CN117946366A - Preparation method of biomass-based waterborne polyurethane, textile and leather - Google Patents
Preparation method of biomass-based waterborne polyurethane, textile and leather Download PDFInfo
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- CN117946366A CN117946366A CN202410187362.XA CN202410187362A CN117946366A CN 117946366 A CN117946366 A CN 117946366A CN 202410187362 A CN202410187362 A CN 202410187362A CN 117946366 A CN117946366 A CN 117946366A
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- biomass
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- polysiloxane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 106
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 106
- 239000002028 Biomass Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000004753 textile Substances 0.000 title claims abstract description 27
- 239000010985 leather Substances 0.000 title claims abstract description 17
- 229920005610 lignin Polymers 0.000 claims abstract description 65
- -1 polysiloxane Polymers 0.000 claims abstract description 65
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 59
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 52
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- CPYAUFLEMLTQAA-UHFFFAOYSA-N 5-bromopyrazine-2,3-diamine Chemical compound NC1=NC=C(Br)N=C1N CPYAUFLEMLTQAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000010695 polyglycol Substances 0.000 claims abstract description 13
- 229920000151 polyglycol Polymers 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 229920000180 alkyd Polymers 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 17
- 239000004744 fabric Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 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 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000006750 UV protection Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 description 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical group [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- 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
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/4825—Polyethers containing two 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
- C08G18/40—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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of biomass-based waterborne polyurethane and textile and leather, and relates to the technical field of chemical material preparation. The preparation method of the biomass-based waterborne polyurethane comprises the following steps: adding diisocyanate, polyglycol and catalyst into a container filled with acetone, and uniformly mixing to obtain a mixed solution; introducing inert gas or nitrogen into the container, heating the mixed solution, and reacting to obtain a first-stage prepolymer; adding dibasic alkyd and 5-bromopyrazine-2, 3-diamine into the first-stage prepolymer, and continuously reacting to obtain a second-stage prepolymer; adding polysiloxane modified lignin into the second-stage prepolymer, continuing to react to obtain a third-stage prepolymer, and then cooling to a preset temperature range; and adding triethylamine and deionized water into the prepolymer in the third stage, and continuing to react to obtain biomass-based waterborne polyurethane. According to the scheme, the biomass-based waterborne polyurethane with high tensile strength and ultraviolet resistance is prepared.
Description
Technical Field
The invention relates to the technical field of chemical material preparation, in particular to a preparation method of biomass-based waterborne polyurethane and textile and leather.
Background
The common aqueous polyurethane has some problems such as poor water resistance, unsatisfactory mechanical properties and the like. The existing improvement method is to introduce a grafting or block chain extender and blend to form a crosslinked network so as to widen the application field of the waterborne polyurethane and improve the performance of the waterborne polyurethane. Currently, the use of research biomass materials is very active because biomass has the advantages of being renewable, a wide range of resources, and low cost. The biomass monomer is introduced into the polyurethane material, so that the mechanical property, water resistance and degradability of polyurethane can be improved, and the polyurethane material has the advantages of green and degradability of natural materials and the like. Therefore, some monomers with special functions are introduced into the polyurethane, so that the durability of the polyurethane on textiles can be improved and the application field of the polyurethane can be expanded.
In the preparation of biomass-based aqueous polyurethanes, it is common to introduce the biomass-based monomers directly into the polyurethane. This approach can impart a range of beneficial functions to aqueous polyurethanes, including excellent thermal stability, biodegradability at room temperature, and increased solids content. However, the current technology also needs to solve the problem that biomass-based waterborne polyurethane is affected by ultraviolet rays in practical application and the mechanical properties of the biomass-based waterborne polyurethane are not ideal enough. This suggests that further research and improvement is needed to develop biomass-based aqueous polyurethanes that are more stable and have better mechanical properties.
Disclosure of Invention
The invention aims to provide a preparation method of biomass-based waterborne polyurethane with high tensile strength and ultraviolet resistance.
A further object of the present invention is to improve the adhesion of biomass-based aqueous polyurethane to a substrate.
In particular, the invention provides a preparation method of biomass-based waterborne polyurethane, which comprises the following steps:
adding diisocyanate, polyglycol and catalyst into a container filled with acetone, and uniformly mixing to obtain a mixed solution;
Introducing inert gas or nitrogen into the container, heating the mixed solution, and reacting to obtain a first-stage prepolymer;
adding dibasic alkyd and 5-bromopyrazine-2, 3-diamine into the first-stage prepolymer, and continuously reacting to obtain a second-stage prepolymer;
adding polysiloxane modified lignin into the second-stage prepolymer, continuing to react to obtain a third-stage prepolymer, and then cooling to a preset temperature range;
and adding triethylamine and deionized water into the prepolymer in the third stage, and continuing to react to obtain biomass-based waterborne polyurethane.
Optionally, the polysiloxane modified lignin is prepared according to the following method: uniformly mixing lignin, polysiloxane, an acid binding agent and acetone, and heating to react to obtain the polysiloxane modified lignin.
Optionally, 2-20 parts by weight of lignin, 5-50 parts by weight of polysiloxane, 1-5 parts by weight of acid binding agent and 20-50 parts by weight of acetone;
Optionally, in the step of heating after uniformly mixing lignin, polysiloxane, acid binding agent and acetone, the heating condition is that the reaction is carried out for 2-5 hours at 20-60 ℃.
Optionally, the molecular weight of the polysiloxane is any value ranging from 500 g/mol to 5000g/mol, and the polysiloxane is one or more of chloro-terminated polydimethylsiloxane and octachloropropyl silsesquioxane;
the acid binding agent is one or more of sodium carbonate, ammonium sulfate, sodium sulfate, potassium sulfate, sodium acetate and potassium carbonate.
Optionally, 3-20 parts by weight of diisocyanate, 5-45 parts by weight of polyglycol, 0.1-2 parts by weight of catalyst, 1-10 parts by weight of dibasic alkyd, 2-8 parts by weight of 5-bromopyrazine-2, 3-diamine and 5-20 parts by weight of polysiloxane modified lignin;
Optionally, the weight part of the triethylamine is 1-10 parts, and the weight part of the deionized water is 50-150 parts.
Optionally, the diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate;
The polyglycol is one or more of polyethylene glycol, polypropylene glycol, polycaprolactone glycol and polytetrahydrofuran;
Optionally, the molecular weight of the polyglycol is any value in the range of 600-2000 g/mol.
Optionally, the dibasic alkyd is one or more of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid;
the catalyst is one or more of N-ethylmorpholine, N-methylmorpholine, N '-diethylpiperazine, pyridine, N-dimethylcyclohexylamine, N' -dimethylpyridine, stannous octoate and dibutyltin dilaurate.
Optionally, in the step of introducing inert gas or nitrogen into the container and then heating the mixed solution, the heating condition is that the mixed solution reacts for 2-3 hours at 40-80 ℃.
In particular, the invention also provides a preparation method of the textile, which comprises the following steps:
coating the biomass-based waterborne polyurethane prepared by the preparation method on the surface of a fabric;
Drying at 40-80 ℃ to obtain the textile.
In particular, the invention also provides leather, which comprises a coating formed by the biomass-based waterborne polyurethane prepared by the preparation method.
According to the scheme of the invention, the polysiloxane modified lignin is introduced, so that not only can the flexibility of polyurethane be improved, but also the biocompatibility of the polyurethane can be increased. The addition of polysiloxane can reduce the surface energy of the waterborne polyurethane, improve the flexibility of the polyurethane and obviously enhance the water resistance. Because of the characteristics of the Gao Jian energy of the siloxane bond of the polysiloxane and the existence of the hydrogen bond between molecular chains, the tensile strength of the biomass-based waterborne polyurethane is obviously increased under multiple actions, and meanwhile, the requirements of plump hand feeling and comfort are also met.
Furthermore, the lignin is added, so that the polyurethane has an ultraviolet-resistant function due to the fact that the lignin is a biological material and is environment-friendly. Therefore, by matching each formula and the addition sequence of each formula in the preparation method, the biomass-based water-based polyurethane with high tensile strength and ultraviolet resistance can be prepared and obtained, and the requirements of flexibility and ultraviolet resistance of textiles and leather can be met.
Furthermore, the 5-bromopyrazine-2, 3-diamine is grafted into the polyurethane, so that on one hand, the molecular weight of the polyurethane can be increased, and on the other hand, the introduced bromine group can be subjected to nucleophilic substitution or covalent bonding with hydroxyl on textiles or leather, namely, a chemical bond is formed, so that the adhesive force of the biomass-based waterborne polyurethane coated on the surfaces of the textiles or leather is improved, and good washing fastness is endowed.
The above, as well as additional objectives, advantages, and features of the present invention will become apparent to those skilled in the art from the following detailed description of a specific embodiment of the present invention when read in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the invention will be described in detail hereinafter by way of example and not by way of limitation with reference to the accompanying drawings. The same reference numbers will be used throughout the drawings to refer to the same or like parts or portions. It will be appreciated by those skilled in the art that the drawings are not necessarily drawn to scale. In the accompanying drawings:
FIG. 1 shows a schematic flow chart of a method for preparing biomass-based aqueous polyurethane according to one embodiment of the present invention;
FIG. 2 shows an infrared spectrum characterization of biomass-based waterborne polyurethane according to an embodiment of the invention;
FIG. 3 shows ultraviolet transmittance graphs for textiles at different lignin contents according to an embodiment of the present invention;
Figure 4 is a bar graph of uv protection index for a textile with varying lignin content in accordance with one embodiment of the present invention.
Detailed Description
Other advantages and effects of the present application will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present application with reference to specific examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. The application may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present application. It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Fig. 1 shows a schematic flow chart of a method for preparing biomass-based aqueous polyurethane according to an embodiment of the present invention. As shown in fig. 1, the preparation method comprises the following steps:
step S100, adding diisocyanate, polyglycol and catalyst into a container filled with acetone, and uniformly mixing to obtain a mixed solution;
step S200, introducing inert gas or nitrogen into a container, and heating the mixed solution to react to obtain a first-stage prepolymer;
Step S300, adding dibasic alkyd and 5-bromopyrazine-2, 3-diamine into the prepolymer in the first stage, and continuing to react to obtain a prepolymer in the second stage;
step S400, adding polysiloxane modified lignin into the second-stage prepolymer, continuing to react to obtain a third-stage prepolymer, and then cooling to a preset temperature range;
and S500, adding triethylamine and deionized water into the prepolymer in the third stage, and continuing to react to obtain biomass-based waterborne polyurethane. Here, the biomass-based aqueous polyurethane is a polysiloxane-modified biomass-based aqueous polyurethane.
According to the scheme of the invention, the polysiloxane modified lignin is introduced, so that not only can the flexibility of polyurethane be improved, but also the biocompatibility of the polyurethane can be increased. Because polysiloxane is a polymer with multiple advantages, the polysiloxane is mainly composed of repeated Si-O chain segments, and has the characteristics of good low-temperature flexibility, low surface tension, flame retardance, weather resistance and the like. The polysiloxane and polyurethane are combined for use, so that the flexibility and biocompatibility of the material can be effectively improved. The addition of polysiloxane can reduce the surface energy of the waterborne polyurethane, improve the flexibility of the polyurethane and obviously enhance the water resistance. Because of the characteristics of the Gao Jian energy of the siloxane bond of the polysiloxane and the existence of the hydrogen bond between molecular chains, the tensile strength of the biomass-based waterborne polyurethane is obviously increased under multiple actions, and meanwhile, the requirements of plump hand feeling and comfort are also met.
Furthermore, the lignin is added, so that the polyurethane has an ultraviolet-resistant function due to the fact that the lignin is a biological material and is environment-friendly. Therefore, by matching each formula and the addition sequence of each formula in the preparation method, the biomass-based water-based polyurethane with high tensile strength and ultraviolet resistance can be prepared and obtained, and the requirements of flexibility and ultraviolet resistance of textiles and leather can be met.
Furthermore, the 5-bromopyrazine-2, 3-diamine is grafted into the polyurethane, so that on one hand, the molecular weight of the polyurethane can be increased, and on the other hand, the introduced bromine group can be subjected to nucleophilic substitution or covalent bonding with hydroxyl on textiles or leather, namely, a chemical bond is formed, so that the adhesive force of the biomass-based waterborne polyurethane coated on the surfaces of the textiles or leather is improved, and good washing fastness is endowed. This modified approach helps to improve the performance of polyurethanes in textile and leather applications, making them more durable and suitable for use in a variety of conditions.
In the above steps S100 to S500, the diisocyanate is 3 to 20 parts by weight, and for example, may be 3 parts, 8 parts, 12 parts, or 20 parts. The weight part of the polyglycol is 5-45 parts, for example 5 parts, 10 parts, 20 parts, 30 parts, 40 parts or 45 parts. The catalyst may be present in an amount of 0.1 to 2 parts by weight, for example 0.1, 0.5, 1 or 2 parts. The weight parts of the dibasic alkyd are 1 to 10 parts, for example, 1 part, 4 parts, 6 parts or 10 parts. The weight part of the 5-bromopyrazine-2, 3-diamine is 2-8 parts, and the weight part of the polysiloxane modified lignin is 5-20 parts, for example, can be 5 parts, 10 parts, 15 parts or 20 parts. The weight part of triethylamine is 1 to 10 parts, and for example, 1 part, 4 parts, 8 parts or 10 parts may be used. The deionized water may be 50-150 parts by weight, for example, 50 parts, 100 parts or 150 parts. According to the parts by weight, the biomass-based waterborne polyurethane can be ensured to have high tensile strength and ultraviolet resistance, and the requirements of flexibility and ultraviolet resistance of textiles and leather can be met. If the weight part of the polysiloxane modified lignin is reduced, the end capping is incomplete, the hydrophilicity and the mechanical properties are affected, and if the weight part of the polysiloxane modified lignin is increased, the polyurethane is affected by the lignin, and the color is too dark.
In step S100, the diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate. The polyglycol is one or more of polyethylene glycol, polypropylene glycol, polycaprolactone glycol and polytetrahydrofuran. The catalyst is one or more of N-ethylmorpholine, N-methylmorpholine, N '-diethylpiperazine, pyridine, N-dimethylcyclohexylamine, N' -dimethylpyridine, stannous octoate and dibutyltin dilaurate.
In step S200, inert gas or nitrogen is introduced into the container, and then the mixed solution is heated under the condition of reaction for 2-3 hours at 40-80 ℃. The heating temperature in this step may be, for example, 40 ℃, 60 ℃ or 80 ℃, or any other value from 40 to 80 ℃. The heating time in this step may be, for example, 2h, 2.5h or 3h, or any other value from 2 to 3h.
In step S400, the preset temperature is 20-40 ℃, for example, 20 ℃, 30 ℃ or 40 ℃, or any other value of 20-40 ℃.
In step S300, the dibasic alkyd is one or more of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid.
In step S100, the molecular weight of the polyglycol is any one of values in the range of 600 to 2000 g/mol. Exceeding this range results in poor flowability due to excessive polyurethane molecular weight, and excessive solvent is required during the reaction; below this range, polyurethane film-forming properties may be poor.
In this example, a polysiloxane modified lignin was prepared as follows: uniformly mixing lignin, polysiloxane, an acid binding agent and acetone, and heating to react to obtain polysiloxane modified lignin. Wherein, the weight part of lignin is 2-20 parts, for example, can be 2 parts, 10 parts, 15 parts or 20 parts. The polysiloxane is 5-50 parts by weight, for example, 5 parts, 10 parts, 20 parts, 30 parts, 40 parts or 50 parts. The weight part of the acid-binding agent is 1-5 parts, for example, 1 part, 2 parts, 3 parts or 5 parts. The weight part of acetone is 20-50 parts, for example, 20 parts, 30 parts, 40 parts or 50 parts. According to the weight parts, lignin and polysiloxane, namely a chain extender are added, so that the chain extension reaction is ensured to be complete, the incomplete chain extension reaction can be caused if the amount is small, and the reaction can be continued if the amount is excessive, thereby influencing the polyurethane synthesis.
In this example, in the step of heating after uniformly mixing lignin, polysiloxane, acid-binding agent and acetone, the heating condition is that the reaction is carried out at 20-60 ℃ for 2-5 hours. The heating temperature in this step may be, for example, 20 ℃, 40 ℃ or 60 ℃, or any other value from 20 to 60 ℃. The heating time in this step may be, for example, 2h, 3h, 4h or 5h, or any other value from 2 to 5h.
The lignin, polysiloxane, acid binding agent and acetone are uniformly mixed and heated, and the molecular weight of the polysiloxane is any value ranging from 500 g/mol to 5000g/mol, and the polysiloxane is one or more of chloro-terminated polydimethylsiloxane and octachloropropyl silsesquioxane. Here, the replacement of the polysiloxane with other components may result in reduced hydrophilicity and flexibility of the polyurethane. This is because polyethylene glycol or other glycol species are normally used for polyurethanes, because Si-O bonds are strong in length and energy to C-C or C-O bonds, at the same time, the surface energy of the polymer or oligomer formed by Si-O is lower than that of the glycol polymer formed by C-O or C-C, so that the final hydrophobicity and flexibility are higher than those of the glycol polymer formed by C-O or C-C. The acid binding agent is one or more of sodium carbonate, ammonium sulfate, sodium sulfate, potassium sulfate, sodium acetate and potassium carbonate. Here, the acid binding agent can absorb acid and weak alkaline substances generated in the reaction to form salts with the acid, so that the acid is prevented from affecting the synthesis of polysiloxane modified lignin. Acetone is used as a solvent for dissolving the reactants.
Fig. 2 shows an infrared spectrum characterization of biomass-based waterborne polyurethane according to an embodiment of the invention. As can be seen in FIG. 2, the disappearance of the peak near 2250cm -1 in the synthesized polyurethane indicates that NCO-has reacted completely, while the enhancement of the peaks at 1100cm -1 and 3400cm -1 (Si-O-Si and OH-groups, respectively) indicates that polysiloxane modified lignin has successfully incorporated into the polyurethane.
Fig. 3 shows a graph of uv transmittance at different lignin contents for a textile according to an embodiment of the present invention, and as can be seen from fig. 3, as the lignin content increases, the transmittance of the ultraviolet wavelength region (280-380 nm) of the coating film gradually decreases, indicating that the lignin has an ability to absorb uv rays, and when the lignin content reaches 2%, the polyurethane coating film has a substantial ability to resist uv rays.
Fig. 4 is a graph showing uv protection index for textiles with different lignin content according to an embodiment of the present invention, and it can be seen from fig. 4 that when the lignin content reaches 2%, the uv protection index UPF of the polyurethane coating film exceeds 50, where, more than 50 is generally considered to have uv protection effect, and when reaching 4%, the UPF reaches 140, indicating that the uv protection effect is very good at this time.
The invention also provides a preparation method of the textile, which comprises the following steps: the biomass-based aqueous polyurethane prepared by the preparation method is coated on the surface of the fabric. Drying at 40-80deg.C to obtain textile. The drying temperature may be, for example, 40 ℃, 50 ℃,60 ℃, 70 ℃ or 80 ℃. The biomass-based aqueous polyurethane coating film is formed on the surface of the fabric by coating the surface of the fabric, and the thickness of the coating film is in the range of 20-200 μm, for example, 20 μm, 50 μm, 80 μm, 100 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 180 μm or 200 μm, or any other value of 20-200 μm. The textile may be, for example, a home textile, a garment, or the like.
In particular, the invention also provides leather, which comprises a coating formed by the biomass-based aqueous polyurethane prepared by the preparation method.
The following is a detailed description of specific embodiments.
Embodiment one:
Preparation of polysiloxane modified lignin: uniformly mixing 10 parts of lignin, 28 parts of chlorine end-capped polydimethylsiloxane, 3 parts of sodium carbonate and 40 parts of acetone, and reacting at 40 ℃ for 4 hours to obtain polysiloxane modified lignin.
Preparation of biomass-based aqueous polyurethane: adding 12 parts of hexamethylene diisocyanate, 33 parts of polytetrahydrofuran and 1 part of stannous octoate into 75 parts of acetone, uniformly mixing, then introducing high-purity nitrogen for 30 minutes, heating the system to 55 ℃ for reaction for 2 hours, adding 6 parts of 2, 2-dimethylolpropionic acid and 5 parts of 5-bromopyrazine-2, 3-diamine into the system for continuous reaction for 2 hours, further adding 12 parts of polysiloxane modified lignin into the system for reaction for 4 hours, finally reducing the temperature of the system to below 40 ℃, and then adding 5 parts of triethylamine and 80 parts of deionized water into the system to obtain the biomass-based waterborne polyurethane.
Application of biomass-based aqueous polyurethane: the biomass-based aqueous polyurethane is coated on the surface of the fabric in a spraying mode, and is dried at 60 ℃ to obtain the biomass-based aqueous polyurethane treated fabric, wherein the thickness of a coating film is 100 mu m.
Embodiment two:
Preparation of polysiloxane modified lignin: uniformly mixing 2 parts of lignin, 5 parts of octachloropropyl silsesquioxane, 1 part of sodium acetate and 20 parts of acetone, and reacting at 20 ℃ for 5 hours to obtain polysiloxane modified lignin.
Preparation of biomass-based aqueous polyurethane: adding 3 parts of diphenylmethane diisocyanate, 5 parts of polyethylene glycol and 0.1 part of N, N' -diethyl piperazine into 30 parts of acetone, uniformly mixing, then introducing high-purity nitrogen for 30 minutes, heating the system to 40 ℃ for reaction for 3 hours, adding 1 part of 2, 2-dimethylolbutyric acid and 2 parts of 5-bromopyrazine-2, 3-diamine into the system for continuous reaction for 3 hours, further adding 5 parts of polysiloxane modified lignin into the system for reaction for 5 hours, finally reducing the temperature of the system to below 40 ℃, and adding 1 part of triethylamine and 50 parts of deionized water into the system to obtain biomass-based waterborne polyurethane.
Application of biomass-based aqueous polyurethane: the biomass-based aqueous polyurethane is coated on the surface of the fabric in a brushing mode, and is dried at 40 ℃ to obtain the biomass-based aqueous polyurethane treated fabric, wherein the thickness of a coating film is 20 mu m.
Embodiment III:
Preparation of polysiloxane modified lignin: uniformly mixing 20 parts of lignin, 50 parts of chlorine-terminated polydimethylsiloxane, 5 parts of sodium sulfate and 50 parts of acetone, and reacting at 60 ℃ for 2 hours to obtain polysiloxane modified lignin.
Preparation of biomass-based aqueous polyurethane: adding 20 parts of toluene diisocyanate, 45 parts of polycaprolactone diol and 2 parts of N, N-dimethylcyclohexylamine into 100 parts of acetone, uniformly mixing, then introducing high-purity nitrogen for 30 minutes, heating the system to 80 ℃ for reaction for 1h, adding 10 parts of 2, 2-dimethylolpropionic acid and 8 parts of 5-bromopyrazine-2, 3-diamine into the system for continuous reaction for 1h, further adding 20 parts of polysiloxane modified lignin into the system for reaction for 3h, finally reducing the temperature of the system to below 40 ℃, and adding 10 parts of triethylamine and 150 parts of deionized water into the system to obtain biomass-based waterborne polyurethane.
Application of biomass-based aqueous polyurethane: the biomass-based aqueous polyurethane is coated on the surface of the fabric in a roller coating mode, and is dried at 50 ℃ to obtain the aqueous polyurethane treated fabric, wherein the thickness of a coating film is 200 mu m.
Embodiment four:
Preparation of polysiloxane modified lignin: uniformly mixing 15 parts of lignin, 45 parts of octachloropropyl silsesquioxane, 4 parts of potassium sulfate and 40 parts of acetone, and reacting at 50 ℃ for 4 hours to obtain polysiloxane modified lignin.
Preparation of biomass-based aqueous polyurethane: adding 15 parts of isophorone diisocyanate, 38 parts of polypropylene glycol and 1.5 parts of N, N' -lutidine into 80 parts of acetone, uniformly mixing, then introducing high-purity nitrogen for 30 minutes, heating the system to 55 ℃ for reaction for 2 hours, adding 8 parts of 2, 2-dimethylol butyric acid and 7 parts of 5-bromopyrazine-2, 3-diamine into the system for continuous reaction for 2 hours, further adding 15 parts of polysiloxane modified lignin into the system for reaction for 2 hours, finally reducing the temperature of the system to below 40 ℃, and adding 7 parts of triethylamine and 100 parts of deionized water into the system to obtain biomass-based waterborne polyurethane.
Application of biomass-based aqueous polyurethane: the biomass-based aqueous polyurethane is coated on the surface of the fabric in a dip-coating mode, and is dried at 70 ℃ to obtain the aqueous polyurethane treated fabric, wherein the thickness of a coating film is 120 mu m.
Fifth embodiment:
preparation of polysiloxane modified lignin: and uniformly mixing 7 parts of lignin, 24 parts of chlorine-terminated polydimethylsiloxane, 2 parts of potassium carbonate and 30 parts of acetone, and reacting at 35 ℃ for 4 hours to obtain polysiloxane modified lignin.
Preparation of biomass-based aqueous polyurethane: adding 7 parts of diphenylmethane diisocyanate, 18 parts of polycaprolactone diol and 0.8 part of dibutyltin dilaurate into 50 parts of acetone, uniformly mixing, then introducing high-purity nitrogen for 30 minutes, heating the system to 50 ℃ for reaction for 1h, adding 4 parts of 2, 2-dimethylolpropionic acid and 4 parts of 5-bromopyrazine-2, 3-diamine into the system for continuous reaction for 2h, further adding 8 parts of polysiloxane modified lignin into the system for reaction for 3h, finally reducing the temperature of the system to below 40 ℃, and then adding 4.5 parts of triethylamine and 65 parts of deionized water into the system to obtain biomass-based waterborne polyurethane.
Application of biomass-based aqueous polyurethane: the biomass-based aqueous polyurethane is coated on the surface of the fabric in a spraying mode, and is dried at 65 ℃ to obtain the aqueous polyurethane treated fabric, wherein the thickness of a coating film is 50 mu m.
Comparative example one:
The preparation method of the blank aqueous polyurethane comprises the following steps: adding 12 parts of hexamethylene diisocyanate, 33 parts of polytetrahydrofuran and 1 part of stannous octoate into 75 parts of acetone, uniformly mixing, then introducing high-purity nitrogen for 30 minutes, heating the system to 55 ℃ for reaction for 2 hours, adding 10 parts of 2, 2-dimethylolpropionic acid into the system for continuous reaction for 2 hours, further adding 10 parts of lignin into the system for reaction for 4 hours, finally reducing the temperature of the system to below 40 ℃, and adding 5 parts of triethylamine and 80 parts of deionized water into the system to obtain the blank aqueous polyurethane. The lignin is not modified by polysiloxane.
Application of blank aqueous polyurethane: and (3) coating the blank aqueous polyurethane on the surface of the fabric in a spraying mode, and drying at 60 ℃ to obtain the blank aqueous polyurethane treated fabric, wherein the thickness of a coating film is 100 mu m.
The following table 1 shows the performance indexes of comparative example one, example one to example five.
As can be seen from the above Table 1, the adhesion of the samples of each example reaches the optimal level 0 and is higher than that of the blank aqueous polyurethane, and meanwhile, in order to be applied to textiles or leather, the tensile strength and elongation at break, that is, the mechanical properties of the biomass-based aqueous polyurethane are far higher than those of the blank aqueous polyurethane, which indicates that the biomass-based aqueous polyurethane has certain flexibility and can be well applied to textiles and leather.
By now it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been shown and described herein in detail, many other variations or modifications of the invention consistent with the principles of the invention may be directly ascertained or inferred from the present disclosure without departing from the spirit and scope of the invention. Accordingly, the scope of the present invention should be understood and deemed to cover all such other variations or modifications.
Claims (10)
1. The preparation method of the biomass-based waterborne polyurethane is characterized by comprising the following steps of:
adding diisocyanate, polyglycol and catalyst into a container filled with acetone, and uniformly mixing to obtain a mixed solution;
Introducing inert gas or nitrogen into the container, heating the mixed solution, and reacting to obtain a first-stage prepolymer;
adding dibasic alkyd and 5-bromopyrazine-2, 3-diamine into the first-stage prepolymer, and continuously reacting to obtain a second-stage prepolymer;
adding polysiloxane modified lignin into the second-stage prepolymer, continuing to react to obtain a third-stage prepolymer, and then cooling to a preset temperature range;
and adding triethylamine and deionized water into the prepolymer in the third stage, and continuing to react to obtain biomass-based waterborne polyurethane.
2. The method of claim 1, wherein the polysiloxane modified lignin is prepared by the following method: uniformly mixing lignin, polysiloxane, an acid binding agent and acetone, and heating to react to obtain the polysiloxane modified lignin.
3. The preparation method according to claim 2, wherein the lignin is 2-20 parts by weight, the polysiloxane is 5-50 parts by weight, the acid-binding agent is 1-5 parts by weight, and the acetone is 20-50 parts by weight;
Optionally, in the step of heating after uniformly mixing lignin, polysiloxane, acid binding agent and acetone, the heating condition is that the reaction is carried out for 2-5 hours at 20-60 ℃.
4. The preparation method according to claim 3, wherein the molecular weight of the polysiloxane is any one of 500-5000g/mol, and the polysiloxane is one or more of chloro-terminated polydimethylsiloxane and octachloropropyl silsesquioxane;
the acid binding agent is one or more of sodium carbonate, ammonium sulfate, sodium sulfate, potassium sulfate, sodium acetate and potassium carbonate.
5. The production method according to any one of claims 1 to 4, wherein the diisocyanate is 3 to 20 parts by weight, the polyglycol is 5 to 45 parts by weight, the catalyst is 0.1 to 2 parts by weight, the dibasic alkyd is 1 to 10 parts by weight, the 5-bromopyrazine-2, 3-diamine is 2 to 8 parts by weight, and the polysiloxane-modified lignin is 5 to 20 parts by weight;
Optionally, the weight part of the triethylamine is 1-10 parts, and the weight part of the deionized water is 50-150 parts.
6. The preparation method according to claim 5, wherein the diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate;
The polyglycol is one or more of polyethylene glycol, polypropylene glycol, polycaprolactone glycol and polytetrahydrofuran;
Optionally, the molecular weight of the polyglycol is any value in the range of 600-2000 g/mol.
7. The preparation method according to claim 6, wherein the dibasic alkyd is one or more of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid;
the catalyst is one or more of N-ethylmorpholine, N-methylmorpholine, N '-diethylpiperazine, pyridine, N-dimethylcyclohexylamine, N' -dimethylpyridine, stannous octoate and dibutyltin dilaurate.
8. The method according to any one of claims 1 to 4, wherein in the step of introducing an inert gas or nitrogen gas into the vessel and thereafter heating the mixed solution, the heating condition is a reaction at 40 to 80 ℃ for 2 to 3 hours.
9. A method for preparing a textile, comprising the steps of:
coating the biomass-based aqueous polyurethane prepared by the preparation method according to any one of claims 1 to 8 on the surface of a fabric;
Drying at 40-80 ℃ to obtain the textile.
10. Leather, characterized by comprising a coating formed by the biomass-based aqueous polyurethane prepared by the preparation method according to any one of claims 1 to 8.
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