CN111205408A - Negative oxygen ion vinyl copolymer retanning agent, preparation method thereof and application of negative oxygen ion vinyl copolymer retanning agent in low-formaldehyde antibacterial leather - Google Patents
Negative oxygen ion vinyl copolymer retanning agent, preparation method thereof and application of negative oxygen ion vinyl copolymer retanning agent in low-formaldehyde antibacterial leather Download PDFInfo
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- CN111205408A CN111205408A CN202010031592.9A CN202010031592A CN111205408A CN 111205408 A CN111205408 A CN 111205408A CN 202010031592 A CN202010031592 A CN 202010031592A CN 111205408 A CN111205408 A CN 111205408A
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- China
- Prior art keywords
- negative oxygen
- oxygen ion
- parts
- initiator
- vinyl
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 70
- 239000001301 oxygen Substances 0.000 title claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 239000010985 leather Substances 0.000 title claims abstract description 43
- 229920006163 vinyl copolymer Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 48
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 15
- -1 oxygen ion Chemical class 0.000 claims abstract description 72
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 33
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 125000004442 acylamino group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 19
- 229920001661 Chitosan Polymers 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000004043 dyeing Methods 0.000 claims description 9
- 102000035118 modified proteins Human genes 0.000 claims description 9
- 108091005573 modified proteins Proteins 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- 229940070527 tourmaline Drugs 0.000 claims description 7
- 229910052613 tourmaline Inorganic materials 0.000 claims description 7
- 239000011032 tourmaline Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 239000012966 redox initiator Substances 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 2
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002192 fatty aldehydes Chemical class 0.000 description 2
- 239000000787 lecithin Substances 0.000 description 2
- 229940067606 lecithin Drugs 0.000 description 2
- 235000010445 lecithin Nutrition 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 101100042271 Mus musculus Sema3b gene Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000000051 wattle Anatomy 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
Abstract
The invention discloses a preparation method of a negative oxygen ion vinyl copolymer retanning agent, which comprises the following steps: weighing 1-10 parts of vinyl monomer containing acylamino, 0-10 parts of vinyl monomer containing carboxyl, 0-10 parts of vinyl quaternary ammonium salt, 1-10 parts of other vinyl monomers, 0-50 parts of water and 0-40 parts of chain transfer agent, fully stirring and uniformly mixing to obtain vinyl monomer mixed solution; taking an initiator and water, and fully stirring and dissolving the initiator and the water until the concentration of an initiator solution is 0.1-30% to obtain an initiator solution; taking a reaction vessel, adding 5-50 parts of water, 1-5 parts of negative oxygen ion material, 10-100 parts of vinyl monomer mixed solution and 5-50 parts of initiator solution into the reaction vessel, stirring and reacting at the constant temperature of 50-100 ℃ for 0.5-10h, standing and cooling; the invention realizes the composite modification of the negative oxygen ion material and the vinyl copolymer, produces the vinyl copolymer retanning agent capable of releasing the negative oxygen ion, can uniformly disperse the negative oxygen ion material in the solution, and can make leather release the negative oxygen ion from inside to outside.
Description
Technical Field
The invention relates to the technical field of leather-making chemistry and engineering, in particular to a negative oxygen ion vinyl copolymer retanning agent, a preparation method thereof and application thereof in low-formaldehyde antibacterial leather.
Background
The negative oxygen ions are called as 'air vitamins' and 'longevity elements' by human beings, have the effects of sterilizing, reducing dust, cleaning air, eliminating formaldehyde, improving immunity and regulating functional balance, have very important influence on the life activity and the service life of the human body, are very beneficial to the health of the human body and have important medical care function. The negative oxygen ion material is introduced into the leather, so that the produced leather has the function of releasing negative oxygen ions, can improve the quality of human living environment, purify ambient air, be pleasant to the mind and body, be beneficial to the physical and mental health of a user, eliminate free formaldehyde in the leather, have the antibacterial function, improve the grade of the leather product and improve the added value of the leather product.
At present, the negative oxygen ion leather is mainly coated on the surface of the leather by a finishing method through dispersing a negative oxygen ion material in the finishing process. As in application No.: 201811544559.5 discloses a leather capable of releasing negative oxygen ions, which comprises leather and a coating attached on the surface of the leather, wherein the coating is composed of the following raw materials: sodium chloride, tourmaline, sulfite, sodium carbonate, sodium fluosilicate and triethanolamine. The method can make the grain surface of the leather produce negative oxygen ions, but the flesh surface and the interior of the leather do not produce negative oxygen ions, thereby weakening the effects of eliminating formaldehyde and resisting bacteria.
If the negative oxygen ions are directly mixed in other procedures for preparing the leather, the produced negative oxygen ion leather is difficult to achieve the due effect when being applied due to poor dispersibility and easy agglomeration of the negative oxygen ion material.
Disclosure of Invention
The embodiment of the application solves the problems that the negative oxygen ion material has poor dispersibility and is easy to agglomerate and the produced negative oxygen leather is difficult to achieve the application effect in the prior art by providing the preparation method of the negative oxygen ion vinyl copolymer retanning agent and the application of the negative oxygen ion vinyl copolymer retanning agent in the low-formaldehyde antibacterial leather, realizes the composite modification of the negative oxygen ion material and the vinyl copolymer, produces the vinyl copolymer retanning agent capable of releasing the negative oxygen ions, can uniformly disperse the negative oxygen ion material in a solution, and can release the negative oxygen ions from inside to outside by bonding the vinyl copolymer retanning agent and leather collagen.
The embodiment of the application provides a preparation method of a negative oxygen ion vinyl copolymer retanning agent, which comprises the following steps:
(a) weighing 1-10 parts of vinyl monomer containing acylamino, 0-10 parts of vinyl monomer containing carboxyl, 0-10 parts of vinyl quaternary ammonium salt, 1-10 parts of other vinyl monomers, 0-50 parts of water and 0-40 parts of chain transfer agent, fully stirring and uniformly mixing to obtain vinyl monomer mixed solution;
(b) taking an initiator and water, and fully stirring and dissolving the initiator and the water until the concentration of an initiator solution is 0.1-30% to obtain an initiator solution;
(c) taking a reaction vessel, adding 5-50 parts of water, 1-5 parts of negative oxygen ion material, 10-100 parts of vinyl monomer mixed solution and 5-50 parts of initiator solution into the reaction vessel, stirring and reacting at the constant temperature of 50-100 ℃ for 0.5-10h, standing and cooling.
Further, the vinyl monomer containing the amido group is at least one of acrylamide, methacrylamide, maleic acid diamine and N-vinyl formamide;
the vinyl monomer containing carboxyl is at least one of acrylic acid, methacrylic acid, maleic acid and maleic acid monoester;
the vinyl-containing quaternary ammonium salt is at least one of dimethyl diallyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride and (3-acrylamidopropyl) trimethyl ammonium chloride;
the other vinyl monomer is at least one of methyl methacrylate, butyl methacrylate, acrylonitrile, styrene and maleic anhydride.
Further, the chain transfer agent is selected from at least one of methanol, isopropanol, sodium bisulfite, mercaptoethanol, mercaptoacetic acid, mercaptopropanol, mercaptopropionic acid, sodium hypophosphite, sodium formate and acetone.
Further, the initiator is any one of a peroxide initiator, an azo initiator and a redox initiator.
Further, the peroxide initiator is selected from any one or more of ammonium persulfate, potassium persulfate, sodium persulfate and tert-butyl hydroperoxide;
the azo initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate;
the redox initiator is selected from any one of tert-butyl hydroperoxide/sodium metabisulfite, ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite and persulfate/mercaptan; the redox initiator is an oxidant and a reductant, and is exemplified by t-butyl hydroperoxide/sodium metabisulfite, t-butyl hydroperoxide as the oxidant and sodium metabisulfite as the reductant.
Further, the negative oxygen ion material is selected from any one of water-soluble negative oxygen ion powder, superfine negative oxygen ion powder, nano negative oxygen ion powder, modified negative oxygen ion powder, nano tourmaline powder, superfine tourmaline powder and modified tourmaline powder;
the reaction vessel is a reaction kettle.
Further, the vinyl monomer mixed solution and the initiator solution in the step (c) are added by adopting a dropping method, and the dropping time is 0.1-3 h;
the concrete steps of the step (c) are as follows: taking a reaction vessel, adding water, negative oxygen ion material, vinyl monomer mixed solution and initiator solution into the reaction vessel, stirring and reacting for 0.5-10h at the constant temperature of 50-100 ℃, standing, cooling, neutralizing, concentrating and removing impurities.
The invention also provides an anionic vinyl copolymer retanning agent which can be obtained by the method described in the invention.
A preparation method of low-formaldehyde antibacterial leather at least comprises the working procedures of softening, retanning, neutralizing, filling dyeing, fatliquoring and color fixing, wherein a negative oxygen ion vinyl copolymer retanning agent is added in at least one of the working procedures of softening, retanning, neutralizing, filling dyeing, fatliquoring and color fixing, and cannot be added with other raw materials at the same time.
Further, at least one of chitosan modified protein filler and formaldehyde scavenger is added in at least one of the procedures of retanning, filling dyeing, fatliquoring and color fixing, and the chitosan modified protein filler and the formaldehyde scavenger cannot be added with other raw materials at the same time.
Further, the preparation method of the chitosan modified protein filler comprises the following steps: dissolving chitosan in acetic acid solution, adding protein extract, adjusting pH to 2-4.5, and reacting for 4-8 hr.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
1. the negative oxygen ion material is grafted to the vinyl copolymer, so that the negative oxygen ion material can be uniformly dispersed in the copolymer solution, and the copolymer retanning agent is combined with the collagen fibers of the leather, so that the negative oxygen ion material is uniformly dispersed in the leather, the leather can release negative oxygen ions from inside to outside, free formaldehyde in the leather is removed, bacteria inside and outside the leather are killed, and the leather has long-acting formaldehyde removing and antibacterial effects.
2. The amino has the effect of capturing formaldehyde, and the formaldehyde removing effect of the negative oxygen ion vinyl copolymer retanning agent can be improved by introducing the vinyl monomer containing the amido into the vinyl copolymer; the quaternary ammonium salt has an antibacterial effect, and the antibacterial effect of the negative oxygen ion vinyl copolymer retanning agent can be improved by introducing the vinyl-containing quaternary ammonium salt into the vinyl copolymer.
3. The protein can be used as a formaldehyde catching agent, the chitosan is a polyamino polymer, has good formaldehyde catching performance and also has an antibacterial effect, so the chitosan modified protein filler can be used as the protein filler to play a filling role, can be used as the formaldehyde catching agent to catch free formaldehyde and can also strengthen the antibacterial effect of leather.
4. The negative oxygen ion vinyl copolymer retanning agent prepared by the invention can be added with other raw materials in the retanning process at the same time, and no extra process is needed because the negative oxygen ion vinyl copolymer retanning agent can not react with other raw materials in the retanning process, and leather can release negative oxygen ions from inside to outside under the condition of not influencing production efficiency and leather making effect.
Detailed Description
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to the description and the specific embodiments.
Example 1
A preparation method of a negative oxygen ion vinyl copolymer retanning agent comprises the following steps:
(a) weighing 4 parts of acrylamide, 2 parts of methyl methacrylate, 2 parts of acrylonitrile, 2 parts of dimethyl diallyl ammonium chloride, 0.2 part of sodium bisulfite and 40 parts of water, and fully stirring and uniformly mixing to obtain a vinyl monomer mixed solution;
(b) weighing 0.5 part of potassium persulfate and 10 parts of water, and fully stirring and dissolving to obtain an initiator solution;
(c) weighing 5 parts of water-soluble negative oxygen ion powder, dissolving the powder in 20 parts of water, adding the powder into a reaction kettle, controlling the reaction temperature to be 80 ℃, dropwise adding the vinyl monomer mixed solution and the initiator solution while stirring, finishing dropwise adding for 1h, reacting at the constant temperature of 80 ℃ for 2h after finishing dropwise adding, standing and cooling.
Example 2
A preparation method of a negative oxygen ion vinyl copolymer retanning agent comprises the following steps:
(a) weighing 4 parts of acrylic acid, 2 parts of methyl methacrylate, 2 parts of acrylamide, 2 parts of maleic anhydride, 20 parts of isopropanol and 20 parts of water, and fully stirring and uniformly mixing to obtain a vinyl monomer mixed solution;
(b) weighing 0.1 part of ammonium persulfate and 10 parts of water, and fully stirring and dissolving to obtain an initiator solution;
(c) weighing 2 parts of superfine negative oxygen ion powder, adding the superfine negative oxygen ion powder into a reaction kettle, adding 20 parts of water, controlling the reaction temperature to be 80 ℃, dropwise adding the vinyl monomer mixed solution and the initiator solution while stirring, completing dropwise adding for 0.5h, reacting at the constant temperature of 80 ℃ for 2h after completion, standing, cooling to room temperature, neutralizing to pH 5-7 with sodium hydroxide, and concentrating, removing impurities and recovering isopropanol by using a distillation method.
Preparation of chitosan modified protein filler
Dissolving 1 part of chitosan into 10 parts of 5% acetic acid solution, adding 4 parts of cowhair keratin extract, adjusting the pH to about 3.5, and reacting for 4 hours to obtain the chitosan modified protein filler.
Preparation of low-formaldehyde antibacterial leather
The method comprises the steps of taking wet blue leather of a leather making enterprise, carrying out wringing, shaving and weighing, then putting into a rotary drum for wet dyeing and finishing, and calculating the chemical material quality by taking the shaved wet blue leather quality as a reference.
The wet dyeing and finishing method comprises the following specific steps:
softening: putting wet blue leather into a rotary drum, adding 200% of water, 0.5% of surfactant SAF (Delui leather chemical Co., Ltd.), 0.5% of oxalic acid into the rotary drum, controlling the temperature at 40 ℃, rotating for 90min, and draining.
Retanning: adding 100% of water, 2% of fatty aldehyde tanning agent PF (German Semaku Co., Ltd.), 2% of lecithin fatting agent BA (German Semaku Co., Ltd.), rotating at 30 deg.C for 30min, adding 3% of chrome tanning agent AB (Turkey Hill group), 2% of negative oxygen ion vinyl copolymer retanning agent, rotating at 30 deg.C for 60min, adding 2% of sodium formate, rotating at 30 deg.C for 15min, adding 0.3% of sodium bicarbonate, rotating at 30 deg.C for 60min, and draining.
Neutralizing: adding 100% water, 2% neutralizing tannin XNL (BASF corporation), 1.5% sodium sulfite into a rotary drum, controlling temperature at 30 deg.C, rotating for 30min, adding 0.5% sodium bicarbonate, rotating for 60min at 30 deg.C, and draining.
Filling and dyeing: adding 50% of water into a rotary drum, adding 2% of synthetic fatting agent BQ (Kyoho chemical Co., Ltd., Pengzhou), 3% of acrylic resin retanning agent R83 (Thompler, Germany), controlling the temperature to be 30 ℃ and rotating for 40min, adding 1% of neutralizing tannin XNL (Pasteur, Ltd.), 3% of wattle extract ME (Jinfeng leather chemical Co., Ltd.), 3% of synthetic tanning agent FO (Pasteur, Ltd.), 2% of melamine resin retanning agent DLF (Pasteur, Ltd.), 3% of synthetic tanning agent BN (Lalangen, Germany), rotating for 60min at 30 ℃, adding 2% of dye, and rotating for 60min at 30 ℃.
And (3) fixation: adding 100% hot water into the rotary drum, adding 1.5% synthetic fatting agent 94S, controlling the temperature at 50 deg.C, rotating for 20min, adding 2% chitosan modified protein filler, rotating for 30min at 50 deg.C, adding 0.6% formic acid, rotating for 10min at 50 deg.C, adding 0.7% formic acid, rotating for 20min at 50 deg.C, and draining.
Fat liquoring: adding 150% of warm water into a rotary drum, adding 1% of fatty aldehyde tanning agent PF (German Sema chemical Co., Ltd.), 3% of mixed fat-liquoring agent DB (German Thompler Co., Ltd.), 3% of synthetic fat-liquoring agent 94S, 3% of lecithin fat-liquoring agent NLM (Steal leather chemical Co., Ltd.), adding 0.5% of formaldehyde catching agent (Sichuan Tingjiang New Material Co., Ltd.), rotating at 50 ℃ for 60min, adding 3% of negative oxygen ion amphoteric acrylic resin, adding 1% of formic acid, rotating at 50 ℃ for 15min, adding 1.5% of formic acid, rotating at 50 ℃ for 20min, and draining.
Color register: adding 200% warm water into a rotary drum, adding 1% dye, controlling the temperature at 50 deg.C, rotating for 15min, adding 0.5% formic acid, rotating for 15min at 50 deg.C, adding 0.5% cationic fatting agent GS (Kelaien chemical Co., Ltd.), rotating for 10min at 50 deg.C, and washing with water to obtain the drum.
Standing the crust leather for 8h, squeezing water and stretching, vacuum drying, hanging and drying, drying in a drying tunnel, returning water, standing for 8h, vibrating and softening, and coating.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (11)
1. The preparation method of the negative oxygen ion vinyl copolymer retanning agent is characterized by comprising the following steps:
(a) weighing 1-10 parts of vinyl monomer containing acylamino, 0-10 parts of vinyl monomer containing carboxyl, 0-10 parts of vinyl quaternary ammonium salt, 1-10 parts of other vinyl monomers, 0-50 parts of water and 0-40 parts of chain transfer agent, fully stirring and uniformly mixing to obtain vinyl monomer mixed solution;
(b) taking an initiator and water, and fully stirring and dissolving the initiator and the water until the concentration of an initiator solution is 0.1-30% to obtain an initiator solution;
(c) taking a reaction vessel, adding 5-50 parts of water, 1-5 parts of negative oxygen ion material, 10-100 parts of vinyl monomer mixed solution and 5-50 parts of initiator solution into the reaction vessel, stirring and reacting at the constant temperature of 50-100 ℃ for 0.5-10h, standing and cooling.
2. The method for preparing a negative oxygen ion vinyl copolymer retanning agent according to claim 1, characterized in that,
the amido-containing vinyl monomer is at least one of acrylamide, methacrylamide, maleic acid diamine and N-vinyl formamide;
the vinyl monomer containing carboxyl is at least one of acrylic acid, methacrylic acid, maleic acid and maleic acid monoester;
the vinyl-containing quaternary ammonium salt is at least one of dimethyl diallyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride and (3-acrylamidopropyl) trimethyl ammonium chloride;
the other vinyl monomer is at least one of methyl methacrylate, butyl methacrylate, acrylonitrile, styrene and maleic anhydride.
3. The method for preparing a negative oxygen ion vinyl copolymer retanning agent according to claim 1, wherein the chain transfer agent is at least one selected from methanol, isopropanol, sodium bisulfite, mercaptoethanol, thioglycolic acid, mercaptopropanol, mercaptopropionic acid, sodium hypophosphite, sodium formate and acetone.
4. The method for preparing the negative oxygen ion vinyl copolymer retanning agent according to claim 1, wherein the initiator is any one of a peroxide initiator, an azo initiator and a redox initiator.
5. The method for preparing a negative oxygen ion vinyl copolymer retanning agent according to claim 4, characterized in that,
the peroxide initiator is selected from any one or more of ammonium persulfate, potassium persulfate, sodium persulfate and tert-butyl hydroperoxide;
the azo initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate;
the redox initiator is any one of tert-butyl hydroperoxide/sodium metabisulfite, ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite and persulfate/mercaptan.
6. The method for preparing a negative oxygen ion vinyl copolymer retanning agent according to claim 1, characterized in that,
the negative oxygen ion material is selected from any one of water-soluble negative oxygen ion powder, superfine negative oxygen ion powder, nano negative oxygen ion powder, modified negative oxygen ion powder, nano tourmaline powder, superfine tourmaline powder and modified tourmaline powder;
the reaction vessel is a reaction kettle.
7. The method for preparing a negative oxygen ion vinyl copolymer retanning agent according to claim 1, characterized in that,
the vinyl monomer mixed solution and the initiator solution in the step (c) are added by adopting a dripping method, and the dripping time is 0.1-3 h;
the concrete steps of the step (c) are as follows: taking a reaction vessel, adding 5-50 parts of water, 1-5 parts of negative oxygen ion material, 10-100 parts of vinyl monomer mixed solution and 5-50 parts of initiator solution into the reaction vessel, stirring and reacting at the constant temperature of 50-100 ℃ for 0.5-10h, standing, cooling, neutralizing, concentrating and removing impurities.
8. An anionic vinyl copolymer retanning agent, characterized in that it is prepared by the method according to any one of claims 1 to 7.
9. A preparation method of low-formaldehyde antibacterial leather at least comprises the working procedures of softening, retanning, neutralization, filling dyeing, fatliquoring and color fixing, and is characterized in that a negative oxygen ion vinyl copolymer retanning agent is added into at least one of the working procedures of softening, retanning, neutralization, filling dyeing, fatliquoring and color fixing.
10. The method for preparing low-formaldehyde antibacterial leather according to claim 9, wherein at least one of chitosan modified protein filler and formaldehyde scavenger is added in at least one of the steps of retanning, filling dyeing, fatliquoring and fixing.
11. The preparation method of the low-formaldehyde antibacterial leather according to claim 9, characterized in that the preparation method of the chitosan modified protein filler comprises the following steps: dissolving chitosan in acetic acid solution, adding protein extract, adjusting pH to 2-4.5, and reacting for 4-8 hr.
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