CN116606578A - Leather finishing agent and preparation method thereof - Google Patents
Leather finishing agent and preparation method thereof Download PDFInfo
- Publication number
- CN116606578A CN116606578A CN202310402151.9A CN202310402151A CN116606578A CN 116606578 A CN116606578 A CN 116606578A CN 202310402151 A CN202310402151 A CN 202310402151A CN 116606578 A CN116606578 A CN 116606578A
- Authority
- CN
- China
- Prior art keywords
- modified cellulose
- cellulose nanofiber
- parts
- reaction
- leather
- 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
- 239000010985 leather Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 229920002678 cellulose Polymers 0.000 claims abstract description 93
- 239000001913 cellulose Substances 0.000 claims abstract description 93
- 239000002121 nanofiber Substances 0.000 claims abstract description 93
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229920002635 polyurethane Polymers 0.000 claims abstract description 10
- 239000004814 polyurethane Substances 0.000 claims abstract description 10
- -1 carboxyethyl Chemical group 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 3
- 229940106681 chloroacetic acid Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- GKNOFYAURJKRPM-UHFFFAOYSA-N hydroxymethyl 2-hydroxyacetate Chemical compound OCOC(=O)CO GKNOFYAURJKRPM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002313 adhesive film Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 238000002444 silanisation Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000007385 chemical modification Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 239000011121 hardwood Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 229920005749 polyurethane resin Polymers 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
-
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- 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
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention relates to a leather finishing agent and a preparation method thereof. The leather finishing agent is specifically modified cellulose nanofiber bonding acrylic acid or polyurethane composite emulsion, wherein the modified cellulose nanofiber is at least one selected from carboxymethyl modified cellulose nanofiber, carboxyethyl modified cellulose nanofiber, silane group modified cellulose nanofiber, carboxymethyl-silanization modified cellulose nanofiber or carboxyethyl-silanization modified cellulose nanofiber. According to the invention, the modified cellulose nanofiber is introduced into the leather finishing material through chemical modification for the first time, so that the leather finishing adhesive film is endowed with excellent tensile strength, elongation at break and tearing strength, and meanwhile, the wear resistance and low-temperature folding endurance of the coating are improved.
Description
Technical Field
The invention relates to the technical field of leather making, in particular to a leather finishing agent and a preparation method thereof.
Background
The leather product has natural and comfortable touch feeling and good air permeability, and is widely applied in daily life. The leather coating has the function of protecting grain surface, and can make leather surface have various colors, luster and styles, and obtain certain waterproof property and easy maintenance. With the increasing consumer demand, there is a growing demand for both performance and functionality of leather products, and improvements in leather quality are largely dependent on leather finishes. At present, most of coating materials in China are imported, and domestic leather coating agents have the defects of low grade, insufficient functionality and the like, so that the development of the leather coating agent with excellent performance is favorable for realizing domestic substitution and breaking monopoly abroad.
The addition of the reinforcing auxiliary agent is a simple and effective means for improving the strength of the leather finishing agent. The nano particles are used as a small-size reinforcing auxiliary agent, have good compatibility with leather finishing agents, and the nano effect and the small-size effect of the nano materials obviously improve the strength, the wear resistance, the bending resistance and the like of the leather finishing agents. Chinese patent CN102286234A, CN101544820a proposes to add carbon nanotubes and organic montmorillonite as nano materials with excellent properties to leather finishing agents, and the solution can improve the properties of the resin, but it is not mentioned whether the tensile strength, elongation at break and tear strength can be simultaneously improved. Cellulose nanofibers (cellulose nanofiber, CNF) are prepared from various renewable plant materials, and as a new generation of green functional materials, show a broad application prospect in the field of high-performance composite materials. The cellulose nanofiber is prepared from natural cellulose fiber, has the characteristics of high strength, high modulus, large specific surface area, high length-diameter ratio and the like, and is a reinforcing material with excellent performance. However, because the specific surface area of the cellulose nanofiber is large and the surface contains a large amount of hydroxyl groups, the cellulose nanofiber is in an energy unstable state, and is extremely easy to form aggregation with surrounding cellulose nanofibers when being directly applied, so that further application of the cellulose nanofiber is limited.
According to the invention, the modified cellulose nanofiber and the acrylic acid or the polyurethane are chemically bonded to form the composite emulsion, so that the dispersibility of the modified cellulose nanofiber in the emulsion is further improved, and the novel leather finishing agent is prepared. The leather finishing agent has obviously improved tensile strength, elongation at break, tearing strength, wear resistance and flexing resistance, and has very important significance for leather requiring coating with high strength, excellent flexing resistance and wear resistance.
Disclosure of Invention
The invention aims to provide a leather finishing agent, which is specifically modified cellulose nanofiber bonding acrylic acid or polyurethane composite emulsion.
Further, the modified cellulose nanofiber is at least one selected from carboxymethyl modified cellulose nanofiber, carboxyethyl modified cellulose nanofiber, silyl modified cellulose nanofiber, carboxymethyl-silanized modified cellulose nanofiber and carboxyethyl-silanized modified cellulose nanofiber.
Further, the preparation method of the modified cellulose nanofiber specifically comprises the following steps: crushing wood pulp, adding the crushed wood pulp into a sodium hydroxide solution, uniformly stirring, adding a modifier for modification, concentrating, heating for reaction, and finally washing, diluting and grinding.
Further, the modifier is at least one selected from chloroacetic acid, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and acrylamide.
The second purpose of the invention is to provide a preparation method of the leather finishing agent, wherein the preparation method of the modified cellulose nanofiber bonding acrylic composite emulsion comprises the following steps:
step one: adding 90-120 parts (weight parts, the same applies below) of deionized water into a three-mouth bottle, heating to 60-70 ℃, and adding 0.8-1.5 parts of emulsifier;
step two: continuously heating to 90-95 ℃, firstly adding 1-3 parts of water phase monomer and 3-9 parts of oil phase monomer, then adding 0.5-0.7 part of potassium persulfate for reaction, and cooling to 80-85 ℃ after 15-20 min;
step three: slowly dripping 3-10 parts of oil phase monomer, 9-30 parts of water phase monomer and 0.1-0.5 part of potassium persulfate at the temperature of 80-85 ℃ for 2-2.5 hours;
step four: heating to 90-95 ℃ after the dripping is completed, and preserving heat for 2-3 h;
step five: cooling to 55-65 ℃, adding 0.5-1 part of emulsifier, stirring for 10-20 min, standing, filtering and discharging;
the adding time of the modified cellulose nanofiber is selected from the group consisting of adding the water phase monomer together in the second step or the third step, and adding the modified cellulose nanofiber after the heat preservation reaction in the fourth step. The adding time can enable the modified cellulose nanofiber to be bonded with different pre-polymerized monomers better, so that a good reinforcing effect is achieved.
In the synthesis process of the modified cellulose nanofiber bonding acrylic acid composite emulsion, the emulsifier is at least one of sodium dodecyl sulfate and tween 80, the water phase monomer is at least one of acrylamide and acrylic acid, and the oil phase monomer is at least one of ethyl acrylate, butyl acrylate, methyl acrylate and acrylonitrile.
The other preparation method of the leather finishing agent, namely the preparation method of the modified cellulose nanofiber bonding polyurethane composite emulsion, comprises the following steps:
step a: 50 to 70 parts of polyether glycol and 30 to 50 parts of diisocyanate are added into a three-mouth bottle to react for 2 to 3 hours at the temperature of 85 to 95 ℃;
step b: the temperature is reduced to 75-85 ℃, 10-20 parts of acetone is added firstly, then 5-10 parts of dimethylolformic acid and 1-5 parts of trimethylolpropane are added, and the reaction is continued for 2-3 hours;
step c: the temperature is reduced to 65-75 ℃, 10-15 parts of diethylene glycol and 15-25 parts of acetone are added and mixed uniformly, and then catalytic stannous octoate is added;
step d: reducing the temperature to 55-65 ℃, adding 60-120 parts of acetone, and continuing to react for 1-2 h;
step e: adding 5-10 parts of triethylamine into a three-mouth bottle, and carrying out neutralization reaction for 15-30 min;
step f: cooling the prepolymer obtained in the three-mouth bottle to room temperature, and then slowly pouring the prepolymer into 400-800 parts of water which is stirred at high speed to uniformly disperse the prepolymer;
step g: slowly heating the mixture to 50-75 ℃ for distillation for 1-2 h, cooling to 45-55 ℃ after distillation, and discharging;
the timing of the addition of the modified cellulose nanofibers can also be selected in various ways and can be added in step d or step f. The addition at these times is mainly because the prepared modified cellulose nanofibers are dispersed with water, and if the isocyanate groups are higher in activity at the time of addition in step a, b or c, the presence of water increases side reactions, whereas if the isocyanate groups are lower in reactivity of the prepolymer at the time of addition in step d or f, even if a small amount of water is present, the isocyanate groups preferentially react with hydroxyl groups on the modified cellulose nanofibers in the presence of a catalyst, thereby achieving chemical bonding of the polyurethane prepolymer with the modified cellulose nanofibers.
Further, the addition amount of the modified cellulose nanofiber in the leather finishing agent is equivalent to 0.2-5.0% of the weight of the dry basis of the reactants.
The cellulose nanofiber in the invention is modified by carboxymethyl, carboxyethyl, silane, carboxymethyl-silanization or carboxyethyl-silanization, so that the problem of agglomeration of the nanomaterial is avoided to a great extent, and excellent water dispersibility and compatibility are provided. Compared with unmodified cellulose nanofiber, the dispersibility of the modified cellulose nanofiber in a water system and the compatibility with other polymer monomers are greatly improved. Based on the characteristics, the modified cellulose nanofiber can be effectively chemically bonded with an acrylic polymer or a polyurethane prepolymer, and intermolecular forces such as chemical bonds, hydrogen bonds and molecular chain winding are formed between the modified cellulose nanofiber and the acrylic polymer or the polyurethane prepolymer, so that when the modified cellulose nanofiber is subjected to external forces, the physical properties of the resin for leather finishing, including tensile strength, elongation at break, tearing strength, wear resistance and bending resistance, are greatly improved.
Compared with the existing leather finishing agent products, the invention has the following main advantages:
(1) Preparing a novel leather finishing agent from cellulose nano fibers subjected to carboxymethyl modification, carboxyethyl modification, silane group modification, carboxymethyl-silanization modification or carboxyethyl-silanization modification through chemical bonding acrylic acid or polyurethane, wherein the leather finishing agent product shows excellent stability;
(2) The prepared leather finishing agent has excellent tensile strength, elongation at break, wear resistance and bending resistance, and compared with the existing vast majority of similar products which can only improve certain single performance, the invention can simultaneously improve the physical properties by optimizing and adjusting the formula;
(3) The cellulose nanofiber selected by the invention belongs to biomass-based materials, and has the characteristics of green, environment-friendly and easy degradation.
Drawings
FIG. 1 is a comparative illustration of the adhesive film formed by the leather finishing agent of comparative example 1, example 1 of the present invention;
FIG. 2 is a comparative drawing of the adhesive film formed by the leather finishing agent of comparative example 2 and example 4.
Detailed Description
In order to make the technical scheme and the beneficial effects of the present invention fully understood by those skilled in the art, the following description is further made with reference to specific embodiments and drawings.
Example 1
Preparation of carboxymethyl modified cellulose nanofiber
Weighing bleached sulfate hardwood pulp with an absolute dry mass of 100g, tearing the bleached sulfate hardwood pulp into pieces, then soaking the pieces in 500g of sodium hydroxide solution with a mass fraction of 20%, stirring to uniformly disperse the pulp, then pouring 300g of chloroacetic acid solution with a mass fraction of 25% into the dispersed suspension, uniformly stirring, concentrating the pulp to a pulp concentration of 20% by using a pulp bag, and repeatedly using the extruded filtrate. And (3) placing the concentrated slurry into a high-concentration mixing reactor, reacting for 1.5 hours at 90 ℃, washing the slurry to be neutral by clear water after the reaction is finished, and diluting the slurry with water until the slurry concentration is 3%. Repeatedly grinding the slurry by using a nanometer fine grinding machine at a rotating speed of 1500r/min until no obvious fiber is visible under an optical microscope, thereby obtaining the carboxymethyl modified cellulose nanofiber.
Preparation of acrylic leather finishing agent
Step one: 100g of deionized water is added into a three-mouth bottle, heated, stirred and warmed to 70 ℃, and 1.5g of sodium dodecyl sulfate is added;
step two: continuously heating to raise the temperature, when the temperature is raised to 95 ℃, simultaneously adding 1g of water phase monomer (acrylamide: acrylic acid=5:1, weight ratio) and 3g of oil phase monomer (butyl acrylate: methyl acrylate: acrylonitrile=10:1:1, weight ratio), then adding 0.67g of potassium persulfate, reacting the obtained mixture at 90 ℃ for 15min, and rapidly cooling to 85 ℃;
step three: when the temperature is stabilized at 85 ℃, dropwise adding the rest 5g of oil phase monomer (the oil phase monomer with the same proportion in the second step), 15g of water phase monomer (the water phase monomer with the same proportion in the second step) and 0.33g of potassium persulfate, and controlling the feeding speed to ensure uniform dropwise adding, wherein the dropwise adding time is 2 hours;
step four: heating to 90 ℃ after the dripping is completed, and reacting for 2.5h at the temperature;
step five: cooling to 60 ℃, adding 0.78g of Tween 80, stirring for 10min, standing for 10min, and then filtering and discharging to obtain the acrylic leather finishing agent.
The addition timing of the carboxymethyl modified cellulose nanofiber: and in the second step, when the temperature reaches 90 ℃, the carboxymethyl modified cellulose nanofiber and the water phase monomer are mixed and added together, and the dosage of the carboxymethyl modified cellulose nanofiber accounts for 0.5 percent of the weight of the total reactant dry basis of the acrylic resin.
Example 2
The carboxymethyl modified cellulose nanofiber and acrylic leather finishing agent were prepared in the same manner as in example 1.
And (3) adjusting the adding time of the carboxymethyl modified cellulose nanofiber to the third step, and dripping the carboxymethyl modified cellulose nanofiber and the water phase monomer together. The dosage of the carboxymethyl modified cellulose nanofiber accounts for 2.0 percent of the weight of the total reactant dry basis of the acrylic resin.
Example 3
Preparation of silyl modified cellulose nanofiber
Weighing bleached sulfate hardwood pulp with an absolute dry mass of 100g, tearing the bleached sulfate hardwood pulp into pieces, then soaking the pieces in 500g of sodium hydroxide solution with a mass fraction of 20%, stirring the pieces to uniformly disperse the pulp, then pouring 300g of 3- (2, 3-glycidoxy) propyl trimethoxy silane solution with a mass fraction of 20% into the dispersed suspension, uniformly stirring the solution, concentrating the slurry to a slurry concentration of 20% by using a slurry bag, and repeatedly using the extruded filtrate. And (3) placing the concentrated slurry into a high-concentration mixing reactor, reacting for 1.5 hours at 90 ℃, washing the slurry to be neutral by clear water after the reaction is finished, and diluting the slurry with water until the slurry concentration is 3%. The slurry was repeatedly ground using a nano fine grinder at a rotational speed of 1500r/min until no obvious fibers were visible under an optical microscope, thereby obtaining silane-based modified cellulose nanofibers.
The preparation process of the acrylic leather finishing agent is the same as in example 1, and the silane-based modified cellulose nanofiber is added after the heat preservation in the fourth step, wherein the addition amount of the silane-based modified cellulose nanofiber accounts for 5.0% of the dry weight of the total reactants of the acrylic resin.
Example 4
Preparation of carboxyethyl modified cellulose nanofiber
Weighing bleached sulfate hardwood pulp with an absolute dry mass of 100g, tearing the bleached sulfate hardwood pulp into pieces, then soaking the pieces in 500g of sodium hydroxide solution with a mass fraction of 20%, stirring to uniformly disperse the pulp, then pouring 300g of acrylamide solution with a mass fraction of 25% into the dispersed suspension, uniformly stirring, concentrating the pulp to a pulp concentration of 20% by using a pulp bag, and repeatedly using the extruded filtrate. And (3) placing the concentrated slurry into a high-concentration mixing reactor, reacting for 1.5 hours at 90 ℃, washing the slurry to be neutral by clear water after the reaction is finished, and diluting the slurry with water until the slurry concentration is 3%. The slurry was repeatedly ground using a nano fine grinder at a rotational speed of 1500r/min until no obvious fibers were visible under an optical microscope, thereby obtaining carboxyethyl modified cellulose nanofibers.
Preparation of polyurethane leather finishing agent
Step one: 62g of polyethylene glycol (molecular weight 1000) and 40g of toluene diisocyanate are weighed and poured into a dry three-mouth bottle, a condenser is opened, the mixture is sealed and stirred uniformly, and then the mixture is heated to 90 ℃ for reaction for 2 hours;
step two: after the temperature is reduced to 80 ℃,15 g of acetone is added so as to dilute the reaction solution, after the acetone and the reaction solution are uniformly mixed, 6g of dimethylolpropionic acid and 1.6g of trimethylolpropane are added, and the reaction is continued for 2 hours;
step three: after the temperature is reduced to 70 ℃, 9.1g of diethylene glycol and 15g of acetone are added, and the acetone is used for diluting the reaction solution again; adding 0.01g of stannous octoate catalyst after acetone and the reaction solution are uniformly mixed, and continuously reacting for 2 hours under sealed stirring;
step four: after the temperature is reduced to 60 ℃, 80g of acetone is added to dilute the reaction solution, and then the reaction is continuously carried out for 1 hour under sealed stirring;
step five: 5.2g of triethylamine is added into the prepolymer for neutralization, and the neutralization reaction time is about 15min;
step six, dispersing and emulsifying: cooling the obtained prepolymer to room temperature, pouring 400g of water into an emulsifier, stirring by a high-speed dispersing machine, and slowly pouring the prepolymer to uniformly disperse the prepolymer;
step seven: distilling the mixture, firstly heating the mixture to 50 ℃ to observe the liquid state, then continuously heating to about 70 ℃ to distill for 1h, and finally cooling to 50 ℃ to obtain the water-based polyurethane leather finishing agent.
The addition timing of the carboxyethyl modified cellulose nanofiber: and (3) adding acetone after the acetone is added in the fourth step, wherein the dosage of the acetone accounts for 3.0% of the weight of the total reactant dry basis of the polyurethane resin.
Example 5
The preparation method of the silyl modified cellulose nanofiber is the same as in example 3, and the preparation method of the polyurethane resin is the same as in example 4.
The adding time of the silane-based modified cellulose nanofiber is adjusted to step six, and the silane-based modified cellulose nanofiber is added together with water, wherein the dosage of the silane-based modified cellulose nanofiber accounts for 2.5% of the weight of the total reactant dry basis of the polyurethane resin.
Comparative example 1
The acrylic finish of example 1 was not added with modified cellulose nanofibers.
Comparative example 2
The polyurethane resin finish of example 4 was not added with modified cellulose nanofibers.
Comparative example 3
Preparation of unmodified cellulose nanofibers
Weighing bleached sulfate hardwood pulp with the absolute dry mass of 100g, tearing into pieces, then soaking in 500g of sodium hydroxide solution with the mass fraction of 20%, stirring to uniformly disperse the pulp, and concentrating the pulp to 20% by using a pulp bag after uniformly stirring. The slurry was washed to neutrality with clean water and then diluted with water to a slurry concentration of 3%. The slurry was repeatedly ground using a nano fine grinder at a rotational speed of 1500r/min until no obvious fibers were visible under an optical microscope, thereby obtaining cellulose nanofibers.
The preparation process of the acrylic leather finishing agent is the same as in example 1, and the unmodified cellulose nanofiber is added after the heat preservation in the fourth step, wherein the dosage of the unmodified cellulose nanofiber accounts for 5.0% of the weight of the total reactant dry basis of the acrylic resin.
Comparative example 4
Preparation of unmodified cellulose nanofibers comparative example 3 was prepared.
The unmodified cellulose nanofibers were added after the acetone addition in step four in the manner of example 4 in an amount of 3.0% based on the total dry weight of the polyurethane resin.
To fully understand the properties of the leather finishes prepared in the various examples, analytical tests were performed on samples of the products of examples 1-5 and comparative examples 1-4 with reference to the standard QB/T2223-1996 acrylic emulsion test method for tanning and QB/T2415-1998 aqueous emulsion polyurethane finishes, the results of which are shown in Table 1 below.
Table 1 mechanical properties comparison table of different leather finishing agent films
As can be seen from table 1, for the acrylic finishes of example 3 and comparative example 1, the tensile strength, elongation at break and tear strength of the adhesive film were all improved to a greater extent, by 113.69%, 80.60% and 37.37%, respectively, after the modified cellulose nanofibers were added; whereas comparative example 4 used the unmodified cellulose nanofiber bonded acrylic composite emulsion, the tensile strength, elongation at break, tear strength of the adhesive film were not significantly improved compared to the modified cellulose nanofiber product, which were 6.10%, 4.57% and 2.31%, respectively. The control experiment shows that the addition of the modified cellulose nanofiber can truly and remarkably improve various mechanical properties of the leather finishing agent adhesive film. In particular, the modified cellulose nanofiber is respectively bonded with the acrylic acid and polyurethane composite emulsion, so that multiple aims of simultaneously improving the tensile strength, the tearing strength and the breaking elongation of the leather finishing agent are achieved.
The adhesive films formed with the leather finishing agents prepared in comparative example 1 (left) and example 1 (right) are shown in fig. 1, and the adhesive films formed with the leather finishing agents prepared in comparative example 2 (left) and example 4 (right) are shown in fig. 2. From the figure, the modified cellulose nanofiber is uniformly dispersed between the leather finishing agent films, and can form a stable three-dimensional network structure with polymer chains in a mode of chemical bond, hydrogen bond, percolation network, chain entanglement, crystallization promotion and the like, and the physical and mechanical properties of the adhesive film can be improved due to the structure.
The leather finishing agents and finishing aids prepared in examples 1-5 and comparative examples 1-4 were used as leather finishing agents: water: pigment paste: hand feeling agent: wax = 6:5: the mass ratio of 2:1.5:1 is mixed, the friction revolution of the same batch of leather samples with obvious abrasion and the low-temperature folding resistance of different samples at the temperature of minus 10 ℃ are tested by referring to the preparation of a standard QB/T2716-2005 leather chemical test sample, and the test results are shown in Table 2.
Table 2 comparison of results of abrasion resistance and Low temperature folding resistance tests for different leather coatings
As can be seen from table 2, for the leather finishing resins such as different acrylic acid and polyurethane resin, the wear resistance of the leather coating is greatly improved, and part of the wear resistance is even improved by several times after the modified cellulose nanofiber is added, which shows that the introduction of the modified cellulose nanofiber remarkably improves the wear resistance of the leather finishing agent. The low-temperature folding resistance change of the leather coating is also obvious, and the leather coating can be improved by 1 to 4 times on the basis of the original leather coating after the modified cellulose nanofiber is added.
Claims (8)
1. A leather finish, characterized by: the leather finishing agent is specifically modified cellulose nanofiber bonding acrylic acid or polyurethane composite emulsion.
2. The leather finish of claim 1 wherein: the modified cellulose nanofiber is at least one selected from carboxymethyl modified cellulose nanofiber, carboxyethyl modified cellulose nanofiber, silyl modified cellulose nanofiber, carboxymethyl-silanized modified cellulose nanofiber and carboxyethyl-silanized modified cellulose nanofiber.
3. The leather finishing agent according to claim 1 or 2, characterized in that the modified cellulose nanofibers are prepared by the following method: crushing wood pulp, adding the crushed wood pulp into a sodium hydroxide solution, uniformly stirring, adding a modifier for modification, concentrating, heating for reaction, and finally washing, diluting and grinding.
4. The leather finish of claim 3 wherein: the modifier is at least one selected from chloroacetic acid, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and acrylamide.
5. A method of preparing a leather finish according to claim 1, comprising the steps of:
step one: adding 90-120 parts of deionized water into a reactor, heating to 60-70 ℃, and adding 0.8-1.5 parts of emulsifier;
step two: continuously heating to 90-95 ℃, then adding 1-3 parts of water phase monomer and 3-9 parts of oil phase monomer, then adding 0.5-0.7 part of potassium persulfate for reaction, and cooling to 80-85 ℃ after the reaction is finished;
step three: controlling the temperature of the reactants to be stable at 80-85 ℃, and slowly dripping 3-10 parts of oil phase monomers, 9-30 parts of water phase monomers and 0.1-0.5 part of potassium persulfate;
step four: after the dripping is finished, heating to 90-95 ℃ and preserving heat for reaction;
step five: cooling to 55-65 ℃, adding 0.5-1 part of emulsifier, fully stirring, standing, filtering, and discharging;
and adding the modified cellulose nanofiber together when the water phase monomer is added dropwise in the second step or the third step, or adding the modified cellulose nanofiber after the heat preservation reaction in the fourth step is finished.
6. The method of claim 5, wherein: the emulsifier is at least one of sodium dodecyl sulfate and Tween 80, the water phase monomer is at least one of acrylamide and acrylic acid, and the oil phase monomer is at least one of ethyl acrylate, butyl acrylate, methyl acrylate and acrylonitrile.
7. A process for preparing a leather finish as claimed in claim 1, comprising the steps of:
step a: 50 to 70 parts of polyether glycol and 30 to 50 parts of diisocyanate are added into a reactor to react at a temperature of between 85 and 95 ℃;
step b: the temperature is reduced to 75-85 ℃, 10-20 parts of acetone is added firstly, then 5-10 parts of dimethylolformic acid and 1-5 parts of trimethylolpropane are added for continuous reaction;
step c: the temperature is reduced to 65-75 ℃, 10-15 parts of diethylene glycol and 15-25 parts of acetone are added and mixed uniformly, and then catalytic stannous octoate is added;
step d: reducing the temperature to 55-65 ℃, adding 60-120 parts of acetone, and continuing the reaction;
step e: adding 5-10 parts of triethylamine to perform neutralization reaction;
step f: cooling the obtained prepolymer to room temperature, and then slowly pouring the prepolymer into 400-800 parts of water which is stirred at a high speed to uniformly disperse the prepolymer;
step g: slowly heating the mixture to 50-75 ℃ for distillation, cooling to 45-55 ℃ after distillation, and discharging;
during which modified cellulose nanofibers are added in step d or step f.
8. The method of claim 5 or 7, wherein: the addition amount of the modified cellulose nanofiber is equivalent to 0.2-5.0% of the total reactant dry basis weight.
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