CN115354507A - Polyurethane synthetic leather and preparation method thereof - Google Patents
Polyurethane synthetic leather and preparation method thereof Download PDFInfo
- Publication number
- CN115354507A CN115354507A CN202211172250.4A CN202211172250A CN115354507A CN 115354507 A CN115354507 A CN 115354507A CN 202211172250 A CN202211172250 A CN 202211172250A CN 115354507 A CN115354507 A CN 115354507A
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- Prior art keywords
- polyurethane
- filler
- bio
- based filler
- synthetic leather
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- Pending
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 66
- 239000004814 polyurethane Substances 0.000 title claims abstract description 66
- 239000002649 leather substitute Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 122
- 238000005187 foaming Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000003607 modifier Substances 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 239000013538 functional additive Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000002715 modification method Methods 0.000 claims abstract description 4
- 240000005979 Hordeum vulgare Species 0.000 claims description 56
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 56
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000002344 surface layer Substances 0.000 claims description 12
- 240000007594 Oryza sativa Species 0.000 claims description 11
- 235000007164 Oryza sativa Nutrition 0.000 claims description 11
- 235000009566 rice Nutrition 0.000 claims description 11
- 238000004513 sizing Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 235000021307 Triticum Nutrition 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 239000004800 polyvinyl chloride Substances 0.000 claims description 8
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 8
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- -1 vinyl t-butylsilane Chemical compound 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 235000015001 Cucumis melo var inodorus Nutrition 0.000 claims description 6
- 240000002495 Cucumis melo var. inodorus Species 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 244000062793 Sorghum vulgare Species 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 235000013399 edible fruits Nutrition 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 244000017020 Ipomoea batatas Species 0.000 claims description 5
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 5
- 235000013339 cereals Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000010985 leather Substances 0.000 claims description 5
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- 244000099147 Ananas comosus Species 0.000 claims description 4
- 235000007119 Ananas comosus Nutrition 0.000 claims description 4
- 244000075850 Avena orientalis Species 0.000 claims description 4
- 235000007319 Avena orientalis Nutrition 0.000 claims description 4
- 235000007558 Avena sp Nutrition 0.000 claims description 4
- 235000005979 Citrus limon Nutrition 0.000 claims description 4
- 244000131522 Citrus pyriformis Species 0.000 claims description 4
- 235000011430 Malus pumila Nutrition 0.000 claims description 4
- 235000015103 Malus silvestris Nutrition 0.000 claims description 4
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 235000004879 dioscorea Nutrition 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 241000675108 Citrus tangerina Species 0.000 claims description 3
- 240000000560 Citrus x paradisi Species 0.000 claims description 3
- 235000006481 Colocasia esculenta Nutrition 0.000 claims description 3
- 244000205754 Colocasia esculenta Species 0.000 claims description 3
- 235000009917 Crataegus X brevipes Nutrition 0.000 claims description 3
- 235000013204 Crataegus X haemacarpa Nutrition 0.000 claims description 3
- 235000009685 Crataegus X maligna Nutrition 0.000 claims description 3
- 235000009444 Crataegus X rubrocarnea Nutrition 0.000 claims description 3
- 235000009486 Crataegus bullatus Nutrition 0.000 claims description 3
- 235000017181 Crataegus chrysocarpa Nutrition 0.000 claims description 3
- 235000009682 Crataegus limnophila Nutrition 0.000 claims description 3
- 240000000171 Crataegus monogyna Species 0.000 claims description 3
- 235000004423 Crataegus monogyna Nutrition 0.000 claims description 3
- 235000002313 Crataegus paludosa Nutrition 0.000 claims description 3
- 235000009840 Crataegus x incaedua Nutrition 0.000 claims description 3
- 235000009847 Cucumis melo var cantalupensis Nutrition 0.000 claims description 3
- 235000009008 Eriobotrya japonica Nutrition 0.000 claims description 3
- 244000061508 Eriobotrya japonica Species 0.000 claims description 3
- 235000009419 Fagopyrum esculentum Nutrition 0.000 claims description 3
- 240000008620 Fagopyrum esculentum Species 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- 244000068988 Glycine max Species 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 240000005561 Musa balbisiana Species 0.000 claims description 3
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 3
- 240000002582 Oryza sativa Indica Group Species 0.000 claims description 3
- 240000008467 Oryza sativa Japonica Group Species 0.000 claims description 3
- 235000010582 Pisum sativum Nutrition 0.000 claims description 3
- 240000004713 Pisum sativum Species 0.000 claims description 3
- 235000014443 Pyrus communis Nutrition 0.000 claims description 3
- 240000001987 Pyrus communis Species 0.000 claims description 3
- 235000007238 Secale cereale Nutrition 0.000 claims description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 3
- 244000061456 Solanum tuberosum Species 0.000 claims description 3
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 3
- 240000006909 Tilia x europaea Species 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 235000010749 Vicia faba Nutrition 0.000 claims description 3
- 240000006677 Vicia faba Species 0.000 claims description 3
- 235000002098 Vicia faba var. major Nutrition 0.000 claims description 3
- 240000004922 Vigna radiata Species 0.000 claims description 3
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 3
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 3
- 235000011453 Vigna umbellata Nutrition 0.000 claims description 3
- 240000001417 Vigna umbellata Species 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 238000004049 embossing Methods 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 235000019713 millet Nutrition 0.000 claims description 3
- 235000012015 potatoes Nutrition 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 claims description 2
- PXKPPXIGPAIWDZ-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propanenitrile Chemical compound C[Si](Cl)(Cl)CCC#N PXKPPXIGPAIWDZ-UHFFFAOYSA-N 0.000 claims description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- OLBGECWYBGXCNV-UHFFFAOYSA-N 3-trichlorosilylpropanenitrile Chemical compound Cl[Si](Cl)(Cl)CCC#N OLBGECWYBGXCNV-UHFFFAOYSA-N 0.000 claims description 2
- DOGMJCPBZJUYGB-UHFFFAOYSA-N 3-trichlorosilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](Cl)(Cl)Cl DOGMJCPBZJUYGB-UHFFFAOYSA-N 0.000 claims description 2
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims description 2
- JXQSCKZGQIKTIC-UHFFFAOYSA-M CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCO[Si](C)(C)C.[Cl-] Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCO[Si](C)(C)C.[Cl-] JXQSCKZGQIKTIC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007730 finishing process Methods 0.000 claims description 2
- 235000021374 legumes Nutrition 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 244000098338 Triticum aestivum Species 0.000 claims 3
- 244000241257 Cucumis melo Species 0.000 claims 1
- 241000220225 Malus Species 0.000 claims 1
- 241001481296 Malus spectabilis Species 0.000 claims 1
- 241000209056 Secale Species 0.000 claims 1
- 229920000620 organic polymer Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 230000000704 physical effect Effects 0.000 abstract description 7
- 238000007385 chemical modification Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 241000209140 Triticum Species 0.000 description 6
- 235000013312 flour Nutrition 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 6
- 244000070406 Malus silvestris Species 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 244000064895 Cucumis melo subsp melo Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 235000005087 Malus prunifolia Nutrition 0.000 description 2
- 244000082988 Secale cereale Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006025 bioresin Polymers 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides polyurethane synthetic leather, which comprises a polyurethane foaming layer, wherein the raw material components of the polyurethane foaming layer comprise polyurethane, a filler, a cross-linking agent, color paste and other functional additives, the filler is a modified bio-based filler, and the modified bio-based filler is prepared by the following method: the surface modified bio-based filler is obtained by the bio-based filler and the modifier through a mechanochemical modification method. The invention also provides a preparation method of the polyurethane synthetic leather. According to the polyurethane synthetic leather containing the modified bio-based filler and the preparation method thereof, various bio-based fillers are modified, the modifier and the bio-based filler are efficiently compounded by a physical and chemical modification method, the adding proportion of the modified bio-based filler in resin is greatly improved, the basic physical properties of a resin formula are greatly reserved, and the storage stability of the formula is greatly improved.
Description
Technical Field
The invention belongs to the technical field of fillers for synthetic leather, and particularly relates to polyurethane synthetic leather containing modified bio-based fillers and a preparation method thereof.
Background
Biobased materials are increasingly gaining attention from various industries, especially the consumer market, in the context of carbon neutralization and the large environment where carbon peaks are reached. The bio-based material may be realized by a bio-based resin material and a bio-based filler. There are several main types of sources of bio-based fillers: 1. cereals including rice (indica rice, japonica rice, rice \31973), wheat (wheat, barley, oat, rye), corn, sorghum, millet, yellow rice, buckwheat, etc.; 2. bean and bean products including soybean, broad bean, pea, mung bean, small red bean, kidney bean, etc.; 3. potatoes, including sweet potatoes, also called sweet potatoes or sweet potatoes, yams, taros, cassava and the like; 4. fruits: apple, crabapple, loquat, hawthorn, pear, tangerine, orange, lemon, lime, grapefruit, honeydew melon, muskmelon, honeydew melon, banana, pineapple and the like.
By recycling the bio-based materials, for example, barley and oat fillers can be prepared from various wheat residues after beer brewing through extraction, separation, grinding, screening and other processes, and apple, lemon and pineapple fillers can be prepared from residues after various fruits are juiced through extraction, separation, grinding, screening and other processes. The biological filler can be added into solvent-free polyurethane and waterborne polyurethane resin to prepare a new generation of biological-based synthetic leather, can be added into epoxy resin to prepare a new generation of products such as biological-based adhesives and engineering plastics, and can also be added into other thermoplastic resins to prepare various consumer products including but not limited to insoles, yoga mats, buttons, zippers and the like.
Various bio-based fillers in the current market generally have the following common problems: 1. the addition is difficult, and the plant-based filler is difficult to be added into various resins in large proportion due to the natural structure, appearance and characteristics of the plant-based filler. Particularly, the synthetic leather with high bio-based content is difficult to be added into a water-based polyurethane resin system; 2. physical properties can not meet actual requirements, and due to the fact that the unmodified filler has a plurality of defects and the strength can not be compared favorably with that of a natural inorganic filler, physical property indexes of the prepared material are greatly reduced, and updating iteration of the existing product is difficult to realize; 3. the compatibility is poor, and the bio-based filler is difficult to be uniformly and stably dissolved in various resins and stably exists due to the loss of polarity and active groups, particularly difficult to stably exist in the waterborne polyurethane resin, and realizes long-term stable production.
Disclosure of Invention
Based on the defects in the prior art, the invention provides the polyurethane synthetic leather containing the modified bio-based filler and the preparation method thereof, various bio-based fillers are modified, the adding proportion of the modified bio-based filler in resin is greatly improved, the basic physical properties of the resin formula are greatly kept, and the storage stability of the formula is greatly improved.
In a first aspect, the invention provides polyurethane synthetic leather, which comprises a polyurethane foaming layer, wherein the raw material components of the polyurethane foaming layer comprise polyurethane, a filler, a cross-linking agent, color paste and other functional additives, and the polyurethane synthetic leather is characterized in that the filler is a modified bio-based filler, and the modified bio-based filler is prepared by the following method: the surface modified bio-based filler is obtained by the bio-based filler and the modifier through a mechanochemical modification method.
According to the invention, the bio-based filler of the invention generates various physical and chemical phenomena under the action of mechanical force, and the internal structure, the physical and chemical properties and the chemical reactivity of the bio-based filler correspondingly generate a series of changes. The bio-based filler is severely impacted under the action of strong mechanical force, and when the surface structure and the shape are damaged, a plasma process can be locally generated, so that the temperature and the activation energy of the system reaction are reduced, and the reaction among substances is induced.
According to a preferred embodiment of the present invention, the mass ratio of the modified bio-based filler to the polyurethane is (10-20): 100.
according to a preferred embodiment of the invention, said bio-based filler is selected from at least one of cereals, legumes, tubers and fruits; wherein the cereal is selected from at least one of rice, wheat, corn, sorghum, millet, yellow rice and buckwheat, the rice comprises indica rice, japonica rice and glutinous rice, and the wheat comprises wheat, barley, oat and rye; the bean product class is at least one selected from soybean, broad bean, pea, mung bean, small red bean and kidney bean; the potatoes are selected from at least one of sweet potatoes, yams, taros and cassava; the fruit is selected from at least one of apple, crab apple, loquat, hawthorn, pear, tangerine, orange, lemon, lime, pomelo, honeydew melon, muskmelon, honeydew melon, banana and pineapple.
According to a preferred embodiment of the present invention, the modifying agent includes a coupling agent, a surfactant, an unsaturated organic acid, and a water-soluble organic high polymer; the coupling agent is selected from at least one of silane, polyether, titanate, aluminate and organic chromium, the silane coupling agent is selected from at least one of vinyl trichlorosilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl triacetoxysilane, vinyl t-butylsilane triperoxide, vinyl methyldichlorosilane, gamma-chloropropyltrichlorosilane, gamma-chloropropylmethyldichlorosilane, gamma-chloropropyltrimethoxysilane, gamma-chloropropyltriethoxysilane, chloromethyl triethoxysilane, beta-cyanoethyltrichlorosilane, beta-cyanoethylmethyldichlorosilane, beta-cyanoethyltriethoxysilane, gamma-cyanoethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, octadecyl-dimethyl- (3-trimethylsiloxypropyl) ammonium chloride, 4-vinylbenzyldimethyl- (3-trimethylsiloxypropyl) ammonium chloride, gamma-methacryloxypropyltrichlorosilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane and gamma-methacryloxypropylmethyldimethoxysilane, the polyether coupling agent is selected from at least one of fatty alcohol polyvinyl chloride ether, phenol polyvinyl chloride ether, lipid polyvinyl chloride ether, fatty amine polyvinyl chloride ether, polyethylene glycol, polypropylene glycol, propylene glycol block polyether, fatty alcohol polyoxypropylene ether and polyether, and the titanate coupling agent comprises a methyl alkoxy type, a poly (propylene glycol ether), a poly (ethylene glycol ether) and a poly (ethylene glycol ether), monoalkoxy pyrophosphate type, integral type, and ligand type.
According to a preferred embodiment of the invention, the modifier is used in an amount of 0.1% to 5% by mass of the bio-based filler.
In a second aspect, the present invention also provides a method for preparing polyurethane synthetic leather as described above, comprising the steps of:
preparing polyurethane surface layer slurry and polyurethane foaming layer slurry, wherein the raw material components of the polyurethane foaming layer comprise polyurethane, a filler, a cross-linking agent, color paste and other functional additives, and the filler is a modified bio-based filler;
step (2), coating and scraping the polyurethane surface layer slurry on release paper, and then putting the release paper into an oven for drying and curing;
step (3), coating foaming slurry on the basis of the polyurethane surface layer obtained in the step (2), and then putting the polyurethane surface layer into an oven for drying and curing;
step (4), coating adhesive glue on the basis of the polyurethane foaming layer obtained in the step (3), then putting the polyurethane foaming layer into an oven for drying and curing, then attaching the polyurethane foaming layer to base cloth, and tearing off release paper;
step (5), placing the leather obtained in the step (4) into an oven for foaming;
and (6) finishing the foamed synthetic leather product to obtain a polyurethane synthetic leather finished product.
According to a preferred embodiment of the present invention, in step (1), the method for preparing the modified bio-based filler comprises: adding a nodular graphite medium, the bio-based filler and the modifier into a ball mill for nodular graphite, grinding at the rotating speed of 30-50rpm for 0.5-5h, discharging, and screening to obtain the modified bio-based filler.
According to a preferred embodiment of the present invention, in the step (2), the sizing amount of the polyurethane surface layer sizing agent is 80-100g/m 2 (ii) a In the step (3), the coating and scraping sizing amount of the polyurethane foaming sizing agent is 200-300g/m 2 (ii) a In the step (4), the coating and sizing amount of the adhesive is 80-140g/m 2 。
According to a preferred embodiment of the present invention, in the step (2), the temperature setting range and the drying time of the oven are as follows: one section is at 80-100 deg.C for 1min, two sections are at 110-120 deg.C for 45S, and three sections are at 120-130 deg.C for 30S; in the step (3), the temperature setting range and the drying time of the oven are as follows: one section is at 80-100 deg.C for 1min, two sections are at 110-120 deg.C for 1min, and three sections are at 120-130 deg.C for 1min; in the step (5), the foaming temperature of the oven is 200-250 ℃, and the foaming time is 2-3min.
According to a preferred embodiment of the invention, the finishing process comprises color changing, embossing, surface treatment and graining.
Compared with the prior art, the invention has the following beneficial effects:
according to the polyurethane synthetic leather containing the modified bio-based filler and the preparation method thereof, various bio-based fillers are modified, the modifier and the bio-based filler are efficiently compounded by a physical and chemical modification method, the adding proportion of the modified bio-based filler in resin is greatly improved, the basic physical properties of a resin formula are greatly reserved, and the storage stability of the formula is greatly improved.
Detailed Description
The present invention will be further described with reference to the following specific examples. It is to be understood that the following examples are illustrative of the present invention only and are not intended to limit the scope of the present invention.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The invention provides polyurethane synthetic leather which comprises a polyurethane foaming layer, wherein the raw material components of the polyurethane foaming layer comprise polyurethane, a filler, a cross-linking agent, color paste and other functional additives, wherein the filler is a modified bio-based filler.
In general, the methods of modifying bio-based fillers can be divided into: wet method and dry method. According to the principle of modification, the method can be divided into the following steps: physical modification and chemical modification, wherein the physical modification comprises the following steps: surface coating, surfactant modification, high-energy surface modification and encapsulation treatment, wherein the chemical modification comprises the following steps: surface deposition, chemical coating, mechanochemistry, monomer adsorption coating and polymerization.
In the invention, the modified bio-based filler is prepared by the following method: the surface modified bio-based filler is obtained by the bio-based filler and the modifier through a mechanochemical modification method. The main principle is that the modifier and the bio-based filler are efficiently compounded through physical and chemical modification, the bio-based filler generates various physical and chemical phenomena under the action of mechanical force, and the internal structure, the physical and chemical properties and the chemical reactivity of the bio-based filler correspondingly generate a series of changes. The bio-based filler is severely impacted under the action of strong mechanical force, and when the surface structure and the shape are damaged, a plasma process can be locally generated, so that the temperature and the activation energy of the system reaction are reduced, and the reaction among substances is induced.
The process for the preparation of the modified bio-based filler according to the invention is described in detail below by means of examples 1-9, all taking barley filler as an example as bio-based filler.
Example 1:
a preparation method of mechanical mechanochemical modified barley filler comprises the following steps: putting alumina balls into a ball mill; the barley filler with the D50 of about 300 meshes and the modifier gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane are simultaneously added into a ball mill, the dosage of the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 1 percent of the mass of the barley filler, the barley filler is ground for 2h to 3h at the rotating speed of 30rpm, the barley filler is discharged and sieved, and modified barley fillers with different particle sizes are obtained by utilizing screens with different pore diameters.
Example 2:
a preparation method of mechanochemical modified barley filler comprises the following steps: loading alumina balls into a ball mill; the barley filler with the D50 of about 300 meshes and the modifier gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane are simultaneously added into a ball mill, the dosage of the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 3 percent of the mass of the barley filler, the barley filler is ground for 2h to 3h at the rotating speed of 50rpm, the barley filler is discharged and sieved, and the modified barley filler with different particle sizes is obtained by utilizing screens with different pore diameters.
Example 3:
a preparation method of mechanical mechanochemical modified barley filler comprises the following steps: putting alumina balls into a ball mill; the method comprises the steps of simultaneously adding barley filler with the D50 of about 600 meshes and modifier gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into a ball mill, wherein the using amount of the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 2% of the mass of the barley filler, grinding for 2h-3h at the rotating speed of 50rpm, discharging, screening, and obtaining the modified barley filler with different particle sizes by using screens with different pore diameters.
Example 4:
a preparation method of mechanical mechanochemical modified barley filler comprises the following steps: putting alumina balls into a ball mill; the barley filler with the D50 of about 300 meshes and the modifier gamma- (2, 3-epoxypropoxy) propyl triethoxysilane are simultaneously added into a ball mill, the dosage of the gamma- (2, 3-epoxypropoxy) propyl triethoxysilane is 2 percent of the weight of the barley filler, the barley filler is ground for 2 to 3 hours at the rotating speed of 50rpm, the barley filler is discharged and sieved, and modified barley fillers with different particle sizes are obtained by utilizing screens with different pore diameters.
Example 5:
a preparation method of mechanochemical modified barley filler comprises the following steps: putting alumina balls into a ball mill; and simultaneously adding the barley filler with the D50 of about 300 meshes and the modifier of vinyltriethoxysilane into a ball mill, wherein the dosage of the vinyltriethoxysilane is 2% of the mass of the barley filler, grinding for 2h-3h at the rotating speed of 50rpm, discharging, sieving, and obtaining the modified barley filler with different particle sizes by using sieves with different apertures.
Example 6:
a preparation method of mechanical mechanochemical modified barley filler comprises the following steps: loading alumina balls into a ball mill; the method comprises the steps of simultaneously adding barley filler with the D50 of about 300 meshes and gamma chloropropyl trimethoxy silane serving as a modifier into a ball mill, grinding for 2-3 h at the rotating speed of 50rpm, discharging, screening, and obtaining the modified barley filler with different particle sizes by using screens with different pore diameters, wherein the dosage of the gamma chloropropyl trimethoxy silane is 2% of the mass of the barley filler.
Example 7:
a preparation method of mechanical mechanochemical modified barley filler comprises the following steps: putting alumina balls into a ball mill; the method comprises the steps of simultaneously adding barley filler with the D50 of about 600 meshes and a modifier of methacryloxypropyl trimethoxy silane into a ball mill, grinding for 2-3 h at the rotating speed of 50rpm to discharge, sieving, and obtaining the modified barley filler with different particle sizes by using sieves with different pore diameters, wherein the usage amount of the methacryloxypropyl trimethoxy silane is 2% of the mass of the barley filler.
Example 8:
a preparation method of mechanochemical modified barley filler comprises the following steps: loading alumina balls into a ball mill; and simultaneously adding the barley filler with the D50 of about 600 meshes and the modifier 3-isocyanatopropyl triethoxysilane into a ball mill, grinding the barley filler for 2-3 h at the rotating speed of 50rpm, discharging, screening, and obtaining the modified barley filler with different particle sizes by using screens with different apertures, wherein the dosage of the 3-isocyanatopropyl triethoxysilane is 2% of the mass of the barley filler.
Example 9:
a preparation method of mechanical mechanochemical modified barley filler comprises the following steps: loading alumina balls into a ball mill; the barley filler with the D50 of about 600 meshes and the modifier of triisostearoyl isopropyl titanate are simultaneously added into a ball mill, the dosage of the triisostearoyl isopropyl titanate is 2 percent of the mass of the barley filler, the barley filler is ground for 2h-3h at the rotating speed of 50rpm, the barley filler is discharged and sieved, and modified barley fillers with different particle sizes are obtained by utilizing screens with different apertures.
The amounts of barley flour and modifier used in examples 1-9 are listed in Table 1 below.
TABLE 1
The application example is as follows:
the modified bio-based filler of the present invention is applied to a foamed layer of polyurethane synthetic leather, for example, a foamed layer of aqueous polyurethane synthetic leather.
The waterborne polyurethane synthetic leather is prepared by adopting a three-coating four-baking process, namely coating a scraping surface layer → drying → cooling → coating foaming slurry → drying → cooling → coating an adhesive layer → drying to semi-drying → cloth sticking → foaming → cooling → separating and coiling leather.
The method comprises the following specific steps:
sl: will be provided withThe aqueous polyurethane surface layer sizing agent is coated and scraped on release paper, and the sizing amount is 90g/m 2 And then putting the mixture into an oven for drying and curing, wherein the temperature setting range and the drying time of the oven are respectively set as follows: one section is 80, 100 ℃ and 1min, two sections are 110, 120 ℃ and 45S, and three sections are 120, 130 ℃ and 30S;
s2: coating foaming slurry on the surface layer of Sl, wherein the coating amount is 250g/m 2 Then putting the mixture into an oven for drying, wherein the temperature setting range and the drying time of the oven are respectively set as follows: first stage 80, 100 deg.C, 1min, second stage 110, 120 deg.C, 1min, first stage 120, 130 deg.C, 1min:
s3: coating adhesive glue on the basis of the foaming layer of S2, wherein the sizing amount is 110g/m 2 Baking the fabric in an oven for 90 seconds, then attaching the fabric to base cloth, and separating paper from leather;
s4: and (4) placing the leather obtained in the step (S3) into an oven for foaming, wherein the temperature is set to be 200 and 250 ℃, and the foaming time is 2 and 3min.
S5: and finishing the foamed synthetic leather product to obtain a finished foamed synthetic leather product, wherein the finishing procedures comprise color changing, embossing, surface treatment and line kneading are the same as the conventional processes.
In the preparation steps of the aqueous polyurethane synthetic leather, the modified barley flour BL 01-BL 08 obtained in examples 1-8 is compared with unmodified barley flour of 300 meshes, and the addition amount of the BL01 modified barley flour is gradually increased, and the aqueous polyurethane synthetic leather foaming layer is applied with the modified barley flour BL 01-BL 08, and the physical property parameters of the obtained finished product are listed in Table 2.
TABLE 2
As can be seen from Table 2, compared with the unmodified barley flour, the viscosity of the foamed layer of the waterborne polyurethane synthetic leather is greatly reduced after foaming under the condition of the same addition amount, which indicates that the addition proportion of the modified bio-based filler in the resin is greatly improved, the basic physical properties of the resin formula are greatly retained, and the storage stability of the formula is greatly improved.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent alterations and modifications are intended to be included within the scope of the present invention, without departing from the spirit and scope of the invention.
Claims (10)
1. The polyurethane synthetic leather comprises a polyurethane foaming layer, and the raw material components of the polyurethane foaming layer comprise polyurethane, a filler, a cross-linking agent, color paste and other functional additives, and is characterized in that the filler is a modified bio-based filler prepared by the following method: the surface modified bio-based filler is obtained by the bio-based filler and the modifier through a mechanochemical modification method.
2. The polyurethane synthetic leather according to claim 1, wherein the mass ratio of the modified bio-based filler to the polyurethane is (10-20): 100.
3. the polyurethane synthetic leather of claim 1, wherein the bio-based filler is selected from at least one of cereals, legumes, yams, and fruits; wherein the cereal is selected from at least one of rice, wheat, corn, sorghum, millet, yellow rice and buckwheat, the rice comprises indica rice, japonica rice and glutinous rice, the wheat comprises wheat, barley, oat and rye; the bean product class is at least one selected from soybean, broad bean, pea, mung bean, small red bean and kidney bean; the potatoes are selected from at least one of sweet potatoes, yams, taros and cassava; the fruit is selected from at least one of apple, chinese flowering apple, loquat, hawthorn, pear, tangerine, orange, lemon, lime, grapefruit, honeydew melon, muskmelon, honeydew melon, banana and pineapple.
4. The polyurethane synthetic leather according to claim 1, wherein the modifier comprises a coupling agent, a surfactant, an unsaturated organic acid and a water-soluble organic polymer; the coupling agent is selected from at least one of silane, polyether, titanate, aluminate and organic chromium, the silane coupling agent is selected from at least one of vinyl trichlorosilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl triacetoxysilane, vinyl t-butylsilane triperoxide, vinyl methyldichlorosilane, gamma-chloropropyltrichlorosilane, gamma-chloropropylmethyldichlorosilane, gamma-chloropropyltrimethoxysilane, gamma-chloropropyltriethoxysilane, chloromethyl triethoxysilane, beta-cyanoethyltrichlorosilane, beta-cyanoethylmethyldichlorosilane, beta-cyanoethyltriethoxysilane, gamma-cyanoethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, octadecyl-dimethyl- (3-trimethylsiloxypropyl) ammonium chloride, 4-vinylbenzyldimethyl- (3-trimethylsiloxypropyl) ammonium chloride, gamma-methacryloxypropyltrichlorosilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane and gamma-methacryloxypropylmethyldimethoxysilane, the polyether coupling agent is selected from at least one of fatty alcohol polyvinyl chloride ether, phenol polyvinyl chloride ether, lipid polyvinyl chloride ether, fatty amine polyvinyl chloride ether, polyethylene glycol, polypropylene glycol, propylene glycol block polyether, fatty alcohol polyoxypropylene ether and polyether, and the titanate coupling agent comprises a methyl alkoxy type, a poly (propylene glycol ether), a poly (ethylene glycol ether) and a poly (ethylene glycol ether), monoalkoxypyrophosphate type, integral type, and ligand type.
5. The polyurethane synthetic leather according to claim 1, wherein the modifier is used in an amount of 0.1-5% by mass of the bio-based filler.
6. A method for preparing polyurethane synthetic leather according to any one of claims 1 to 5, comprising the steps of:
preparing polyurethane surface layer slurry and polyurethane foaming layer slurry, wherein the polyurethane foaming layer comprises the following raw material components of polyurethane, a filler, a cross-linking agent, color paste and other functional additives, and the filler is a modified bio-based filler;
step (2), coating the polyurethane surface layer slurry on release paper, and then putting the release paper into an oven for drying and curing;
step (3), coating foaming slurry on the basis of the polyurethane surface layer obtained in the step (2), and then putting the polyurethane surface layer into an oven for drying and curing;
step (4), coating adhesive glue on the basis of the polyurethane foaming layer obtained in the step (3), then putting the polyurethane foaming layer into an oven for drying and curing, then attaching the polyurethane foaming layer to base cloth, and tearing off release paper;
step (5), placing the leather obtained in the step (4) into an oven for foaming;
and (6) finishing the foamed synthetic leather product to obtain a polyurethane synthetic leather finished product.
7. The preparation method according to claim 6, wherein in the step (1), the preparation method of the modified bio-based filler comprises the following steps: adding the nodular graphite medium, the bio-based filler and the modifier into a ball mill for nodular graphite, grinding at the rotating speed of 30-50rpm for 0.5-5h, discharging, and screening to obtain the modified bio-based filler.
8. The method according to claim 6, wherein the polyurethane top coat slurry is applied in the amount of 80 to 100g/m in the step (2) 2 (ii) a In the step (3), the coating and scraping sizing amount of the polyurethane foaming sizing agent is 200-300g/m 2 (ii) a In the step (4), the coating and sizing amount of the adhesive is 80-140g/m 2 。
9. The method according to claim 6, wherein in the step (2), the temperature setting range and the drying time of the oven are as follows: one section is at 80-100 deg.C for 1min, two sections are at 110-120 deg.C for 45S, and three sections are at 120-130 deg.C for 30S; in the step (3), the temperature setting range and the drying time of the oven are as follows: one stage at 80-100 deg.C for 1min, two stage at 110-120 deg.C for 1min, and three stage at 120-130 deg.C for 1min; in the step (5), the foaming temperature of the oven is 200-250 ℃, and the foaming time is 2-3min.
10. The method of claim 6, wherein the finishing process comprises color changing, embossing, surface treatment, and graining.
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| WO2020084029A1 (en) * | 2018-10-25 | 2020-04-30 | Leoni Kabel Gmbh | Bio-based artificial leather |
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| CN101941321A (en) * | 2010-08-03 | 2011-01-12 | 丽水市优耐克水性树脂科技有限公司 | Method for manufacturing synthetic leather and synthetic leather |
| CN103805044A (en) * | 2014-01-23 | 2014-05-21 | 福建宝利特集团有限公司 | Method for preparing waterborne polyurethane foaming slurry for synthetic leather in ultrasonic-assisted manner |
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