CN107857869B - Aqueous polyurethane and its preparation method and application - Google Patents
Aqueous polyurethane and its preparation method and application Download PDFInfo
- Publication number
- CN107857869B CN107857869B CN201711203141.3A CN201711203141A CN107857869B CN 107857869 B CN107857869 B CN 107857869B CN 201711203141 A CN201711203141 A CN 201711203141A CN 107857869 B CN107857869 B CN 107857869B
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- China
- Prior art keywords
- aqueous polyurethane
- preparation
- functionality
- polyurethane according
- acetone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 73
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229920000642 polymer Polymers 0.000 claims abstract description 74
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 58
- 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 abstract description 58
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 35
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 31
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 30
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- 239000010985 leather Substances 0.000 claims abstract description 24
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000376 reactant Substances 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 150000001412 amines Chemical group 0.000 claims description 12
- 229920001610 polycaprolactone Polymers 0.000 claims description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 150000003384 small molecules Chemical group 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 4
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 9
- 229920006264 polyurethane film Polymers 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 2
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 19
- 239000006185 dispersion Substances 0.000 description 18
- 239000000839 emulsion Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- -1 isophorone diisocyanate Ester Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance 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
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
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- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
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- C08G18/40—High-molecular-weight compounds
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- C08G18/4833—Polyethers containing oxyethylene units
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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
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- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- 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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- 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
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- 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
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
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- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to polymeric material fields, more particularly to a kind of aqueous polyurethane and its preparation method and application, by the way that HDI trimer or IPDI tripolymers are carried out polymerisation with polyethylene glycol, it reacts product to form isocyanate-terminated three-functionality-degree polymer with hexamethylene diisocyanate or isophorone diisocyanate again, acetone is used in combination to adjust viscosity.It carries out HDI or IPDI and di-alcohols monomer and hydrophilic monomer that linear Waterborne Polyurethane Prepolymer is obtained by the reaction, acetone is used in combination to adjust viscosity.After isocyanate-terminated three-functionality-degree polymer and linear Waterborne Polyurethane Prepolymer are carried out cross-linking reaction under the action of chain extender, aqueous polyurethane is obtained after removing acetone.Softness is preferable after the aqueous polyurethane film forming obtained by the preparation method, reaches the surface touch that leather finish is submissive, soft, while having preferable physical property.
Description
Technical field
The present invention relates to polymeric material fields, in particular to a kind of aqueous polyurethane and preparation method thereof and answer
With.
Background technology
Aqueous polyurethane is to replace organic solvent as the new polyurethane system of decentralized medium using water, also referred to as water-dispersed poly-
Urethane, aqueous polyurethane or water-based polyurethane.Aqueous polyurethane is pollution-free, safe and reliable, mechanical performance is excellent using water as solvent
Good, the advantages that compatibility is good, easily modified.It is necessary to have preferable as leather top finishing for aqueous polyurethane leather gloss agent
Physical property.Physical property (performances such as water-fast solvent resistant, abrasion performance, Bearable dry and wet wipe) is used to improve it, it usually needs aqueous
Polyfunctional group, which is introduced, during polyurethane polymerization forms cross-linked structure.It is easy when existing introducing method is larger there are crosslinking degree
It causes performed polymer viscosity excessive, easily forms gel, cause difficulties in dispersion, in addition, lacking after the aqueous polyurethane film forming after crosslinking
Compliance, film forming is harder, and submissive surface touch cannot be obtained in leather finish.
Invention content
First of the present invention is designed to provide a kind of aqueous polyurethane, so that compliance is preferable after its film forming, film forming
It is softer.
Second object of the present invention is to provide the preparation method of above-mentioned aqueous polyurethane, passes through simple technique stream
Journey, avoid crosslinking degree it is larger when to be easy to cause performed polymer viscosity excessive, the problem of easily forming gel, cause difficulties in dispersion,
And compliance is preferable after making the aqueous polyurethane being prepared film forming, film forming is softer.
Third object of the present invention is to provide application of the above-mentioned aqueous polyurethane in preparing leather, to reach leather
Submissive, soft surface touch is covered with paint, lacquer, colour wash, etc., while there is preferable physical property.
Fourth object of the present invention is to provide a kind of leather, so that the leather finish on its surface is submissive, soft
Surface touch, while there is preferable physical property.
The present invention solves its technical problem using following technical scheme to realize.
A kind of preparation method of aqueous polyurethane provided by the invention comprising following steps：By HDI trimer or IPDI
Tripolymer and polyethylene glycol carry out polymerisation, obtain hydroxy-end capped three-functionality-degree polymer, then by hydroxy-end capped three-functionality-degree
Polymer reacts that form isocyanate-terminated three-functionality-degree poly- with hexamethylene diisocyanate or isophorone diisocyanate
Object is closed, acetone is used in combination to adjust viscosity.By hexamethylene diisocyanate or isophorone diisocyanate and di-alcohols monomer
And hydrophilic monomer carries out that linear Waterborne Polyurethane Prepolymer is obtained by the reaction, and acetone is used in combination to adjust viscosity.Viscosity will be adjusted
Isocyanate-terminated three-functionality-degree polymer and adjusted effect of the linear Waterborne Polyurethane Prepolymer in chain extender of viscosity
After lower carry out cross-linking reaction, acetone is removed.
The invention further relates to a kind of aqueous polyurethanes, are prepared by the preparation method of above-mentioned aqueous polyurethane.
The invention further relates to a kind of leather, the surface of leather is coated with the painting by being formed after above-mentioned aqueous polyurethane film forming
Adorn layer.
The invention further relates to application of the above-mentioned aqueous polyurethane in preparing leather.
The preparation process of the aqueous polyurethane is not involved in prepolymer reaction, does not interfere with performed polymer viscosity, is readily produced work
Skill controls, and is not required to add a large amount of solvents.Softness is preferable after the aqueous polyurethane film forming obtained by the preparation method, reaches leather
Submissive, soft surface touch is covered with paint, lacquer, colour wash, etc., while there is preferable physical property.
Specific implementation mode
It, below will be to embodiment party of the present invention to keep the purpose, technical scheme and advantage of embodiment of the present invention clearer
Technical solution in formula is clearly and completely described.The person that is not specified actual conditions in embodiment or embodiment, according to routine
The condition that condition or manufacturer suggest carries out.Reagents or instruments used without specified manufacturer, being can be by commercially available purchase
Buy the conventional products of acquisition.
A kind of aqueous polyurethane of embodiment of the present invention and its preparation method and application is specifically described below.
Some embodiments of the present invention provide a kind of preparation method of aqueous polyurethane comprising following steps：
S1, HDI trimer or IPDI tripolymers and polyethylene glycol are subjected to polymerisation, obtain hydroxy-end capped three-functionality-degree
Polymer, then by hydroxy-end capped three-functionality-degree polymer and hexamethylene diisocyanate (HDI) or isophorone diisocyanate
Ester (IPDI) reaction forms isocyanate-terminated three-functionality-degree polymer, and acetone is used in combination to adjust viscosity.
S2, by hexamethylene diisocyanate or isophorone diisocyanate and di-alcohols monomer and hydrophily list
Body carries out that linear Waterborne Polyurethane Prepolymer is obtained by the reaction, and acetone is used in combination to adjust viscosity.
S3, by the isocyanate-terminated three-functionality-degree polymer for adjusting viscosity and the linear aqueous poly- ammonia for adjusting viscosity
After ester performed polymer carries out cross-linking reaction under the action of chain extender, acetone is removed.
It should be noted that the sequence of S1 steps and S2 steps can exchange, any shadow no to the formation of final products
It rings.
In embodiments of the present invention, by first HDI trimer or IPDI tripolymers with polyethylene glycol polymerize instead
It answers, access ethylene oxide (EO) segment is polymerize with HDI or IPDI again, to obtain isocyanate-terminated three-functionality-degree polymerization
Object, which is the hydrophilic crosslinked monomer of macromolecular, and then realizes its hydrophily.By hexamethylene diisocyanate, different
Isophorone diisocyanate, di-alcohols monomer and hydrophilic monomer carry out that linear Waterborne Polyurethane Prepolymer is obtained by the reaction, from
And the isocyanate-terminated three-functionality-degree polymer of the hydrophilic crosslinked monomer of macromolecular can exist with linear Waterborne Polyurethane Prepolymer
It crosslinks and reacts with chain extender effect during water-dispersed, carry out forming space net structure macromolecular, and can pass through
The length of ethylene oxide (EO) segment is controlled to reach the film forming softness for controlling finally formed aqueous polyurethane, reaches leather painting
Submissive, soft surface touch is adornd, while there is preferable physical property.In addition, polymerizeing in isocyanate-terminated three-functionality-degree
Object and linear Waterborne Polyurethane Prepolymer are respectively adjusted viscosity by acetone before being reacted, so that cross-linking reaction
It can successfully carry out, and avoid performed polymer viscosity excessive, easily form gel, cause difficulties in dispersion.
According to some embodiments, the molecular weight of polyethylene glycol is 400~1500, in the polyethylene glycol of the molecular weight ranges
The length of the ethylene oxide segment of access can preferably meet the demand of the film forming softness of finally formed aqueous polyurethane.
In some embodiments, HDI trimer or the molar ratio of IPDI tripolymers and polyethylene glycol are 1：3, HDI trimer or IPDI tri-
When aggressiveness is reacted with polyethylene glycol, the molar ratio between reactant is 1：3 could generate hydroxy-end capped three wanted
Degree of functionality polymer.
According to some embodiments, the temperature 75 of HDI trimer or IPDI tripolymers and polyethylene glycol progress polymerisation
~85 DEG C, preferably 78~82 DEG C, more preferable 80 DEG C, the reaction time is 1~3 hour, preferably 1.5~2.5 hours.In above-mentioned temperature
With occur polymerisation under conditions of the reaction time, more preferably, throughput rate higher can be abundant between reactant for polymerization effect
It is reacted.
According to some embodiments, the hexamethylene diisocyanate with hydroxy-end capped three-functionality-degree polymer reaction
(HDI) or the mole of isophorone diisocyanate (IPDI) is equal with the mole of polyethylene glycol.Mole of HDI or IPDI
Amount is equal with the mole of polyethylene glycol can fully to polymerize big point of formation completely with hydroxy-end capped three-functionality-degree polymer
The isocyanate-terminated three-functionality-degree polymer of the hydrophilic crosslinked monomer of son.
According to some embodiments, hydroxy-end capped three-functionality-degree polymer and hexamethylene diisocyanate or isophorone
The temperature of di-isocyanate reaction is 70~90 DEG C, and preferably 73~85 DEG C, more preferable 78~82 DEG C, the reaction time is 1~3 small
When, preferably 1.5~2.5 hours.Occur polymerisation under conditions of above-mentioned temperature and reaction time, polymerization effect more preferably,
Throughput rate higher can fully be reacted between reactant.
According to some embodiments, the viscosity that isocyanate-terminated three-functionality-degree polymer is adjusted with acetone is 58~65
It is carried out at a temperature of DEG C, the isocyanate-terminated three-functionality-degree polymer obtained after polymerisation can will specifically occur and cool down
It to 58~65 DEG C, preferably 60 DEG C, adds acetone and is stirred, and it is for use to continue to be cooled to room temperature, it can also be by isocyanates
After sealing end three-functionality-degree polymer cools to room temperature, need to carry out viscosity reduction in use, being heated to 58~65 DEG C and acetone being added, so
After to be cooled to room temperature for use.
According to some embodiments, the additive amount of acetone is the reactant for generating isocyanate-terminated three-functionality-degree polymer
Gross mass 5%~20%.The acetone of the dosage can arrive the viscosity-adjusting agent of isocyanate-terminated three-functionality-degree polymer
One suitable range is conducive to the dispersion of isocyanate-terminated three-functionality-degree polymer in water, so that follow-up crosslinking
Reaction can be carried out preferably.
According to some embodiments, by hexamethylene diisocyanate, isophorone diisocyanate, di-alcohols monomer
The temperature reacted with hydrophilic monomer is 60~100 DEG C, preferably 70~90 DEG C, more preferable 70~80 DEG C, the reaction time 2
~8 hours, preferably 3~7 hours, more preferable 4~7 hours.
Under the temperature range and reaction time so that methylene diisocyanate, isophorone diisocyanate, binary
Alcohols monomer and hydrophilic monomer can fully be reacted, and the linear Waterborne Polyurethane Prepolymer of pending reaction is generated.
According to some embodiments, the viscosity with acetone linear adjustment Waterborne Polyurethane Prepolymer is the temperature at 58~65 DEG C
Degree is lower to carry out, the isocyanate-terminated three-functionality-degree polymer for occurring to obtain after polymerisation can specifically cool to 58~
65 DEG C, preferably 60 DEG C, add acetone and are stirred, and it is for use to continue to be cooled to room temperature, can also be by isocyanate-terminated three
After degree of functionality polymer cools to room temperature, needs to carry out viscosity reduction in use, being heated to 58~65 DEG C and acetone being added, then cool down
It is for use to room temperature.
According to some embodiments, the additive amount of acetone make a living linear Waterborne Polyurethane Prepolymer reactant total matter
The 10%~30% of amount.The acetone of the dosage can be by the viscosity-adjusting agent of linear Waterborne Polyurethane Prepolymer to a suitable model
It encloses, is conducive to the dispersion of linear Waterborne Polyurethane Prepolymer in water, so that follow-up cross-linking reaction can be carried out preferably.
According to some embodiments, by hexamethylene diisocyanate or isophorone diisocyanate and di-alcohols list
Body and hydrophilic monomer reacted in isophorone diisocyanate and glycol monomer molar ratio be 3~5：1, it is hydrophilic
The dosage of property monomer is the hexamethylene diisocyanate reacted or isophorone diisocyanate and di-alcohols monomer
Gross mass 3.5%~8%.By the proportioning between various components reaction can preferably be carried out, does not have too many
Remaining reactant do not participate in reaction, and then the performance of the linear Waterborne Polyurethane Prepolymer of generation is impacted.
According to some embodiments, the molecular weight of di-alcohols monomer is 1000~3000, in some embodiments, binary
Alcohols monomer include in polypropylene glycol, polycaprolactone diols, polycarbonate glycol and polytetrahydrofuran ether dihydric alcohol extremely
Few one kind, for example, di-alcohols monomer is polypropylene glycol, polycaprolactone diols, polycarbonate glycol or PolyTHF
The mixture etc. of ether dihydric alcohol or polypropylene glycol and polycaprolactone diols, certainly, in other embodiment, di-alcohols list
Body packet may be other conventional dihydric alcohols.
According to some embodiments, the one kind or two of hydrophilic monomer in dihydromethyl propionic acid and dimethylolpropionic acid
Kind.Dihydromethyl propionic acid is a kind of multiduty Organic Ingredients, polyurethane can be made obtained from breast in aqueous polyurethane manufacture
Change performance, the self-emulsifying aqueous polyurethane of excellent in stability is made.Dimethylolpropionic acid is considered as aqueous polyurethane with new one
For environmental type chain extender and internal emulsifying agent, Aqueous Polyurethane Adhesives are produced, without using organic solvent, organic residue
It is zero.
According to some embodiments, isocyanate-terminated three-functionality-degree polymer and linear Waterborne Polyurethane Prepolymer carry out
Cross-linking reaction is by isocyanate-terminated three-functionality-degree polymer and linear Waterborne Polyurethane Prepolymer after mixing with three second
Amine is neutralized, and after the liquid after neutralization is dispersed with stirring in deionized water, adds chain extender, is continued to be dispersed with stirring, be subtracted
Pressure distills out acetone.
According to some embodiments, the mole dosage of triethylamine is the 80%~120% of the mole dosage of hydrophilic monomer,
It is that isocyanate-terminated three-functionality-degree polymer and linear Waterborne Polyurethane Prepolymer is added in triethylamine that triethylamine, which neutralize,
Mixed liquor in stir 5~30 minutes.
According to some embodiments, the rotating speed that the liquid of neutralization is dispersed with stirring in deionized water be 500~3000 turns/
Minute, it is 2~5 minutes to be dispersed with stirring the time.It can make two by rotating speed for 500~3000 revs/min be vigorously stirred
The reactant that kind participates in cross-linking reaction preferably can fully be disperseed in water, be not easy to form gel.
According to some embodiments, it is 1~3 hour that chain extender, which is added, and is stirred the mixing time of dispersion.Some are implemented
In mode, chain extender is small molecule binary amine chain extender, and small molecule binary amine chain extender includes hydrazine hydrate, ethylenediamine, fourth
At least one of diamines and hexamethylene diamine, for example, chain extender can be hydrazine hydrate, ethylenediamine, butanediamine or hexamethylene diamine, it can also
For two or three therein of composition.
According to some embodiments, the mole dosage of chain extender be the mole of unreacted isocyanate group 15%~
40%.
According to some embodiments, the matter of isocyanate-terminated three-functionality-degree polymer and linear Waterborne Polyurethane Prepolymer
Amount is than being 0.05~0.4：1, preferably 0.2~0.4：1.
The preparation method for the aqueous polyurethane that some embodiments of the present invention provide, specifically includes：
A. the polyethylene glycol in molar ratio 1 for being 400~1500 with molecular weight by HDI trimer or IPDI tripolymers:3 75
Polymerisation 1~3 hour at~85 DEG C forms hydroxy-end capped three-functionality-degree polymer.
The HDI or IPDI with polyethylene glycol equimolar amounts are added, the reaction was continued 1-3 hours under 70~90 degree, finally
Form isocyanate-terminated three-functionality-degree polymer.
It is cooled to the acetone solvent viscosity reduction of the 5%-20% of the gross mass of 58~62 DEG C of addition reactants and continues to be cooled to
Room temperature is for use.
B. IPDI, HDI, di-alcohols monomer, hydrophilic monomer are reacted 2~8 hours at 60~100 DEG C, obtains line
Property Waterborne Polyurethane Prepolymer, is cooled to 60 degree, the acetone viscosity reduction of the 10%~30% of the gross mass of reactant is added, continue to drop
Temperature to 45 degree it is for use.
C. by isocyanate-terminated three-functionality-degree polymer and linear Waterborne Polyurethane Prepolymer in 15~35 degree of water
It is uniformly mixed, triethylamine is then added and is neutralized, continues stirring 5~30 minutes, deionized water is added and is vigorously stirred point
It dissipates 2~5 minutes, small molecule binary amine aqueous solution is added after being uniformly dispersed in performed polymer, continues to be dispersed with stirring 1~3 hour, and decompression is steamed
Acetone is distillated, the 20% solid property of water-bearing polyaminoester emulsion of 40~150nm of final obtained grain size.
Wherein, by chain extender be diluted with water for 5-10% aqueous solutions it is spare.
Some embodiments of the present invention further relate to a kind of aqueous polyurethane, by the preparation side of above-mentioned aqueous polyurethane
Method is prepared.
Some embodiments of the present invention additionally provide a kind of leather, and the surface of leather is coated with above-mentioned aqueous polyurethane
The coatings formed after film forming.
Some embodiments of the present invention further relate to application of the above-mentioned aqueous polyurethane in preparing leather.
By foregoing description it is found that the preparation process of the aqueous polyurethane is not involved in prepolymer reaction, pre-polymerization is not interfered with
Body viscosity, is readily produced technology controlling and process, is not required to add a large amount of solvents.After the aqueous polyurethane film forming obtained by the preparation method
Softness is preferable, reaches the surface touch that leather finish is submissive, soft, while having preferable physical property.
The feature and performance of the present invention are described in further detail with reference to embodiments.
The raw material sources related generally in following embodiment are as follows：IPDI, HDI, Ying Chuan company, industrial goods；IPDI, HDI
Tripolymer, Ying Chuan companies, industrial goods.
Polytetrahydrofuran ether glycol (PTMEG, molecular weight 1000,2000) South Korea PTG is produced, industrial goods.
Polypropylene glycol (PPG, molecular weight 1000,2000), Historic Area of Zhongshan in Nanjing City petrochemical iy produced, industrial goods.
Polycaprolactone glycol (PCL, molecular weight 1000,2000)：PERSTORP companies, industrial goods.
DMPA, U.S. GEO, industrial goods, polyethylene glycol (PEG, molecular weight 400-1500), BASF AG, industrial goods.
Polycarbonate glycol (PCDL, molecular weight 1000,2000), Asahi Kasei Corporation, industrial goods.
Embodiment 1
The polyethylene glycol in molar ratio 1 for being 600 by IPDI tripolymers and molecular weight：3 are added in there-necked flask, and stirring is warming up to
80 DEG C are reacted 3 hours, are obtained hydroxy-end capped three-functionality-degree polymer, are added the HDI with polyethylene glycol equimolar amounts, at 85 DEG C
Lower the reaction was continued 3 hours, forms isocyanate-terminated three-functionality-degree polymer, is cooled to 60 DEG C and acetone is added and dilutes and continue to cool down
To room temperature, component A is obtained.Wherein, acetone is the gross mass for the reactant for generating isocyanate-terminated three-functionality-degree polymer
10%.
Equipped with blender, condensing reflux pipe, thermocouple 250m1 four-hole boiling flasks in, be added IPDI, 2000 molecular weight
PTMEG and DMPA reacts 3 hours production of linear Waterborne Polyurethane Prepolymers at 90 DEG C, is then cooled to 60 DEG C and acetone drop is added
It is viscous, obtain component B.Wherein, the molar ratio of IPDI and PTMEG is 4：1, DMPA dosage is the IPDI and PTMEG reacted
Gross mass 5%.The additive amount of acetone make a living linear Waterborne Polyurethane Prepolymer reactant gross mass 20%.
By component A and component B, insulated and stirred is added during triethylamine carries out and three second is added after ten minutes in 25 DEG C of water
Amine heat preservation disperses 4min in deionized water with high speed emulsion dispersion machine under 1000r/min high-speed stirreds after ten minutes, disperses
Ethylenediamine solution is added after uniformly, Blue-Color Semitransparent aqueous polyurethane emulsion is obtained after continuing dispersion 90 minutes.Wherein, isocyanide
It is 0.2 that acid esters, which blocks three-functionality-degree polymer and the mass ratio of linear Waterborne Polyurethane Prepolymer,：1.The mole dosage of triethylamine
It is the 100% of the mole dosage of DMPA, the dosage of deionized water is 3.4 times of the gross mass of component A and component B.Chain extender
Mole dosage is the 30% of the mole of unreacted isocyanate group.
Embodiment 2
The polyethylene glycol in molar ratio 1 for being 1200 by IPDI tripolymers and molecular weight：3 are added in there-necked flask, stirring heating
It is reacted 2.5 hours to 76 DEG C, obtains hydroxy-end capped three-functionality-degree polymer, add the HDI with polyethylene glycol equimolar amounts,
The reaction was continued at 90 DEG C 2.5 hours, forms isocyanate-terminated three-functionality-degree polymer, be cooled to 60 DEG C be added acetone dilution after
It is continuous to be cooled to room temperature, obtain component A.Wherein, acetone be generate isocyanate-terminated three-functionality-degree polymer reactant it is total
The 20% of quality.
Equipped with blender, condensing reflux pipe, thermocouple 250m1 four-hole boiling flasks in, be added HDI, 2000 molecular weight PCL
3 hours production of linear Waterborne Polyurethane Prepolymers are reacted at 90 DEG C with DMPA, are then cooled to 60 DEG C of addition acetone viscosity reductions, are obtained
To component B.Wherein, the molar ratio of HDI and PCL is 5：1, DMPA dosage is the HDI reacted and the gross mass of PCL
8%.The additive amount of acetone make a living linear Waterborne Polyurethane Prepolymer reactant gross mass 30%.
By component A and component B, insulated and stirred is added during triethylamine carries out and three second is added after ten minutes in 18 DEG C of water
Amine heat preservation disperses 4min in deionized water with high speed emulsion dispersion machine under 2800r/min high-speed stirreds after ten minutes, disperses
Ethylenediamine solution is added after uniformly, Blue-Color Semitransparent aqueous polyurethane emulsion is obtained after continuing dispersion 180 minutes.Wherein, different
It is 0.4 that cyanate, which blocks three-functionality-degree polymer and the mass ratio of linear Waterborne Polyurethane Prepolymer,：1.Triethylamine mole with
Amount is the 120% of the mole dosage of DMPA, and the dosage of deionized water is 3 times of the gross mass of component A and component B.Chain extender
Mole dosage is the 40% of the mole of unreacted isocyanate group.
Embodiment 3
The polyethylene glycol in molar ratio 1 for being 1200 by HDI trimer and molecular weight：3 are added in there-necked flask, and stirring is warming up to
76 DEG C are reacted 2.5 hours, are obtained hydroxy-end capped three-functionality-degree polymer, are added the IPDI with polyethylene glycol equimolar amounts,
The reaction was continued at 90 DEG C 2.5 hours, forms isocyanate-terminated three-functionality-degree polymer, be cooled to 60 DEG C be added acetone dilution after
It is continuous to be cooled to room temperature, obtain component A.Wherein, acetone be generate isocyanate-terminated three-functionality-degree polymer reactant it is total
The 20% of quality.
Equipped with blender, condensing reflux pipe, thermocouple 250m1 four-hole boiling flasks in, be added IPDI, 2000 molecular weight
PCDL and DMPA reacts 4 hours production of linear Waterborne Polyurethane Prepolymers at 90 DEG C, is then cooled to 65 DEG C and acetone drop is added
It is viscous, obtain component B.Wherein, the molar ratio of IPDI and PCDL is 3：1, DMPA dosage is the IPDI and PCDL reacted
The 3.5% of gross mass.The additive amount of acetone make a living linear Waterborne Polyurethane Prepolymer reactant gross mass 10%.
By component A and component B, insulated and stirred is added during triethylamine carries out and three second is added after ten minutes in 30 DEG C of water
Amine heat preservation disperses 3min in deionized water with high speed emulsion dispersion machine under 2800r/min high-speed stirreds after ten minutes, disperses
Ethylenediamine solution is added after uniformly, Blue-Color Semitransparent aqueous polyurethane emulsion is obtained after continuing dispersion 70 minutes.Wherein, isocyanide
It is 0.1 that acid esters, which blocks three-functionality-degree polymer and the mass ratio of linear Waterborne Polyurethane Prepolymer,：1.The mole dosage of triethylamine
It is the 80% of the mole dosage of DMPA, the dosage of deionized water is 3.2 times of the gross mass of component A and component B.Chain extender rubs
Your dosage is the 15% of the mole of unreacted isocyanate group.
Embodiment 4
The polyethylene glycol in molar ratio 1 for being 1000 by HDI trimer and molecular weight：3 are added in there-necked flask, and stirring is warming up to
80 DEG C are reacted 2.5 hours, are obtained hydroxy-end capped three-functionality-degree polymer, are added the IPDI with polyethylene glycol equimolar amounts,
The reaction was continued at 90 DEG C 2.5 hours, forms isocyanate-terminated three-functionality-degree polymer, be cooled to 60 DEG C be added acetone dilution after
It is continuous to be cooled to room temperature, obtain component A.Wherein, acetone be generate isocyanate-terminated three-functionality-degree polymer reactant it is total
The 10% of quality.
Equipped with blender, condensing reflux pipe, thermocouple 250m1 four-hole boiling flasks in, be added IPDI, 2000 molecular weight
PPG and DMPA reacts 4 hours production of linear Waterborne Polyurethane Prepolymers at 90 DEG C, is then cooled to 65 DEG C and acetone drop is added
It is viscous, obtain component B.Wherein, the molar ratio of IPDI and PPG is 3：1, DMPA dosage is the total of the IPDI reacted and PPG
The 3.5% of quality.The additive amount of acetone make a living linear Waterborne Polyurethane Prepolymer reactant gross mass 10%.
By component A and component B, insulated and stirred is added during triethylamine carries out and three second is added after ten minutes in 35 DEG C of water
Amine heat preservation disperses 3min in deionized water with high speed emulsion dispersion machine under 2800r/min high-speed stirreds after ten minutes, disperses
Ethylenediamine solution is added after uniformly, Blue-Color Semitransparent aqueous polyurethane emulsion is obtained after continuing dispersion 70 minutes.Wherein, isocyanide
It is 0.1 that acid esters, which blocks three-functionality-degree polymer and the mass ratio of linear Waterborne Polyurethane Prepolymer,：1.The mole dosage of triethylamine
It is the 80% of the mole dosage of DMPA, the dosage of deionized water is 3.2 times of the gross mass of component A and component B.Chain extender rubs
Your dosage is the 15% of the mole of unreacted isocyanate group.
Embodiment 5
The polyethylene glycol in molar ratio 1 for being 1000 by HDI trimer and molecular weight：3 are added in there-necked flask, and stirring is warming up to
82 DEG C are reacted 2.5 hours, are obtained hydroxy-end capped three-functionality-degree polymer, are added the IPDI with polyethylene glycol equimolar amounts,
The reaction was continued at 80 DEG C 1.5 hours, forms isocyanate-terminated three-functionality-degree polymer, be cooled to 60 DEG C be added acetone dilution after
It is continuous to be cooled to room temperature, obtain component A.Wherein, acetone be generate isocyanate-terminated three-functionality-degree polymer reactant it is total
The 15% of quality.
Equipped with blender, condensing reflux pipe, thermocouple 250m1 four-hole boiling flasks in, be added IPDI, 2000 molecular weight
PPG and DMPA reacts 2.5 hours at 100 DEG C generates linear Waterborne Polyurethane Prepolymer, is then cooled to 65 DEG C of addition acetone
Viscosity reduction obtains component B.Wherein, the molar ratio of IPDI and PPG is 3：1, DMPA dosage is the IPDI and PPG reacted
The 3.5% of gross mass.The additive amount of acetone make a living linear Waterborne Polyurethane Prepolymer reactant gross mass 10%.
By component A and component B, insulated and stirred is added during triethylamine carries out and three second is added after ten minutes in 15 DEG C of water
Amine heat preservation disperses 4min in deionized water with high speed emulsion dispersion machine under 1300r/min high-speed stirreds after ten minutes, disperses
Ethylenediamine solution is added after uniformly, Blue-Color Semitransparent aqueous polyurethane emulsion is obtained after continuing dispersion 120 minutes.Wherein, different
It is 0.3 that cyanate, which blocks three-functionality-degree polymer and the mass ratio of linear Waterborne Polyurethane Prepolymer,：1.Triethylamine mole with
Amount is the 80% of the mole dosage of DMPA, and the dosage of deionized water is 3.2 times of the gross mass of component A and component B.Chain extender
Mole dosage is the 15% of the mole of unreacted isocyanate group.
Embodiment 6
The polyethylene glycol in molar ratio 1 for being 800 by IPDI tripolymers and molecular weight：3 are added in there-necked flask, and stirring is warming up to
81 DEG C are reacted 1.5 hours, are obtained hydroxy-end capped three-functionality-degree polymer, the HDI with polyethylene glycol equimolar amounts are added, 90
The reaction was continued at DEG C 2.5 hours, forms isocyanate-terminated three-functionality-degree polymer, is cooled to 62 DEG C and acetone dilution continuation is added
It is cooled to room temperature, obtains component A.Wherein, acetone is the total matter for the reactant for generating isocyanate-terminated three-functionality-degree polymer
The 7% of amount.
Equipped with blender, condensing reflux pipe, thermocouple 250m1 four-hole boiling flasks in, be added HDI, 2000 molecular weight PCL
8 hours production of linear Waterborne Polyurethane Prepolymers are reacted at 60 DEG C with DMPA, are then cooled to 60 DEG C of addition acetone viscosity reductions, are obtained
To component B.Wherein, the molar ratio of HDI and PCL is 5：1, DMPA dosage is the HDI reacted and the gross mass of PCL
8%.The additive amount of acetone make a living linear Waterborne Polyurethane Prepolymer reactant gross mass 30%.
By component A and component B, insulated and stirred is added during triethylamine carries out and three second is added after ten minutes in 32 DEG C of water
Amine heat preservation disperses 4min in deionized water with high speed emulsion dispersion machine under 2800r/min high-speed stirreds after ten minutes, disperses
Ethylenediamine solution is added after uniformly, Blue-Color Semitransparent aqueous polyurethane emulsion is obtained after continuing dispersion 180 minutes.Wherein, different
It is 0.4 that cyanate, which blocks three-functionality-degree polymer and the mass ratio of linear Waterborne Polyurethane Prepolymer,：1.Triethylamine mole with
Amount is the 120% of the mole dosage of DMPA, and the dosage of deionized water is 3.3 times of the gross mass of component A and component B.Chain extender
Mole dosage be unreacted isocyanate group mole 40%.
Comparative example
The aqueous polyurethane of Guangdong Guangdong U.S. Chemical Manufacture.
Test example
Film hardness test is carried out respectively to the polyurethane of Examples 1 to 6 and comparative example：According to GB/T2411-2008, use
Shore durometer detects；Form a film tensile property test：Test equipment uses GOTECH GT-7010-AEP, according to ASTM D882
Standard is tested；Leather abrasion resistance test：Test equipment uses GOTECH GT-7012-T, is marked according to GB/T 2726-2005
Standard is tested；Leather Bearable dry and wet wipe is tested：Test equipment uses GOTECH GT-7034-E2, is marked according to GB/T2537-2001
Standard is tested；Emulsion particle diameter is tested：It is detected using Malvern ParticleSizer ZEN1690；Color inhibition is tested：Use GOTECH GT-
7035-UA is tested according to ASTM D1148 standards；Storage stability：Lotion is taken to be placed in centrifugal separator,
It is centrifuged 15 minutes under 3000rpm/min, illustrates room temperature storage stability at 6 months or more if being generated without precipitation.Test
As a result such as table one.
Table one
As can be seen from Table I, the soluble polyurethane of the embodiment of the present invention is than the film forming softness of comparative example and physical
Can be good, enable to the surface touch that leather finish is submissive, soft.
In conclusion the preparation process of the aqueous polyurethane is not involved in prepolymer reaction, performed polymer viscosity is not interfered with, easily
In controlling of production process, it is not required to add a large amount of solvents.Softness is preferable after the aqueous polyurethane film forming obtained by the preparation method,
Reach the surface touch that leather finish is submissive, soft, while there is preferable physical property.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (25)
1. a kind of preparation method of aqueous polyurethane, which is characterized in that it includes the following steps：
HDI trimer or IPDI tripolymers are subjected to polymerisation with polyethylene glycol, obtain hydroxy-end capped three-functionality-degree polymer,
The hydroxy-end capped three-functionality-degree polymer is reacted into shape with hexamethylene diisocyanate or isophorone diisocyanate again
At isocyanate-terminated three-functionality-degree polymer, acetone is used in combination to adjust viscosity；
Hexamethylene diisocyanate or isophorone diisocyanate are carried out with di-alcohols monomer and hydrophilic monomer
Linear Waterborne Polyurethane Prepolymer is obtained by the reaction, acetone is used in combination to adjust viscosity；
By the isocyanate-terminated three-functionality-degree polymer for adjusting viscosity and adjusted the described linear aqueous poly- of viscosity
After urethane performed polymer carries out cross-linking reaction under the action of chain extender, acetone is removed.
2. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that the molecular weight of the polyethylene glycol
It is 400~1500, the HDI trimer or the molar ratio of the IPDI tripolymers and the polyethylene glycol are 1：3.
3. the preparation method of aqueous polyurethane according to claim 2, which is characterized in that the HDI trimer is described
IPDI tripolymers carry out 75~85 DEG C of the temperature of polymerisation with the polyethylene glycol, and the reaction time is 1~3 hour.
4. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that with the hydroxy-end capped trifunctional
The mole of the hexamethylene diisocyanate or the isophorone diisocyanate of spending polymer reaction is gathered with described
The mole of ethylene glycol is equal.
5. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that the hydroxy-end capped three-functionality-degree
The temperature that polymer is reacted with hexamethylene diisocyanate or isophorone diisocyanate is 70~90 DEG C, and the reaction time is
1~3 hour.
6. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that adjust the isocyanic acid with acetone
The viscosity that ester blocks three-functionality-degree polymer is carried out at a temperature of 58~65 DEG C, and the additive amount of the acetone is described in generation
The 5%~20% of the gross mass of the reactant of isocyanate-terminated three-functionality-degree polymer.
7. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that by two isocyanide of the hexa-methylene
The temperature that acid esters, the isophorone diisocyanate, the di-alcohols monomer and the hydrophilic monomer are reacted is
60~100 DEG C, the reaction time is 2~8 hours.
8. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that by two isocyanide of the hexa-methylene
The temperature that acid esters, the isophorone diisocyanate, the di-alcohols monomer and the hydrophilic monomer are reacted is
70~90 DEG C, the reaction time is 3~7 hours.
9. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that by two isocyanide of the hexa-methylene
The temperature that acid esters, the isophorone diisocyanate, the di-alcohols monomer and the hydrophilic monomer are reacted is
70~80 DEG C, 4~7 hours reaction time.
10. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that the hexa-methylene two is different
During cyanate or the isophorone diisocyanate are reacted with the di-alcohols monomer and the hydrophilic monomer, institute
The molar ratio for stating hexamethylene diisocyanate or the isophorone diisocyanate and the glycol monomer is 3~5：1.
11. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that the dosage of hydrophilic monomer is
The hexamethylene diisocyanate reacted or the isophorone diisocyanate and the di-alcohols monomer
The 3.5%~8% of gross mass.
12. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that the di-alcohols monomer
Molecular weight is 1000~3000.
13. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that the di-alcohols monomer packet
Include at least one of polypropylene glycol, polycaprolactone diols, polycarbonate glycol and polytetrahydrofuran ether dihydric alcohol.
14. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that hydrophilic monomer is selected from dihydroxy
One or both of methylpropanoic acid and dimethylolpropionic acid.
15. the preparation method of aqueous polyurethane according to claim 1, which is characterized in that adjusted with acetone described linear
The viscosity of Waterborne Polyurethane Prepolymer is carried out at a temperature of 58~65 DEG C, and the additive amount of the acetone is that generation is described linear
The 10%~30% of the gross mass of the reactant of Waterborne Polyurethane Prepolymer.
16. the preparation method of the aqueous polyurethane according to claim 1~15 any one, which is characterized in that described different
It is by the isocyanic acid that cyanate, which blocks three-functionality-degree polymer and the linear Waterborne Polyurethane Prepolymer progress cross-linking reaction,
Ester blocks three-functionality-degree polymer and the linear Waterborne Polyurethane Prepolymer and is neutralized after mixing with triethylamine, will in
After liquid with after is dispersed with stirring in deionized water, the chain extender is added, continues to be dispersed with stirring, is evaporated under reduced pressure out third
Ketone.
17. the preparation method of aqueous polyurethane according to claim 16, which is characterized in that the triethylamine mole with
Amount is the 80%~120% of the mole dosage of the hydrophilic monomer.
18. the preparation method of aqueous polyurethane according to claim 16, which is characterized in that triethylamine carry out neutralize be by
The mixing of the isocyanate-terminated three-functionality-degree polymer and the linear Waterborne Polyurethane Prepolymer is added in the triethylamine
It is stirred 5~30 minutes in liquid.
19. the preparation method of aqueous polyurethane according to claim 16, which is characterized in that by the liquid of neutralization go from
The rotating speed being dispersed with stirring in sub- water is 500~3000 revs/min, and it is 2~5 minutes to be dispersed with stirring the time.
20. the preparation method of aqueous polyurethane according to claim 16, which is characterized in that the chain extender is added and carries out
The mixing time being dispersed with stirring is 1~3 hour.
21. the preparation method of aqueous polyurethane according to claim 16, which is characterized in that chain extender is small molecule binary
Amine chain extender, the small molecule binary amine chain extender include at least one in hydrazine hydrate, ethylenediamine, butanediamine and hexamethylene diamine
Kind, the mole dosage of the chain extender is the 15%~40% of the mole of unreacted isocyanate group.
22. the preparation method of aqueous polyurethane according to claim 16, which is characterized in that described isocyanate-terminated three
The mass ratio of degree of functionality polymer and the linear Waterborne Polyurethane Prepolymer is 0.05~0.4：1, carry out the temperature of cross-linking reaction
Degree is 15~35 DEG C.
23. a kind of aqueous polyurethane, which is characterized in that it is by the aqueous polyurethane described in claim 1~22 any one
Preparation method is prepared.
24. a kind of leather, which is characterized in that the surface of the leather be coated with by the aqueous polyurethane described in claim 23 at
The coatings formed after film.
25. application of the aqueous polyurethane according to claim 23 in preparing leather.
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