CN114351444B - Antibacterial non-woven fabric and preparation method thereof - Google Patents
Antibacterial non-woven fabric and preparation method thereof Download PDFInfo
- Publication number
- CN114351444B CN114351444B CN202210118712.8A CN202210118712A CN114351444B CN 114351444 B CN114351444 B CN 114351444B CN 202210118712 A CN202210118712 A CN 202210118712A CN 114351444 B CN114351444 B CN 114351444B
- Authority
- CN
- China
- Prior art keywords
- woven fabric
- parts
- polylactic acid
- antibacterial
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 126
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004626 polylactic acid Substances 0.000 claims abstract description 79
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 78
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 65
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- -1 zeolite imidazole ester Chemical group 0.000 claims abstract description 29
- 229920001690 polydopamine Polymers 0.000 claims abstract description 24
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 13
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 13
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 13
- 239000003599 detergent Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 13
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000006750 UV protection Effects 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 5
- 229910052711 selenium Inorganic materials 0.000 description 34
- 239000011669 selenium Substances 0.000 description 34
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 33
- 239000002105 nanoparticle Substances 0.000 description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- 239000004744 fabric Substances 0.000 description 19
- 239000000835 fiber Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000813 microbial effect Effects 0.000 description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000000670 limiting effect Effects 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
- 241000894006 Bacteria Species 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- 229920000388 Polyphosphate Polymers 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001205 polyphosphate Substances 0.000 description 6
- 235000011176 polyphosphates Nutrition 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 210000000170 cell membrane Anatomy 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000034994 death Effects 0.000 description 4
- 231100000517 death Toxicity 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 244000052769 pathogen Species 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 241001116389 Aloe Species 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 235000011399 aloe vera Nutrition 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000018102 proteins Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- ZKHQWZAMYRWXGA-KQYNXXCUSA-J ATP(4-) Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-J 0.000 description 2
- ZKHQWZAMYRWXGA-UHFFFAOYSA-N Adenosine triphosphate Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(=O)OP(O)(=O)OP(O)(O)=O)C(O)C1O ZKHQWZAMYRWXGA-UHFFFAOYSA-N 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000124008 Mammalia Species 0.000 description 2
- 102000008114 Selenoproteins Human genes 0.000 description 2
- 108010074686 Selenoproteins Proteins 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- ICFDARKVIMXWIR-UHFFFAOYSA-N [Co].[Se]=O Chemical class [Co].[Se]=O ICFDARKVIMXWIR-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 230000005778 DNA damage Effects 0.000 description 1
- 231100000277 DNA damage Toxicity 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 208000010428 Muscle Weakness Diseases 0.000 description 1
- 206010049565 Muscle fatigue Diseases 0.000 description 1
- 206010028372 Muscular weakness Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000001266 bandaging Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 210000004962 mammalian cell Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- FJQXCDYVZAHXNS-UHFFFAOYSA-N methadone hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(CC(C)N(C)C)(C(=O)CC)C1=CC=CC=C1 FJQXCDYVZAHXNS-UHFFFAOYSA-N 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The invention discloses an antibacterial non-woven fabric and a preparation method thereof. The preparation method of the antibacterial non-woven fabric comprises the following steps: firstly, washing polylactic acid non-woven fabric by using a detergent, then, preparing a mixed solution by adopting ammonium polyphosphate, tris (hydroxymethyl) aminomethane and polydopamine, pretreating the polylactic acid non-woven fabric in the mixed solution, and then, carrying out chemical grafting reaction with zeolite imidazole ester skeleton-67 and selenium dioxide to prepare the antibacterial non-woven fabric. Compared with the prior art, the antibacterial non-woven fabric prepared by the invention has the characteristics of biodegradability, and the characteristics of antibacterial property, ultraviolet resistance, flame retardance and durability of the polylactic acid non-woven fabric are enhanced.
Description
Technical Field
The invention relates to the technical field of textile, in particular to an antibacterial non-woven fabric and a preparation method thereof.
Background
Nonwoven fabrics play a vital role in life from clothing accessories, bedding, facial masks, tissues to bandaging materials and wound dressings. The non-woven fabric is also called non-woven fabric, and compared with the traditional textile fabric, the non-woven fabric does not need procedures of spinning, spooling, weaving and the like, but is formed by forming a fiber net structure by directional or random fibers or filaments through random arrangement and processing through melt blowing, needling or other mechanical and chemical methods; the non-woven fabric has the advantages of simpler processing technology, faster efficiency, short process flow, fast production rate, high yield, low cost, wide application, multiple raw material sources and the like, and is called the fabric because of the appearance and certain properties of the fabric. The non-woven fabric has the characteristics of ventilation, moisture retention, flexibility, light weight, easy decomposition, low price, recycling and the like, can lead to the enrichment of nutrient components in the non-woven fabric, and the wet climatic environment after moisture absorption of the non-woven fabric is very suitable for the growth and propagation of germ microorganisms. With the development of society, the requirements of people on the antibacterial property, the comfort, the fashion and the like of non-woven fabrics are continuously improved along with the improvement of the living material level, and particularly, the non-woven fabric with the antibacterial property is important in the medical field. The non-woven fabric material can be used as a host and a carrier for transmitting germ microorganisms. It is estimated that in europe, about 410 tens of thousands of patients are infected at least once a year with pathogens, leading directly to 3.7 tens of thousands of deaths and 11 additional tens of thousands of deaths per year. In addition, the abuse of antibiotics leads to the occurrence of drug resistance of pathogens, so that the viability of the pathogens is stronger, and the development of an antibacterial non-woven fabric has important significance.
With the development of antibacterial technology, some inorganic nanoparticles such as silver, copper and zinc have been applied to nonwoven fabrics against drug-resistant pathogens. The metal nano particles inhibit the growth and reproduction of bacteria by inhibiting the activity of protein, and the inhibition mode is different from antibiotics, so that the bacteria are not easy to generate drug resistance. Silver nano-particles have strong broad-spectrum antibacterial activity, are one of the most widely used antibacterial inorganic nano-particles at present, and are widely used in cosmetics, textiles, pharmacy and medical products. However, silver nanoparticles have been classified as a carcinogen in the united states, mainly because silver nanoparticles have a certain toxicity to mammalian cells and have an adverse effect on the environment, and thus development of a nonwoven fabric having high antibacterial properties, which is harmless to the human body, is urgently required.
To impart antibacterial properties to a nonwoven fabric, CN110978662a discloses a method for preparing an antibacterial nonwoven fabric, which comprises the steps of: soaking pure cotton cloth in aloe juice with viscosity of 1-5 cP to adsorb aloe; drying pure cotton cloth adsorbed with aloe juice in a drying chamber; heating the first side of the non-woven fabric to 150-160 ℃ to soften the first side of the non-woven fabric; placing the dried pure cotton cloth between two non-woven fabric surface layers softened on the first surface; extruding the two non-woven fabrics to enable the dried pure cotton cloth to be embedded into the softened surfaces of the two non-woven fabrics, and enabling the two non-woven fabrics to be bonded together to form a combined non-woven fabric; coating the front side and the back side of the combined non-woven fabric with antibacterial liquid with the viscosity of 10cP to 30 cP; and (3) airing the non-woven fabric coated with the antibacterial liquid to obtain the antibacterial non-woven fabric. The prepared antibacterial non-woven fabric has long antibacterial time, high stability, adopts natural antibacterial components, and is nontoxic and harmless. The antibacterial requirement of the special field on the non-woven fabric is met. However, the method only simply coats the natural antibacterial agent on the surface of the non-woven fabric, so that the antibacterial components are easy to fall off, and the fabric is three-layer composite, has larger thickness and has rough hand feeling.
Publication No. CN111379161A relates to a preparation method of silver ion antibacterial non-woven fabric. The preparation method of the silver ion antibacterial non-woven fabric comprises the following steps: preparing an antibacterial finishing agent, performing after-finishing treatment on the non-woven fabric by using the antibacterial finishing agent, and drying at 115-125 ℃ to obtain the finished product; the antibacterial finishing agent is an aqueous solution containing 0.1-15% of silver ion antibacterial agent. The preparation method is simple, can ensure that the non-woven fabric has an antibacterial effect, and expands the application range of the non-woven fabric. However, the method for bonding the silver ion antibacterial agent by adopting water-soluble starch has the defects of rough fabric hand feeling, weak antibacterial property and high toxicity.
The publication number CN108486875A discloses an antibacterial non-woven fabric for medical and health, and a preparation method and application thereof, wherein the antibacterial non-woven fabric for medical and health is obtained by immersing the non-woven fabric in an antibacterial finishing liquid and drying. According to the antibacterial non-woven fabric for medical and health, a large amount of researches are carried out on the preparation process, and proper raw materials are selected to prepare the non-woven fabric with a broad-spectrum antibacterial function, and the material has antibacterial and bactericidal capabilities and can be well used for medical products such as surgical gowns, protective gowns, masks and the like; soft hand feeling, broad antibacterial spectrum, lasting antibacterial performance, safety and reliability, meets the requirements of surgical gowns, has the performances of antibacterial, ventilation, radiation protection, comfortable wearing and the like, and has wide application prospect. But the non-woven fabric antibacterial agent is prepared from 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione and 2-chloro-4- (4-sulfoanilino) -6- (3-hydroxypropyl-5, 5-dimethyl hydantoin) -1,3, 5-triazine according to the mass ratio of 1: (2-3), which has a certain toxicity and has the problems of complex preparation process and high cost.
Disclosure of Invention
In view of the defects of poor hand feeling, high toxicity and unstable antibacterial performance of the fabric in the prior art, the invention aims to solve the technical problems that the polylactic acid non-woven fabric is pretreated by adopting ammonium polyphosphate, tris (hydroxymethyl) aminomethane and polydopamine, and then chemical grafting reaction is carried out between the polylactic acid non-woven fabric and a zeolite imidazole ester skeleton-67 and selenium dioxide to construct the antibacterial non-woven fabric.
The preparation method of the antibacterial non-woven fabric comprises the following steps of:
step 1, mixing ammonium polyphosphate and tris (hydroxymethyl) aminomethane with water, adjusting the temperature of a mixed solution to 60-80 ℃, and stirring and reacting for 20-50 min to prepare a reaction solution; adjusting the pH value to 8.0-9.0 by using 0.01-0.3 mol/L sodium hydroxide aqueous solution; then adding polydopamine into the reaction solution to obtain a pretreatment solution;
step 2, washing the polylactic acid non-woven fabric with a detergent for 1-4 times; then immersing the mixture in the pretreatment solution prepared in the step 1, adjusting the temperature of the solution to be 20-25 ℃ and reacting for 15-30 h; drying the immersed polylactic acid non-woven fabric at 60-90 ℃ for 1-3 hours to obtain a pretreated polylactic acid non-woven fabric;
step 3, mixing zeolite imidazole ester skeleton-67, selenium dioxide, 30-50wt% ammonia water, cobalt nitrate hexahydrate, a curing agent and methanol to prepare a mixed solution; immersing the pretreated polylactic acid non-woven fabric prepared in the step (2) in a mixed solution, and circularly performing padding treatment in the mixed solution; then standing for 6-15 h, cleaning for 1-4 times by using a detergent, and drying for 1-5 h at 60-90 ℃ to obtain the antibacterial non-woven fabric.
Preferably, the components in the step 1 are calculated in parts by weight: 8-15 parts of ammonium polyphosphate, 10-30 parts of tris (hydroxymethyl) aminomethane, 200-500 parts of water and 3-10 parts of polydopamine.
Preferably, the components in the step 2 are calculated in parts by weight: 10-30 parts of polylactic acid non-woven fabric and 60-100 parts of pretreatment solution prepared in the step 1.
Preferably, the gram weight of the polylactic acid non-woven fabric in the step 2 is 150-500 g/m 2 。
Preferably, the detergent in the step 2 or the step 3 is one of 60-80 wt% ethanol water solution and 70-85 wt% methanol water solution.
Preferably, in the step 3, each component is calculated in parts by weight: 10 to 30 parts of zeolite imidazole ester skeleton-67, 1 to 5 parts of selenium dioxide, 10 to 30 parts of 40wt% ammonia water, 0.3 to 1.2 parts of cobalt nitrate hexahydrate, 0.8 to 1.6 parts of curing agent, 40 to 80 parts of methanol and 10 to 30 parts of pretreated polylactic acid non-woven fabric prepared in the step 2.
Preferably, the curing agent in the step 3 is formed by combining one or two or more of 2-methylimidazole, methyltetrahydrophthalic anhydride and isophorone diisocyanate.
Preferably, the padding treatment in the step 3 has the following process parameters: the pressurizing pressure is 0.6-1.2 kg/cm 2 The axial speed of the double roller is 1-4 m/min, and the padding treatment time is 2-8 h.
Selenium nanoparticles are of interest because of their anti-tumor and antioxidant properties. Selenium is a trace element essential to the human body, and the lack of selenium causes health problems such as weakening of the immune system, muscle weakness and fatigue, while high concentrations of selenium have much lower toxicity to mammals than silver. Selenium nanoparticles have been found to be extremely low toxic to mammals by in vitro and in vivo studies compared to other forms of selenium, and unlike metallic nanoparticles such as silver and copper, elemental selenium is generally considered insoluble in aqueous environments and can be converted to organic forms (e.g., selenoaminoacids and selenoproteins) by interactions with microorganisms. Selenium can replace sulfur-containing amino acids such as cysteine and methionine due to chemical similarity. Excessive selenoprotein can lead to the creation of lesions, causing DNA damage, altered protein structure and enzyme dysfunction. However, the presence of some stabilizers on the particle surface may result in insufficient interactions between the nanoparticle and bacterial cells, thus impeding their antimicrobial activity, and thus combining with the metal framework material becomes an effective antimicrobial treatment. In the patent, a method is developed, a large number of hydroxyl functional groups are grafted on a polylactic acid chain through modification, a large number of sites are provided for the interaction between ions, and selenium dioxide is added on the surface of the cationized polylactic acid to prepare the selenium nanoparticle in situ.
Polylactic acid (PLA) is a typical renewable and biodegradable polymer extracted from plant resources, and has wide application prospects in the fields of indoor decoration, agriculture, clothing, sanitation, protection devices and the like. The novel polylactic acid fiber is an important supplement to biodegradable fabrics such as natural cotton, hemp, silk and the like, and still has some problems to be solved. Melt droplets of polylactic acid during combustion are the most prominent problem, and there is a problem of easy nourishment of bacteria, and uv resistance and antibacterial properties are often required in commercial applications. Therefore, the polylactic acid non-woven fabric is modified and grafted to improve the comprehensive performance of the polylactic acid non-woven fabric. The tris (hydroxymethyl) aminomethane polyphosphate and polydopamine can effectively improve the external structure of polylactic acid fibers and increase the grafting rate and the fireproof performance of the metal organic frame. Through atomic layer deposition, in-situ growth and other methods, zeolite imidazole ester skeleton-67 and selenium dioxide material are added to react on the polylactic acid non-woven fabric, and finally the zeolite imidazole ester skeleton-67 and the reduced selenium nano particles are combined with each other, so that the polylactic acid non-woven fabric has the functions of oil-water separation, adsorption, catalysis, antibiosis and the like.
Firstly, removing impurities on the surface of polylactic acid by adopting a detergent, then, pretreating the polylactic acid non-woven fabric by adopting ammonium polyphosphate and tris (hydroxymethyl) aminomethane for polymerization and adding polydopamine, generating more hydroxyl groups and cations on the surface of the polylactic acid, enhancing the in-situ growth of zeolite imidazole ester skeleton-67, reducing selenium dioxide into selenium nano particles in a mixed solution, and mixing and grafting the selenium nano particles with the in-situ grown zeolite imidazole ester skeleton-67 to prepare the antibacterial, ultraviolet-resistant and flame-retardant degradable polylactic acid non-woven fabric.
The tris (hydroxymethyl) aminomethane polyphosphate and polydopamine contain a large number of phenolic hydroxyl groups and nitrogen-containing groups, have strong adsorption capacity on various heavy metal ions, and catechol and amino functional groups on polydopamine can form coordination bonds with a zeolite imidazole ester skeleton-67 and an empty valence electron orbit of selenium nano particles to generate covalent and non-covalent interactions, and in addition, polydopamine also has certain reducibility, and can reduce selenium dioxide into the selenium nano particles. In the invention, the polydopamine is introduced to strengthen the combination of polylactic acid fiber, zeolite imidazole ester skeleton-67 and selenium nano particles, so as to prevent the functional material from falling off in the subsequent use process. When selenium nano-particles and zeolite imidazole ester skeleton-67 contact the microbial cell membrane, the selenium nano-particles and zeolite imidazole ester skeleton-67 are attracted by the micro-dynamic effect coulomb force due to the negative charge of the cell membrane, and then penetrate the cell membrane and enter the microbial body to be solidified through the reaction of sulfhydryl groups on protein, so that the activity of microbial synthase is destroyed, the synthesis of microbial DNA is disturbed, the death of the microorganism is finally caused, and the bacteria are difficult to simultaneously evolve drug resistance to the actions. Meanwhile, the super-hydrophobicity and the self-cleaning performance of the composite fabric are endowed.
The zeolite imidazole ester skeleton-67 and selenium nano-particle composite has synergistic effect, and the zeolite imidazole ester skeleton-67 is degraded into cobalt oxide (CoO, co) at high temperature 2 O 3 、Co 3 O 4 And the like), selenium dioxide can be generated by the selenium nano particles, the cobalt selenium oxides are gathered on the surface of the carbon layer and form a thermal oxidation stable barrier with polylactic acid, the flame retardant property of the polylactic acid non-woven fabric can be enhanced, and molten liquid drops are eliminated. In the carbonization process, the oxide catalytic pyrolysis product forms a condensation coke layer, which is also helpful for reducing smoke release, oxide clusters formed by carbonization are inlaid on the surface, a compact coke layer structure is favorable for inhibiting heat conduction, preventing further entry of heat and oxygen, improving the thermal stability of the coke layer, and the formed carbon layer structure protects further pyrolysis of polylactic acid by preventing mass transfer and heat transfer of a polylactic acid matrix.
The addition of the zeolite imidazole ester skeleton-67 and the selenium nanoparticle composite material improves the ultraviolet resistance of the polylactic acid. The in-situ grown zeolite imidazole ester skeleton-67 is combined with selenium nanoparticle crystals to cover the surface of the fiber and fill in certain gaps of the fiber, and can reflect and scatter ultraviolet rays. In addition, the excellent ultraviolet resistance can prevent the oxidative degradation of the polylactic acid fiber, and the service life and the economic value are improved.
Due to the adoption of the technical scheme, compared with the prior art, the preparation method of the antibacterial non-woven fabric has the advantages that: 1) The polylactic acid non-woven fabric prepared by taking polylactic acid fibers as a matrix has the characteristic of biodegradability. 2) The external structure of the polylactic acid fiber can be effectively improved by adopting ammonium polyphosphate, tris (hydroxymethyl) aminomethane and polydopamine, the grafting rate of the metal organic framework and the selenium nano particles is increased, and the antibacterial, anti-ultraviolet and flame-retardant properties of the polylactic acid non-woven fabric are endowed. 3) The metal organic framework and the selenium nano particles are grafted onto the polylactic acid non-woven fabric in a chemical bond mode, and the prepared antibacterial non-woven fabric has the advantages of stable function and high durability.
Detailed Description
The sources of the main raw materials in the examples:
tris (hydroxymethyl) aminomethane: wuhan Kamick technologies Co., ltd., CAS number: 77-86-1.
Polydopamine: siankafuo Biotechnology Co., ltd., particle size: 300-400 nm.
Zeolite imidazole ester framework-67: sianaruixi Biotech Co., ltd., purity: 95%.
Selenium dioxide: shandong polymer chemical Co., ltd., appearance: white shiny needle crystals, CAS no: 7446-08-4.
Cobalt nitrate hexahydrate: shandong Denno New Material technologies Co., ltd., molecular weight: 291.03, cas No.: 10026-22-9.
2-methylimidazole: jinan Hui jin Chuan chemical Co., ltd., CAS number: 693-98-1.
Example 1
The preparation method of the antibacterial non-woven fabric comprises the following steps of:
step 1, mixing 12 parts of ammonium polyphosphate, 20 parts of tris (hydroxymethyl) aminomethane and 300 parts of water, adjusting the temperature of a mixed solution to 70 ℃, and stirring and reacting for 30 minutes by using a magnetic stirrer to prepare a reaction solution; adjusting the pH to 8.5 by using 0.1mol/L sodium hydroxide aqueous solution; then 7 parts of polydopamine is added into the reaction solution to obtain a pretreatment solution;
step 2, 20 parts of the mixture are weighed to 300g/m 2 Washing polylactic acid non-woven fabric with 70wt% ethanol water solution for 3 times; then immersing in 80 parts of the pretreatment solution prepared in the step 1, adjusting the temperature of the solution to 22 ℃, and reacting for 20 hours; drying the impregnated polylactic acid non-woven fabric at 80 ℃ for 2 hours to obtain a pretreated polylactic acid non-woven fabric;
step 3, 20 parts of zeolite imidazole ester skeleton-67, 3 parts of selenium dioxide, 20 parts of 40wt% ammonia water, 0.85 part of cobalt nitrate hexahydrate,1.25 parts of 2-methylimidazole and 60 parts of methanol are mixed to prepare a mixed solution; immersing 20 parts of the pretreated polylactic acid non-woven fabric prepared in the step 2 in the mixed solution; padding the mixed solution by adopting double roll shaft circulation, wherein the padding pressure is 0.9kg/cm 2 The axial speed of the double roller is 2m/min, and the padding treatment time is 5h; then standing for 12h, cleaning with 70wt% ethanol water solution for 3 times, and drying for 3h at 80 ℃ in a vacuum oven to obtain the antibacterial non-woven fabric.
Example 2
The preparation method of the antibacterial non-woven fabric comprises the following steps of:
step 1, mixing 12 parts of ammonium polyphosphate, 20 parts of tris (hydroxymethyl) aminomethane and 300 parts of water, adjusting the temperature of a mixed solution to 70 ℃, and stirring and reacting for 30 minutes by using a magnetic stirrer to prepare a reaction solution; adjusting the pH to 8.5 by using 0.1mol/L sodium hydroxide aqueous solution; then 7 parts of polydopamine is added into the reaction solution to obtain a pretreatment solution;
step 2, 20 parts of the mixture are weighed to 300g/m 2 Washing polylactic acid non-woven fabric with 70wt% ethanol water solution for 3 times; then immersing in 80 parts of the pretreatment solution prepared in the step 1, adjusting the temperature of the solution to 22 ℃, and reacting for 20 hours; drying the impregnated polylactic acid non-woven fabric at 80 ℃ for 2 hours to obtain a pretreated polylactic acid non-woven fabric;
step 3, mixing 3 parts of selenium dioxide, 20 parts of 40wt% ammonia water, 0.85 part of cobalt nitrate hexahydrate, 1.25 parts of 2-methylimidazole and 60 parts of methanol to prepare a mixed solution; immersing 20 parts of the pretreated polylactic acid non-woven fabric prepared in the step 2 in the mixed solution; padding the mixed solution by adopting double roll shaft circulation, wherein the padding pressure is 0.9kg/cm 2 The axial speed of the double roller is 2m/min, and the padding treatment time is 5h; then standing for 12h, cleaning with 70wt% ethanol water solution for 3 times, and drying for 3h at 80 ℃ in a vacuum oven to obtain the antibacterial non-woven fabric.
Example 3
The preparation method of the antibacterial non-woven fabric comprises the following steps of:
step 1, mixing 12 parts of ammonium polyphosphate, 20 parts of tris (hydroxymethyl) aminomethane and 300 parts of water, adjusting the temperature of a mixed solution to 70 ℃, and stirring and reacting for 30 minutes by using a magnetic stirrer to prepare a reaction solution; adjusting the pH to 8.5 by using 0.1mol/L sodium hydroxide aqueous solution; then 7 parts of polydopamine is added into the reaction solution to obtain a pretreatment solution;
step 2, 20 parts of the mixture are weighed to 300g/m 2 Washing polylactic acid non-woven fabric with 70wt% ethanol water solution for 3 times; then immersing in 80 parts of the pretreatment solution prepared in the step 1, adjusting the temperature of the solution to 22 ℃, and reacting for 20 hours; drying the impregnated polylactic acid non-woven fabric at 80 ℃ for 2 hours to obtain a pretreated polylactic acid non-woven fabric;
step 3, mixing 20 parts of zeolite imidazole ester skeleton-67, 20 parts of 40wt% ammonia water, 0.85 part of cobalt nitrate hexahydrate, 1.25 parts of 2-methylimidazole and 60 parts of methanol to prepare a mixed solution; immersing 20 parts of the pretreated polylactic acid non-woven fabric prepared in the step 2 in the mixed solution; padding the mixed solution by adopting double roll shaft circulation, wherein the padding pressure is 0.9kg/cm 2 The axial speed of the double roller is 2m/min, and the padding treatment time is 5h; then standing for 12h, cleaning with 70wt% ethanol water solution for 3 times, and drying for 3h at 80 ℃ in a vacuum oven to obtain the antibacterial non-woven fabric.
Comparative example 1
The preparation method of the antibacterial non-woven fabric comprises the following steps of:
step 1, mixing 12 parts of ammonium polyphosphate, 20 parts of tris (hydroxymethyl) aminomethane and 300 parts of water, adjusting the temperature of a mixed solution to 70 ℃, and stirring and reacting for 30 minutes by using a magnetic stirrer to prepare a reaction solution; adjusting the pH to 8.5 by using 0.1mol/L sodium hydroxide aqueous solution; then 7 parts of polydopamine is added into the reaction solution to obtain a pretreatment solution;
step 2, 20 parts of the mixture are weighed to 300g/m 2 Washing polylactic acid non-woven fabric with 70wt% ethanol water solution for 3 times; then immersing in 80 parts of the pretreatment solution prepared in the step 1, adjusting the temperature of the solution to 22 ℃, and reacting for 20 hours; drying the impregnated polylactic acid non-woven fabric at 80 ℃ for 2 hours to obtain a pretreated polylactic acid non-woven fabric;
step 3, 23 parts ofSilver nitrate, 20 parts of 40wt% ammonia water, 0.85 part of cobalt nitrate hexahydrate, 1.25 parts of 2-methylimidazole and 60 parts of methanol are mixed to prepare a mixed solution; immersing 20 parts of the pretreated polylactic acid non-woven fabric prepared in the step 2 in the mixed solution; padding the mixed solution by adopting double roll shaft circulation, wherein the padding pressure is 0.9kg/cm 2 The axial speed of the double roller is 2m/min, and the padding treatment time is 5h; then standing for 12h, cleaning with 70wt% ethanol water solution for 3 times, and drying for 3h at 80 ℃ in a vacuum oven to obtain the antibacterial non-woven fabric.
Comparative example 2
The preparation method of the antibacterial non-woven fabric comprises the following steps of:
step 1, mixing 12 parts of ammonium polyphosphate, 20 parts of tris (hydroxymethyl) aminomethane and 300 parts of water, adjusting the temperature of a mixed solution to 70 ℃, and stirring and reacting for 30 minutes by using a magnetic stirrer to prepare a reaction solution; adjusting the pH to 8.5 by using 0.1mol/L sodium hydroxide aqueous solution; then 7 parts of polydopamine is added into the reaction solution to obtain a pretreatment solution;
step 2, 20 parts of the mixture are weighed to 300g/m 2 Washing polylactic acid non-woven fabric with 70wt% ethanol water solution for 3 times; then immersing in 80 parts of the pretreatment solution prepared in the step 1, adjusting the temperature of the solution to 22 ℃, and reacting for 20 hours; drying the impregnated polylactic acid non-woven fabric at 80 ℃ for 2 hours to obtain a pretreated polylactic acid non-woven fabric;
step 3, mixing 20 parts of 40wt% ammonia water, 0.85 part of cobalt nitrate hexahydrate, 1.25 parts of 2-methylimidazole and 60 parts of methanol to prepare a mixed solution; immersing 20 parts of the pretreated polylactic acid non-woven fabric prepared in the step 2 in the mixed solution; padding the mixed solution by adopting double roll shaft circulation, wherein the padding pressure is 0.9kg/cm 2 The axial speed of the double roller is 2m/min, and the padding treatment time is 5h; then standing for 12h, cleaning with 70wt% ethanol water solution for 3 times, and drying for 3h at 80 ℃ in a vacuum oven to obtain the antibacterial non-woven fabric.
Test example 1
Limiting oxygen index test:
the limiting oxygen indices of the examples and comparative examples were determined using a FYH830 critical oxygen index tester according to the test method of GB/T5454-1997 oxygen index for textile combustion Performance test.
Under the specified test conditions, the minimum oxygen concentration required by the material in the oxygen/nitrogen mixed gas to just keep the combustion state is the limiting oxygen index.
The test is carried out in an environment with the temperature of 10-30 ℃ and the relative humidity of 30-80%. Firstly, clamping a sample on the sample clamp, vertically placing a combustion cylinder below the sample, controlling oxygen and nitrogen to flow upwards, igniting the sample, observing the combustion characteristics of the sample, and immediately self-extinguishing the sample after ignition, wherein the time of continuous combustion, smoldering combustion or continuous combustion and smoldering combustion is less than 2 minutes, or the oxygen concentration is too low when the damage length is less than 40mm, so that the oxygen concentration must be improved; the oxygen concentration must be reduced if the sample is too high for a post-ignition, smoldering or both post-and smoldering time of more than 2 minutes or if the damage length exceeds 40 mm. After a series of tests on different oxygen concentrations, the lowest oxygen concentration value during combustion maintenance is screened, each group of materials is tested three times, the limiting oxygen index value is calculated according to a formula, and the average value is obtained.
LOI＝C F +Kd
Wherein: loi—limiting oxygen index;
C F -last oxygen concentration in test, taking one decimal,%;
d- -the difference between the two oxygen concentrations, taking the decimal place,%;
k-coefficient (look-up table);
table 1: limiting oxygen index test results
| Experimental protocol | Limiting oxygen index LOI (%) |
| Example 1 | 34.9 |
| Example 2 | 32.4 |
| Example 3 | 31.2 |
| Comparative example 1 | 30.3 |
| Comparative example 2 | 27.1 |
The test result of the limiting oxygen index shows that the limiting oxygen index of the embodiment 1 is highest, the flame retardant effect is best, and the modified polylactic acid non-woven fabric has obviously improved flame retardant property. The possible reason is that the tris (hydroxymethyl) aminomethane polyphosphate and polydopamine can effectively improve the external structure of the polylactic acid fiber and increase the grafting rate of the metal organic frame. Adding zeolite imidazole ester skeleton-67 and selenium dioxide material to react on polylactic acid non-woven fabric, combining zeolite imidazole ester skeleton-67 and reduced selenium nano particles, and preparing flame-retardant polylactic acid on the polylactic acid non-woven fabric through in-situ growth deposition. The zeolite imidazole ester skeleton-67 and selenium nano-particle composite has synergistic effect, and the zeolite imidazole ester skeleton-67 is degraded into cobalt oxide (CoO, co) at high temperature 2 O 3 、Co 3 O 4 And the like), selenium dioxide can be generated by the selenium nano particles, the cobalt selenium oxides are gathered on the surface of the carbon layer and form a thermal oxidation stable barrier with polylactic acid, the flame retardant property of the polylactic acid non-woven fabric can be enhanced, and molten liquid drops are eliminated. In the carbonization process, the oxide catalytic pyrolysis product forms a condensation coke layer, which also helps to reduce smoke release, oxide clusters formed by carbonization are embedded on the surface, the compact coke layer structure is favorable for inhibiting heat conduction, preventing further entry of heat and oxygen, improving the thermal stability of the coke layer, and formingThe carbon layer structure of the polylactic acid is used for protecting the further pyrolysis of the polylactic acid by preventing the mass transfer and the heat transfer of the polylactic acid matrix.
Test example 2
Antibacterial property test of fabric
Antibacterial Properties reference GB/T20944.3-2008 section 3 evaluation of antibacterial Properties of textiles: the test was carried out with the provisions of the Oscillating method using E.coli AATCC 8099, candida albicans AATCC 10231 and Staphylococcus aureus AATCC 6538 as test species.
Taking appropriate amounts of the above three strains under aseptic environment, placing into 20mL broth sterilized at high temperature, and preparing into 3×10 5 4g of the samples of the examples and the comparative examples are weighed out by cfu/mL of the bacterial culture solution, the samples are sheared into pieces with the size of 5 multiplied by 5mm, the pieces are placed into the corresponding bacterial culture solution, the bacterial culture solution without the samples is used as a control group in an experiment, the broth is placed into a constant temperature shaking table, the temperature is set to be 37 ℃, the rotating speed is 150rpm/min, and the culture is carried out for 24 hours. 100. Mu.L was plated on agar plates. After 4h incubation, the number of bacteria on the dishes was recorded by plate counting. Three groups of samples were averaged and the test results are shown in table 2. The antimicrobial properties of fabrics can be calculated using the following formula:
R＝(B-A)/B×100％
wherein R represents the antibacterial ratio, and A, B is the bacterial concentration of the sample and the control group, respectively.
Test example 3
Wear-resistant antibacterial property test
Determination of abrasion resistance of textile Martindale fabrics, part 3, see GB/T21196.3-2007: determination of quality loss using YG522 disc fabric flat grinder (Lyocell electronic instruments Co., ltd.). Cutting a non-woven fabric sample into a circular sample with the diameter of 125mm, selecting a heavy hammer with the weight of 250g, running at the speed of 60 revolutions per minute, and rubbing for 2 minutes. The nonwoven fabric after friction was tested for its antibacterial properties after abrasion resistance by the same method as in test example 2. The test results are shown in Table 2.
Table 2: antibacterial property test result of fabric
As can be seen from table 2, the antibacterial performance of example 1 before and after rubbing is the best, and the change of the antibacterial performance after rubbing is small, probably because the tris-hydroxymethyl-aminomethane polyphosphate and polydopamine contain a large amount of phenolic hydroxyl groups and nitrogen-containing groups, have strong adsorption capacity to various heavy metal ions, and a large amount of hydroxyl groups on the tris-hydroxymethyl-aminomethane polyphosphate and catechol and amino functional groups on polydopamine can form coordination bonds with the zeolite imidazole skeleton-67 and the empty electronic orbitals of the selenium nanoparticles to generate covalent and non-covalent interactions, and moreover, polydopamine has a certain reducibility and can reduce selenium dioxide into selenium nanoparticles. In the invention, the combination of polylactic acid fiber, zeolite imidazole ester skeleton-67 and selenium nano particles is enhanced by introducing the tris (hydroxymethyl) aminomethane polyphosphate and polydopamine, so that the functional material is prevented from falling off in the subsequent use process, and the silver ion in comparative example 1 is insufficient in the bonding degree on the surface of the polylactic acid, so that the antibacterial performance is obviously reduced after friction. When selenium nanoparticles and zeolite imidazole skeleton-67 contact the microbial cell membrane, the coulomb force in the micro-dynamic effect attracts the selenium nanoparticles and zeolite imidazole skeleton-67, which then penetrate the cell membrane and enter the microbial body, solidify through the reaction of sulfhydryl groups on proteins, thereby destroying the activity of microbial synthase, interfering with the synthesis of microbial DNA, and selenium nanoparticle treated staphylococcus aureus can lead to the exhaustion of Adenosine Triphosphate (ATP), and depolarization of bacterial membrane and change of cell morphology, eventually leading to the death of microbial bacteria, and make it difficult for bacteria to evolve tolerance to these effects.
Test example 4
Anti-ultraviolet performance test
Referring to GB/T18830-2009 evaluation of ultraviolet resistance of textiles, a UV-1000F fabric ultraviolet resistance tester is adopted for testing. The ultraviolet protection factor (UPF value) is adopted as a main evaluation index of the ultraviolet resistance of the fabric, and the higher the UPF value is, the better the ultraviolet resistance is. Each group of samples was tested three times to average and the test results are shown in table 3.
Table 3: ultraviolet resistance test results
| Experimental protocol | UPF |
| Example 1 | 59.29 |
| Example 2 | 48.91 |
| Example 3 | 47.31 |
| Comparative example 1 | 36.22 |
| Comparative example 2 | 25.60 |
The results in Table 3 show that example 1 has the best UV resistance, probably due to the improved UV resistance of the polylactic acid by the addition of the zeolite imidazole ester framework-67 and selenium nanoparticle composite. The in-situ grown zeolite imidazole ester skeleton-67 is combined with selenium nanoparticle crystals to cover the surface of the fiber and fill in certain gaps of the fiber, and can reflect and scatter ultraviolet rays. In addition, the excellent ultraviolet resistance can prevent the oxidative degradation of polylactic acid fibers, and the service life and the economic value of the non-woven fabric are improved.
Claims (6)
1. The preparation method of the antibacterial non-woven fabric is characterized by comprising the following steps of:
step 1, mixing ammonium polyphosphate and tris (hydroxymethyl) aminomethane with water, adjusting the temperature of a mixed solution to 60-80 ℃, and stirring and reacting for 20-50 min to prepare a reaction solution; adjusting the pH value to 8.0-9.0 by using 0.01-0.3 mol/L sodium hydroxide aqueous solution; then adding polydopamine into the reaction solution to obtain a pretreatment solution;
step 2, washing the polylactic acid non-woven fabric with a detergent for 1-4 times; then immersing in the pretreatment solution prepared in the step 1, adjusting the temperature of the solution to be 20-25 ℃, reacting for 15-30 h, and drying the immersed polylactic acid non-woven fabric at 60-90 ℃ for 1-3 h; obtaining pretreated polylactic acid non-woven fabrics;
step 3, mixing zeolite imidazole ester skeleton-67, selenium dioxide, 30-50wt% ammonia water, cobalt nitrate hexahydrate, a curing agent and methanol to prepare a mixed solution; immersing the pretreated polylactic acid non-woven fabric prepared in the step (2) in a mixed solution, and circularly performing padding treatment in the mixed solution; then standing for 6-15 h, cleaning for 1-4 times by using a detergent, and drying for 1-5 h at 60-90 ℃ to obtain the antibacterial non-woven fabric;
the components in the step 1 are calculated according to parts by weight: 8-15 parts of ammonium polyphosphate, 10-30 parts of tris (hydroxymethyl) aminomethane, 200-500 parts of water and 3-10 parts of polydopamine;
the components in the step 2 are calculated according to parts by weight: 10-30 parts of polylactic acid non-woven fabric and 60-100 parts of the pretreatment solution prepared in the step 1;
the components in the step 3 are calculated according to parts by weight: 10 to 30 parts of zeolite imidazole ester skeleton-67, 1 to 5 parts of selenium dioxide, 10 to 30 parts of 40wt% ammonia water, 0.3 to 1.2 parts of cobalt nitrate hexahydrate, 0.8 to 1.6 parts of curing agent, 40 to 80 parts of methanol and 10 to 30 parts of pretreated polylactic acid non-woven fabric prepared in the step 2.
2. The method for preparing an antibacterial nonwoven fabric according to claim 1, characterized in that: the gram weight of the polylactic acid non-woven fabric in the step 2 is 150-500 g/m 2 。
3. The method for preparing an antibacterial nonwoven fabric according to claim 1, characterized in that: the detergent in the step 2 or the step 3 is one of 60-80 wt% ethanol water solution and 70-85 wt% methanol water solution.
4. The method for preparing an antibacterial nonwoven fabric according to claim 1, characterized in that: the curing agent in the step 3 is formed by combining one or more than two of 2-methylimidazole, methyltetrahydrophthalic anhydride and isophorone diisocyanate.
5. The method for preparing an antibacterial nonwoven fabric according to claim 1, wherein the padding treatment in the step 3 has the following process parameters: the pressurizing pressure is 0.6-1.2 kg/cm 2 The axial speed of the double roller is 1-4 m/min, and the padding treatment time is 2-8 h.
6. An antibacterial nonwoven fabric, characterized in that: the antibacterial nonwoven fabric according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210118712.8A CN114351444B (en) | 2022-02-08 | 2022-02-08 | Antibacterial non-woven fabric and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210118712.8A CN114351444B (en) | 2022-02-08 | 2022-02-08 | Antibacterial non-woven fabric and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114351444A CN114351444A (en) | 2022-04-15 |
| CN114351444B true CN114351444B (en) | 2024-01-23 |
Family
ID=81093698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210118712.8A Active CN114351444B (en) | 2022-02-08 | 2022-02-08 | Antibacterial non-woven fabric and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114351444B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116200063A (en) * | 2023-03-08 | 2023-06-02 | 辽宁顺风新材料科技有限公司 | Environment-friendly flame-retardant smoke-suppressing antistatic filler for water-based epoxy resin coating and preparation method thereof |
| CN117822310A (en) * | 2024-03-05 | 2024-04-05 | 苏州金泉新材料股份有限公司 | Non-stimulated polylactic acid non-woven fabric with natural weak acid and antibacterial effect |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436977A (en) * | 2013-08-28 | 2013-12-11 | 江苏博特新材料有限公司 | Flame-retardant melt-spun high-strength high-modulus polyvinyl alcohol fiber and preparation method thereof |
| WO2018140304A1 (en) * | 2017-01-27 | 2018-08-02 | Sabic Global Technologies B.V. | Hierarchical zeolite-based core/shell nano- or microcapsule |
| CN109577005A (en) * | 2018-11-28 | 2019-04-05 | 吉林大学 | A kind of preparation method and applications of the ZIF-8 functionalized nano-fiber film of poly-dopamine modification |
| KR101983910B1 (en) * | 2017-12-04 | 2019-05-30 | 함지연 | A nonwoven fabric having an excellent antibiotic activity and the method for preparing the same |
| CN111793972A (en) * | 2019-10-08 | 2020-10-20 | 伍亚舟 | Preparation method of high-strength flame-retardant elastic fabric |
| KR102203261B1 (en) * | 2020-08-31 | 2021-01-14 | 김철원 | Textile fabrics with excellent antibacterial properties and manufacturing method thereof |
| CN113005634A (en) * | 2021-02-24 | 2021-06-22 | 李思鹏 | Moisture-absorbing and bacteriostatic spunlace non-woven fabric and preparation method thereof |
-
2022
- 2022-02-08 CN CN202210118712.8A patent/CN114351444B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436977A (en) * | 2013-08-28 | 2013-12-11 | 江苏博特新材料有限公司 | Flame-retardant melt-spun high-strength high-modulus polyvinyl alcohol fiber and preparation method thereof |
| WO2018140304A1 (en) * | 2017-01-27 | 2018-08-02 | Sabic Global Technologies B.V. | Hierarchical zeolite-based core/shell nano- or microcapsule |
| KR101983910B1 (en) * | 2017-12-04 | 2019-05-30 | 함지연 | A nonwoven fabric having an excellent antibiotic activity and the method for preparing the same |
| CN109577005A (en) * | 2018-11-28 | 2019-04-05 | 吉林大学 | A kind of preparation method and applications of the ZIF-8 functionalized nano-fiber film of poly-dopamine modification |
| CN111793972A (en) * | 2019-10-08 | 2020-10-20 | 伍亚舟 | Preparation method of high-strength flame-retardant elastic fabric |
| KR102203261B1 (en) * | 2020-08-31 | 2021-01-14 | 김철원 | Textile fabrics with excellent antibacterial properties and manufacturing method thereof |
| CN113005634A (en) * | 2021-02-24 | 2021-06-22 | 李思鹏 | Moisture-absorbing and bacteriostatic spunlace non-woven fabric and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114351444A (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114351444B (en) | Antibacterial non-woven fabric and preparation method thereof | |
| Gao et al. | Construction of durable antibacterial and anti-mildew cotton fabric based on P (DMDAAC-AGE)/Ag/ZnO composites | |
| Ilić et al. | The influence of silver content on antimicrobial activity and color of cotton fabrics functionalized with Ag nanoparticles | |
| Tan et al. | A review of antimicrobial fabric containing nanostructures metal‐based compound | |
| Zhang et al. | Application of silver nanoparticles to cotton fabric as an antibacterial textile finish | |
| Perera et al. | Morphological, antimicrobial, durability, and physical properties of untreated and treated textiles using silver-nanoparticles | |
| Shahidi et al. | Antibacterial agents in textile industry | |
| US10550511B2 (en) | Antimicrobial cellulose fiber and fabric comprising multiple antimicrobial cellulose fibers | |
| CA2669438C (en) | Nanosilver coated bacterial cellulose | |
| CN101597860B (en) | Complex antibacterial fiber, fabric and preparation method thereof | |
| Vijayalakshmi et al. | Synthesis, characterization and applications of nanochitosan/sodium alginate/microcrystalline cellulose film | |
| EP2274470B1 (en) | Method of manufacturing natural or synthetic fibres containing silver nano-particles | |
| Montazer et al. | Simultaneous synthesis and fabrication of nano Cu 2 O on cellulosic fabric using copper sulfate and glucose in alkali media producing safe bio-and photoactive textiles without color change | |
| CN105887227B (en) | The preparation method of antibacterial and deodouring viscose rayon | |
| Qin et al. | Structure and properties of Cu (II) complex bamboo pulp fabrics | |
| Qu et al. | Anchoring silver nanoparticles using catechol-derived resins: an efficient and versatile approach for producing durable antimicrobial fabrics | |
| Gawish et al. | Antimicrobial polypropylene loaded by silver nano particles | |
| CN112442893A (en) | Special efficient nano copper antibacterial agent and preparation method thereof | |
| Amani et al. | Low starch/corn silk/ZnO as environmentally friendly nanocomposites assembling on PET fabrics | |
| Scacchetti et al. | Preparation and characterization of cotton fabrics with antimicrobial properties through the application of chitosan/silver-zeolite film | |
| Taheri et al. | Antibacterial cotton fabrics via immobilizing silver phosphate nanoparticles onto the chitosan nanofiber coating | |
| Liu et al. | Highly effective antibacterial AgNPs@ hinokitiol grafted chitosan for construction of durable antibacterial fabrics | |
| Maryan et al. | One step synthesis of silver nanoparticles and discoloration of blue cotton denim garment in alkali media | |
| Lazić et al. | A study of the antibacterial activity and stability of dyed cotton fabrics modified with different forms of silver | |
| Arif et al. | Synthesis of nanomaterials and their applications in textile industry |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231221 Address after: No. 18 Tianxian Avenue, Tianmen Industrial Park, Tianmen City, Jingzhou City, Hubei Province, China, 431728 Applicant after: Hubei ZhuoLe medical supplies Co.,Ltd. Address before: 510240 room 1013, No. 5, Fuchang Road, Haizhu District, Guangzhou City, Guangdong Province Applicant before: Guangzhou V-Love Apparel Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: No. 18 Tianxian Avenue, Tianmen Industrial Park, Tianmen City, Hubei Province, 431728 Applicant after: Hubei ZhuoLe medical supplies Co.,Ltd. Address before: No. 18 Tianxian Avenue, Tianmen Industrial Park, Tianmen City, Jingzhou City, Hubei Province, China, 431728 Applicant before: Hubei ZhuoLe medical supplies Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |