 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 lower clear solution, adding isopropyl ether for precipitation, performing centrifugal separation on the precipitate, and performing vacuum drying on the precipitate to obtain quaternized tannic acid;
the mass ratio of the micromolecular quaternary ammonium salt, the tannic acid and the potassium carbonate in the mixed solution is 10: 5-8: 0.2 to 5.
The carboxymethyl group can be prepared by the following steps:
uniformly dispersing the natural substance in isopropanol, stirring and dispersing for 30-60 minutes to obtain natural dispersion liquid, slowly dripping a sodium hydroxide solution with the mass concentration of 25-35% into the natural dispersion liquid for several times, stirring for 1-2 hours, heating to 50-60 ℃, adding a chloroacetic acid-isopropanol solution for several times while stirring, reacting for 8-10 hours, filtering, washing a filter cake for 3 times by ethanol and acetone in sequence, and freeze-drying the filter cake to obtain white flocculent carboxymethyl natural substance;
wherein the mass volume ratio of the natural substance to the isopropanol, the sodium hydroxide solution and the chloroacetic acid-isopropanol solution is 1 g: 10-15 ml: 1.2-2 ml: 5-8 g;
wherein the chloroacetic acid-isopropanol solution is prepared from chloroacetic acid and isopropanol according to a mass-volume ratio of 1 g: 4-5 ml.
The quaternization product can be prepared according to the following steps:
uniformly dispersing the natural substance in isopropanol, stirring and dispersing for 30-60 minutes to obtain natural dispersion liquid, slowly dripping 25-35% sodium hydroxide in percentage by weight into the natural dispersion liquid, stirring for 1-2 hours, heating to 50-60 ℃, adding 2, 3-epoxypropyltrimethylammonium chloride-isopropanol solution in percentage by weight under stirring, reacting for 8-10 hours, filtering, washing a filter cake for 3 times by ethanol and acetone in sequence, and freeze-drying the filter cake to obtain white flocculent quaternized natural substance;
wherein the mass volume ratio of the natural substance to the isopropanol to the sodium hydroxide solution to the 2, 3-epoxypropyltrimethylammonium chloride-isopropanol solution is 1 g: 10-15 ml: 1.2-2 ml: 15-20 g;
wherein the 2, 3-epoxypropyltrimethyl ammonium chloride-isopropanol solution is prepared from 2, 3-epoxypropyltrimethyl ammonium chloride and isopropanol according to the mass-volume ratio of 1 g: 2-3 ml.
The amino-modified polysiloxane can be regarded as a product in which methyl groups in polydimethylsiloxane are partially substituted with amino hydrocarbon groups such as primary amine, secondary amine, tertiary amine, arylamine group and the like, such as-CH2CH2CH2NH2，-CH2CH2CH2NHCH2CH2NH2，-CH2CH2CH2OC6H4NH2and-CH2CH2CH2NHC6H11. Preferably, the amino-modified polysiloxane is a pendant aminopropylpolysiloxane, a bis-terminal aminopropylpolysiloxane or a pendant N- (2-aminoethyl) -3-aminopropylpolysiloxane.
Further preferably, the amino-modified polysiloxane is represented by formula I, formula II or formula III:
n in the formula I, the formula II or the formula III is 100-650, and m is 100-800; the molecular weight of the amino-modified polysiloxanes of the formula I, II or III is generally in the order of magnitude of 103～105Preferably of the order of 104。
Preferably, n is 220-480, and m is 110-540, so that the molecular weight of the material is moderate, and the performance is more excellent.
The side chain aminopropylpolysiloxane of formula I can be prepared by the following method:
the first method comprises the following steps: prepared from methylaminopropyldimethoxysilane and octamethylcyclotetrasiloxane (hereinafter referred to as D)4) And hexamethyldisiloxane (hereinafter abbreviated as MM) is subjected to a co-catalytic equilibrium reaction by using a basic catalyst to obtain the side amino functional polysiloxane:
and the second method comprises the following steps:
hydrolyzing methylaminopropyldimethoxysilane to obtain hydrolysate, and reacting with D4And MM is subjected to a co-catalytic equilibrium reaction with a basic catalyst to obtain the side amino functional polysiloxane, and the specific steps are as follows:
adding methylaminopropyldimethoxysilane into deionized water to obtain a mixed solution (the mass ratio of the methylaminopropyldimethoxysilane to the deionized water is 1:5-10), dropwise adding hydrochloric acid () accounting for 0.01-0.8% of the mass of the mixed solution as a hydrolysis catalyst, and hydrolyzing at 80 ℃ for 1-2 hours to obtain the hydrolyzed polymer with the aminopropyl-containing side chain.
Adding D into a reaction kettle4MM and tetramethylammonium hydroxide silicon alkoxide (Me)4NOH silicon alkoxide) is introduced with nitrogen, at least 20 minutes are carried out, the mechanical stirring is carried out, the temperature is increased to 80-85 ℃, the equilibrium polymerization reaction is carried out for 2-3 hours, the hydrolytic polymer with the side chain containing aminopropyl is added, the reaction temperature is controlled to be 95-105 ℃, the equilibrium stirring is carried out for 8-10 hours, the reaction is completed, the temperature is rapidly increased to 130-140 ℃ to decompose Me4NOH silicon alkoxide, and removing low-boiling-point substances by decompression to obtain light yellow side chain aminopropyl polysiloxane;
wherein D4The mass ratio of MM to tetramethylammonium hydroxide silicon alkoxide to the side chain aminopropyl-containing hydrolyzed polymer is 40-52: 5-9: 1: 15-30;
the reaction equation is as follows:
and the third is that:
the cyano group in the cyanoethyl group-containing lateral polysiloxane can be reduced by a reducing agent to prepare a functionalized polysiloxane containing an amino group in the side chain:
the bisaminopropyl polysiloxane of formula II can be prepared by the following steps:
the first method comprises the following steps:
base-catalyzed equilibrium method: 1, 3-diaminopropyl-1, 1, 3, 3-tetramethyldisiloxane and D4The preparation method comprises the following steps of (1) carrying out equilibrium polymerization under the action of an alkali catalyst:
and the second method comprises the following steps:
hydrosilylation: the bi-terminal aminopropyl polysiloxane is obtained by the hydrosilylation reaction of hydrogen end socket polysiloxane and allylamine under the catalysis of platinum, and specifically comprises the following steps:
adding D into a reaction kettle according to the mass ratio of 7-10: 14、MMH(Dihydrotetramethyldisiloxane, Wuhan Fine chemical Co., Ltd.), introducing nitrogen for at least 20 minutes, and dropwise adding concentrated H2SO4(accounting for 2-4 percent of the total reactants), mechanically stirring and heating to 80-85 ℃, carrying out equilibrium polymerization for 7-8 hours to obtain hydrogen terminated polysiloxane, and heating to 180 ℃ after equilibrium is finished to remove low-boiling-point substances.
Taking hydrogen terminated polysiloxane and allylamine (the mass ratio is 1: 2-5), introducing nitrogen for at least 30 minutes, and dropwise adding a Pt catalyst (H)2PtCl6·6H2O, Shenyang non-ferrous metal research institute) (accounting for 0.1% -1.5% of the total reactants), stirring and heating at 70-75 ℃, stirring for 2-3 hours under equilibrium, and removing low-boiling-point substances under reduced pressure to obtain light yellow double-endAminopropylpolysiloxane;
the reaction equation is as follows:
the side chain N- (2-aminoethyl) -3-aminopropylpolysiloxane of formula III can be prepared as follows:
silane coupling agents KH550 (3-aminopropyltriethoxysilane), D4MM basic catalysts (e.g. tetramethylammonium hydroxide Me)4NOH) co-catalyzed equilibrium reaction, the synthetic route is as follows:
the reaction process is as follows: adding D into a reaction kettle4MM and tetramethylammonium hydroxide silicon alkoxide (Me)4NOH silicon alkoxide) is introduced with nitrogen, at least 20 minutes are carried out, the mechanical stirring is carried out, the temperature is increased to 80-85 ℃, the equilibrium polymerization reaction is carried out for 2-3 hours, KH550 is added, the reaction temperature is controlled to be 95-105 ℃, the equilibrium stirring is carried out for 8-10 hours, the reaction is completed, the temperature is rapidly increased to 130-140 ℃ to decompose Me4NOH silicon alkoxide, and removing low-boiling-point substances by decompression to obtain light yellow viscous N-2-aminoethyl-3-aminopropyl methyl dimethoxy polysiloxane;
wherein D4The mass ratio of MM to tetramethylammonium hydroxide silicon alkoxide to KH550 is 45-55: 5-8: 1: 20-30;
the invention also comprises the application of the natural polysaccharide-polyphenol medical protective material in preparing antibacterial and bacteriostatic spray or medical protective coating.
Preferably, the antibacterial and bacteriostatic spray or the medical protective coating comprises the following components in parts by weight: 8-12 parts of a 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 hydrophilic modified natural polysaccharide; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin 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 stirring and mixing 8-12 parts by weight of the natural polysaccharide-polyphenol medical protective material and 25-30 parts by weight of deionized water uniformly, then spraying the mixture on the surface of a fabric uniformly, 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 the weight 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 the medical protective coating better.
The preferable preparation method of the medical protective coating comprises the following steps of uniformly stirring and mixing 8-12 parts by weight of the natural polysaccharide-polyphenol medical protective material, 25-30 parts by weight of deionized water and a plasticizer, uniformly spraying the mixture on the surface of a fabric, heating the fabric at 50-95 ℃ for 20-200 minutes, and drying the fabric by blowing air 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 medical protective product, such as woven fabric (e.g., cotton fiber, polyester fiber (PET)), nonwoven fabric (e.g., polypropylene (PP) spunbond nonwoven fabric, polypropylene (PP) meltblown nonwoven fabric, spunbond-meltblown-spunbond nonwoven fabric (SMS)), thin film material (e.g., polyethylene film (PE), polyurethane film (PU), polytetrafluoroethylene film (PTFE), thermoplastic polyurethane film (TPU), polyvinyl alcohol film (PVA)), and composite material thereof (e.g., PE/PP, PET/PTFE/PET, PET/PU/PET, PET/TPU/PET, PVA/PP), and even expanded to sponge products. The medical protective coating is suitable for medical protection and epidemic prevention products, and is particularly suitable for disposable or repeatedly used medical protective clothing, operating gowns and mask products.
The invention is further described with reference to specific examples.
The silane coupling agent KH550 in the embodiment of the invention is purchased from Nanjing Yude Hengzheng Fine chemical Co., Ltd, D4Purchased from Zhejiang Xinan chemical group Co., Ltd, MM purchased from Zhejiang Xinan chemical group Co., Ltd, and an alkaline catalyst such as tetramethylammonium hydroxide Me4NOH, etc. available from Beijing Ruichi chemical auxiliary Co., Ltd, MMH(Dihydrotetramethyldisiloxane) available from Wuhan Fine chemical Co., Ltd., Pt catalyst (H)2PtCl6·6H2O) purchased from the Shenyang nonferrous metals research 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 native polysaccharide; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin polyphenol; the mass ratio of the membranous matrix to the modified tannin-amino polysiloxane is 2: 9;
the natural polysaccharide-polyphenol medical protective material is prepared according to the following steps:
dissolving 1kg of tannic acid in 1kg of water, adding 0.2kg of 2, 3-epoxypropyltrimethylammonium chloride, heating to 75 ℃, carrying out condensation reflux reaction for 20 hours, cooling to room temperature, carrying out suction filtration, washing a filter cake with 600ml of water, collecting a lower clear liquid, adding isopropanol for precipitation, carrying out centrifugal separation on the precipitate at 1500rpm for 10 minutes, and carrying out vacuum drying on the obtained precipitate at 55-65 ℃ to obtain quaternized tannic acid;
synthesis of Aninoethylaminopropyl polysiloxane
4.5kg of D was added to the reaction vessel40.5kg MM and 0.1kg tetramethylammonium hydroxide siliconate (Me)4NOH silicon alkoxide) is introduced with nitrogen, at least 20 minutes are carried out, the mechanical stirring is carried out, the temperature is raised to 80-85 ℃, the equilibrium polymerization reaction is carried out for 2-3 hours, 2kg of KH550 is added, the reaction temperature is controlled to be 95-105 ℃, the equilibrium stirring is carried out for 8-10 hours, the reaction is completed, the temperature is rapidly raised until the reaction is completedDecomposing Me at 130-140 DEG C4NOH silicon alkoxide, removing low-boiling-point substances under reduced pressure to obtain yellowish viscous N-2-aminoethyl-3-aminopropyl methyl dimethoxy polysiloxane with molecular weight of 4.3 × 104；
Adding 1kg of the quaternized tannic acid obtained in the step I and 5kg of N-2-aminoethyl-3-aminopropyl methyl dimethoxy polysiloxane into 7kg of ethanol, then adding 10kg of Tris-HCl solution, stirring and reacting for 12 hours to obtain a reaction solution, performing suction filtration, washing a filter cake with distilled water and isopropanol in sequence, and performing vacuum drying on the filter cake at 50 ℃ to obtain modified tannic acid-amino polysiloxane;
③ uniformly dispersing 1kg of natural substance in 10L of isopropanol, stirring and dispersing for 30 minutes to obtain natural dispersion liquid, then slowly dripping 1.2kg of sodium hydroxide solution with the mass concentration of 25% into the natural dispersion liquid 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 filter cakes by 800ml of ethanol and 800ml of acetone in sequence, and freeze-drying the filter cakes to obtain white flocculent carboxymethyl substance;
wherein the chloroacetic acid-isopropanol solution is prepared from chloroacetic acid and isopropanol according to a mass-volume ratio of 1 g: 4ml of the composition;
fourthly, 200g of carboxymethyl obtained in the third step and 900g of modified tannic acid-amino polysiloxane obtained in the second step are added into 3.5kg of isopropanol, 1kg of Tris-HCl solution is added into the mixture, the mixture is stirred for 12 hours, filtered, a filter cake is washed by distilled water and isopropanol, and then the filter cake is dried in vacuum at 50 ℃ to obtain a natural polysaccharide-polyphenol medical protective material;
the hydrophilic modification may be a carboxymethyl group.
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 cellulose; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin polyphenol; the mass ratio of the membranous matrix to the modified tannin-amino polysiloxane is 4: 9.
the preparation method of the natural polysaccharide-polyphenol medical protective material comprises the following steps:
preparing a small molecular quaternary ammonium salt of formula IV:
weighing 200g of 1, 6-dibromohexane and 40g N, N-dimethyl N-octylamine, adding into a reaction kettle, stirring for reaction for 15 hours, adding 300g of isopropanol for precipitation, washing, and drying in vacuum to obtain the micromolecular quaternary ammonium salt shown in the formula IV, wherein the reaction equation is as follows:
dissolving 200g of the micromolecular quaternary ammonium salt of the formula IV obtained in the step I and 100g of bromodecane in 500g N, N-dimethyl amide to obtain a mixed solution for later use;
dissolving and dispersing 100g of tannic acid and 4g of potassium carbonate in 500g N, N-dimethyl amide under stirring, slowly adding the mixed solution obtained in the step II, controlling the temperature of a reaction system to be not more than 80 ℃ when adding the mixed solution, then carrying out condensation reflux reaction for 24 hours, cooling to room temperature, carrying out suction filtration, washing a filter cake with 100ml of water, collecting a lower layer clear solution, adding 500g of isopropyl ether for precipitation, carrying out centrifugal separation on the precipitate, and carrying out vacuum drying on the precipitate to obtain 276g of quaternized tannic acid;
preparing the double-end aminopropyl polysiloxane by a hydrosilylation method:
3.5kg of D4 and 0.5kg of MM were added to the reaction vesselHIntroducing nitrogen for at least 20 minutes, dropwise adding concentrated sulfuric acid into the reaction kettle, after dropwise adding, heating to 80-85 ℃ under mechanical stirring, carrying out equilibrium polymerization for 7-8 hours, after the reaction is finished, heating to 180 ℃, and removing low-boiling-point 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 at 70-75 ℃, stirring for 2-3 hours under equilibrium, and removing low-boiling-point substances under reduced pressure to obtain 2.6kg of faint yellow bi-terminal aminopropylpolysiloxane with the molecular weight Mw of 2.3 multiplied by 104；
Fifthly, adding 200g of quaternized tannic acid obtained in the third step and 1.6kg of aminopropylpolysiloxane at the second end into 5kg of methanol, adding 2kg of Tris-HCl solution into the methanol, stirring the mixture to react for 12 to 15 hours to obtain a reaction solution, performing suction filtration, washing a filter cake with distilled water and isopropanol in sequence, and performing vacuum drying on the filter cake at the temperature of between 50 and 60 ℃ to obtain 1.75kg of modified tannic acid-amino polysiloxane;
sixthly, uniformly dispersing 1kg of natural substance in 15L of isopropanol, stirring and dispersing for 60 minutes to obtain natural dispersion liquid, then slowly dripping 2L of 35% sodium hydroxide solution with mass concentration into the natural dispersion liquid for 5 times, stirring for 2 hours, heating to 60 ℃, adding 8kg of chloroacetic acid-isopropanol solution for several times while stirring, reacting for 10 hours, filtering, washing a filter cake with 500ml of ethanol and 500ml of acetone in sequence, and freeze-drying the filter cake to obtain 1.1kg of white flocculent carboxymethyl;
wherein the chloroacetic acid-isopropanol solution is prepared from chloroacetic acid and isopropanol according to a mass-volume ratio of 1 g: 5ml of the composition;
seventhly, adding 0.4kg of hydrophilic modification obtained in the step (c) and 0.9kg of modified tannic acid-amino polysiloxane obtained in the step (c) into 3.5kg of isopropanol, then adding 2kg of Tris-HCl solution into the obtained mixture, stirring the obtained mixture for 12 hours, carrying out suction filtration, washing a filter cake by using distilled water and isopropanol, and then carrying out vacuum drying at the temperature of 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 obtained by quaternization; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin polyphenol; the mass ratio of the membranous matrix to the modified tannin-amino polysiloxane is 3: 8.
the preparation method of the natural polysaccharide-polyphenol medical protective material comprises the following steps:
dissolving 1kg of tannic acid in 1.2kg of water, adding 5kg of 2, 3-epoxypropyltrimethylammonium chloride, heating to 75 ℃, carrying out condensation reflux reaction for 25 hours, cooling to room temperature, carrying out suction filtration, washing a filter cake with 600ml of water, collecting a lower clear liquid, adding isopropanol for precipitation, carrying out centrifugal separation on the precipitate at 1500rpm for 10 minutes, and carrying out vacuum drying on the obtained precipitate at 55-65 ℃ to obtain quaternized tannic acid;
(ii) side chain aminopropylpolysiloxane (molecular weight Mw: 3.7X 10)4) The preparation of (1):
adding 2kg of methylaminopropyldimethoxysilane and 10kg of deionized water into a reaction kettle, dropwise adding 1.2g of hydrochloric acid serving as a hydrolysis catalyst into the reaction kettle, and hydrolyzing at 80 ℃ for 2 hours to obtain a hydrolyzed polymer with a side chain containing aminopropyl;
4kg of D was added to the reaction vessel40.5kg MM and 0.1kg tetramethylammonium hydroxide siliconate (Me)4NOH silicon alkoxide) is filled with nitrogen, at least 20 minutes are carried out, the mechanical stirring is carried out, the temperature is increased to 80-85 ℃, the equilibrium polymerization reaction is carried out for 3 hours, 1.5kg of hydrolytic polymer with aminopropyl in the side chain is added, the reaction temperature is controlled to be 95-105 ℃, the equilibrium stirring is carried out for 10 hours, the reaction is completed, the temperature is rapidly increased to 130-140 ℃ to decompose Me4NOH silicon alkoxide, and removing low-boiling-point substances by decompression to obtain light yellow side chain aminopropyl polysiloxane;
thirdly, adding 0.5kg of quaternized tannic acid obtained in the step I and 3kg of side chain aminopropyl polysiloxane obtained in the step II into 10kg of isopropanol, then adding 6kg of Tris-HCl solution into the mixture, stirring the mixture for reaction for 13 hours to obtain reaction liquid, performing suction filtration, washing a filter cake with distilled water and isopropanol in sequence, and performing vacuum drying on the filter cake at 55 ℃ to obtain modified tannic acid-amino polysiloxane;
uniformly dispersing 1kg of natural ammonium chloride in 12L of isopropanol, stirring and dispersing for 40 minutes to obtain natural dispersion liquid, then slowly dripping 1.5L of sodium hydroxide with the mass concentration of 28% into the natural dispersion liquid for several times, stirring for 1.5 hours, heating to 54 ℃, adding 16kg of 2, 3-epoxypropyltrimethylammonium chloride-isopropanol solution for several times while stirring, reacting for 8-10 hours, filtering, washing a filter cake for 3 times by ethanol and acetone in sequence, and freeze-drying the filter cake to obtain white flocculent quaternized natural ammonium chloride;
wherein the 2, 3-epoxypropyltrimethyl ammonium chloride-isopropanol solution is prepared from 2, 3-epoxypropyltrimethyl ammonium chloride and isopropanol according to the mass-volume ratio of 1 g: 2ml of the composition;
fifthly, 0.3kg of quaternary ammonium obtained in the step (iv) and 0.8kg of modified tannic acid-amino polysiloxane obtained in the step (iv) are added into 2.8kg of isopropanol, then 1.2kg of Tris-HCl solution is added into the mixture, the mixture is stirred for 14 hours, the mixture is filtered, a filter cake is washed by distilled water and isopropanol, and then the mixture is dried in vacuum 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 obtained by quaternization; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin polyphenol; the mass ratio of the membranous matrix to the modified tannin-amino polysiloxane is 1: 2.
a preparation method of a natural polysaccharide-polyphenol medical protective material comprises the following steps:
preparation steps of modified tannic acid-amino polysiloxane the modified tannic acid-amino polysiloxane is obtained according to the method described in example 2, steps (i) to (v);
the method is obtained by the following steps:
uniformly dispersing 1kg of natural substance in 15L of isopropanol, stirring and dispersing for 50 minutes to obtain natural dispersion liquid, slowly dripping 2L of sodium hydroxide with the mass concentration of 30% into the natural dispersion liquid for 6 times, stirring for 1.5 hours, heating to 55 ℃, adding 20kg of 2, 3-epoxypropyltrimethylammonium chloride-isopropanol solution for several times under stirring, reacting for 8-10 hours, filtering, washing a filter cake for 3 times by ethanol and acetone in sequence, and freeze-drying the filter cake to obtain white flocculent quaternized natural substance;
wherein the 2, 3-epoxypropyltrimethyl ammonium chloride-isopropanol solution is prepared from 2, 3-epoxypropyltrimethyl ammonium chloride and isopropanol according to the mass-volume ratio of 1 g: 2.5 ml;
thirdly, adding 0.3kg of quaternized urea and 0.6kg of modified tannic acid-amino polysiloxane into 3kg of isopropanol, then adding 1.5kg of Tris-HCl solution, stirring for 14 hours, carrying out suction filtration, washing 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 and 250g of deionized water in the embodiment 1 are adopted to prepare a medical protective coating material 1, and 80g of the natural polysaccharide-polyphenol medical protective material, 250g of deionized water and 0.8g of glycerol in the embodiment 1 are adopted to prepare a medical protective coating material 2;
cutting a reusable medical protective clothing/operating clothing (the surface layer and the inner layer are made of polyester fibers, the middle sandwich is made of a microporous polyurethane film, 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 of each is 0.8mm) on the PET polyester fiber woven fabric on the surface layer, heating a flat plate to 80 ℃ for 15min, and drying by blowing to obtain the reusable medical protective clothing fabric subjected to coating treatment. Cutting a 10cm × 10cm coated fabric, performing high-temperature moist heat sterilization (at 134 ℃ for 4min), and testing the performances of the fabric without coating, with coating and after-treatment of the coating.
The results of testing the properties of the uncoated, coated and post-sterilization treated coated fabrics are shown in tables 1-1-1, tables 1-1-2, tables 1-2-1 and tables 1-2-2. The medical protective coating material 1 is coated in tables 1-1-1 and 1-1-2, the medical protective coating material 2 is coated in tables 1-2-1 and 1-2-2, the penetrability of the blood-borne pathogens is tested according to the YY/T0689 + 2008 method, the penetrability of the pollution-resistant liquid aerosol is tested according to the YY/T1799-2020 appendix B method, the penetrability of the wet microorganisms is tested according to the YY/T0506.6-2009 method, the water impermeability is tested according to the GB/T4744-2013 method, the antistatic property is tested according to the method specified in 7.2 in GB/T12703-1991, and the flame retardancy is tested according to the GB/T5455-2014 vertical method; the breaking strength-dry state and the breaking strength-wet state are tested according to the method GB/T3923.1-2013, the wear resistance is tested according to the methods GB/T21196.2-2007 and GB 2457-2009, and the flex damage resistance is tested according to the method GB/T12586-2003.
TABLE 1-1
Tables 1-1-2
TABLE 1-2-1
Tables 1-2
As can be seen from the data in tables 1-1-1, 1-1-2 and 1-2-1 and 1-2-2, after the PET/PU/PET fabric is sprayed with the natural polysaccharide-polyphenol medical protective material, the total number of microbe-bacteria colony resistance is obviously reduced, and the test data of pathogen penetrability of blood transmission resistance, pollutant liquid aerosol penetrability and microorganism penetrability in a damp state are shown, so that the capability of resisting pathogenic bacteria is better, the water permeability resistance is increased, the antistatic property is increased, and the flame retardant property is increased; and after the natural polysaccharide-polyphenol medical protective material is used and sterilized again, the coating still has good capability of defending germs, excellent water permeability resistance, antistatic property and flame retardant property, and the natural polysaccharide-polyphenol medical protective material is not only suitable for disposable medical protective clothing fabrics, but also suitable for repeatedly used medical protective clothing fabrics.
As can be seen from the comparison among tables 1-1-1, tables 1-1-2 and tables 1-2-1 and tables 1-2-2, the flexibility and antistatic property of the fabric are obviously improved after the glycerol is added as the plasticizer. The plasticizer such as glycerin can weaken the secondary valence bonds between polymer molecules, namely Van der Waals force, so that the mobility of the polymer molecular chains of the coating is increased, the crystallinity of the polymer molecular chains of the coating is reduced, namely the plasticity of the coating is increased, and the performances of breaking strength (including longitudinal direction and transverse direction) in a dry state and a wet state, abrasion resistance (counted by the number of cycles needed for generating damage) and flex damage resistance (counted by the number of cycles needed for generating damage in a warp direction and a weft direction) of the coating are improved. In addition, it has been found that similar effects can be obtained by replacing glycerin with stearate or sorbitol.
The medical protective coating material is prepared by adopting 120g of the natural polysaccharide-polyphenol medical protective material and 300g of deionized water in the embodiment 2, the fabric of the disposable operating coat/medical protective clothing (polyethylene film-coated polypropylene spun-bonded non-woven fabric material, PE/PP) is cut into 15cm multiplied by 15cm, the medical protective coating (50 mu m) is uniformly sprayed on the PE film on the surface layer, the flat plate is heated to 79 ℃ for 19min, and the coating is dried by blowing to obtain the coated fabric of the disposable medical protective clothing. The fabric properties were tested for uncoated, coated and post-coated treatments.
The results of testing the properties of the uncoated, coated fabrics are shown in table 2. The Bacterial Filtration Efficiency (BFE) is tested according to a GB19082-2009 method, the non-oily Particle Filtration Efficiency (PFE) is tested according to a GB19082-2009 method, the synthetic blood penetration resistance is tested according to a GB19082-2009 method, the antistatic property is tested according to a method specified by 7.2 in GB/T12703-1991, and the flame retardance is tested according to a GB/T5455-2014 vertical method.
TABLE 2
The results in table 2 show that after the natural polysaccharide-polyphenol medical protective material is coated on the PE/PP fabric, the filtration efficiency of bacteria is improved from the original 96.41% to 99.95%, the filtration efficiency of non-oily particles is improved to 100%, the penetration resistance of synthetic blood is improved, the antibacterial effect is remarkable, and the natural polysaccharide-polyphenol medical protective material has better antistatic property and flame retardant property.
Preparing a medical protective coating material by adopting 90g of the natural polysaccharide-polyphenol medical protective material obtained in the example 3 and 260g of deionized water, and preparing a medical protective coating material 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 surgical mask (polypropylene spun-bonded non-woven fabric-polypropylene melt-blown non-woven fabric-polypropylene spun-bonded non-woven fabric, PP-SMS) fabric 9cm multiplied by 7cm, uniformly spraying the medical protective coating material (0.5mm) on the PP spun-bonded non-woven fabric on the blue surface layer, heating a flat plate to 69 ℃ for 16min, and drying by blowing to obtain the surgical mask fabric subjected to coating treatment.
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 that of the detection item in Table 2.
TABLE 3
The results in table 3 show that the natural polysaccharide-polyphenol medical protective material of the invention, after being coated on a PP-SMS fabric, has the advantages of significantly improved bacterial filtration efficiency, improved filtration efficiency of non-oily particles, improved anti-penetration of synthetic blood, significant antibacterial effect, and better antistatic property and flame retardant property, so that the natural polysaccharide-polyphenol medical protective material of the invention has excellent protective property and application prospect.
The natural polysaccharide-polyphenol medical protective material is prepared into an antibacterial and bacteriostatic spray for carrying out bacteriostatic performance detection. The process is as follows:
an LB (Luria-Bertani) culture medium is prepared by 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 culture medium to 7.2 +/-0.1, heating for fully dissolving, subpackaging in conical flasks, sealing with a plug, and sterilizing at 121 ℃ for 25 min.
A potato glucose agar culture medium is prepared by cleaning potato, peeling, cutting, weighing 200g potato pieces, adding 1000mL distilled water, boiling for 0.5h, tearing with a glass rod, filtering, adding distilled water into the filtrate to 1000mL, adding 20.0g agar and 20.0g glucose, subpackaging in conical bottles, sealing with plugs, and sterilizing at 121 deg.C for 25 min. Cooling to 60 deg.C, pouring into a sterile workbench, cooling, solidifying, and coating with activated bacteria liquid (Escherichia coli, Staphylococcus aureus, Fusarium fungi liquid, and self-made culture in laboratory).
The natural polysaccharide-polyphenol medical protective material of the embodiment 1-4 is used for preparing an antibacterial and bacteriostatic spray, and the composition is shown in table 4:
TABLE 4
Preparing the spray agent 1-8 into a film (the thickness is 0.55mm), punching the film into a circular film with the diameter of 6mm by using a puncher, sterilizing, drying, operating in an aseptic workbench, uniformly coating three test bacteria in a culture dish containing an LB culture medium and a potato glucose agar culture medium respectively, attaching a spare film sample and a blank sample to the culture medium coated with the strains by using an aseptic ophthalmic forceps, culturing the LB culture medium for 24 hours at 37 ℃, culturing the potato culture medium for 36 hours at 30 ℃, observing, measuring and recording the size of a bacteriostatic ring, wherein the test results are shown in the following table 5.
TABLE 5
The results in table 5 show that the spray film has a certain bacteriostatic action on escherichia coli, staphylococcus aureus and fusarium, and the bacteriostatic action on fusarium and staphylococcus aureus is slightly higher than that of escherichia coli.
Claims (9)
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 obtained by hydrophilic modification; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2-4: 2-9;
the hydrophilic modification may be either carboxymethyl or quaternized.
2. The method for preparing the natural polysaccharide-polyphenol medical protective material as claimed in claim 1, is characterized in that: the method comprises the following steps:
quaternizing tannic acid to obtain quaternized tannic acid;
adding the quaternized tannic acid and amino modified polysiloxane obtained in the step one into organic alcohol, adding a Tris-HCl solution into the organic alcohol, stirring the mixture to react for 12 to 15 hours to obtain a reaction solution, performing suction filtration, washing a filter cake with distilled water and isopropanol in sequence, and performing vacuum drying on the filter cake at the temperature of between 50 and 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;
the organic alcohol is methanol, ethanol or isopropanol;
thirdly, adding the modified tannic acid-amino polysiloxane obtained in the second step into first isopropanol, then adding a Tris-HCl solution into the first isopropanol, stirring the mixture for 12 to 15 hours, carrying out suction filtration, washing 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 hydrophilic modified polysiloxane, modified tannin-amino polysiloxane, first isopropanol and Tris-HCl solution is (2-4): 2-9: 25-35: 10-20;
the hydrophilic modification may be either carboxymethyl or quaternized.
3. The method for preparing the natural polysaccharide-polyphenol medical protective material as claimed in claim 2, wherein the method comprises the following steps: the specific process of the step I is as follows:
dissolving tannic acid in water, adding 2, 3-epoxypropyl trimethyl ammonium chloride, heating to 75-80 ℃, condensing, refluxing and reacting for 20-25 hours, cooling to room temperature, performing suction filtration, washing a filter cake with water, collecting a lower clear liquid, adding isopropanol for precipitation, performing centrifugal separation on a precipitate, and performing vacuum drying on the precipitate to obtain quaternized tannic acid; wherein the mass ratio of the tannic acid to the 2, 3-epoxypropyltrimethylammonium chloride is 1: 0.2 to 5.
4. The method for preparing the natural polysaccharide-polyphenol medical protective material as claimed in claim 2, wherein the method comprises the following steps: the specific process of the step I 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 drying in vacuum to obtain micromolecular quaternary ammonium salt; dissolving small molecular quaternary ammonium salt and bromodecane in N, N-dimethyl amide 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;
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-dimethyl amide, stirring, slowly adding the mixed solution obtained in the step A, controlling the temperature of a reaction system to be not more than 80 ℃ when 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 lower clear solution, adding isopropyl ether for precipitation, performing centrifugal separation on the precipitate, and performing vacuum drying on the precipitate to obtain quaternized tannic acid;
the mass ratio of the micromolecular quaternary ammonium salt, the tannic acid and the potassium carbonate in the mixed solution is 10: 5-8: 0.2 to 5.
5. The method for preparing the natural polysaccharide-polyphenol medical protective material as claimed in claim 2, wherein the method comprises the following steps: the amino modified polysiloxane is side chain aminopropyl polysiloxane, bi-terminal aminopropyl polysiloxane or side chain N- (2-aminoethyl) -3-aminopropyl polysiloxane.
6. The method for preparing the natural polysaccharide-polyphenol medical protective material as claimed in claim 3, wherein the method comprises the following steps: the amino modified polysiloxane is shown as a formula I, a formula II or a formula III:
in the formula I, the formula II or the formula III, n is 100-650, and m is 100-800.
7. The use of the natural polysaccharide-polyphenol medical protective material of claim 1, which is characterized in that: the application in preparing antibacterial and bacteriostatic spray or medical protective coating.
8. The use of the natural polysaccharide-polyphenol medical protective material as claimed in claim 7, wherein: the antibacterial and bacteriostatic spray or the medical protective coating comprises the following components in parts by weight: 8-12 parts of a 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 hydrophilic modified natural polysaccharide; the modified tannin-amino polysiloxane is amino polysiloxane coordinated by quaternization tannin polyphenol; the mass ratio of the membranous matrix to the modified tannic acid-amino polysiloxane is 2-4: 2 to 9.
9. The use of the natural polysaccharide-polyphenol medical protective material as claimed in claim 8, 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 true CN114032695A (en) | 2022-02-11 |
| CN114032695B 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 (9)
| 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 |
| US20180016445A1 (en) * | 2016-07-12 | 2018-01-18 | The University Of Massachusetts | Crosslinked phenolic compound, method of forming, and polymer composition containing the same |
| 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 |
-
2021
- 2021-10-19 CN CN202111214885.1A patent/CN114032695B/en active Active
Patent Citations (9)
| 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 |
| US20180016445A1 (en) * | 2016-07-12 | 2018-01-18 | The University Of Massachusetts | Crosslinked phenolic compound, method of forming, and polymer composition containing the same |
| 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 |
|---|---|
| CN114032695B (en) | 2023-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Luo et al. | Polymeric antibacterial materials: Design, platforms and applications | |
| DE69126972T2 (en) | USE OF AN ANTIBACTERIAL ACTIVE SUBSTANCE CONTAINING A POLYELECTROLYTE COMPLEX AND ANTIBACTERIAL MATERIAL | |
| CN109293948B (en) | Hydrogel and preparation method and application thereof | |
| US20090320849A1 (en) | Anti-Viral Face Mask and Filter Material | |
| JP6858330B2 (en) | Antiviral material | |
| CN112007426B (en) | Preparation method of high-performance mesoporous silica-chitosan composite antibacterial filter sheet | |
| CN110306340B (en) | Antibacterial natural textile material with surface modified borneol and preparation method and application thereof | |
| CN114908562B (en) | Antibacterial antiviral agent, preparation method thereof and antibacterial antiviral mask | |
| EP1830639B1 (en) | Antimicrobial and antiviral product | |
| US20240237765A1 (en) | Antibacterial and antiviral degradable mask and manufacturing method thereof | |
| CN114032695A (en) | Natural polysaccharide-polyphenol medical protective material and preparation method and application thereof | |
| CN102061614B (en) | Dual mode high-efficiency antibacterial and antiviral adsorbing material | |
| CN111235871A (en) | Antiviral filter layer prepared from copper-containing chitosan fiber and application thereof | |
| CN105624920B (en) | A kind of high antibacterial, the novel slightly soluble non-woven fabrics for adsorbing heavy metal molecule | |
| CN112962324B (en) | Preparation method of graphene oxide/nano-silver composite coating non-woven material | |
| CN105755673A (en) | Manufacturing method for antibacterial high selectivity nanofiber membrane | |
| CN111155177B (en) | Electrostatic spinning antiviral thin layer and application thereof in antiviral field | |
| JP2022177994A (en) | Protective non-woven and woven fabric manufacturing methods and protective articles | |
| CN114318569A (en) | Antibacterial breathable fabric, preparation method thereof and underpants | |
| CN113840552A (en) | Method for manufacturing antiviral fiber product and antiviral mask manufactured by using same | |
| CN111138828A (en) | A thin-layer material with both disinfecting and filtering functions and its application in the field of anti-virus | |
| WO2022034494A1 (en) | Anti-viral biodegradable modified polysaccharides | |
| KR20220011426A (en) | Antispray Face Mask with Natural Antibacterial Substances and Method of Manufacturing the Same | |
| CN111607977A (en) | A kind of antibacterial and antiviral leather and its preparation method and application | |
| CN111171549B (en) | A kind of selectively permeable anti-virus thin layer material and its application in the field of anti-virus |
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 |