CN108468204A - 抗菌无机金属盐改性纤维素纤维的制备方法 - Google Patents
抗菌无机金属盐改性纤维素纤维的制备方法 Download PDFInfo
- Publication number
- CN108468204A CN108468204A CN201810188879.5A CN201810188879A CN108468204A CN 108468204 A CN108468204 A CN 108468204A CN 201810188879 A CN201810188879 A CN 201810188879A CN 108468204 A CN108468204 A CN 108468204A
- Authority
- CN
- China
- Prior art keywords
- ammonium
- cellulose fibre
- salt
- preparation
- octyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 78
- 239000002184 metal Substances 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 238000009938 salting Methods 0.000 claims abstract description 34
- 238000007654 immersion Methods 0.000 claims abstract description 31
- 238000002791 soaking Methods 0.000 claims abstract description 26
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 22
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- -1 octylphosphonic acid ammonium Chemical compound 0.000 claims description 18
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 16
- PHFDTSRDEZEOHG-UHFFFAOYSA-N hydron;octan-1-amine;chloride Chemical class Cl.CCCCCCCCN PHFDTSRDEZEOHG-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 12
- 150000003751 zinc Chemical class 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- ACQYZSFXPXXIHL-UHFFFAOYSA-N 2-phenylmethoxycarbonyl-3,4-dihydro-1h-isoquinoline-1-carboxylic acid Chemical compound C1CC2=CC=CC=C2C(C(=O)O)N1C(=O)OCC1=CC=CC=C1 ACQYZSFXPXXIHL-UHFFFAOYSA-N 0.000 claims description 8
- BZVNOXWNSUSLQB-UHFFFAOYSA-N CCCCCCCCN.CCCCCCCCN.CCCCCCCCN.OB(O)O Chemical compound CCCCCCCCN.CCCCCCCCN.CCCCCCCCN.OB(O)O BZVNOXWNSUSLQB-UHFFFAOYSA-N 0.000 claims description 8
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- ITCMXBVIXVDAKR-UHFFFAOYSA-M azanium tetrabutylazanium diacetate Chemical compound C(C)(=O)[O-].[NH4+].C(CCC)[N+](CCCC)(CCCC)CCCC.C(C)(=O)[O-] ITCMXBVIXVDAKR-UHFFFAOYSA-M 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- 239000006012 monoammonium phosphate Substances 0.000 claims description 8
- 229940067739 octyl sulfate Drugs 0.000 claims description 8
- NSJANQIGFSGFFN-UHFFFAOYSA-N octylazanium;acetate Chemical class CC([O-])=O.CCCCCCCC[NH3+] NSJANQIGFSGFFN-UHFFFAOYSA-N 0.000 claims description 8
- OXDRMTKMIYRQLY-UHFFFAOYSA-N octylazanium;hydroxide Chemical compound [OH-].CCCCCCCC[NH3+] OXDRMTKMIYRQLY-UHFFFAOYSA-N 0.000 claims description 8
- HBZSVMFYMAOGRS-UHFFFAOYSA-N octylazanium;iodide Chemical class [I-].CCCCCCCC[NH3+] HBZSVMFYMAOGRS-UHFFFAOYSA-N 0.000 claims description 8
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 claims description 8
- WGYONVRJGWHMKV-UHFFFAOYSA-M tetrabutylazanium;benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.CCCC[N+](CCCC)(CCCC)CCCC WGYONVRJGWHMKV-UHFFFAOYSA-M 0.000 claims description 8
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical group C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 6
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 6
- 229940071536 silver acetate Drugs 0.000 claims description 6
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 6
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-M benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-M 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- DHIVLKMGKIZOHF-UHFFFAOYSA-N 1-fluorooctane Chemical compound CCCCCCCCF DHIVLKMGKIZOHF-UHFFFAOYSA-N 0.000 claims 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 229940107816 ammonium iodide Drugs 0.000 claims 1
- KCFKHWSNVPJBEP-UHFFFAOYSA-N butylazanium;sulfate Chemical compound CCCCN.CCCCN.OS(O)(=O)=O KCFKHWSNVPJBEP-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 claims 1
- AMCYFOSVYJWEBU-UHFFFAOYSA-N tetrabutylazanium borate Chemical compound [O-]B([O-])[O-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC AMCYFOSVYJWEBU-UHFFFAOYSA-N 0.000 claims 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 30
- 229920002678 cellulose Polymers 0.000 abstract description 5
- 239000001913 cellulose Substances 0.000 abstract description 5
- 238000003491 array Methods 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- YLKHWDVISHHINP-UHFFFAOYSA-N octylazanium;fluoride Chemical class [F-].CCCCCCCC[NH3+] YLKHWDVISHHINP-UHFFFAOYSA-N 0.000 description 7
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 7
- ZXUCBXRTRRIBSO-UHFFFAOYSA-L tetrabutylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC ZXUCBXRTRRIBSO-UHFFFAOYSA-L 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- WXJVQQPLIMTRFK-UHFFFAOYSA-N C(CCC)[P](CCCC)(CCCC)CCCC Chemical compound C(CCC)[P](CCCC)(CCCC)CCCC WXJVQQPLIMTRFK-UHFFFAOYSA-N 0.000 description 6
- ODJZWVFLHZHURI-UHFFFAOYSA-M [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] Chemical compound [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] ODJZWVFLHZHURI-UHFFFAOYSA-M 0.000 description 6
- VWSRWGFGAAKTQG-UHFFFAOYSA-N ammonium benzoate Chemical compound [NH4+].[O-]C(=O)C1=CC=CC=C1 VWSRWGFGAAKTQG-UHFFFAOYSA-N 0.000 description 6
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 230000002421 anti-septic effect Effects 0.000 description 5
- 229940116318 copper carbonate Drugs 0.000 description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229940064004 antiseptic throat preparations Drugs 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QXFADXLALKKHIZ-UHFFFAOYSA-N 2-octylbenzoic acid Chemical class CCCCCCCCC1=CC=CC=C1C(O)=O QXFADXLALKKHIZ-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- BEESDQRFAOEVAJ-UHFFFAOYSA-N C(CCC)Cl(CCCC)(CCCC)CCCC Chemical compound C(CCC)Cl(CCCC)(CCCC)CCCC BEESDQRFAOEVAJ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical class [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
- D06M11/42—Oxides or hydroxides of copper, silver or gold
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
本发明涉及一种抗菌无机金属盐改性纤维素纤维的制备方法。制备方法包括以下步骤：将纤维素纤维放入复合碱液中浸泡处理，复合碱液中含有浓度1％‑15％的氢氧化锂以及浓度1％‑25％的铵盐，浴比范围为1:10至1:200，浸泡时间为1至120分钟，浸泡温度范围是35‑100摄氏度；随后将纤维素纤维压榨或离心，随后烘干；将纤维素纤维放入金属无机盐溶液中浸泡处理；最后将纤维素纤维压榨或离心，随后烘干。本发明先采用氢氧化锂及铵盐来有效降低纤维素的结晶度，纤维素分子间不再紧密排列，有利于金属无机盐有效进入纤维素分子内部，然后浸泡金属无机盐溶液中，形成具有长久抗菌效果的纤维素纤维。
Description
技术领域
本发明涉及改性纤维素纤维，尤其涉及一种抗菌无机金属盐改性纤维素纤维的制备方法。
背景技术
基于纤维素纤维的织物，包括棉、麻、莫代尔等等，具有透气、亲肤、穿着舒适、吸湿性好等优点，被广泛应用于服装以及家居行业，特别是作为贴身内衣内裤、袜子或床单。但是，这些织物具有高吸湿性，加上人体表皮的代谢物和脱落物，为细菌的生长提供了适宜的温床，造成过敏以及细菌感染。近年来，病原性微生物引发的全球性流行病不断威胁着人类的健康，而且由于抗生素的滥用，越来越多的细菌产生了耐药性。所以赋予织物抗菌性就变得尤为重要。一些抗菌纺织品已经发明，比如有机季铵盐类的产品。但是长期使用这些产品，细菌产生了耐药性。以锌铜等材料为代表的无机抗菌材料因具有高效、安全，不易产生耐药性等特点，对人体无害但是具有显著的抗菌性，成为功能材料领域的研究热点。这些材料已经成功的应用于合成纤维，比如聚酯(一种铜改性的抗菌聚酯纤维及其制备方法CN103981591B，一种双色铜系抗菌复合纤维的制备方法CN106192104A)，尼龙(一种有机铜抗菌锦纶丝、有机铜配合物制备方法WO2015149412A1)，腈纶等,但是将这些抗菌材料整合到纤维素织物中是非常困难的。
基于纤维素的抗菌研究或应用非常困难。因为纤维素分子内大量的氢键，使得纤维素分子之间排列非常紧密有序，造成非常高的结晶度(结晶度超过80％)。因为高结晶度，所以无机盐抗菌剂很难进入到纤维素分子的内部，只有一些无机抗菌剂附着在表面。而在多次水洗之后，无机抗菌剂脱落的速度很快，抗菌失效。目前市面上有一些采用了无机盐的抗菌剂(比如纳米银、纳米铜)，但是水洗20-30次后，这些抗菌剂脱落，基本上就没有抗菌效果了，有待改进。
发明内容
本发明的目的在于为克服现有技术的缺陷，而提供一种抗菌无机金属盐改性纤维素纤维的制备方法，用以制造抗菌性能优良、具有优良耐水洗的纤维素纤维。
为实现上述目的，本发明采用以下技术方案：
抗菌无机金属盐改性纤维素纤维的制备方法包括以下步骤：
将纤维素纤维放入复合碱液中浸泡处理，复合碱液中含有浓度1％-15％的氢氧化锂以及浓度1％-25％的铵盐，浴比范围为1:10至1:200，浸泡时间为1至120分钟，浸泡温度范围是35-100摄氏度；
随后将纤维素纤维压榨或离心，随后烘干；
将纤维素纤维放入金属无机盐溶液中浸泡处理；
最后将纤维素纤维压榨或离心，随后烘干。
进一步地，复合碱液中的铵盐的结构式为
其中n＝1-12，A-为碘离子、氯离子、溴离子、氟离子、醋酸根、硫酸根、磷酸根、磷酸二氢根、磷酸一氢根、苯甲酸根、硼酸根、氢氧根中的任一种。
进一步地，铵盐为以下物质的至少一种：四丁基碘化铵，四丁基溴化铵，四丁基氯化铵，四丁基氟化铵，四丁基醋酸铵，四丁基氯化铵，四丁基硫酸铵，四丁基磷酸铵，四丁基磷酸二氢铵，四丁基磷酸一氢铵，四丁基苯甲酸铵，四丁基四丁基硼酸铵，四丁基氢氧化铵，四辛基碘化铵，四辛基溴化铵，四辛基氯化铵，四辛基氟化铵，四辛基醋酸铵，四辛基氯化铵，四辛基硫酸铵，四辛基磷酸铵，四辛基磷酸二氢铵，四辛基磷酸一氢铵，四辛基苯甲酸铵，四辛基四辛基硼酸铵，四辛基氢氧化铵。
进一步地，将纤维素纤维进行烘干的温度为60摄氏度。
进一步地，将纤维素纤维放入金属无机盐溶液中浸泡处理的时间范围是1-120分钟，浸泡温度范围25-95摄氏度。金属无机盐溶液中，金属无机盐的浓度范围为0.1％-20％。金属无机盐溶液中的金属无机盐由铜盐、锌盐和银盐组成，三种组分的占比分别为0-100％、0-100％和0-100％。铜盐是：硫酸铜、氯化铜、醋酸铜、碳酸铜或者氢氧化铜。锌盐是醋酸锌、氯化锌或者硫酸锌。银盐是碳酸银、硝酸银或醋酸银。
针对现有技术中存在的问题——不能有效将金属无机盐整合到纤维素纤维中，本发明先采用氢氧化锂及铵盐来有效降低纤维素的结晶度，纤维素分子间不再紧密排列，有利于金属无机盐有效进入纤维素分子内部，然后浸泡金属无机盐溶液中，形成具有长久抗菌效果的纤维素纤维。
现有技术中降低纤维素结晶度的方法包括超声、微波、溶剂法等等，但是这些办法目前不能有效降低结晶度。目前比较有效的方法是利用氢氧化钠以及尿素或离子液体(专利号:CN201210498768或CN 201310244994)。氢氧化钠使纤维素分子带上负电，相互排斥，分子间出现空挡，有利于无机盐分子(或离子)的渗透。但是氢氧化钠降低结晶度的效果较差，工艺过程需要将纤维素分子溶液冷冻(专利号:CN 201310244994)。这个利用氢氧化钠的工艺方法虽然在小规模实验室有效，难以应用于规模化生产中，特别是低温冷冻带来的成本以及低效率的问题。本发明采用的氢氧化锂及铵盐的复合碱液无需冷冻溶液，生产效率也比较高，适合规模化生产。
附图说明
图1为现有技术中采用氢氧化钠作为碱来分散纤维素分子时的分子结构示意图。
图2为本发明制备方法采用锂离子来分散纤维素分子时的分子结构示意图。
图3为本发明制备方法制造的纤维素纤维水洗100次过程中铜离子含量变化表。
图4为本发明制备方法制造的纤维素纤维水洗100次过程中抗菌性能变化表。
具体实施方式
为了更充分理解本发明的技术内容，下面结合具体实施例对本发明的技术方案作进一步介绍和说明。
实施例一
纤维素纤维的制备方法包括以下步骤：
1)将纤维素纤维放入复合碱液中浸泡处理；
2)随后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干；
3)将纤维素纤维放入金属无机盐溶液中浸泡处理；
4)最后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干。
在实施例一中，复合碱液中含有浓度1％的氢氧化锂以及浓度1％的铵盐，浴比范围为1:10，浸泡时间为20分钟，浸泡温度范围是40摄氏度。将纤维素纤维放入复合碱液中浸泡处理之后，可将使用过后的剩余复合碱液回收再利用。
而其中，复合碱液中的铵盐为以下物质的至少一种：四丁基碘化铵，四丁基溴化铵，四丁基氯化铵，四丁基氟化铵，四丁基醋酸铵，四丁基氯化铵，四丁基硫酸铵，四丁基磷酸铵，四丁基磷酸二氢铵，四丁基磷酸一氢铵，四丁基苯甲酸铵，四丁基四丁基硼酸铵，四丁基氢氧化铵，四辛基碘化铵，四辛基溴化铵，四辛基氯化铵，四辛基氟化铵，四辛基醋酸铵，四辛基氯化铵，四辛基硫酸铵，四辛基磷酸铵，四辛基磷酸二氢铵，四辛基磷酸一氢铵，四辛基苯甲酸铵，四辛基四辛基硼酸铵，四辛基氢氧化铵。
在实施例一中，将纤维素纤维放入金属无机盐溶液中浸泡处理的时间范围是120分钟，浸泡温度范围35摄氏度。金属无机盐溶液中，金属无机盐的浓度范围为0.1％。金属无机盐溶液中的金属无机盐为铜盐。铜盐是：硫酸铜、氯化铜、醋酸铜、碳酸铜或者氢氧化铜。
实施例二
纤维素纤维的制备方法包括以下步骤：
1)将纤维素纤维放入复合碱液中浸泡处理；
2)随后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干；
3)将纤维素纤维放入金属无机盐溶液中浸泡处理；
4)最后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干。
在实施例二中，复合碱液中含有浓度7％的氢氧化锂以及浓度13％的铵盐，浴比范围为1:35，浸泡时间为60分钟，浸泡温度范围是60摄氏度。将纤维素纤维放入复合碱液中浸泡处理之后，可将使用过后的剩余复合碱液回收再利用。
而其中，复合碱液中的铵盐为以下物质的至少一种：四丁基碘化铵，四丁基溴化铵，四丁基氯化铵，四丁基氟化铵，四丁基醋酸铵，四丁基氯化铵，四丁基硫酸铵，四丁基磷酸铵，四丁基磷酸二氢铵，四丁基磷酸一氢铵，四丁基苯甲酸铵，四丁基四丁基硼酸铵，四丁基氢氧化铵，四辛基碘化铵，四辛基溴化铵，四辛基氯化铵，四辛基氟化铵，四辛基醋酸铵，四辛基氯化铵，四辛基硫酸铵，四辛基磷酸铵，四辛基磷酸二氢铵，四辛基磷酸一氢铵，四辛基苯甲酸铵，四辛基四辛基硼酸铵，四辛基氢氧化铵。
在实施例二中，将纤维素纤维放入金属无机盐溶液中浸泡处理的时间范围是50分钟，浸泡温度范围50摄氏度。金属无机盐溶液中，金属无机盐的浓度范围为10％。金属无机盐溶液中的金属无机盐为锌盐，锌盐是醋酸锌、氯化锌或者硫酸锌。
实施例三
纤维素纤维的制备方法包括以下步骤：
1)将纤维素纤维放入复合碱液中浸泡处理；
2)随后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干；
3)将纤维素纤维放入金属无机盐溶液中浸泡处理；
4)最后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干。
在实施例三中，复合碱液中含有浓度15％的氢氧化锂以及浓度25％的铵盐，浴比范围为1:200，浸泡时间为30分钟，浸泡温度范围是80摄氏度。将纤维素纤维放入复合碱液中浸泡处理之后，可将使用过后的剩余复合碱液回收再利用。
而其中，复合碱液中的铵盐为以下物质的至少一种：四丁基碘化铵，四丁基溴化铵，四丁基氯化铵，四丁基氟化铵，四丁基醋酸铵，四丁基氯化铵，四丁基硫酸铵，四丁基磷酸铵，四丁基磷酸二氢铵，四丁基磷酸一氢铵，四丁基苯甲酸铵，四丁基四丁基硼酸铵，四丁基氢氧化铵，四辛基碘化铵，四辛基溴化铵，四辛基氯化铵，四辛基氟化铵，四辛基醋酸铵，四辛基氯化铵，四辛基硫酸铵，四辛基磷酸铵，四辛基磷酸二氢铵，四辛基磷酸一氢铵，四辛基苯甲酸铵，四辛基四辛基硼酸铵，四辛基氢氧化铵。
在实施例三中，将纤维素纤维放入金属无机盐溶液中浸泡处理的时间范围是1分钟，浸泡温度范围25摄氏度。金属无机盐溶液中，金属无机盐的浓度范围为20％。金属无机盐溶液中的金属无机盐为银盐，银盐是碳酸银、硝酸银或醋酸银。
实施例四
纤维素纤维的制备方法包括以下步骤：
1)将纤维素纤维放入复合碱液中浸泡处理；
2)随后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干；
3)将纤维素纤维放入金属无机盐溶液中浸泡处理；
4)最后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干。
在实施例四中，复合碱液中含有浓度4.5％的氢氧化锂以及浓度8.7％的铵盐，浴比范围为1:45，浸泡时间为60分钟，浸泡温度范围是80摄氏度。将纤维素纤维放入复合碱液中浸泡处理之后，可将使用过后的剩余复合碱液回收再利用。
而其中，复合碱液中的铵盐为以下物质的至少一种：四丁基碘化铵，四丁基溴化铵，四丁基氯化铵，四丁基氟化铵，四丁基醋酸铵，四丁基氯化铵，四丁基硫酸铵，四丁基磷酸铵，四丁基磷酸二氢铵，四丁基磷酸一氢铵，四丁基苯甲酸铵，四丁基四丁基硼酸铵，四丁基氢氧化铵，四辛基碘化铵，四辛基溴化铵，四辛基氯化铵，四辛基氟化铵，四辛基醋酸铵，四辛基氯化铵，四辛基硫酸铵，四辛基磷酸铵，四辛基磷酸二氢铵，四辛基磷酸一氢铵，四辛基苯甲酸铵，四辛基四辛基硼酸铵，四辛基氢氧化铵。
在实施例四中，将纤维素纤维放入金属无机盐溶液中浸泡处理的时间范围是90分钟，浸泡温度范围95摄氏度。金属无机盐溶液中，金属无机盐的浓度范围为2.3％。金属无机盐溶液中的金属无机盐由铜盐、锌盐和银盐组成，三种组分的占比分别为40％、30％和30％。铜盐是：硫酸铜、氯化铜、醋酸铜、碳酸铜或者氢氧化铜。锌盐是醋酸锌、氯化锌或者硫酸锌。银盐是碳酸银、硝酸银或醋酸银。
实施例五
纤维素纤维的制备方法包括以下步骤：
1)将纤维素纤维放入复合碱液中浸泡处理；
2)随后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干；
3)将纤维素纤维放入金属无机盐溶液中浸泡处理；
4)最后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干。
在实施例五中，复合碱液中含有浓度8％的氢氧化锂以及浓度10％的铵盐，浴比范围为1:80，浸泡时间为50分钟，浸泡温度范围是35摄氏度。而将纤维素纤维放入复合碱液中浸泡处理之后，可将使用过后的剩余复合碱液回收再利用。
而其中，复合碱液中的铵盐为以下物质的至少一种：四丁基碘化铵，四丁基溴化铵，四丁基氯化铵，四丁基氟化铵，四丁基醋酸铵，四丁基氯化铵，四丁基硫酸铵，四丁基磷酸铵，四丁基磷酸二氢铵，四丁基磷酸一氢铵，四丁基苯甲酸铵，四丁基四丁基硼酸铵，四丁基氢氧化铵，四辛基碘化铵，四辛基溴化铵，四辛基氯化铵，四辛基氟化铵，四辛基醋酸铵，四辛基氯化铵，四辛基硫酸铵，四辛基磷酸铵，四辛基磷酸二氢铵，四辛基磷酸一氢铵，四辛基苯甲酸铵，四辛基四辛基硼酸铵，四辛基氢氧化铵。
在实施例五中，将纤维素纤维放入金属无机盐溶液中浸泡处理的时间范围是60分钟，浸泡温度范围60摄氏度。金属无机盐溶液中，金属无机盐的浓度范围为9％。金属无机盐溶液中的金属无机盐由铜盐、锌盐和银盐组成，三种组分的占比分别为60％、30％和10％。铜盐是：硫酸铜、氯化铜、醋酸铜、碳酸铜或者氢氧化铜。锌盐是醋酸锌、氯化锌或者硫酸锌。银盐是碳酸银、硝酸银或醋酸银。
实施例六
纤维素纤维的制备方法包括以下步骤：
1)将纤维素纤维放入复合碱液中浸泡处理；
2)随后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干；
3)将纤维素纤维放入金属无机盐溶液中浸泡处理；
4)最后将纤维素纤维压榨或离心，随后进行60摄氏度的烘干。
在实施例六中，复合碱液中含有浓度11％的氢氧化锂以及浓度21％的铵盐，浴比范围为1:130，浸泡时间为70分钟，浸泡温度范围是55摄氏度。将纤维素纤维放入复合碱液中浸泡处理之后，可将使用过后的剩余复合碱液回收再利用。
而其中，复合碱液中的铵盐为以下物质的至少一种：四丁基碘化铵，四丁基溴化铵，四丁基氯化铵，四丁基氟化铵，四丁基醋酸铵，四丁基氯化铵，四丁基硫酸铵，四丁基磷酸铵，四丁基磷酸二氢铵，四丁基磷酸一氢铵，四丁基苯甲酸铵，四丁基四丁基硼酸铵，四丁基氢氧化铵，四辛基碘化铵，四辛基溴化铵，四辛基氯化铵，四辛基氟化铵，四辛基醋酸铵，四辛基氯化铵，四辛基硫酸铵，四辛基磷酸铵，四辛基磷酸二氢铵，四辛基磷酸一氢铵，四辛基苯甲酸铵，四辛基四辛基硼酸铵，四辛基氢氧化铵。
在实施例六中，将纤维素纤维放入金属无机盐溶液中浸泡处理的时间范围是30分钟，浸泡温度范围50摄氏度。金属无机盐溶液中，金属无机盐的浓度范围为15％。金属无机盐溶液中的金属无机盐由铜盐、锌盐和银盐组成，三种组分的占比分别为50％、25％和25％。铜盐是：硫酸铜、氯化铜、醋酸铜、碳酸铜或者氢氧化铜。锌盐是醋酸锌、氯化锌或者硫酸锌。银盐是碳酸银、硝酸银或醋酸银。
以上陈述仅以实施例来进一步说明本发明的技术内容，以便于读者更容易理解，但不代表本发明的实施方式仅限于此，任何依本发明所做的技术延伸或再创造，均受本发明的保护。
现有的研究都是用氢氧化钠作为碱来分散纤维素分子，但是钠离子与阳离子的结合力不好。在水溶液中，由于离子快速交换，纤维素分子中的氢氧基团不能有效的脱氢带负电，因此纤维素分子仍然紧密结合在一起，如图1。而在本发明中，采用了锂离子来做碱，锂离子体积比钠离子小很多，与氧离子的直径几乎一样，与氧离子的结合效果好很多，因此产生带负电荷的纤维素分子。由于同电荷相互排斥的原理，纤维素分子可以很容易的分开，有利于无机盐分子(或离子)的渗透，如图2。另外，本发明的纤维素分子中有多支结构，这些结构具有带正电的铵离子，与氧负离子结合，产生树枝状的结构插入，可以有效防止纤维素分子由于氢键作用而相互结合。
本发明的制备方法可以有效的打乱纤维素分子的内部结晶结构，有利于金属无机盐分子的渗透、进入。这些无机盐分子或离子与纤维素分子的氢氧基团紧密结合，让织物表现出优良的耐水洗性能。图3为本发明制造的纤维素纤维水洗100次过程中铜离子含量变化表，图4为本发明制造的纤维素纤维水洗100次过程中抗菌性能变化表。从图3、4可以看出，水洗100次以后，铜离子还保留有70％以上的含量，纤维素纤维抗菌性能保持有99％，证明了本发明的制备方法制作的纤维素纤维具备长效耐水洗的抗菌能力。
Claims (11)
1.抗菌无机金属盐改性纤维素纤维的制备方法，其特征在于，所述方法包括以下步骤：
将纤维素纤维放入复合碱液中浸泡处理，所述复合碱液中含有浓度1％-15％的氢氧化锂以及浓度1％-25％的铵盐，浴比范围为1:10至1:200，浸泡时间为1至120分钟，浸泡温度范围是35-100摄氏度；
随后将纤维素纤维压榨或离心，随后烘干；
将纤维素纤维放入金属无机盐溶液中浸泡处理；
最后将纤维素纤维压榨或离心，随后烘干。
2.如权利要求1所述的制备方法，其特征在于，将纤维素纤维放入复合碱液中浸泡处理之后，使用过后的剩余复合碱液回收再利用。
3.如权利要求1所述的制备方法，其特征在于，将纤维素纤维进行烘干的温度为60摄氏度。
4.如权利要求1所述的制备方法，其特征在于，所述复合碱液中的铵盐的结构式为
其中n＝1-12，A-为碘离子、氯离子、溴离子、氟离子、醋酸根、硫酸根、磷酸根、磷酸二氢根、磷酸一氢根、苯甲酸根、硼酸根、氢氧根中的任一种。
5.如权利要求4所述的制备方法，其特征在于，所述铵盐为以下物质的至少一种：四丁基碘化铵，四丁基溴化铵，四丁基氯化铵，四丁基氟化铵，四丁基醋酸铵，四丁基氯化铵，四丁基硫酸铵，四丁基磷酸铵，四丁基磷酸二氢铵，四丁基磷酸一氢铵，四丁基苯甲酸铵，四丁基四丁基硼酸铵，四丁基氢氧化铵，四辛基碘化铵，四辛基溴化铵，四辛基氯化铵，四辛基氟化铵，四辛基醋酸铵，四辛基氯化铵，四辛基硫酸铵，四辛基磷酸铵，四辛基磷酸二氢铵，四辛基磷酸一氢铵，四辛基苯甲酸铵，四辛基四辛基硼酸铵，四辛基氢氧化铵。
6.如权利要求1所述的制备方法，其特征在于，所述金属无机盐溶液中，金属无机盐的浓度范围为0.1％-20％。
7.如权利要求1或6所述的制备方法，其特征在于，将纤维素纤维放入金属无机盐溶液中浸泡处理的时间范围是1-120分钟，浸泡温度范围25-95摄氏度。
8.如权利要求1或6所述的制备方法，其特征在于，所述金属无机盐溶液中的金属无机盐由铜盐、锌盐和银盐组成，三种组分的占比分别为0-100％、0-100％和0-100％。
9.如权利要求8所述的制备方法，其特征在于，所述铜盐是：硫酸铜、氯化铜、醋酸铜、碳酸铜或者氢氧化铜。
10.如权利要求8所述的制备方法，其特征在于，所述锌盐是醋酸锌、氯化锌或者硫酸锌。
11.如权利要求8所述的制备方法，其特征在于，所述银盐是碳酸银、硝酸银或醋酸银。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810188879.5A CN108468204A (zh) | 2018-03-08 | 2018-03-08 | 抗菌无机金属盐改性纤维素纤维的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810188879.5A CN108468204A (zh) | 2018-03-08 | 2018-03-08 | 抗菌无机金属盐改性纤维素纤维的制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108468204A true CN108468204A (zh) | 2018-08-31 |
Family
ID=63265198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810188879.5A Pending CN108468204A (zh) | 2018-03-08 | 2018-03-08 | 抗菌无机金属盐改性纤维素纤维的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108468204A (zh) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54101997A (en) * | 1978-01-26 | 1979-08-10 | Toyo Boseki | Quality improving finish for long fabric containing cellulose fiber |
| CN101157761A (zh) * | 2007-09-20 | 2008-04-09 | 东华大学 | 一种溶解纤维素的新型溶剂及其制备方法和用途 |
| CN101381957A (zh) * | 2008-09-11 | 2009-03-11 | 东华大学 | 一种抗变色银盐抗菌织物的整理方法 |
| CN101412813A (zh) * | 2008-05-26 | 2009-04-22 | 东华大学 | 一种低能耗制备的纤维素溶液及其新方法 |
| CN101787646A (zh) * | 2010-03-05 | 2010-07-28 | 浙江理工大学 | 一种含纤维素纤维纺织品的抗菌整理方法 |
| CN102702365A (zh) * | 2012-05-30 | 2012-10-03 | 华南理工大学 | 一种超低结晶度的微纳米纤维素的制备方法 |
| CN104470951A (zh) * | 2012-07-13 | 2015-03-25 | 赛佩荷兰服务有限公司 | 制备非衍生化纳米纤维素的低能耗方法 |
| CN107177040A (zh) * | 2017-06-05 | 2017-09-19 | 武汉大学 | 一种纤维素溶液及其溶解方法和应用 |
-
2018
- 2018-03-08 CN CN201810188879.5A patent/CN108468204A/zh active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54101997A (en) * | 1978-01-26 | 1979-08-10 | Toyo Boseki | Quality improving finish for long fabric containing cellulose fiber |
| CN101157761A (zh) * | 2007-09-20 | 2008-04-09 | 东华大学 | 一种溶解纤维素的新型溶剂及其制备方法和用途 |
| CN101412813A (zh) * | 2008-05-26 | 2009-04-22 | 东华大学 | 一种低能耗制备的纤维素溶液及其新方法 |
| CN101381957A (zh) * | 2008-09-11 | 2009-03-11 | 东华大学 | 一种抗变色银盐抗菌织物的整理方法 |
| CN101787646A (zh) * | 2010-03-05 | 2010-07-28 | 浙江理工大学 | 一种含纤维素纤维纺织品的抗菌整理方法 |
| CN102702365A (zh) * | 2012-05-30 | 2012-10-03 | 华南理工大学 | 一种超低结晶度的微纳米纤维素的制备方法 |
| CN104470951A (zh) * | 2012-07-13 | 2015-03-25 | 赛佩荷兰服务有限公司 | 制备非衍生化纳米纤维素的低能耗方法 |
| CN107177040A (zh) * | 2017-06-05 | 2017-09-19 | 武汉大学 | 一种纤维素溶液及其溶解方法和应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101187092A (zh) | 多离子海藻酸盐海洋纤维及其制备方法 | |
| CN102787380B (zh) | 一种秸秆再生纤维素纤维的制备方法 | |
| CN103835124B (zh) | 载银棉织物抗菌材料及其制备方法 | |
| CN102921049A (zh) | 抗菌医用导管及其制备方法 | |
| CN105401247A (zh) | 一种聚丙烯腈基高强度导电纤维的制备方法 | |
| CN105839229A (zh) | 铜离子改性壳聚糖纤维及其制备方法 | |
| CN112900076A (zh) | 一种多功能涤纶纤维及其制备方法 | |
| CN106012510B (zh) | 具耐洗性的抗菌纤维、抗菌纺织物及其制备方法 | |
| CN103835025A (zh) | 一种永久抗菌聚胍海藻纤维的制备方法 | |
| CN107675328A (zh) | 一种多功能面料的制造方法 | |
| CN113136633B (zh) | 一种长效抑菌阻燃双效莱赛尔纤维及其制备方法 | |
| CN106978642A (zh) | 防晒抗菌纤维原丝的制备方法 | |
| CN109778528A (zh) | 一种环保型抗菌纺织制品的制备方法 | |
| CN104233756B (zh) | 一种蚕丝织物砂洗工艺 | |
| CN108468204A (zh) | 抗菌无机金属盐改性纤维素纤维的制备方法 | |
| CN206501534U (zh) | 一种抗菌阻燃针织布 | |
| CN100362152C (zh) | 一种抗菌粘胶纤维及其生产方法 | |
| CN105088791B (zh) | 具有阻燃、抗菌和导电功能的织物及其制备方法 | |
| CN105714399A (zh) | 一种浅色碘化亚铜/聚丙烯腈复合导电纤维的制备方法 | |
| CN105780194B (zh) | 一种抗菌海藻纤维及其制备工艺 | |
| CN87104346A (zh) | 耐久性导电纤维的制造方法 | |
| CN110656391B (zh) | 一种复合导电面料及其制造方法 | |
| JP2023547271A (ja) | テキスタイル用抗微生物処理剤の調製方法 | |
| CN105369608A (zh) | 负载铜(ii)离子的功能纤维及其合成方法 | |
| CN108708017A (zh) | 一种具备阻燃效果的粘胶纤维与麻纤维混纺纱线的生产方法 |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180831 |
|
| RJ01 | Rejection of invention patent application after publication |